JP7183593B2 - Photosensitive coloring composition, cured product, colored spacer, and image display device - Google Patents

Description

The present invention relates to a photosensitive coloring composition and the like. Specifically, for example, a photosensitive coloring composition preferably used for forming a colored spacer or the like in a color filter such as a liquid crystal display, a cured product and a colored spacer obtained by curing the photosensitive colored composition, and an image comprising the colored spacer. It relates to a display device.

A liquid crystal display (LCD) utilizes the property that the arrangement of liquid crystal molecules is switched by turning on and off a voltage to the liquid crystal. On the other hand, most of the members constituting the cell of the liquid crystal display are formed by a method using a photosensitive composition, typified by photolithography. The photosensitive composition is expected to be widely used in the future because it facilitates the formation of a fine structure and facilitates the processing of large-sized substrates.
In addition, LED backlights are now widely used in the mobile terminal and television industries because of their features such as high resolution, low cost, and thin form factor.

In recent years, in order to respond to the further increase in definition and brightness of color liquid crystal displays, color filter on array method (COA method) in which color filters are provided on the TFT element substrate side in active matrix liquid crystal displays, A black matrix on array system (BOA system) has been proposed in which only a black matrix is provided on the TFT element substrate side. Compared to the case where the black matrix is formed on the color filter side, this method does not require a margin for alignment with the active element side, so the aperture ratio can be increased, resulting in higher brightness. can be planned. Such a black matrix structure is required to have high light shielding properties and to suppress light leakage in the visible light region as much as possible.

In addition, along with the simplification of liquid crystal display structures and manufacturing processes, so-called columnar spacers, which are used to keep a constant distance between two substrates in a liquid crystal display, and colored spacers in which a photospacer and a black matrix are integrated. are also being developed. As such colored spacers, colored spacers using a plurality of kinds of organic coloring pigments have been proposed (see, for example, Patent Documents 1 and 2).
On the other hand, as in Patent Documents 3 to 5, there have also been proposed liquid crystal displays in which one or more color filter layers are provided in the portion facing the colored spacer in the frame portion.

JP 2012-181509 A WO2013/062011 Korean Patent Publication No. 10-2013-0015734 Korean Patent Publication No. 10-2014-0119912 Korean Patent Publication No. 10-2017-0017447

As a result of investigations by the present inventors, among various panel structures, in particular, in a liquid crystal display equipped with an LED backlight, in the case of a structure in which a blue color filter layer is provided in a portion facing a colored spacer in the frame portion is easy to transmit the blue light component derived from the LED, and the colored spacer formed using the photosensitive colored composition described in Patent Documents 1 and 2 suppresses light leakage at a wavelength of 400 to 500 nm and has light shielding properties. It has been found to be difficult to reconcile.
In addition, when manufacturing a liquid crystal display, a process of pressing a substrate having colored spacers and a counter substrate together is performed. , that is, mechanical properties such as elastic recovery rate are required.

The present invention has been made in view of the above circumstances, and provides a photosensitive coloring composition capable of forming a colored spacer that suppresses light leakage at a wavelength of 400 to 500 nm, has excellent light shielding properties, and has excellent mechanical properties. for the purpose.

As a result of intensive studies by the present inventors to solve the above problems, a specific pigment is used as a coloring agent, the content of the pigment is set in a specific range, and the content of the coloring agent is set in a specific range. As a result, the inventors have found that the above problems can be solved, and have completed the present invention.
That is, the present invention has the following configurations [1] to [8].

[1] A photosensitive coloring composition containing (a) a coloring agent, (b) an alkali-soluble resin, (c) a photopolymerization initiator, and (d) an ethylenically unsaturated compound,
The content of the (a) colorant is 23% by mass or less in the total solid content of the photosensitive coloring composition,
The (a) colorant comprises a yellow pigment and a red pigment and/or an orange pigment,
A photosensitive coloring composition, wherein the content of the yellow pigment in the coloring agent (a) is 40% by mass or more.
[2] The yellow pigment is C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, and C.I. I. The photosensitive coloring composition according to [1], comprising at least one selected from the group consisting of Pigment Yellow 150.
[3] The red pigment is C.I. I. Pigment Red 177, C.I. I. Pigment Red 254, and C.I. I. The photosensitive coloring composition according to [1] or [2], comprising at least one selected from the group consisting of Pigment Red 272.
[4] The orange pigment is C.I. I. Pigment Orange 13, C.I. I. Pigment Orange 43, C.I. I. Pigment Orange 64, and C.I. I. The photosensitive coloring composition according to any one of [1] to [3], comprising at least one selected from the group consisting of Pigment Orange 72.

[5] The photosensitive coloring composition according to any one of [1] to [4], wherein the content of the (a) coloring agent is 1% by mass or more in the total solid content of the photosensitive coloring composition. .
[6] The photosensitive coloring composition according to any one of [1] to [5], which is for forming a colored spacer.

[7] A cured product obtained by curing the photosensitive coloring composition according to any one of [1] to [6].
[8] A colored spacer composed of the cured product of [7].
[9] An image display device comprising the colored spacer according to [8].

According to the present invention, light leakage at a wavelength of 400 to 500 nm is suppressed, and a photosensitive coloring composition capable of forming a colored spacer having excellent light shielding properties and excellent mechanical properties, a cured product, a colored spacer, and further such An image display device with colored spacers can be provided.

FIG. 1 shows the emission spectrum of the light source used for color tone evaluation.

Embodiments of the present invention will be specifically described below, but the present invention is not limited to the following embodiments, and can be carried out with various modifications within the scope of the gist thereof.
In the present invention, "(meth)acryl" means "acryl and/or methacryl", and the same applies to "(meth)acrylate" and "(meth)acryloyl".

"(Co)polymer" means including both a single polymer (homopolymer) and a copolymer (copolymer), and "acid (anhydride)", "(anhydride) ... acid" , is meant to include both acids and their anhydrides. In the present invention, the "acrylic resin" means a (co)polymer containing (meth)acrylic acid and a (co)polymer containing a (meth)acrylic acid ester having a carboxyl group.

In the present invention, the term "monomer" is a term corresponding to so-called high-molecular substances (polymers), and in addition to narrowly defined monomers (monomers), it also includes dimers, trimers, oligomers, and the like. is.
In the present invention, the "total solid content" means all components other than the solvent contained in the photosensitive coloring composition or the ink described later.
In the present invention, the "weight average molecular weight" refers to the polystyrene-equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography).
In the present invention, unless otherwise specified, the "amine value" represents the amine value in terms of effective solid content, and is a value represented by the mass of KOH equivalent to the amount of base per 1 g of solid content of the dispersant. is. In addition, the measuring method will be described later. On the other hand, the "acid value" means the acid value in terms of effective solid content unless otherwise specified, and is calculated by neutralization titration.

Moreover, in this specification, percentages and parts represented by "mass" are synonymous with percentages and parts represented by "weight".
Further, in this specification, specific examples of pigments are sometimes indicated by pigment number, and terms such as "C.I. Pigment Red 2" mean color index (C.I.).

[Photosensitive coloring composition]
The photosensitive coloring composition of the present invention is
(a) a colorant (b) an alkali-soluble resin (c) a photopolymerization initiator (d) an ethylenically unsaturated compound is contained as an essential component, and if necessary, an adhesion improver such as a silane coupling agent, an interface It contains other compounding ingredients such as activators (coatability improvers), pigment derivatives, photoacid generators, cross-linking agents, mercapto compounds, development modifiers, ultraviolet absorbers, antioxidants, etc. Components are used in a state of being dissolved or dispersed in a solvent.

The photosensitive coloring composition of the present invention is a photosensitive coloring composition containing (a) a coloring agent, (b) an alkali-soluble resin, (c) a photopolymerization initiator, and (d) an ethylenically unsaturated compound. The content of the (a) colorant is 23% by mass or less in the total solid content of the photosensitive coloring composition, and the (a) colorant is a yellow pigment, a red pigment and/or an orange pigment. A photosensitive coloring composition, wherein the content of the yellow pigment in the (a) colorant is 40% by mass or more.

<(a) Colorant>
The (a) colorant contained in the photosensitive coloring composition of the present invention is a component that colors the photosensitive coloring composition. (a) A desired light absorption property can be obtained by containing a coloring agent. (a) As the colorant, a pigment may be used, or a dye may be used.

In the photosensitive coloring composition of the present invention, (a) the coloring agent contains a yellow pigment and a red pigment and/or an orange pigment, and (a) the content of the yellow pigment in the coloring agent is 40% by mass. That's it.
Since the yellow pigment has a maximum absorption peak wavelength near a wavelength of 400 to 450 nm in the absorption spectrum, the inclusion of the yellow pigment can efficiently reduce light leakage at a wavelength of 400 to 500 nm. In particular, the yellow pigment is contained. It is considered that the light leakage can be reduced to a practically sufficient level by setting the ratio to the above lower limit or higher. On the other hand, since the absorption at a wavelength of less than 400 nm is low, there is little overlap with the absorption band of the photopolymerization initiator, which is effective from the viewpoint of photocurability and sensitivity.
In addition, since red pigments and orange pigments have absorption peak maximum wavelengths in the vicinity of wavelengths of 450 to 600 nm in the absorption spectrum, it is considered that optical density (OD) increases by further containing red pigments and / or orange pigments. . Since the maximum wavelength of the absorption peak of a red pigment is on the longer wavelength side than that of an orange pigment, it is preferable to contain a red pigment from the viewpoint of optical density (OD). From a viewpoint, it is preferable that an orange pigment is included.

As a yellow pigment, C.I. I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95,97,100,101,104,105,108,109,110,111,116,117,119,120,126,127,127:1,128,129,133,134,136,138,139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208 can be mentioned. Among these, from the viewpoint of dispersibility and reliability, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180 and 185 are preferred, and C.I. I. Pigment Yellow 138, 139 and 150 are more preferred, and C.I. I. Pigment Yellow 139 is particularly preferred.

(a) The content of the yellow pigment in the colorant is not particularly limited as long as it is 40% by mass or more, but from the viewpoint of suppressing the transmittance at a wavelength of 400 to 500 nm, it is preferably 50% by mass or more, and 60% by mass or more. is more preferable, 70% by mass or more is more preferable, and 75% by mass or more is particularly preferable. On the other hand, from the viewpoint of optical density (OD), it is preferably 90% by mass or less, more preferably 80% by mass or less.

On the other hand, as a red pigment, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81: 3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276. Among these, C.I. I. Pigment Red 48: 1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment Red 177, 209, 224, 254 may be mentioned. In terms of dispersibility and light-shielding properties, C.I. I. Pigment Red 177, 254, and 272 are preferably used, and when the photosensitive coloring composition is cured with ultraviolet rays, it is preferable to use a red pigment having a low ultraviolet absorption rate. I. Pigment Red 254, 272 is more preferably used.

As an orange pigment (orange pigment), C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 can be mentioned. Among these, C.I. I. Pigment Orange 13, 43, 64, 72 is preferably used, and when the photosensitive coloring composition is cured with ultraviolet rays, it is preferable to use an orange pigment having a low ultraviolet absorption rate. C. I. Pigment Orange 64 and 72 are more preferred, and C.I. I. Pigment Orange 64 is particularly preferred.

(a) The total content of the red pigment and the orange pigment in the colorant is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and 15% by mass or more. is particularly preferable, 20% by mass or more is most preferable, and is usually 60% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 35% by mass or less, and 30% by mass or less. Especially preferred. The optical density (OD) tends to increase when it is at least the lower limit, and the transmittance at a wavelength of 400 to 500 nm tends to be sufficiently suppressed when it is at most the upper limit.

When the (a) colorant contains a red pigment, the content of the red pigment in the (a) colorant is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, and 10% by mass or more. It is more preferably 15% by mass or more, most preferably 20% by mass or more, and is usually 60% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less, and further 35% by mass or less. Preferably, 30% by mass or less is particularly preferable. The optical density (OD) tends to increase when it is at least the lower limit, and the transmittance at a wavelength of 400 to 500 nm tends to be sufficiently suppressed when it is at most the upper limit.

(a) When the colorant contains an orange pigment, the content of the orange pigment in the (a) colorant is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, and 10% by mass or more. more preferably 15% by mass or more, most preferably 20% by mass or more, and usually 60% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 35% by mass or less, 30 mass % or less is particularly preferable. By setting it to the lower limit or more, there is a tendency to easily achieve both optical density (OD) and transmittance suppression at a wavelength of 400 to 500 nm, and by setting it to the upper limit or less, the transmittance at a wavelength of 400 to 500 nm is sufficiently obtained. tend to be suppressed.

(a) The colorant may contain a colorant other than the yellow pigment, the red pigment and the orange pigment (hereinafter abbreviated as "other colorant"). Other coloring agents include pigments and dyes, and pigments are preferred from the viewpoint of heat resistance, and organic pigments are preferred from the viewpoints of color tone, photocurability and sensitivity.

Examples of pigments include organic coloring pigments such as blue pigments, purple pigments, green pigments, and brown pigments.

As a blue pigment, C.I. I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 can be mentioned. Among these, C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, more preferably C.I. I. Pigment Blue 15:6,16 may be mentioned.
In terms of dispersibility and light-shielding properties, C.I. I. Pigment Blue 15:6, 16, 60 is preferably used, and when the photosensitive coloring composition is cured with ultraviolet rays, it is preferable to use a blue pigment having a low ultraviolet absorption rate. C. I. Pigment Blue 60 is more preferably used. On the other hand, as described in Korean Patent No. 10-1840984, C.I. I. Pigment Blue 16 is preferably used.

As a purple pigment, C.I. I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 can be mentioned. Among these, C.I. I. Pigment Violet 19, 23, more preferably C.I. I. Pigment Violet 23 may be mentioned.
On the other hand, from the viewpoint of dispersibility, C.I. I. Pigment Violet 29 is preferably used.

As a green pigment, C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59 . Among these, from the viewpoint of dispersibility, C.I. I. Pigment Green 7, 36 can be mentioned.

As a brown pigment (brown pigment), C.I. I. Pigment Brown 23, 25, 26, 28, 38, 41, 83, 93 can be mentioned. Among these, C.I. I. Pigment Brown 26, 28, 83, 93 may be mentioned.

Among these organic coloring pigments, from the viewpoint of color tone, for example, it is preferable that the content of blue pigments and violet pigments is low. From this point of view, the total content of the blue pigment and the purple pigment in the (a) colorant is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and 20% by mass or less. is particularly preferred, and 0% by mass is most preferred. That is, it is most preferable that (a) the colorant does not contain a blue pigment and a purple pigment.

(a) The content of the blue pigment in the colorant is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, particularly preferably 20% by mass or less, and most preferably 0% by mass. preferable. By making it below the said upper limit, there exists a tendency which becomes favorable color tone.

(a) The content of the purple pigment in the colorant is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, particularly preferably 20% by mass or less, and most preferably 0% by mass. preferable. By making it below the said upper limit, there exists a tendency which becomes favorable color tone.

On the other hand, from the viewpoint of light shielding properties, it may contain a blue pigment and/or a purple pigment. In that case, the total content of the blue pigment and the purple pigment in the (a) colorant is preferably 2% by mass or more, more preferably 5% by mass or more, further preferably 8% by mass or more, and 10% by mass. 50% by mass or less is preferable, 40% by mass or less is more preferable, 30% by mass or less is even more preferable, 20% by mass or less is even more preferable, and 15% by mass or less is particularly preferable. When it is above the lower limit, the optical density (OD) tends to increase, and when it is below the upper limit, the transmittance at a wavelength of 400 to 500 nm tends to decrease.

Moreover, a black pigment may be included as another coloring agent. Examples of black pigments include organic black pigments and inorganic black pigments. As an organic black pigment, for example, an organic containing at least one selected from the group consisting of a compound represented by the following formula (1), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound A black pigment is mentioned.

wherein R ¹ and R ⁶ are each independently a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;
^R2 , ^R3 , ^R4 , ^R5 , ^R7 , ^R8 , ^R9 and ^R10 are each independently a hydrogen atom, a halogen atom, ^R11 , COOH, ^COOR11 , ^COO- , _CONH2 , ^CONHR11 , ^{CONR11R12 ,} CN, OH, ^OR11 , ^COCR11 , _OOCNH2 , ^{OOCNHR11 , OOCNR11R12} , NO2 ^, _NH2 , ^NHR11 , ^NR11R12 , ^{NHCOR12 ,} _NR11COR12 , ^N = _CH2 , _N = ^{CHR11 ,} N ₌ ^CR11R12 , SH, ^SR11 , ^SOR11 _, ^{SO2R11 , SO3R11} , _SO3H , _SO3- ^, _SO2NH2 , _SO2NHR11 ^or _SO2NR11R12 ^;
and at least one combination selected from the group consisting of ^R2 and ^R3 , ^R3 and ^R4 , ^R4 and ^R5 , ^R7 and ^R8 , ^R8 and ^R9 , and ^R9 and ^R10 , can be directly linked to each other or linked to each other by an oxygen atom, sulfur atom, NH or NR ¹¹ bridge;
R ¹¹ and R ¹² each independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or a cycloalkenyl group having 3 to 12 carbon atoms. 2 to 12 alkynyl groups.

The geometric isomers of the compound represented by the general formula (1) have the following core structure (the substituents in the structural formula are omitted), and the trans-trans isomer is probably the most stable. be.

When the compound of general formula (1) is anionic, its charge can be transferred to any known suitable cation, such as metallic, organic, inorganic or metal-organic cations, especially alkali metals, alkaline earth metals. , a transition metal, a primary ammonium, a secondary ammonium, a tertiary ammonium such as a trialkylammonium, a quaternary ammonium such as a tetraalkylammonium or a salt compensated by an organometallic complex. Moreover, when the geometric isomer of the compound represented by general formula (1) is anionic, it is preferably a similar salt.

In the substituents of the general formula (1) and their definitions, the following are preferable because the shielding rate tends to be high. This is because the following substituents have no absorption and are considered not to affect the hue of the pigment.
R ² , R ⁴ , R ⁵ , R ⁷ , R ⁹ and R ¹⁰ are each independently preferably a hydrogen atom, a fluorine atom or a chlorine atom, more preferably a hydrogen atom.
R ³ and R ⁸ are each independently preferably hydrogen atom, NO ₂ , OCH ₃ , OC ₂ H ₅ , bromine atom, chlorine atom, CH ₃ , C ₂ H ₅ , N(CH ₃ ) ₂ , N(CH ₃ ) (C ₂ H ₅ ), N(C ₂ H ₅ ) ₂ , α-naphthyl, β-naphthyl, SO ₃ H or SO ₃ ^- , more preferably a hydrogen atom or SO ₃ H.

R ¹ and R ⁶ are each independently preferably a hydrogen atom, CH ₃ or CF ₃ , more preferably a hydrogen atom.
Preferably, at least one combination selected from the group consisting of R ¹ and R ⁶ , R ² and R ⁷ , R ³ and R ⁸ , R ⁴ and R ⁹ , and R ⁵ and R ¹⁰ is the same, more preferably is the same as R ⁶ , R ² is the same as R ⁷ , R ³ is the same ^as R ⁸ , R ⁴ is the same as R ⁹ , and R ⁵ is the same as R ¹⁰ are identical.

Alkyl groups having 1 to 12 carbon atoms are, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, 2-methylbutyl group, n- pentyl group, 2-pentyl group, 3-pentyl group, 2,2-dimethylpropyl group, n-hexyl group, heptyl group, n-octyl group, 1,1,3,3-tetramethylbutyl group, 2-ethylhexyl nonyl group, decyl group, undecyl group or dodecyl group.

Cycloalkyl groups having 3 to 12 carbon atoms are, for example, cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, trimethylcyclohexyl, thuzyl, norbornyl, bornyl, and norcalyl groups. , a karyl group, a menthyl group, a norpinyl group, a pinyl group, a 1-adamantyl group or a 2-adamantyl group.

Alkenyl groups having 2 to 12 carbon atoms are, for example, vinyl group, allyl group, 2-propen-2-yl group, 2-buten-1-yl group, 3-buten-1-yl group, 1,3-butadiene -2-yl group, 2-penten-1-yl group, 3-penten-2-yl group, 2-menthyl-1-buten-3-yl group, 2-methyl-3-buten-2-yl group, 3-methyl-2-buten-1-yl group, 1,4-pentadien-3-yl group, hexenyl group, octenyl group, nonenyl group, decenyl group or dodecenyl group.

Cycloalkenyl groups having 3 to 12 carbon atoms are, for example, 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2 , 4-cyclohexadien-1-yl group, 1-p-menthen-8-yl group, 4(10)-thugen-10-yl group, 2-norbornen-1-yl group, 2,5-norbornadiene-1 -yl group, 7,7-dimethyl-2,4-norcaladien-3-yl group or camphenyl group.

Alkynyl groups having 2 to 12 carbon atoms are, for example, 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl group, 1,4-pentadiyn-3-yl group, 1,3-pentadiyn-5-yl group, 1-hexyn-6-yl group, cis-3-methyl-2-penten-4-yn-1-yl group, trans-3-methyl-2-penten-4-yn-1-yl group, 1,3-hexadiyn-5-yl group, 1-octin-8-yl group, 1-nonin-9-yl group, 1-decyn-10-yl group or 1-dodecyn-12-yl group.

A halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The organic black pigment is preferably a compound represented by the following general formula (2) and/or a geometric isomer of the compound, more preferably a compound represented by the following general formula (2).

A specific example of such an organic black pigment is Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF).
This organic black pigment is preferably used by dispersing it with a dispersant, solvent, and method, which will be described later. Further, at the time of dispersion, the sulfonic acid derivative of the compound represented by the general formula (1) or the sulfonic acid derivative of the compound, particularly the sulfonic acid derivative of the compound represented by the general formula (2) or the geometry of the compound The presence of isomeric sulfonic acid derivatives may improve dispersibility and storage stability.
In addition, as an organic black pigment, from the viewpoint of optical properties and reliability, the organic black pigment described in Korean Patent Publication No. 10-2018-0052502 and the organic black pigment described in Korean Patent Publication No. 10-2018-0052864. It is preferable to use an organic black pigment that has been used.

Other organic black pigments include aniline black, cyanine black, perylene black, and the like. Carbon black, which is an inorganic black pigment, may also be used. Examples of carbon black include the following carbon blacks.

Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600, MCF88, #5, #10, #20, #25, #30, #32, #33, #40 , #44, #45, #47, #50, #52, #55, #650, #750, #850, #900, #950, #960, #970, #980, #990, #1000, # 2200, #2300, #2350, #2400, #2600, #2650, #3030, #3050, #3150, #3250, #3400, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B , OIL11B, OIL30B, OIL31B
Degussa Corporation: Printex (registered trademark, hereinafter the same) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex Printx Printx L, Printex Printx Printx L Ｖ、ＰｒｉｎｔｅｘＧ、ＳｐｅｃｉａｌＢｌａｃｋ５５０、ＳｐｅｃｉａｌＢｌａｃｋ３５０、ＳｐｅｃｉａｌＢｌａｃｋ２５０、ＳｐｅｃｉａｌＢｌａｃｋ１００、ＳｐｅｃｉａｌＢｌａｃｋ６、ＳｐｅｃｉａｌＢｌａｃｋ５、ＳｐｅｃｉａｌＢｌａｃｋ４、Ｃｏｌｏｒ Ｂｌａｃｋ ＦＷ１、Ｃｏｌｏｒ Ｂｌａｃｋ ＦＷ２、Ｃｏｌｏｒ Ｂｌａｃｋ ＦＷ２Ｖ、Ｃｏｌｏｒ Ｂｌａｃｋ ＦＷ１８、Ｃｏｌｏｒ Ｂｌａｃｋ ＦＷ２００、Ｃｏｌｏｒ Ｂｌａｃｋ Ｓ１６０、Ｃｏｌｏｒ Ｂｌａｃｋ Ｓ１７０
Cabot Corporation: Monarch (registered trademark, hereinafter the same) 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL (registered trademark, the same hereinafter) 99, REGAL 99, REGAL 99 REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN® XC72R, ELFTEX®-8
ビルラー社製：ＲＡＶＥＮ（登録商標、以下同じ。）１１、ＲＡＶＥＮ１４、ＲＡＶＥＮ１５、ＲＡＶＥＮ１６、ＲＡＶＥＮ２２ＲＡＶＥＮ３０、ＲＡＶＥＮ３５、ＲＡＶＥＮ４０、ＲＡＶＥＮ４１０、ＲＡＶＥＮ４２０、ＲＡＶＥＮ４５０、ＲＡＶＥＮ５００、ＲＡＶＥＮ７８０、ＲＡＶＥＮ８５０、ＲＡＶＥＮ８９０Ｈ、ＲＡＶＥＮ１０００、ＲＡＶＥＮ１０２０、ＲＡＶＥＮ１０４０、ＲＡＶＥＮ１０６０Ｕ、ＲＡＶＥＮ１０８０Ｕ , RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

Carbon black that is coated with a resin may be used. The use of resin-coated carbon black has the effect of improving the adhesion to the glass substrate and the volume resistivity. As the resin-coated carbon black, for example, carbon black described in JP-A-09-71733 can be preferably used. Resin-coated carbon black is preferably used in terms of volume resistance and dielectric constant.

These pigments are preferably dispersed so that the average particle size is usually 1 μm or less, preferably 0.5 μm or less, more preferably 0.25 μm or less. Here, the standard for the average particle size is the number of pigment particles.
In addition, in the photosensitive coloring composition, the average particle size of the pigment is a value obtained from the pigment particle size measured by dynamic light scattering (DLS). Particle size measurement is performed with a sufficiently diluted photosensitive coloring composition (usually diluted to prepare a pigment concentration of about 0.005 to 0.2% by mass. However, if there is a concentration recommended by the measuring instrument, that concentration) and measured at 25°C.

In addition to the pigments described above, dyes may also be used as other colorants. Dyes that can be used as other colorants include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
Examples of azo dyes include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Mordan Tread 7, C.I. I. Mordant Yellow 5, C.I. I. mordant black 7 and the like.

Examples of anthraquinone dyes include C.I. I. bat blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 and the like can be mentioned.
In addition, as a phthalocyanine dye, for example, C.I. I. Pad Blue 5 and the like are quinone imine dyes, for example, C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes, for example, C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro-based dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Examples include Disperse Yellow 42 and the like.

<(b) Alkali-soluble resin>
The (b) alkali-soluble resin used in the present invention is not particularly limited as long as it is a resin containing a carboxyl group or a hydroxyl group. Urethane resins, novolak-based resins, polyvinylphenol-based resins, and the like can be mentioned, but (b1) epoxy (meth)acrylate-based resins (b2) acrylic-based resins are preferably used from the viewpoint of excellent plate-making properties. These can be used individually by 1 type or in mixture of multiple types.

<(b1) Epoxy (meth)acrylate resin>
(b1) Epoxy (meth)acrylate resin is a reaction product of an epoxy resin (epoxy compound) and an α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group. , a resin obtained by further reacting the hydroxyl group produced by the reaction with a polybasic acid and/or its anhydride.
Also, before reacting the polybasic acid and/or its anhydride with a hydroxyl group, after reacting a compound having two or more substituents capable of reacting with the hydroxyl group, the polybasic acid and/or its anhydride is reacted. The resin obtained by the reaction is also included in the (b1) epoxy (meth)acrylate resin.

The epoxy (meth)acrylate resin (b1) also includes a resin obtained by reacting the carboxyl group of the resin obtained by the above reaction with a compound having a reactive functional group.
Thus, the epoxy (meth)acrylate resin has substantially no epoxy group due to its chemical structure, and is not limited to "(meth)acrylate", but an epoxy compound (epoxy resin) is a raw material. and "(meth)acrylate" is a typical example, so it is named in this way according to common practice.

Specifically, the (b1) epoxy (meth)acrylate resin used in the present invention includes the following epoxy (meth)acrylate resin (b1-1) and/or epoxy (meth)acrylate resin (b1-2) (hereinafter sometimes referred to as "carboxyl group-containing epoxy (meth)acrylate resin") is preferably used from the viewpoint of developability and reliability.

<Epoxy (meth)acrylate resin (b1-1)>
Obtained by adding an α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting a polybasic acid and/or its anhydride. alkali-soluble resin.
<Epoxy (meth)acrylate resin alkali-soluble resin (b1-2)>
An α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group is added to an epoxy resin, and a polyhydric alcohol and a polybasic acid and/or its anhydride are added. Alkali-soluble resin obtained by reacting.

Here, the epoxy resin includes a raw material compound before forming a resin by thermosetting, and the epoxy resin can be appropriately selected and used from known epoxy resins. As the epoxy resin, a compound obtained by reacting a phenolic compound and epihalohydrin can be used. The phenolic compound is preferably a compound having two or more phenolic hydroxyl groups, and may be either a monomer or a polymer.
The types of epoxy resins used as raw materials include cresol novolak type epoxy resin, phenol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenolmethane type epoxy resin, biphenyl novolak type epoxy resin, and naphthalene novolak type epoxy resin. Epoxy resins, epoxy resins which are reaction products of polyaddition reaction products of dicyclopentadiene and phenol or cresol and epihalohydrin, adamantyl group-containing epoxy resins, fluorene-type epoxy resins, and the like can be suitably used. Those having an aromatic ring in the main chain can be preferably used.

Further, specific examples of the epoxy resin include, for example, bisphenol A type epoxy resin (for example, "jER (registered trademark, hereinafter the same.) -828", "jER-1001", "jER-1002" manufactured by Mitsubishi Chemical Corporation). , "jER-1004", "NER-1302" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 323, softening point 76 ° C.), etc.), bisphenol F type resin (for example, manufactured by Mitsubishi Chemical Corporation "jER-807", " jER-4004P", "jER-4005P", "jER-4007P", Nippon Kayaku's "NER-7406" (epoxy equivalent 350, softening point 66 ° C.), etc.), bisphenol S-type epoxy resin, biphenyl glycidyl ether (For example, "jER-YX4000" manufactured by Mitsubishi Chemical Corporation), phenolic novolac type epoxy resin (for example, "EPPN (registered trademark, the same shall apply hereinafter)-201" manufactured by Nippon Kayaku Co., Ltd., "jER" manufactured by Mitsubishi Chemical Corporation -152", "jER-154", "DEN-438" manufactured by Dow Chemical Co.), (o, m, p-) cresol novolak type epoxy resin (for example, Nippon Kayaku Co., Ltd. "EOCN (registered trademark, The same shall apply hereinafter.)-102S”, “EOCN-1020”, “EOCN-104S”), triglycidyl isocyanurate (for example, “TEPIC (registered trademark)” manufactured by Nissan Chemical Industries, Ltd.), trisphenolmethane-type epoxy resin (for example, , “EPPN-501”, “EPPN-502”, “EPPN-503” manufactured by Nippon Kayaku Co., Ltd.), alicyclic epoxy resin (manufactured by Daicel “Celoxide (registered trademark, hereinafter the same) 2021P”, “ Celoxide EHPE"), epoxy resin obtained by glycidylating phenolic resin by reaction of dicyclopentadiene and phenol (for example, "EXA-7200" manufactured by DIC, "NC-7300" manufactured by Nippon Kayaku), the following general formula Epoxy resins represented by (B1) to (B4) and the like can be preferably used. Specifically, "XD-1000" manufactured by Nippon Kayaku Co., Ltd. as the epoxy resin represented by the following general formula (B1), and "XD-1000" manufactured by Nippon Kayaku Co., Ltd. as the epoxy resin represented by the following general formula (B2) NC-3000", and "ESF-300" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. as an epoxy resin represented by the following general formula (B4).

In the above general formula (B1), a is an average value and represents a number from 0 to 10. R ¹¹¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group. Plural R ¹¹¹ in one molecule may be the same or different.

In the above general formula (B2), b is an average value and represents a number from 0 to 10. R ¹²¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group. Plural R ¹²¹ in one molecule may be the same or different.

In general formula (B3) above, X represents a linking group represented by general formula (B3-1) or (B3-2) below. However, it contains one or more adamantane structures in its molecular structure. c represents 2 or 3;

In general formulas (B3-1) and (B3-2) above, R ¹³¹ to R ¹³⁴ and R ¹³⁵ to R ¹³⁷ each independently represent an optionally substituted adamantyl group, a hydrogen atom, or a substituent. represents an optionally substituted alkyl group having 1 to 12 carbon atoms or a phenyl group optionally having a substituent; * represents a bond.

In general formula (B4) above, p and q each independently represent an integer of 0 to 4, and R ¹⁴¹ and R ¹⁴² each independently represent an alkyl group having 1 to 4 carbon atoms or a halogen atom. R ¹⁴³ and R ¹⁴⁴ each independently represent an alkylene group having 1 to 4 carbon atoms. x and y each independently represent an integer of 0 or more.

Among these, epoxy resins represented by any one of general formulas (B1) to (B4) are preferably used.

α,β-unsaturated monocarboxylic acids and/or α,β-unsaturated monocarboxylic acid esters having a carboxyl group include (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, Monocarboxylic acids such as α-position haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyladipic acid, 2 - (meth) acryloyloxyethyl phthalate, 2-(meth) acryloyloxyethyl hexahydrophthalate, 2-(meth) acryloyloxyethyl maleate, 2-(meth) acryloyloxypropyl succinate, 2 - (meth) acryloyloxypropyl adipate, 2-(meth) acryloyloxypropyl tetrahydrophthalate, 2-(meth) acryloyloxypropyl phthalate, 2-(meth) acryloyloxypropyl maleate, 2- (Meth) acryloyloxybutyl succinate, 2-(meth) acryloyloxybutyl adipate, 2-(meth) acryloyloxybutyl hydrophthalate, 2-(meth) acryloyloxybutyl phthalate, 2-( meth) Acryloyloxybutyl maleate (meth), a monomer obtained by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone to acrylic acid, or hydroxy Acids (anhydrides) such as (anhydride) succinic acid, (anhydride) phthalic acid, and (anhydride) maleic acid are added to alkyl (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate. monomer, (meth)acrylic acid dimer, and the like.
Among these, (meth)acrylic acid is particularly preferable from the viewpoint of sensitivity.

As a method for adding an α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, a known technique can be used. For example, an α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group is reacted with an epoxy resin at a temperature of 50 to 150° C. in the presence of an esterification catalyst. be able to. Examples of the esterification catalyst used here include tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine and benzyldiethylamine, quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride and dodecyltrimethylammonium chloride. .

The epoxy resin, the α,β-unsaturated monocarboxylic acid and/or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group, and the esterification catalyst may be used singly. You may use 2 or more types together.
The amount of the α,β-unsaturated monocarboxylic acid and/or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group is in the range of 0.5 to 1.2 equivalents per equivalent of the epoxy group of the epoxy resin. is preferred, more preferably in the range of 0.7 to 1.1 equivalents. By setting the amount of the α,β-unsaturated monocarboxylic acid and/or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group to the above lower limit or more, the introduction amount of the unsaturated group can be suppressed, Subsequent reaction with polybasic acid and/or its anhydride tends to be sufficient as well. On the other hand, by setting it to the above upper limit or less, it is possible to suppress the remaining unreacted matter of the α,β-unsaturated monocarboxylic acid and/or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group, and to improve the curing characteristics. It is recognized that there is a tendency to make things easier.

Polybasic acids and/or their anhydrides include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid. One or more selected from acids, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, anhydrides thereof, and the like.

Maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or anhydrides thereof are preferred. Particularly preferred are tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, and biphenyltetracarboxylic dianhydride.

A known method can also be used for the addition reaction of polybasic acids and/or their anhydrides. The desired product can be obtained by continuing the reaction under the same conditions as the addition reaction of the carboxylic acid ester. The amount of polybasic acid and/or its anhydride component to be added is preferably such that the resulting carboxyl group-containing epoxy (meth)acrylate resin has an acid value in the range of 10 to 150 mgKOH/g. It is preferred to be in the range of 20 to 140 mgKOH/g. Alkali developability tends to be improved by setting the amount to the above lower limit or more, and curing performance tends to be improved by setting the amount to the above upper limit or less.

A multi-branched structure may be introduced by adding a polyhydric alcohol such as trimethylolpropane, pentaerythritol or dipentaerythritol during the addition reaction of the polybasic acid and/or its anhydride.

A carboxyl group-containing epoxy (meth)acrylate resin is usually a reaction product of an epoxy resin and an α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group. After mixing a basic acid and/or its anhydride, or to a reaction product of an epoxy resin and an α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group, It is obtained by heating after mixing a polybasic acid and/or its anhydride and a polyhydric alcohol. In this case, the order of mixing the polybasic acid and/or its anhydride and the polyhydric alcohol is not particularly limited. Any present in a mixture of a reaction product of an epoxy resin and an α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group and a polyhydric alcohol when heated A polybasic acid and/or its anhydride undergoes an addition reaction with the hydroxyl group of .

As the carboxyl group-containing epoxy (meth) acrylate resin, in addition to the above-mentioned ones, Korean Patent No. 10-2013-0022955, Korean Patent No. 10-0965189, JP 2005-165294, JP 2005-165294, Examples thereof include those described in JP-A-2006-312704.

The polystyrene equivalent weight average molecular weight (Mw) of the epoxy (meth)acrylate resin measured by gel permeation chromatography (GPC) is usually 1,000 or more, preferably 1,500 or more, more preferably 2,000 or more. , more preferably 2,500 or more, usually 10,000 or less, preferably 8,000 or less, more preferably 6,000 or less, still more preferably 5,000 or less, particularly preferably 4,000 or less. When the lower limit value or more is used, the solubility in the developer tends to be suppressed from becoming too high, and when the upper limit value or less is used, the solubility in the developer tends to be improved.

The acid value of the epoxy (meth)acrylate resin is not particularly limited, but is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, and preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less, and 100 mgKOH/g. g or less is more preferable, and 50 mgKOH/g or less is particularly preferable. When the content is at least the above lower limit, there is a tendency to obtain appropriate development solubility, and when the content is at most the above upper limit, there is a tendency to suppress film dissolution due to excessive development.

Although the chemical structure of the epoxy (meth)acrylate resin (b1) is not particularly limited, for example, epoxy (meth)acrylate resin (b1-A) having a partial structure (1) represented by the following general formula (I) (hereinafter sometimes abbreviated as “epoxy (meth)acrylate resin (b1-A)”). Since the epoxy (meth)acrylate resin (b1-A) has three or more (meth)acryloyloxy groups in the partial structure represented by formula (I), the amount of ethylenic double bonds in one molecule of the resin is In many cases, when a colored spacer is formed using a photosensitive coloring composition containing the resin, the cross-linking density increases, and the elution of impurities into the solvent is suppressed to ensure high reliability, and the cross-linking density of the spacer is high. There is a tendency for the mechanical properties to improve as a result.

(Partial structure (1))

In formula (I) above, R ¹ represents a hydrogen atom or a methyl group. R ² , R ³ , R ⁵ and R ⁶ each independently represent an optionally substituted alkylene group.
R ⁴ represents an n+1-valent linking group.
^R7 represents an optionally substituted alkylene group, an optionally substituted alkenylene group or an optionally substituted aromatic ring group.
l and m each independently represent an integer of 0 to 12;
n represents an integer of 3 or more. * represents a bond.

( ^R2 , ^R3 , ^R5 and ^R6 )
In formula (I), R ² , R ³ , R ⁵ and R ⁶ each independently represent an optionally substituted alkylene group.
Alkylene groups may be linear, branched, cyclic, or combinations thereof. Although the number of carbon atoms is not particularly limited, it is usually 1 or more, and usually 8 or less, preferably 6 or less, more preferably 4 or less, and still more preferably 2 or less. The compatibility with other components tends to be improved by setting the content to the above upper limit or less.

Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, and a cyclohexylene group. From the viewpoint of compatibility with other components, a methylene group or an ethylene group is preferred, and a methylene group is more preferred. .

Examples of the substituent that the alkylene group may have include an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxy group, a carboxyl group, and the like. It is preferably unsubstituted.

( ^R4 )
In the general formula (I), R ⁴ represents an n+1-valent linking group. Although the chemical structure of the n+1-valent linking group is not particularly limited, examples thereof include an optionally substituted n+1-valent hydrocarbon group. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group from the viewpoint of developability. Further, a carbon-carbon single bond in the hydrocarbon group may be interrupted by at least one selected from the group consisting of -O-, -CO- and -NH-.

Specific examples of the n+1-valent linking group include the following. * in the chemical formula represents a bond.

( ^R7 )
In the above formula (I), R ⁷ is an optionally substituted alkylene group, an optionally substituted alkenylene group or an optionally substituted divalent aromatic ring group represents

The alkylene group for ^R7 may be linear, branched, cyclic, or a combination thereof. Although the number of carbon atoms is not particularly limited, it is usually 1 or more, preferably 2 or more, and usually 8 or less, preferably 6 or less, more preferably 4 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, curability tends to be improved.

Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a hexylene group, and a cyclohexylene group. From the viewpoint of curability, a methylene group or an ethylene group is preferred, and an ethylene group is more preferred.

Examples of the substituent that the alkylene group may have include an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxy group, a carboxyl group, and the like. Substitution is preferred.

The alkenylene group at ^R7 may be linear, branched, cyclic, or a combination thereof. Although the number of carbon atoms is not particularly limited, it is usually 2 or more, preferably 4 or more, and usually 8 or less, preferably 6 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, curability tends to be improved.

Specific examples of the alkenylene group include an ethenylene group, a propenylene group, a butenylene group, and a cyclohexenylene group. From the viewpoint of curability, an ethenylene group or a cyclohexenylene group is preferred, and an ethenylene group is more preferred.

Examples of the substituent that the alkenylene group may have include an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxy group, a carboxyl group, and the like. Substitution is preferred.

The divalent aromatic ring group for R ⁷ includes a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, preferably 40 or less, more preferably 30 or less, further preferably 20 or less, even more preferably 15 or less, and 10 or less. Especially preferred. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, curability tends to be improved.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. The divalent aromatic hydrocarbon ring group includes, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, which have two free valences, Groups such as triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring can be mentioned.
In addition, the aromatic heterocycle in the divalent aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of divalent aromatic heterocyclic groups include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, and indole ring having two free valences. ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, groups such as pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring and azulene ring; .
Among the divalent aromatic ring groups, from the viewpoint of photocurability, a benzene ring or a naphthalene ring having two free valences is preferred, and a benzene ring having two free valences is more preferred.

Examples of substituents that the divalent aromatic ring group may have include alkyl groups, alkoxy groups, halogen atoms (-F, -Cl, -Br, -I), hydroxy groups, carboxyl groups, and the like. . Among these, unsubstituted is preferred from the viewpoint of curability.

Among these, from the viewpoint of curability, R ⁷ is preferably an optionally substituted alkylene group, more preferably an unsubstituted alkylene group, and even more preferably an ethylene group.

(l and m)
In the general formula (I), l and m each independently represent an integer of 0-12. From the viewpoint of development adhesion, it is preferably 0 or more, more preferably 1 or more, and from the viewpoint of curability, it is preferably 8 or less, more preferably 6 or less, and 4 The following are more preferable, and 2 or less are particularly preferable. On the other hand, it is preferably 0 from the viewpoint of curability.

(n)
In the general formula (I), n represents an integer of 3 or more. n is preferably 4 or more, more preferably 5 or more, preferably 10 or less, more preferably 8 or less, still more preferably 7 or less, and particularly preferably 6 or less. When the content is at least the lower limit, curability tends to be good, and when the content is at most the upper limit, solubility in development tends to be good.

(Partial structure (2))
From the viewpoint of development solubility, the epoxy (meth)acrylate resin (b1-A) preferably has a partial structure (2) represented by the following general formula (II).

In formula (II) above, R ⁸ represents an optionally substituted alkylene group, an optionally substituted alkenylene group, or an optionally substituted aromatic ring group. * represents a bond.

( ^R8 )
In the above formula (II), R ⁸ is an optionally substituted alkylene group, an optionally substituted alkenylene group or an optionally substituted divalent aromatic ring group represents

The alkylene group for R ⁸ may be linear, branched, cyclic, or a combination thereof. Although the number of carbon atoms is not particularly limited, it is usually 1 or more, preferably 2 or more, and usually 8 or less, preferably 6 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, curability tends to be improved.

Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a hexylene group, and a cyclohexylene group. From the viewpoint of curability, a methylene group or an ethylene group is preferred, and an ethylene group is more preferred.

Examples of the substituent that the alkylene group may have include an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxy group, a carboxyl group, and the like. Substitution is preferred.

The alkenylene group at R ⁸ may be linear, branched, cyclic, or a combination thereof. Although the number of carbon atoms is not particularly limited, it is usually 2 or more, preferably 4 or more, and usually 8 or less, preferably 6 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, curability tends to be improved.

Specific examples of the alkenylene group include an ethenylene group, a propenylene group, a butenylene group, and a cyclohexenylene group. From the viewpoint of curability, an ethenylene group or a cyclohexenylene group is preferred, and a cyclohexenylene group is more preferred.

Examples of the substituent that the alkenylene group may have include an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxy group, a carboxyl group, and the like. Substitution is preferred.

The divalent aromatic ring group for R ⁸ includes a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, preferably 40 or less, more preferably 30 or less, further preferably 20 or less, even more preferably 15 or less, and 10 or less. Especially preferred. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, curability tends to be improved.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. The divalent aromatic hydrocarbon ring group includes, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, which have two free valences, Groups such as triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring can be mentioned.
In addition, the aromatic heterocycle in the divalent aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of divalent aromatic heterocyclic groups include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, and indole ring having two free valences. ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, groups such as pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring and azulene ring; . Among these, from the viewpoint of photocurability, a benzene ring or a naphthalene ring having two free valences is preferred, and a benzene ring having two free valences is more preferred.

Examples of substituents that the divalent aromatic ring group may have include alkyl groups, alkoxy groups, halogen atoms (-F, -Cl, -Br, -I), hydroxy groups, carboxyl groups, and the like. . Among these, unsubstituted is preferred from the viewpoint of curability.

Among these, from the viewpoint of curability, R ⁸ is preferably an optionally substituted alkenylene group, more preferably an unsubstituted alkenylene group, and further preferably a cyclohexenylene group. preferable.

Specific examples of the partial structure (2) represented by the formula (II) include the following. * in the chemical formula represents a bond.

(Partial structure (3))
From the viewpoint of curability, the epoxy (meth)acrylate resin (b1-A) preferably has a partial structure (3) represented by the following general formula (III).

In formula (III) above, R ⁹ represents an epoxy resin residue. p represents an integer of 1 or more. * represents a bond.

( ^R9 )
In formula (III) above, R ⁹ represents an epoxy resin residue. An epoxy resin residue means a residue obtained by removing an epoxy group from an epoxy resin.
Here, the epoxy resin has the same meaning as described above.

(p)
In formula (III), p represents an integer of 1 or more. From the viewpoint of compatibility between curability and development solubility, p is preferably 2. On the other hand, from the viewpoint of curability, p is preferably 2 or more, more preferably 5 or more, even more preferably 10 or more, and from the viewpoint of development solubility, p is 20 or less. is preferred, 15 or less is more preferred, and 12 or less is even more preferred. When the content is at least the lower limit, curability tends to be improved, and when the content is at most the upper limit, solubility in development tends to be improved.

(Partial structure (3-1))
The partial structure (3) represented by the general formula (III) is preferably the partial structure (3-1) represented by the following general formula (III-1) from the viewpoint of development solubility.

In formula (III-1) above, γ represents a divalent linking group. The benzene ring in formula (III-1) may be further substituted with any substituent. * represents a bond.

(γ)
In formula (III-1) above, γ represents a divalent linking group. The divalent linking group includes a single bond, an optionally substituted alkylene group, --CO-- or --SO ₂ -- from the viewpoint of development solubility.
Alkylene groups may be linear, branched, cyclic, or combinations thereof. Although the number of carbon atoms is not particularly limited, it is usually 1 or more, preferably 2 or more, and usually 8 or less, preferably 6 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, curability tends to be improved.

Specific examples of the alkylene group include methylene group, ethylene group, propylene group, butylene group, hexylene group, cyclohexylene group, heptylene group, octylene group, and dodecylene group. Preferred is the propylene group.

Examples of the substituent that the alkylene group may have include an alkoxy group, a halogen atom (-F, -Cl, -Br, -I), a hydroxy group, a carboxyl group, and the like. Substitution is preferred.
When having substituents, the number thereof is not limited, and may be one or two or more.

Further, when both of the two hydrogen atoms of the methylene group ( _--CH.sub.2-- ) in the alkylene group are substituted with substituents, even if the two substituents are linked together to form a hydrocarbon ring. good. Specific examples of γ in that case include a group represented by the following formula (IV) and a group represented by the following formula (V). * in the chemical formula represents a bond.

Further, the optional substituents that the benzene ring in the formula (III-1) may have include, for example, a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group, and the like. is mentioned. The number of substituents is also not particularly limited, and may be one or two or more. Further, when the benzene ring in formula (III-1) above has a substituent, the two benzene rings in formula (III-1) may be linked by the substituent.

Among these, from the viewpoint of curability, γ is preferably an optionally substituted alkylene group, more preferably an unsubstituted alkylene group, and even more preferably a propylene group.

(Partial structure (3-2))
From the viewpoint of curability, the partial structure (3) represented by the general formula (III) is preferably the partial structure (3-2) represented by the following general formula (III-2).

The benzene ring in formula (III-2) above may be further substituted with any substituent. * represents a bond.

Examples of optional substituents that the benzene ring in formula (III-2) may have include a hydroxyl group, an alkyl group, and an alkoxy group. The number of substituents is also not particularly limited, and may be one or two or more. Among these, an alkyl group is preferred, a cycloalkyl group is more preferred, and an adamantyl group is even more preferred, from the viewpoint of development adhesion.

(Partial structure (3-3))
From the viewpoint of curability, the partial structure (3) represented by the general formula (III) preferably includes a partial structure (3-3) represented by the following general formula (III-3).

In formula (III-3) above, R ¹⁰ represents a divalent hydrocarbon group which may have a substituent. The benzene ring in formula (III-3) may be further substituted with any substituent. * represents a bond.

( ^R10 )
In formula (III-3) above, R ¹⁰ represents a divalent hydrocarbon group which may have a substituent.
The divalent hydrocarbon group includes a divalent aliphatic group, a divalent aromatic ring group, and a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked. mentioned.

The divalent aliphatic group includes linear, branched, cyclic, and combinations thereof. Among these, linear ones are preferred from the viewpoint of development solubility, while cyclic ones are preferred from the viewpoint of development adhesion. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, curability tends to be improved.

Specific examples of divalent linear aliphatic groups include methylene, ethylene, n-propylene, n-butylene, n-hexylene and n-heptylene groups. Among these, a methylene group is preferable from the viewpoint of curability.
Specific examples of the divalent branched aliphatic group include the divalent straight-chain aliphatic group described above and a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and n-butyl as a side chain. groups, iso-butyl groups, sec-butyl groups, tert-butyl groups, and the like.
Although the number of rings possessed by the divalent cyclic aliphatic group is not particularly limited, it is generally preferably 1 or more and 2 or more, and generally 10 or less and 5 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, curability tends to be improved. Specific examples of the divalent cyclic aliphatic group include groups obtained by removing two hydrogen atoms from a ring such as cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring and adamantane ring. be done. Among these, a group obtained by removing two hydrogen atoms from an adamantane ring is preferable from the viewpoint of rigidity of the skeleton.

Substituents which the divalent aliphatic group may have include a hydroxyl group; an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a nitro group; a cyano group; and a carboxyl group. Among these, unsubstituted groups are preferred from the viewpoint of ease of synthesis.

Moreover, a bivalent aromatic-hydrocarbon ring group and a bivalent aromatic heterocyclic group are mentioned as a bivalent aromatic ring group. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, curability tends to be improved.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. The divalent aromatic hydrocarbon ring group includes, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, which have two free valences, Groups such as triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring can be mentioned.
In addition, the aromatic heterocycle in the divalent aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of divalent aromatic heterocyclic groups include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, and indole ring having two free valences. ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, Groups such as pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring and azulene ring.
Among these, from the viewpoint of photocurability, a benzene ring or a naphthalene ring having two free valences is preferred, and a benzene ring having two free valences is more preferred.

Examples of substituents that the divalent aromatic ring group may have include hydroxyl group, methyl group, methoxy group, ethyl group, ethoxy group, propyl group, propoxy group and the like. Among these, unsubstituted is preferred from the viewpoint of curability.

Further, as the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked, one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic Groups in which one or more cyclic groups are linked can be mentioned.
Although the number of divalent aliphatic groups is not particularly limited, it is generally preferably 1 or more and 2 or more, generally 10 or less and 5 or less, and more preferably 3 or less. The curability tends to be improved by setting it to the above lower limit or more, and the curability tends to be improved by setting it to the above upper limit or less.
The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. The curability tends to be improved by setting it to the above lower limit or more, and the curability tends to be improved by setting it to the above upper limit or less.

Specific examples of groups in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked are represented by the following formulas (III-3-A) to (III-3-E) and the like. Among these, a group represented by the following formula (III-3-A) is preferable from the viewpoint of development solubility. * in the chemical formula represents a bond.

As described above, the benzene ring in formula (III-3) may be further substituted with any substituent. Examples of the substituent include hydroxyl group, methyl group, methoxy group, ethyl group, ethoxy group, propyl group, propoxy group and the like. The number of substituents is also not particularly limited, and may be one or two or more.
Among these, from the viewpoint of curability, unsubstituted is preferred.

(Partial structure (3-4))
From the viewpoint of curability, the partial structure (3) represented by the general formula (III) preferably contains a partial structure (3-4) represented by the following general formula (III-4).

In formula (III-4) above, γ represents a divalent linking group. The benzene ring in formula (III-4) may be further substituted with any substituent. * represents a bond.

As γ in the formula (III-4), those described as γ in the formula (III-1) can be preferably employed.
Further, as an optional substituent that the benzene ring in the formula (III-4) may have, an optional substituent that the benzene ring in the formula (III-1) may have Those described can be preferably employed.

Among the partial structures (3-1) to (3-4), the epoxy (meth)acrylate resin (b1-A) has the partial structure (3-1) from the viewpoint of development solubility. is preferred.

As a specific method for producing the epoxy (meth)acrylate resin (b1-A), the method described in JP-A-2007-119718 can be employed.

From the viewpoint of curability, the epoxy (meth)acrylate resin (b1-B) having a partial structure represented by the following formula (i) (hereinafter referred to as "epoxy (meth)acrylate may be abbreviated as "epoxy (b1-B)") and epoxy (meth)acrylate resin (b1-C) having a partial structure represented by the following general formula (ii) (hereinafter referred to as "epoxy ( meth)acrylate resin (b1-C)” is preferred. From the viewpoint of reliability, the epoxy (meth)acrylate resin (b1-C) is more preferable.

In formula (i), R ^a represents a hydrogen atom or a methyl group, and R ^b represents a divalent hydrocarbon group which may have a substituent. The benzene ring in formula (i) may be further substituted with any substituent. * represents a bond.

In formula (ii), each R ^c independently represents a hydrogen atom or a methyl group. R ^d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. * represents a bond.

(R ^b )
In formula (i) above, R ^b represents a divalent hydrocarbon group which may have a substituent.
The divalent hydrocarbon group includes a divalent aliphatic group, a divalent aromatic ring group, and a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked. mentioned.

The divalent aliphatic group includes linear, branched, cyclic, and combinations thereof. Among these, linear ones are preferred from the viewpoint of development solubility, while cyclic ones are preferred from the viewpoint of development adhesion. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, curability tends to be improved.

Specific examples of divalent linear aliphatic groups include methylene, ethylene, n-propylene, n-butylene, n-hexylene and n-heptylene groups. Among these, a methylene group is preferable from the viewpoint of curability.
Specific examples of the divalent branched aliphatic group include the divalent straight-chain aliphatic group described above and a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and n-butyl as a side chain. groups, iso-butyl groups, sec-butyl groups, tert-butyl groups, and the like.
Although the number of rings possessed by the divalent cyclic aliphatic group is not particularly limited, it is generally preferably 1 or more and 2 or more, and generally 10 or less and 5 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, curability tends to be improved. Specific examples of the divalent cyclic aliphatic group include groups obtained by removing two hydrogen atoms from a ring such as cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring and adamantane ring. be done. Among these, a group obtained by removing two hydrogen atoms from an adamantane ring is preferable from the viewpoint of rigidity of the skeleton.

Substituents which the divalent aliphatic group may have include a hydroxyl group; an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a nitro group; a cyano group; and a carboxyl group. Among these, unsubstituted groups are preferred from the viewpoint of ease of synthesis.

Moreover, a bivalent aromatic-hydrocarbon ring group and a bivalent aromatic heterocyclic group are mentioned as a bivalent aromatic ring group. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, curability tends to be improved.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. The divalent aromatic hydrocarbon ring group includes, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, which have two free valences, Groups such as triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring can be mentioned.
In addition, the aromatic heterocycle in the divalent aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of divalent aromatic heterocyclic groups include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, and indole ring having two free valences. ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, Groups such as pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring and azulene ring. Among these, from the viewpoint of photocurability, a benzene ring or a naphthalene ring having two free valences is preferred, and a benzene ring having two free valences is more preferred.

Examples of substituents that the divalent aromatic ring group may have include hydroxyl group, methyl group, methoxy group, ethyl group, ethoxy group, propyl group, propoxy group and the like. Among these, unsubstituted is preferred from the viewpoint of curability.

Further, as the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked, one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic Groups in which one or more cyclic groups are linked can be mentioned.
Although the number of divalent aliphatic groups is not particularly limited, it is generally preferably 1 or more and 2 or more, generally 10 or less and 5 or less, and more preferably 3 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, curability tends to be improved.
The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. The curability tends to be improved by setting it to the above lower limit or more, and the curability tends to be improved by setting it to the above upper limit or less.

Specific examples of groups in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include groups represented by the following formulas (iA) to (iE), etc. is mentioned. Among these, a group represented by the following formula (iA) is preferable from the viewpoint of developing solubility. * in the chemical formula represents a bond.

As described above, the benzene ring in formula (i) may be further substituted with optional substituents. Examples of the substituent include hydroxyl group, methyl group, methoxy group, ethyl group, ethoxy group, propyl group, propoxy group and the like. The number of substituents is also not particularly limited, and may be one or two or more.
Among these, from the viewpoint of curability, unsubstituted is preferred.

From the viewpoint of curability, the partial structure represented by the general formula (i) is preferably a partial structure represented by the following general formula (i-1).

In formula (i-1), R ^a and R ^b have the same definitions as in formula (i) above. R ^X represents a hydrogen atom or a polybasic acid residue. * represents a bond. The benzene ring in formula (i-1) may be further substituted with any substituent.

A polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endomethylenetetrahydrophthalic acid. One or more selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid can be mentioned.
Among these, from the viewpoint of patterning properties, preferred polybasic acids are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid. acid, more preferably tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic acid, and biphenyltetracarboxylic acid.

The partial structure represented by the formula (i-1) contained in one molecule of the epoxy (meth)acrylate resin (b1-B) may be one or two or more. For example, R ^X is a hydrogen atom. and those in which R ^X is a polybasic acid residue may be mixed.

The number of partial structures represented by the formula (i) contained in one molecule of the epoxy (meth)acrylate resin (b1-B) is not particularly limited, but is preferably 1 or more, more preferably 3 or more. , and preferably 20 or less, more preferably 15 or less. When the content is at least the lower limit, curability tends to be good, and when the content is at most the upper limit, solubility in development tends to be good.

Specific examples of the epoxy (meth)acrylate resin (b1-B) are given below.

( ^Rd )
In formula (ii) above, R ^d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
The cyclic hydrocarbon group includes an aliphatic ring group or an aromatic ring group.

Although the number of rings possessed by the aliphatic ring group is not particularly limited, it is usually preferably 1 or more and 2 or more, and is usually 10 or less and 5 or less, preferably 3 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, curability tends to be improved.
The number of carbon atoms in the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly 15 or less. preferable. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, curability tends to be improved.
Specific examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring and adamantane ring. Among these, an adamantane ring is preferable from the viewpoint of reliability.

On the other hand, the number of rings possessed by the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less, and more preferably 4 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, curability tends to be improved.
Aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, even more preferably 10 or more, particularly preferably 12 or more, and preferably 40 or less, and 30 or less. It is more preferably 20 or less, and particularly preferably 15 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, curability tends to be improved.
Specific examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, A fluorene ring and the like can be mentioned. Among these, a fluorene ring is preferable from the viewpoint of patterning properties.

In addition, the divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited. and a group in which a divalent aliphatic group and one or more divalent aromatic ring groups are linked.

The divalent aliphatic group includes linear, branched, cyclic, and combinations thereof. Among these, linear ones are preferred from the viewpoint of compatibility, while cyclic ones are preferred from the viewpoint of reliability. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 25 or less, more preferably 20 or less, and even more preferably 15 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, curability tends to be improved.

Specific examples of divalent linear aliphatic groups include methylene, ethylene, n-propylene, n-butylene, n-hexylene and n-heptylene groups. Among these, a methylene group is preferable from the viewpoint of curability.
Specific examples of the divalent branched aliphatic group include the divalent straight-chain aliphatic group described above and a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and n-butyl as a side chain. groups, iso-butyl groups, sec-butyl groups, tert-butyl groups, and the like.
Although the number of rings possessed by the divalent cyclic aliphatic group is not particularly limited, it is usually preferably 1 or more and 2 or more, and is usually 10 or less, 5 or less, and more preferably 3 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, curability tends to be improved. Specific examples of the divalent cyclic aliphatic group include groups obtained by removing two hydrogen atoms from a ring such as cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring and adamantane ring. be done. Among these, from the viewpoint of reliability, a group obtained by removing two hydrogen atoms from an adamantane ring is preferable.

Substituents which the divalent aliphatic group may have include a hydroxyl group; an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a nitro group; a cyano group; and a carboxyl group. Among these, unsubstituted groups are preferred from the viewpoint of ease of synthesis.

Moreover, a bivalent aromatic-hydrocarbon ring group and a bivalent aromatic heterocyclic group are mentioned as a bivalent aromatic ring group. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, curability tends to be improved.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. The divalent aromatic hydrocarbon ring group includes, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, which have two free valences, Groups such as triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring can be mentioned.
Moreover, the aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of divalent aromatic heterocyclic groups include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, and indole ring having two free valences. ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, Groups such as pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring and azulene ring.
Among divalent aromatic ring groups, from the viewpoint of patterning properties, a benzene ring having two free valences, a naphthalene ring having two free valences, or a fluorene ring having two free valences is preferred, A fluorene ring with two free valences is more preferred.

Examples of substituents that the divalent aromatic ring group may have include hydroxyl group, methyl group, methoxy group, ethyl group, ethoxy group, propyl group, propoxy group and the like. Among these, unsubstituted is preferred from the viewpoint of development solubility and moisture absorption resistance.

Further, as the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked, one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic Groups in which one or more cyclic groups are linked can be mentioned.
Although the number of divalent aliphatic groups is not particularly limited, it is generally preferably 1 or more and 2 or more, generally 10 or less and 5 or less, and more preferably 3 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, curability tends to be improved.
The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, curability tends to be improved.

Specific examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include the groups represented by the above formulas (iA) to (iE), etc. is mentioned. Among these, the group represented by the above formula (iC) is preferable from the viewpoint of reliability.

The bonding mode of the side chain cyclic hydrocarbon group to these divalent hydrocarbon groups is not particularly limited, but for example, one hydrogen atom of an aliphatic group or an aromatic ring group is substituted with the side chain. and a mode in which a cyclic hydrocarbon group, which is a side chain, is formed including one of the carbon atoms of the aliphatic group.

From the viewpoint of compatibility, the partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-1).

In formula (ii-1), R ^c has the same meaning as in formula (ii) above. R ^α represents a monovalent cyclic hydrocarbon group which may have a substituent. n is an integer of 1 or more. The benzene ring in formula (ii-1) may be further substituted with any substituent. * represents a bond.

(R ^α )
In formula (ii-1) above, R ^α represents a monovalent cyclic hydrocarbon group which may have a substituent.
The cyclic hydrocarbon group includes an aliphatic ring group or an aromatic ring group.

Although the number of rings possessed by the aliphatic ring group is not particularly limited, it is generally preferably 1 or more and 2 or more, and generally 6 or less and 4 or less, and more preferably 3 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, curability tends to be improved.
The number of carbon atoms in the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly 15 or less. preferable. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, curability tends to be improved.
Specific examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring and adamantane ring. Among these, an adamantane ring is preferable from the viewpoint of compatibility.

On the other hand, although the number of rings possessed by the aromatic ring group is not particularly limited, it is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less and 5 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, curability tends to be improved.
Aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, curability tends to be improved.
Specific examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring and the like. Among these, a fluorene ring is preferable from the viewpoint of reliability.

Examples of substituents that the cyclic hydrocarbon group may have include hydroxyl group, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, Alkyl groups having 1 to 5 carbon atoms such as amyl group and iso-amyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; nitro group; cyano group; Among these, unsubstituted is preferred from the viewpoint of ease of synthesis.

Although n represents an integer of 1 or more, 2 or more is preferable, and 3 or less is preferable. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, curability tends to be improved.

Among these, from the viewpoint of compatibility, R ^α is preferably a monovalent aliphatic cyclic group, more preferably an adamantyl group.

As described above, the benzene ring in formula (ii-1) may be further substituted with any substituent. Examples of the substituent include hydroxyl group, methyl group, methoxy group, ethyl group, ethoxy group, propyl group, propoxy group and the like. The number of substituents is also not particularly limited, and may be one or two or more.
Among these, non-substitution is preferred from the viewpoint of patterning properties.

Specific examples of the partial structure represented by formula (ii-1) are given below.

From the viewpoint of reliability, the partial structure represented by the general formula (ii) is preferably a partial structure represented by the following general formula (ii-2).

In formula (ii-2), R ^c has the same definition as in formula (ii) above. R ^β represents a divalent cyclic hydrocarbon group which may have a substituent. The benzene ring in formula (ii-2) may be further substituted with any substituent. * represents a bond.

( ^Rβ )
In formula (ii-2) above, R ^β represents a divalent cyclic hydrocarbon group which may have a substituent.
The cyclic hydrocarbon group includes an aliphatic ring group or an aromatic ring group.

Although the number of rings possessed by the aliphatic ring group is not particularly limited, it is generally preferably 1 or more and 2 or more, and is generally preferably 10 or less and 5 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, curability tends to be improved.
The number of carbon atoms in the aliphatic ring group is generally 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, curability tends to be improved.
Specific examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring and the like. Among these, an adamantane ring is preferable from the viewpoint of compatibility.

On the other hand, although the number of rings possessed by the aromatic ring group is not particularly limited, it is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less and 5 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, curability tends to be improved.
Examples of the aromatic ring group include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and 10 40 or less is more preferable, 30 or less is more preferable, 20 or less is more preferable, and 15 or less is particularly preferable. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, curability tends to be improved.
Specific examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring and the like. Among these, a fluorene ring is preferable from the viewpoint of reliability.

Examples of substituents that the cyclic hydrocarbon group may have include hydroxyl group, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, Alkyl groups having 1 to 5 carbon atoms such as amyl group and iso-amyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; nitro group; cyano group; Among these, non-substituted groups are preferred from the viewpoint of ease of synthesis.

Among these, from the viewpoint of compatibility, R ^β is preferably a divalent aliphatic cyclic group, more preferably a divalent adamantane cyclic group.
On the other hand, from the viewpoint of reliability, R ^β is preferably a divalent aromatic ring group, more preferably a divalent fluorene ring group.

As described above, the benzene ring in formula (ii-2) may be further substituted with any substituent. Examples of the substituent include hydroxyl group, methyl group, methoxy group, ethyl group, ethoxy group, propyl group, propoxy group and the like. The number of substituents is also not particularly limited, and may be one or two or more. Also, two benzene rings in formula (ii-2) may be linked via these substituents.
Among these, non-substitution is preferred from the viewpoint of patterning properties.

Specific examples of the partial structure represented by formula (ii-2) are given below.

On the other hand, the partial structure represented by the general formula (ii) is preferably a partial structure represented by the following general formula (ii-3) from the viewpoint of compatibility.

In formula (ii-3), R ^c and R ^d have the same definitions as in formula (ii) above. R ^Z represents a hydrogen atom or a polybasic acid residue.

A polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. In addition, one more OH group may be removed and shared with R ^{Z in} another molecule represented by formula (ii-3), that is, a plurality of formula (ii-3 ) may be linked.
Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endomethylenetetrahydrophthalic acid. One or more selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid can be mentioned.
Among these, from the viewpoint of patterning properties, preferred polybasic acids are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid. acid, more preferably tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic acid, and biphenyltetracarboxylic acid.

The partial structure represented by the formula (ii-3) contained in one molecule of the epoxy (meth)acrylate resin (b1-C) may be one or two or more. For example, R ^X is a hydrogen atom. and those in which R ^Z is a polybasic acid residue may be mixed.

The number of partial structures represented by the formula (ii) contained in one molecule of the epoxy (meth)acrylate resin (b1-C) is not particularly limited, but is preferably 1 or more, more preferably 3 or more. Also, it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. When the content is at least the lower limit, curability tends to be good, and when the content is at most the upper limit, solubility in development tends to be good.

The epoxy (meth)acrylate resin (b1) may be used singly or in combination of two or more resins.
Also, a part of the epoxy (meth)acrylate resin (b1) may be replaced with another binder resin. That is, the epoxy (meth)acrylate resin (b1) may be used in combination with another binder resin. In this case, the ratio of the epoxy (meth)acrylate resin (b1) in the alkali-soluble resin (b) is preferably 5% by mass or more, more preferably 10% by mass or more, and 20% by mass or more. more preferably 30% by mass or more, particularly preferably 40% by mass or more, and most preferably 50% by mass or more. The content is preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, and particularly preferably 60% by mass or less.

Other binder resins that can be used in combination with the epoxy (meth)acrylate resin (b1) are not limited, and may be selected from resins commonly used in photosensitive coloring compositions. Examples thereof include binder resins described in JP-A-2007-271727, JP-A-2007-316620, JP-A-2007-334290, and the like. In addition, from the viewpoint of reliability and surface smoothness, (meth)acrylic copolymer resins described in International Publication No. 2017/110893 are preferred. Any of the other binder resins may be used alone or in combination of two or more.

As the (b) alkali-soluble resin, it is preferable to use (b2) an acrylic resin from the viewpoint of compatibility with a coloring agent, a dispersant, and the like.

Examples of acrylic resins include ethylenically unsaturated monomers having one or more carboxyl groups (hereinafter referred to as "unsaturated monomers (b2-1)") and other copolymerizable ethylenic A copolymer with an unsaturated monomer (hereinafter referred to as "unsaturated monomer (b2-2)") can be mentioned.
Examples of unsaturated monomers (b2-1) include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; maleic acid, maleic anhydride, and fumaric acid; , citraconic acid, citraconic anhydride, mesaconic acid and other unsaturated dicarboxylic acids or their anhydrides; mono[2-(meth)acryloyloxyethyl] succinate, mono[2-(meth)acryloyloxyethyl] phthalate Mono [(meth)acryloyloxyalkyl] esters of polyvalent carboxylic acids with a valence of 2 or more such as; ) acrylate; p-vinyl benzoic acid and the like.
These unsaturated monomers (b2-1) can be used alone or in combination of two or more.

Examples of unsaturated monomers (b2-2) include N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy- aromatic vinyl compounds such as α-methylstyrene, p-vinylbenzyl glycidyl ether, acenaphthylene;

Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol (degree of polymerization 2 ~10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2-10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2-10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2-10) ) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide-modified paracumylphenol (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[( (meth)acrylic acid esters such as meth)acryloyloxymethyl]oxetane, 3-[(meth)acryloyloxymethyl]-3-ethyloxetane;

Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3-(vinyloxymethyl)-3-ethyloxetane macromonomers having a mono(meth)acryloyl group at the end of the polymer molecular chain, such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate, and polysiloxane;
These unsaturated monomers (b2-2) can be used alone or in combination of two or more.

In the copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably 5. to 50% by mass, more preferably 10 to 40% by mass. By copolymerizing the unsaturated monomer (b2-1) in such a range, there is a tendency that a photosensitive colored composition excellent in alkali developability and storage stability can be obtained.

Specific examples of the copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2) include, for example, JP-A-7-140654, JP-A-8-259876, Disclosed in JP-A-10-31308, JP-A-10-300922, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, etc. A copolymer can be mentioned.
A copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2) can be produced by a known method. The structure, Mw, and Mw/Mn can also be controlled by the methods disclosed in Japanese Patent Application Laid-Open No. 2006-259680, International Publication No. 2007/029871, and the like.

<(c) Photoinitiator>
(c) The photopolymerization initiator is a component that has the function of directly absorbing light, causing a decomposition reaction or a hydrogen abstraction reaction, and generating polymerization active radicals. Additives such as polymerization accelerators (chain transfer agents) and sensitizing dyes may be added as necessary.
Examples of photopolymerization initiators include metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197; hexaarylbiimidazoles described in JP-A-2000-56118. Derivatives; halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acids, described in JP-A-10-39503 Salts, radical activators such as N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; oxime ester compounds described in JP-A-2000-80068, JP-A-2006-36750, etc. etc.

Specifically, for example, metallocene compounds include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis(2,3,4,5,6-pentafluorophenyl ), dicyclopentadienyl titanium bis(2,3,5,6-tetrafluorophenyl), dicyclopentadienyl titanium bis(2,4,6-trifluorophenyl), dicyclopentadienyl titanium di( 2,6-difluorophenyl), dicyclopentadienyl titanium di(2,4-difluorophenyl), di(methylcyclopentadienyl) titanium bis(2,3,4,5,6-pentafluorophenyl), di(methylcyclopentadienyl)titanium bis(2,6-difluorophenyl), dicyclopentadienyltitanium bis[2,6-difluoro-3-(1-pyrrolyl)phenyl] and the like.

Further, biimidazole derivatives include 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer and 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazole. dimer, 2-(2′-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2′-methoxyphenyl)-4,5-diphenylimidazole dimer, (4′-methoxyphenyl )-4,5-diphenylimidazole dimer and the like.

Further, halomethylated oxadiazole derivatives include 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'- benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2′-(6″-benzofuryl)vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole and the like.

Further, halomethyl-s-triazine derivatives include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis( trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl) -s-triazine and the like.

Further, α-aminoalkylphenone derivatives include 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4- morpholinophenyl)-butanone-1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate -, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino-3-(4 -diethylaminobenzoyl)coumarin, 4-(diethylamino)chalcone and the like.

As a photopolymerization initiator, oxime ester compounds are particularly effective in terms of sensitivity and plate-making properties. Such an oxime ester compound having excellent sensitivity is useful. Oxime ester compounds have a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals, so they are highly sensitive even in small amounts and are stable against thermal reactions. and it is possible to obtain a highly sensitive photosensitive coloring composition in a small amount.

Examples of oxime ester compounds include compounds represented by the following general formula (IV).

In formula (IV) above, R ^21a represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aromatic ring group.
R ^21b represents any substituent containing an aromatic ring.
R ^22a represents an optionally substituted alkanoyl group or an optionally substituted aryloyl group.
n represents an integer of 0 or 1;

Although the number of carbon atoms in the alkyl group in R ^21a is not particularly limited, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, from the viewpoint of solvent solubility and sensitivity. is. Specific examples of alkyl groups include methyl, ethyl, propyl, cyclopentylethyl, and propyl groups.
Examples of substituents that the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, and 4-(2-methoxy-1-methyl)ethoxy-2-methylphenyl. group, N-acetyl-N-acetoxyamino group, etc., and from the viewpoint of ease of synthesis, it is preferably unsubstituted.

The aromatic ring group for R ^21a includes aromatic hydrocarbon ring groups and aromatic heterocyclic groups. Although the number of carbon atoms in the aromatic ring group is not particularly limited, it is preferably 5 or more from the viewpoint of solubility in the photosensitive coloring composition. From the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and even more preferably 12 or less.

Specific examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, a furyl group, and the like. Among these, from the viewpoint of developability, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.
Examples of the substituent that the aromatic ring group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, an alkyl group, an alkoxy group, and groups in which these substituents are linked. From the viewpoint of sexuality, an alkyl group, an alkoxy group, or a group in which these are linked is preferable, and a linked alkoxy group is more preferable.
Among these, from the viewpoint of developability, R ^21a is preferably an optionally substituted aromatic ring group, more preferably an aromatic ring group having a linked alkoxy group as a substituent. preferable.

R ^21b is preferably an optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group or an optionally substituted diphenylsulfide group. Among these, an optionally substituted carbazolyl group is preferable from the viewpoint of sensitivity.

The number of carbon atoms in the alkanoyl group in R ^22a is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity, it is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 15 or less, more preferably It is 10 or less, more preferably 5 or less. Specific examples of alkanoyl groups include acetyl, propanoyl and butanoyl groups.
Examples of substituents that the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, and an amide group. is preferred.

The number of carbon atoms in the aryloyl group in R ^22a is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity, usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less. Specific examples of the aryloyl group include benzoyl group and naphthoyl group.
Examples of substituents that the aryloyl group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, an alkyl group, etc. From the viewpoint of ease of synthesis, unsubstituted groups are preferred. .
Among these, from the viewpoint of sensitivity, R ^22a is preferably an optionally substituted alkanoyl group, more preferably an unsubstituted alkanoyl group, and even more preferably an acetyl group.

In addition, the initiator described in JP-A-2016-133574 is also preferably used from the viewpoint of reducing contamination of the liquid crystal layer by the colorant.

A photoinitiator may be used individually by 1 type, or may be used in combination of 2 or more types.
For the purpose of increasing sensitivity, the photopolymerization initiator can be blended with a sensitizing dye and a polymerization accelerator depending on the wavelength of the image exposure light source, if necessary. Sensitizing dyes include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, coumarins having heterocycles described in JP-A-3-239703 and JP-A-5-289335. Dyes, JP-A-3-239703, 3-ketocoumarin compounds described in JP-A-5-289335, pyrromethene dyes described in JP-A-6-19240, others, JP-A-47-2528, JP-A JP-A-54-155292, JP-B-45-37377, JP-A-48-84183, JP-A-52-112681, JP-A-58-15503, JP-A-60-88005 Publications, JP-A-59-56403, JP-A-2-69, JP-A-57-168088, JP-A-5-107761, JP-A-5-210240, JP-A-4-288818 Examples thereof include dyes having a dialkylaminobenzene skeleton described in publications.

Preferred among these sensitizing dyes are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone , benzophenone compounds such as 3,4-diaminobenzophenone; 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5 ] benzoxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-oxazole, 2-(p-dimethylaminophenyl ) benzothiazole, 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2-(p-diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)- 1,3,4-thiadiazole, (p-dimethylaminophenyl)pyridine, (p-diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine , p-dialkylaminophenyl group-containing compounds such as (p-diethylaminophenyl)pyrimidine. Among these, the most preferred is 4,4'-dialkylaminobenzophenone.
The sensitizing dyes may be used singly or in combination of two or more.

Examples of the polymerization accelerator include aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate, aliphatic amines such as n-butylamine and N-methyldiethanolamine, and mercapto compounds described later. be done.
A polymerization accelerator may be used individually by 1 type, or may be used in combination of 2 or more type.

<(d) ethylenically unsaturated compound>
The photosensitive coloring composition of the present invention contains (d) an ethylenically unsaturated compound. (d) Sensitivity is improved by including an ethylenically unsaturated compound.
The ethylenically unsaturated compound used in the present invention is a compound having at least one ethylenically unsaturated group in its molecule. Specifically, for example, (meth)acrylic acid, (meth)acrylic acid alkyl ester, acrylonitrile, styrene, and a carboxylic acid having one ethylenically unsaturated bond, a polyhydric or monohydric alcohol monoester, and the like. mentioned.

In the present invention, it is particularly desirable to use polyfunctional ethylenic monomers having two or more ethylenically unsaturated groups in one molecule. The number of ethylenically unsaturated groups possessed by the polyfunctional ethylenic monomer is not particularly limited, but is usually 2 or more, preferably 4 or more, more preferably 5 or more, and preferably It is 8 or less, more preferably 7 or less. When the concentration is equal to or higher than the lower limit, there is a tendency for the sensitivity to be high, and when the concentration is equal to or lower than the upper limit, the solubility in a solvent tends to be improved. The combination of the upper limit and the lower limit is, for example, preferably 2 to 8, more preferably 4 to 7, even more preferably 5 to 7.
Examples of polyfunctional ethylenic monomers include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatic poly Esters obtained by an esterification reaction between a polyhydric hydroxy compound such as a hydroxy compound and an unsaturated carboxylic acid or a polybasic carboxylic acid are included.

Esters of the aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Acrylic acid esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate, and methacrylic acid esters obtained by replacing the acrylates of these exemplary compounds with methacrylates Similarly, itaconate instead of itaconate, crotonate instead of clonate, maleate instead of maleate, and the like.

Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate. etc.

Polybasic carboxylic acid and unsaturated carboxylic acid, the ester obtained by the esterification reaction of the polyhydric hydroxy compound is not necessarily a single substance, but representative specific examples include acrylic acid, phthalic acid, and Examples include condensates of ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin.

Other examples of polyfunctional ethylenic monomers used in the present invention include a polyisocyanate compound and a hydroxyl group-containing (meth)acrylic acid ester or a polyisocyanate compound, a polyol and a hydroxyl group-containing (meth)acrylic acid ester. Urethane (meth)acrylates such as those obtained; epoxy acrylates such as addition reaction products of polyepoxy compounds and hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylenebisacrylamide; diallyl phthalate and vinyl group-containing compounds such as divinyl phthalate are useful.

Examples of the urethane (meth)acrylates include, for example, DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U -10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), UV-1700B, UV -7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) and the like.

Among these, it is preferable to use (meth)acrylic acid alkyl ester as the (d) ethylenically unsaturated compound from the viewpoint of curability, and it is more preferable to use dipentaerythritol hexaacrylate.
These may be used individually by 1 type, and may use 2 or more types together.

<(e) Solvent>
The photosensitive coloring composition of the present invention may contain (e) a solvent. (e) By containing a solvent, the pigment can be dispersed in the solvent, and there is a tendency that coating is facilitated.
The photosensitive coloring composition of the present invention usually contains (a) a coloring agent, (b) an alkali-soluble resin, (c) a photopolymerization initiator, and (d) an ethylenically unsaturated compound, and optionally used Other various components are dissolved or dispersed in a solvent before use. Among the solvents, organic solvents are preferred from the viewpoint of dispersibility and coatability.

Among the organic solvents, it is preferable to select one having a boiling point in the range of 100 to 300° C., more preferably one having a boiling point in the range of 120 to 280° C., from the viewpoint of coating properties. The boiling point here means the boiling point at a pressure of 1013.25 hPa, and the same applies to all boiling points below.

Examples of such organic solvents include the following.
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl glycol monoalkyl ethers such as ethers, triethylene glycol monoethyl ether, tripropylene glycol methyl ether;
glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl glycol alkyl ether acetates such as ether acetate, 3-methyl-3-methoxybutyl acetate;
Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate;
Alkyl acetates such as cyclohexanol acetate;
Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;

Acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methylhexyl ketone, methyl nonyl ketone, methoxymethyl pentanone ketones;
Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol;
Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;

aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Chain or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride, amyl chloride;
ether ketones such as methoxymethylpentanone;
nitriles such as acetonitrile and benzonitrile;

Commercially available organic solvents corresponding to the above include Mineral Spirit, Valsol #2, Apco #18 Solvent, Apco Thinner, Socal Solvent No. 1 and no. 2, Solvesso #150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve (“cellosolve” is a registered trademark. The same shall apply hereinafter.), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (any are also trade names).
These organic solvents may be used alone or in combination of two or more.

When forming colored spacers by photolithography, it is preferable to select an organic solvent having a boiling point in the range of 100 to 200°C. More preferably, it has a boiling point of 120-170°C.

Among the above organic solvents, glycol alkyl ether acetates are preferable because they have a good balance of applicability, surface tension, etc., and relatively high solubility of constituent components in the composition.
Also, the glycol alkyl ether acetates may be used alone, or may be used in combination with other organic solvents. Glycol monoalkyl ethers are particularly preferred as organic solvents to be used in combination. Among them, propylene glycol monomethyl ether is particularly preferred because of the solubility of the constituents in the composition. Glycol monoalkyl ethers have a high polarity, and if the amount added is too large, the pigment tends to aggregate, and the viscosity of the photosensitive coloring composition obtained later tends to decrease, resulting in a decrease in storage stability. , the ratio of the glycol monoalkyl ether in the solvent is preferably 5% by mass to 30% by mass, more preferably 5% by mass to 20% by mass.

It is also preferable to use an organic solvent having a boiling point of 150° C. or higher (hereinafter sometimes referred to as a “high boiling point solvent”). By using such a high boiling point solvent in combination, the photosensitive coloring composition becomes difficult to dry, but has the effect of preventing the uniformly dispersed state of the pigment in the composition from being destroyed by rapid drying. That is, for example, there is an effect of preventing the occurrence of foreign matter defects due to deposition and solidification of a coloring agent at the tip of a slit nozzle. Among the various solvents described above, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferred because of their high effects.

When a high-boiling solvent is used in combination, the content of the high-boiling solvent in the organic solvent is preferably 3% to 50% by mass, more preferably 5% to 40% by mass, particularly 5% to 30% by mass. preferable. By setting the temperature to the above lower limit or higher, for example, it tends to be possible to suppress the deposition and solidification of a coloring agent at the tip of the slit nozzle and causing foreign matter defects. It tends to be possible to suppress problems such as takt failure in the vacuum drying process and pin marks in prebaking.

The high boiling solvent having a boiling point of 150°C or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a high boiling solvent having a boiling point of 150°C or higher is separately contained. It doesn't matter if you don't.
Examples of preferred high-boiling solvents include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate, and 1,6-hexanol diacetate. Acetate, triacetin and the like.

<(f) Dispersant>
The photosensitive coloring composition of the present invention may contain (f) a dispersant for the purpose of finely dispersing the (a) colorant and stabilizing the dispersed state.
(f) As the dispersant, a polymer dispersant having a functional group is preferable. Further, from the viewpoint of dispersion stability, a carboxyl group; a phosphoric acid group; a sulfonic acid group; or a base thereof; primary, secondary or tertiary Polymeric dispersants having functional groups such as amino groups; quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine and pyrazine are preferred. Above all, polymeric dispersants having basic functional groups such as primary, secondary or tertiary amino groups; quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine and pyrazine disperse pigments. It is particularly preferable from the viewpoint that it can be dispersed with a small amount of dispersant.

Examples of polymeric dispersants include urethane-based dispersants, acrylic dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, dispersants composed of a monomer having an amino group and a macromonomer, and polyoxyethylene alkyl ethers. Examples include system dispersants, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.

Specific examples of such dispersants include trade names of EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by BYK-Chemie), Disparon (registered trademark, manufactured by Kusumoto Kasei), and SOLSPERSE. (registered trademark, manufactured by Lubrizol Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and Ajisper (registered trademark, manufactured by Ajinomoto Co., Inc.).
One of these polymer dispersants may be used alone, or two or more thereof may be used in combination.

The weight average molecular weight (Mw) of the polymeric dispersant is usually 700 or more, preferably 1000 or more, and usually 100,000 or less, preferably 50,000 or less.
Among these, from the viewpoint of pigment dispersibility, (f) the dispersant preferably contains a urethane-based polymer dispersant and/or an acrylic polymer dispersant having a functional group. It is particularly preferred to include
From the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and a polyester bond and/or a polyether bond is preferred.

Examples of urethane-based and acrylic polymer dispersants include DISPERBYK 160-166, 182 series (all of which are urethane-based), DISPERBYK 2000, 2001, BYK-LPN21116, etc. (all of which are acrylic-based) (all manufactured by BYK-Chemie). .
A specific example of a preferred chemical structure as a urethane polymer dispersant is, for example, a polyisocyanate compound, a compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the molecule, and a molecule Dispersion resins having a weight-average molecular weight of 1,000 to 200,000, which are obtained by reacting a compound having an active hydrogen and a tertiary amino group therein, and the like. By treating these with a quaternizing agent such as benzyl chloride, all or part of the tertiary amino groups can be converted to quaternary ammonium bases.

Examples of the above polyisocyanate compounds include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate. Aromatic diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, aliphatic diisocyanate such as dimer acid diisocyanate, isophorone diisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate), ω,ω Alicyclic diisocyanates such as '-diisocyanate dimethylcyclohexane, xylylene diisocyanate, aliphatic diisocyanates having aromatic rings such as α,α,α',α'-tetramethylxylylene diisocyanate, lysine ester triisocyanate, 1, 6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris(isocyanatophenylmethane), tris(isocyanatophenyl)thiophosphate and triisocyanates such as triisocyanates, trimers thereof, water adducts, and polyol adducts thereof. Preferred polyisocyanates are trimers of organic diisocyanates, most preferred are trimers of tolylene diisocyanate and trimers of isophorone diisocyanate. These may be used individually by 1 type, and may use 2 or more types together.

As a method for producing a trimer of isocyanate, the above-mentioned polyisocyanates are treated with a suitable trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, etc. to convert the isocyanate group part After the trimerization is terminated by adding a catalyst poison, unreacted polyisocyanate is removed by solvent extraction and thin film distillation to obtain the desired isocyanurate group-containing polyisocyanate.

Compounds having a number average molecular weight of 300 to 10,000 and having one or two hydroxyl groups in the molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, etc., and one terminal hydroxyl group of these compounds has one carbon atom. and mixtures of two or more of these.
Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more thereof. Examples of polyether diols include those obtained by homopolymerizing or copolymerizing alkylene oxides, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol and these. and mixtures of two or more of

Polyetherester diols include those obtained by reacting ether group-containing diols or mixtures with other glycols with dicarboxylic acids or their anhydrides, or by reacting polyester glycols with alkylene oxides, e.g. oxytetramethylene) adipate and the like. The most preferred polyether glycols are polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, and compounds in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

Polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol , 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1 ,6-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2 ,5-hexanediol, 1,8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol, 1,9-nonanediol and other aliphatic glycols; bishydroxymethylcyclohexane and other aliphatic glycols; aromatic glycols such as lenglycol and bishydroxyethoxybenzene; N-alkyldialkanolamines such as N-methyldiethanolamine; , polyethylene/propylene adipate, etc., or polylactone diols or polylactone monools obtained by using the above diols or monohydric alcohols having 1 to 25 carbon atoms as initiators, such as polycaprolactone glycol, polymethylvalerolactone and these Mixtures of two or more are included. The most preferred polyester glycol is polycaprolactone glycol or polycaprolactone initiated by an alcohol having 1 to 25 carbon atoms.

Examples of polycarbonate glycols include poly(1,6-hexylene) carbonate and poly(3-methyl-1,5-pentylene) carbonate, and examples of polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. is mentioned.
These may be used individually by 1 type, and may use 2 or more types together.

The compound having one or two hydroxyl groups in the molecule generally has a number average molecular weight of 300 to 10,000, preferably 500 to 6,000, more preferably 1,000 to 4,000.

A compound having an active hydrogen and a tertiary amino group in the molecule used in the present invention will be explained.
Active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom, includes hydrogen atoms in functional groups such as a hydroxyl group, an amino group, and a thiol group. A hydrogen atom of the amino group of is preferred.

The tertiary amino group is not particularly limited, but includes, for example, an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, more specifically an imidazole ring or a triazole ring.
Examples of such compounds having active hydrogen and a tertiary amino group in the molecule include N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, N, N-dipropyl-1,3-propanediamine, N,N-dibutyl-1,3-propanediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dipropylethylenediamine, N,N- dibutylethylenediamine, N,N-dimethyl-1,4-butanediamine, N,N-diethyl-1,4-butanediamine, N,N-dipropyl-1,4-butanediamine, N,N-dibutyl-1, 4-butanediamine and the like.

Further, when the tertiary amino group is a nitrogen-containing heterocyclic structure, the nitrogen-containing heterocyclic ring includes a pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzo 5-membered nitrogen-containing hetero ring such as triazole ring, benzoxazole ring, benzothiazole ring, benzothiadiazole ring; 6-membered nitrogen-containing hetero ring such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, isoquinoline ring ring. Preferred among these nitrogen-containing heterocycles are imidazole rings and triazole rings.

Specific examples of compounds having an imidazole ring and an amino group include 1-(3-aminopropyl)imidazole, histidine, 2-aminoimidazole, 1-(2-aminoethyl)imidazole and the like. Specific examples of compounds having a triazole ring and an amino group include 3-amino-1,2,4-triazole, 5-(2-amino-5-chlorophenyl)-3-phenyl-1H-1 , 2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1 ,4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like. Among them, N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, 1-(3-aminopropyl)imidazole, 3-amino-1,2,4-triazole preferable.
These may be used individually by 1 type, and may use 2 or more types together.

A preferred blending ratio of raw materials for producing a urethane-based polymer dispersant is 10 to 100 parts by mass of a compound having a number average molecular weight of 300 to 10,000 and having one or two hydroxyl groups in the molecule per 100 parts by mass of a polyisocyanate compound. 200 parts by mass, preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, and 0.2 to 25 parts by mass, preferably 0.3 to 24 parts by mass of a compound having active hydrogen and a tertiary amino group in the molecule part by mass.

The urethane polymer dispersant is produced according to a known method for producing polyurethane resins. Solvents used in the production generally include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone, esters such as ethyl acetate, butyl acetate, and cellosolve acetate, benzene, toluene, xylene, and hexane. Some alcohols such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl Aprotic polar solvents such as pyrrolidone and dimethylsulfoxide are used. These may be used individually by 1 type, and may use 2 or more types together.

A urethanization reaction catalyst is usually used for the above production. Examples of this catalyst include tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate and stannus octoate; iron-based catalysts such as iron acetylacetonate and ferric chloride; class amines, and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types.

The introduction amount of the compound having active hydrogen and tertiary amino group in the molecule is preferably controlled in the range of 1 to 100 mgKOH/g in terms of amine value after the reaction. More preferably, it is in the range of 5-95 mgKOH/g. The amine value is a value expressed in mg of KOH corresponding to the acid value obtained by neutralizing and titrating the basic amino group with an acid. When the content is equal to or higher than the lower limit, the dispersing ability tends to be improved, and when the content is equal to or lower than the upper limit, deterioration of developability tends to be suppressed.

When the isocyanate group remains in the polymer dispersant after the reaction described above, it is preferable to crush the isocyanate group with an alcohol or an amino compound, since the stability of the product over time increases.
The weight-average molecular weight (Mw) of the urethane polymer dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. When the content is at least the above lower limit, dispersibility and dispersion stability tend to be improved, and when it is at most the above upper limit, deterioration in solubility and dispersibility tends to be suppressed.

On the other hand, as the acrylic polymer dispersant, an unsaturated group-containing monomer having a functional group (the functional group here is the functional group described above as the functional group contained in the polymer dispersant) It is preferable to use a random copolymer, a graft copolymer, or a block copolymer of a polymer and an unsaturated group-containing monomer having no functional group. These copolymers can be produced by known methods.

Examples of unsaturated group-containing monomers having functional groups include (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acrylic acid, royloxyethyl hexahydrophthalic acid, unsaturated monomers having a carboxyl group such as acrylic acid dimer, tertiary amino groups such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate and quaternary products thereof, Specific examples include unsaturated monomers having a quaternary ammonium base. These may be used individually by 1 type, and may use 2 or more types together.

Examples of unsaturated group-containing monomers having no functional group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( meth)acrylate, t-butyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, cyclohexyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxymethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate Acrylate, isobornyl (meth)acrylate, tricyclodecane (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N-vinylpyrrolidone, styrene and its derivatives, α-methylstyrene, N-cyclohexylmaleimide, N-phenylmaleimide, N - N-substituted maleimides such as benzylmaleimide, acrylonitrile, vinyl acetate and polymethyl (meth)acrylate macromonomers, polystyrene macromonomers, poly 2-hydroxyethyl (meth)acrylate macromonomers, polyethylene glycol macromonomers, polypropylene glycol macromonomers, poly Examples include macromonomers such as caprolactone macromonomers. These may be used individually by 1 type, and may use 2 or more types together.

The acrylic polymer dispersant is particularly preferably an AB or BAB block copolymer consisting of an A block having a functional group and a B block having no functional group. In addition to the partial structure derived from the unsaturated group-containing monomer containing the functional group, the block may contain a partial structure derived from the unsaturated group-containing monomer that does not contain the functional group. may be contained in the A block in any form of random copolymerization or block copolymerization. The content of the partial structure containing no functional group in the A block is usually 80% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass or less.

The B block consists of a partial structure derived from an unsaturated group-containing monomer that does not contain the above functional group, but one B block contains partial structures derived from two or more monomers. These may be contained in the B block in any form of random copolymerization or block copolymerization.
The AB or BAB block copolymer is prepared, for example, by the following living polymerization method.
The living polymerization method includes an anion living polymerization method, a cationic living polymerization method, and a radical living polymerization method. Of these, in the anionic living polymerization method, the polymerization active species is an anion, and is represented by, for example, the following scheme.

In the above scheme, Ar ¹ is a monovalent organic group, Ar ² is a monovalent organic group different from Ar ¹ , M is a metal atom, and s and t are integers of 1 or more.

In the radical living polymerization method, the polymerization active species is a radical, and is shown, for example, in the scheme below.

In the above scheme, Ar ¹ is a monovalent organic group, Ar ² is a monovalent organic group different from Ar ¹ , j and k are each an integer of 1 or more, and ^Ra is a hydrogen atom or 1 is a valent organic group, and R ^b is a hydrogen atom or a monovalent organic group different from R ^a .

In synthesizing this acrylic polymer dispersant, JP-A-9-62002 and P.S. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984), B.P. C. Anderson, G.; D. Andrews et al, Macromolecules, 14, 1601 (1981), K.K. Hatada, K.; Ute, et al, Polym. J. 17, 977 (1985), 18, 1037 (1986), Kouichi Ugimoto, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Kobunshi Ronbunshu, 46, 189 (1989), M. Kuroki, T.; Aida, J.; Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), D. Y. Sogoh, W.; R. A known method such as described in Hertler et al., Macromolecules, 20, 1473 (1987) can be employed.

The acrylic polymer dispersant that can be used in the present invention may be an AB block copolymer or a BAB block copolymer, and the A block constituting the copolymer The /B block ratio is preferably 1/99 to 80/20, particularly 5/95 to 60/40 (mass ratio), and by setting it within this range, it is possible to ensure a balance between dispersibility and storage stability. Tend.
In addition, the amount of the quaternary ammonium base in 1 g of the AB block copolymer and BAB block copolymer that can be used in the present invention is usually preferably 0.1 to 10 mmol. Within the range, there is a tendency to ensure good dispersibility.

Such a block copolymer may usually contain an amino group generated during the production process, and the amine value thereof is about 1 to 100 mgKOH/g, and from the viewpoint of dispersibility, It is preferably 10 mgKOH/g or more, more preferably 30 mgKOH/g or more, still more preferably 50 mgKOH/g or more, and preferably 90 mgKOH/g or less, more preferably 80 mgKOH/g or less, still more preferably 75 mgKOH/g or less.
Here, the amine value of dispersants such as these block copolymers is expressed by the mass of KOH equivalent to the amount of base per 1 g of solid content excluding the solvent in the dispersant sample, and is measured by the following method.
Accurately weigh 0.5 to 1.5 g of a dispersant sample in a 100 mL beaker and dissolve it in 50 mL of acetic acid. Using an automatic titrator equipped with a pH electrode, this solution is neutralized and titrated with a 0.1 mol/L HClO ₄ acetic acid solution. The inflection point of the titration pH curve is defined as the end point of the titration, and the amine value is obtained by the following formula.

Amine value [mgKOH/g] = (561 x V)/(W x S)
[However, W: Amount of weighed dispersant sample [g], V: Amount of titration [mL] at the end point of titration, S: Solid content concentration [% by mass] of dispersant sample. ]
In addition, the acid value of this block copolymer depends on the presence and type of acidic groups that are the source of the acid value, but generally it is preferably lower, usually 10 mgKOH / g or less, and its weight average molecular weight (Mw ) is preferably in the range of 1000 to 100,000. Within the above range, there is a tendency to ensure good dispersibility.

When the acrylic polymer dispersant has a quaternary ammonium base as a functional group, the specific structure of the acrylic polymer dispersant is not particularly limited. (hereinafter sometimes referred to as “repeating unit (i)”).

In the above formula (i), each of R ³¹ to R ³³ is independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or a and two or more of R ³¹ to R ³³ may combine with each other to form a cyclic structure. ^R34 is a hydrogen atom or a methyl group. X is a divalent linking group and Y ⁻ is a counter anion.

The number of carbon atoms in the optionally substituted alkyl group in R ³¹ to R ³³ in the above formula (i) is not particularly limited, but is usually 1 or more and preferably 10 or less. The following are more preferable. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like. is preferably a group, a pentyl group, or a hexyl group, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. In addition, it may be linear or branched. Moreover, a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group may be included.

Although the number of carbon atoms in the optionally substituted aryl group in R ³¹ to R ³³ in the above formula (i) is not particularly limited, it is usually 6 or more and preferably 16 or less. The following are more preferable. Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group and an anthracenyl group. , dimethylphenyl group, or diethylphenyl group, and more preferably phenyl group, methylphenyl group, or ethylphenyl group.

The number of carbon atoms in the optionally substituted aralkyl group in R ³¹ to R ³³ of formula (i) is not particularly limited, but is usually 7 or more and preferably 16 or less, and 12 The following are more preferable. Specific examples of the aralkyl group include phenylmethyl group (benzyl group), phenylethyl group (phenethyl group), phenylpropyl group, phenylbutyl group, phenylisopropyl group and the like. is preferably a group, a phenylpropyl group, or a phenylbutyl group, and more preferably a phenylmethyl group or a phenylethyl group.

Among these, from the viewpoint of dispersibility, it is preferable that R ³¹ to R ³³ are each independently an alkyl group or an aralkyl group. Specifically, R ³¹ and R ³³ are each independently a methyl group or an ethyl group. and R ³² is preferably a phenylmethyl group or a phenylethyl group, and more preferably R ³¹ and R ³³ are methyl groups and R ³² is a phenylmethyl group.

Further, when the acrylic polymer dispersant has a tertiary amino group as a functional group, from the viewpoint of dispersibility, a repeating unit represented by the following formula (ii) (hereinafter referred to as "repeating unit (ii)" It is preferable to have

In formula (ii) above, each of R ³⁵ and R ³⁶ is independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or a substituted and R ³⁵ and R ³⁶ may combine with each other to form a cyclic structure. ^R37 is a hydrogen atom or a methyl group. Z is a divalent linking group.

As the optionally substituted alkyl group for R ³⁵ and R ³⁶ in the above formula (ii), those exemplified as R ³¹ to R ³³ in the above formula (i) can be preferably employed. can.
Similarly, as the optionally substituted aryl group for R ³⁵ and R ³⁶ in the above formula (ii), those exemplified as R ³¹ to R ³³ in the above formula (i) are preferably employed. can be done. As the optionally substituted aralkyl group for R ³⁵ and R ³⁶ in the above formula (ii), those exemplified as R ³¹ to R ³³ in the above formula (i) can be preferably employed. can.

Among these, R ³⁵ and R ³⁶ are preferably each independently an optionally substituted alkyl group, more preferably a methyl group or an ethyl group.

Examples of substituents that the alkyl group, aralkyl group or aryl group in R ³¹ to R ³³ in the above formula (i) and R ³⁵ and R ³⁶ in the above formula (ii) may have include a halogen atom, an alkoxy group, A benzoyl group, a hydroxyl group, and the like can be mentioned.

In the above formulas (i) and (ii), the divalent linking groups X and Z include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, a —CONH—R ⁴³ — group, —COOR ⁴⁴ — group [wherein R ⁴³ and R ⁴⁴ are a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms] and the like, which are preferred. is a --COO--R ⁴⁴ -- group.
In the above formula (i), the counter anion Y ⁻ includes Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , PF ₆ ⁻ and the like.

The content ratio of the repeating unit represented by the formula (i) is not particularly limited, but from the viewpoint of dispersibility, the content ratio of the repeating unit represented by the formula (i) and the content ratio of the repeating unit represented by the formula (ii) It is preferably 60 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% or less, particularly preferably 35 mol% or less, relative to the total content of repeating units, and , preferably 5 mol % or more, more preferably 10 mol % or more, still more preferably 20 mol % or more, and particularly preferably 30 mol % or more.

In addition, the content ratio of the repeating unit represented by the formula (i) in the total repeating units of the polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 1 mol% or more, and 5 mol. % or more, more preferably 10 mol% or more, preferably 50 mol% or less, more preferably 30 mol% or less, and 20 mol% or less. is more preferable, and 15 mol % or less is particularly preferable.

In addition, the content ratio of the repeating unit represented by the formula (ii) in the total repeating units of the polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 5 mol% or more, and 10 mol. % or more, more preferably 15 mol% or more, particularly preferably 20 mol% or more, and preferably 60 mol% or less, and 40 mol% or less. is more preferably 30 mol % or less, and particularly preferably 25 mol % or less.

In addition, from the viewpoint of enhancing compatibility with binder components such as solvents and improving dispersion stability, the polymer dispersant is a repeating unit represented by the following formula (iii) (hereinafter referred to as “repeating unit (iii) ).

In formula (iii) above, R ⁴⁰ is an ethylene group or a propylene group, R ⁴¹ is an optionally substituted alkyl group, and R ⁴² is a hydrogen atom or a methyl group. n is an integer from 1 to 20;

The number of carbon atoms in the optionally substituted alkyl group in R ⁴¹ of formula (iii) is not particularly limited, but is usually 1 or more, preferably 2 or more, and 10 or less. is preferred, and 6 or less is more preferred. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like. is preferably a group, a pentyl group, or a hexyl group, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. In addition, it may be linear or branched. Moreover, a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group may be included.

In addition, n in the above formula (iii) is preferably 1 or more, more preferably 2 or more, and preferably 10 or less from the viewpoint of compatibility and dispersibility with respect to a binder component such as a solvent. , 5 or less.

In addition, the content ratio of the repeating unit represented by the formula (iii) in the total repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol % or more, and preferably 2 mol % or more. It is more preferably 4 mol % or more, more preferably 30 mol % or less, more preferably 20 mol % or less, and even more preferably 10 mol % or less. Within the above range, it tends to be possible to achieve both compatibility with a binder component such as a solvent and dispersion stability.

In addition, from the viewpoint of enhancing the compatibility of the dispersant with a binder component such as a solvent and improving the dispersion stability, the polymer dispersant is a repeating unit represented by the following formula (iv) (hereinafter referred to as “repeating unit (iv )”.).

In formula (iv) above, R ³⁸ is an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group. ^R39 is a hydrogen atom or a methyl group.

The number of carbon atoms in the optionally substituted alkyl group in R ³⁸ of formula (iv) is not particularly limited, but is usually 1 or more, preferably 2 or more, and preferably 4 or more. More preferably, it is 10 or less, and more preferably 8 or less. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like. is preferably a group, a pentyl group, or a hexyl group, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. In addition, it may be linear or branched. Moreover, a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group may be included.

The number of carbon atoms in the optionally substituted aryl group in R ³⁸ of formula (iv) is not particularly limited, but is usually 6 or more, preferably 16 or less, and 12 or less. is more preferable, and 8 or less is even more preferable. Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group and an anthracenyl group. , dimethylphenyl group, or diethylphenyl group, and more preferably phenyl group, methylphenyl group, or ethylphenyl group.

Although the number of carbon atoms in the optionally substituted aralkyl group in R ³⁸ of the formula (iv) is not particularly limited, it is usually 7 or more, preferably 16 or less, and 12 or less. is more preferable, and 10 or less is even more preferable. Specific examples of the aralkyl group include a phenylmethyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a phenylisopropyl group and the like. A butyl group is preferable, and a phenylmethyl group or a phenylethyl group is more preferable.

Among these, from the viewpoint of solvent compatibility and dispersion stability, R ³⁸ is preferably an alkyl group or an aralkyl group, more preferably a methyl group, an ethyl group or a phenylmethyl group.
Examples of substituents that the alkyl group in R ³⁸ may have include a halogen atom and an alkoxy group. Further, examples of the substituent that the aryl group or aralkyl group may have include a chain alkyl group, a halogen atom, an alkoxy group, and the like. The chain alkyl group represented by R ³⁸ includes both straight chain and branched chain alkyl groups.

In addition, the content of the repeating unit represented by the formula (iv) in the total repeating units of the polymer dispersant is preferably 30 mol% or more, more preferably 40 mol% or more, from the viewpoint of dispersibility. more preferably 50 mol % or more, more preferably 80 mol % or less, more preferably 70 mol % or less.

The polymer dispersant may have repeating units other than repeating unit (i), repeating unit (ii), repeating unit (iii) and repeating unit (iv). Examples of such repeating units include styrene-based monomers such as styrene and α-methylstyrene; (meth)acrylate-based monomers such as (meth)acrylic acid chloride; (meth)acrylamide, N- Repeating units derived from monomers such as (meth)acrylamide-based monomers such as methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl crotonate; N-methacryloylmorpholine.

From the viewpoint of further increasing the dispersibility, the polymer dispersant includes an A block having the repeating unit (i) and the repeating unit (ii) and a B block having no repeating unit (i) and the repeating unit (ii) and is preferably a block copolymer. The block copolymer is preferably an AB block copolymer or a BAB block copolymer. Introducing not only a quaternary ammonium base but also a tertiary amino group into the A block unexpectedly tends to significantly improve the dispersing ability of the dispersant. Also, the B block preferably has the repeating unit (iii), and more preferably has the repeating unit (iv).

In the A block, the repeating unit (i) and the repeating unit (ii) may be contained in any form of random copolymerization or block copolymerization. Two or more kinds of repeating units (i) and repeating units (ii) may be contained in one A block. It may be contained in any mode of block copolymerization.

In addition, repeating units other than repeating units (i) and repeating units (ii) may be contained in the A block. Repeating units derived from mers and the like are included. The content of repeating units other than repeating units (i) and repeating units (ii) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%. Most preferably it is not contained in a block.

Repeating units other than repeating units (iii) and (iv) may be contained in the B block. Examples of such repeating units include styrene-based monomers such as styrene and α-methylstyrene; (Meth)acrylate-based monomers such as meth)acrylic acid chloride; (meth)acrylamide-based monomers such as (meth)acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl crotonate Examples include repeating units derived from monomers such as ether; N-methacryloylmorpholine. The content of repeating units other than the repeating units (iii) and (iv) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, but such repeating units are B Most preferably it is not contained in a block.

From the viewpoint of improving dispersion stability, (f) the dispersant is preferably used in combination with the pigment derivative described later.

<Other ingredients of the photosensitive coloring composition>
In addition to the components described above, the photosensitive coloring composition of the present invention contains an adhesion improver such as a silane coupling agent, a surfactant (coatability improver), a pigment derivative, a photoacid generator, a cross-linking agent, and a mercapto compound. , a development improver, an ultraviolet absorber, an antioxidant, and the like can be added as appropriate.

(1) Adhesion Improver The photosensitive coloring composition of the present invention may contain an adhesion improver in order to improve adhesion to a substrate. As the adhesion improver, silane coupling agents, phosphoric acid group-containing compounds, and the like are preferable.
As the types of silane coupling agents, epoxy, (meth)acrylic, amino, and the like can be used singly or in combination of two or more.

Preferred silane coupling agents include (meth)acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. , epoxysilanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, ureidosilanes such as 3-ureidopropyltriethoxysilane, Examples include isocyanate silanes such as 3-isocyanatopropyltriethoxysilane, and particularly preferred are silane coupling agents of epoxysilanes.
As the phosphoric acid group-containing compound, (meth)acryloyl group-containing phosphates are preferable, and those represented by the following general formula (g1), (g2) or (g3) are preferable.

In general formulas (g1), (g2) and (g3) above, R ⁵¹ represents a hydrogen atom or a methyl group, l and l' are integers of 1 to 10, and m is 1, 2 or 3.
These phosphoric acid group-containing compounds may be used singly or in combination of two or more.

(2) Surfactant The photosensitive coloring composition of the present invention may contain a surfactant in order to improve coating properties.

Various surfactants such as anionic, cationic, nonionic and amphoteric surfactants can be used as the surfactant. Among them, it is preferable to use nonionic surfactants because they are less likely to adversely affect various properties. Among them, fluorine-based or silicon-based surfactants are effective in terms of coatability.
Examples of such surfactants include TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by BYK-Chemie), KP340. (manufactured by Shin-Etsu Silicone Co., Ltd.), Megafac F-470, Megafac F-475, Megafac F-478, Megafac F-554, Megafac F-559 (manufactured by DIC), SH7PA (manufactured by Dow Corning Toray Co., Ltd.) ), DS-401 (manufactured by Daikin), L-77 (manufactured by Nippon Unicar), FC4430 (manufactured by 3M) and the like.
In addition, 1 type may be used for surfactant and it may use 2 or more types together by arbitrary combinations and ratios.

(3) Pigment Derivative The photosensitive coloring composition of the present invention may contain a pigment derivative as a dispersing aid in order to improve dispersibility and storage stability.
Pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, and dioxazine. Among them, phthalocyanine-based and quinophthalone-based derivatives are preferred.
Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and their quaternary salts, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, and the like, which may be directly attached to the pigment skeleton or may be attached to the skeleton of the pigment. Examples thereof include those bonded via a ring group or the like, preferably a sulfonic acid group. A single pigment skeleton may be substituted with a plurality of these substituents.

Specific examples of pigment derivatives include phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, and dioxazine sulfonic acid derivatives. These may be used individually by 1 type, and may use 2 or more types together.

(4) Photo-acid generator A photo-acid generator is a compound that can generate an acid upon exposure to ultraviolet light, and the action of the acid generated upon exposure may include a cross-linking agent such as a melamine compound. Then, the cross-linking reaction proceeds. Among such photoacid generators, those having high solubility in solvents, particularly those used in photosensitive coloring compositions, are preferred. Iodonium, bis(m-nitrophenyl)iodonium, bis(p-tert-butylphenyl)iodonium, bis(p-chlorophenyl)iodonium, bis(n-dodecyl)iodonium, p-isobutylphenyl(p-tolyl)iodonium, p - chlorides, bromides or borofluorides, hexafluorophosphates, hexafluoroarsenates, aromatic sulfonates of diaryliodonium such as isopropylphenyl(p-tolyl)iodonium or triarylsulfonium such as triphenylsulfonium , tetrakis (pentafluorophenyl) borate salts, etc., sulfonium organoboron complexes such as diphenylphenacylsulfonium (n-butyl) triphenylborate, or 2-methyl-4,6-bistrichloromethyltriazine, 2-( Triazine compounds such as 4-methoxyphenyl)-4,6-bistrichloromethyltriazine and the like can be mentioned, but are not limited to these.

(5) Cross-linking agent The photosensitive coloring composition of the present invention may further contain a cross-linking agent such as a melamine or guanamine compound. Examples of these cross-linking agents include melamine- or guanamine-based compounds represented by the following general formula (6).

In formula ⁽ 6 ^{) ,} R ^{61 represents} a -NR ⁶⁶ R ^{67 group} or an aryl group having 6 ^to 12 carbon atoms ^; , R ⁶⁶ and R ⁶⁷ represent —CH ₂ OR ⁶⁸ , and when R ⁶¹ is an aryl group having 6 to 12 carbon atoms, one of R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ is —CH ₂ OR ⁶⁸ and the rest of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ independently represent hydrogen or —CH ₂ OR ⁶⁸ group, where R ⁶⁸ is hydrogen atom or C 1-4 represents an alkyl group of
Here, the aryl group having 6 to 12 carbon atoms is typically a phenyl group, 1-naphthyl group or 2-naphthyl group, and these phenyl groups and naphthyl groups include alkyl groups, alkoxy groups, halogen atoms and the like. may be bonded. The alkyl group and the alkoxy group can each have about 1 to 6 carbon atoms. Among the above, the alkyl group represented by R ⁶⁸ is preferably a methyl group or an ethyl group, especially a methyl group.

Melamine-based compounds corresponding to general formula (6), that is, compounds of the following general formula (6-1) include hexamethylolmelamine, pentamethylolmelamine, tetramethylolmelamine, hexamethoxymethylmelamine, pentamethoxymethylmelamine, tetramethoxy Methylmelamine, hexaethoxymethylmelamine and the like are included.

In formula (6-1), when one of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ is an aryl group, one of R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ is —CH ₂ represents an OR ⁶⁸ group, and the remainder of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ independently represent a hydrogen atom or a —CH ₂ OR ⁶⁸ group, wherein R ⁶⁸ is a hydrogen atom or represents an alkyl group.

Further, guanamine-based compounds corresponding to general formula (6), that is, compounds in which R ⁶¹ in general formula (6) is aryl, include tetramethylolbenzoguanamine, tetramethoxymethylbenzoguanamine, trimethoxymethylbenzoguanamine, and tetraethoxymethylbenzoguanamine. etc. are included.

Furthermore, a cross-linking agent having a methylol group or a methylol alkyl ether group can also be used. Examples are given below.
2,6-bis(hydroxymethyl)-4-methylphenol, 4-tert-butyl-2,6-bis(hydroxymethyl)phenol, 5-ethyl-1,3-bis(hydroxymethyl)perhydro-1,3 ,5-triazin-2-one (commonly known as N-ethyldimethyloltriazone) or its dimethyl ether, dimethyloltrimethylene urea or its dimethyl ether, 3,5-bis(hydroxymethyl)perhydro-1,3,5- Oxadiazin-4-one (commonly known as dimethyloluron) or its dimethyl ether derivative, tetramethylolglyoxaldiurein or its tetramethyl ether derivative.

In addition, these crosslinking agents may be used individually by 1 type, or may be used in combination of 2 or more type. The amount of the cross-linking agent used is preferably 0.1 to 15% by mass, particularly preferably 0.5 to 10% by mass, based on the total solid content of the photosensitive coloring composition.

(6) Mercapto compound A mercapto compound can be added as a polymerization accelerator and for improving adhesion to the substrate.

Types of mercapto compounds include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bis Thioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropio pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, ethylene glycol bis(3-mercaptobutyrate), butanediol bis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyrate) aryloxy)butane, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), ethylene glycol bis(3-mercaptoisobutyrate) , butanediol bis(3-mercaptoisobutyrate), trimethylolpropane tris(3-mercaptoisobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine- Mercapto compounds having a heterocyclic ring such as 2,4,6(1H,3H,5H)-trione or aliphatic polyfunctional mercapto compounds are included. These various things can be used individually by 1 type, or in mixture of 2 or more types.

<Amount of components in photosensitive coloring composition>
In the photosensitive coloring composition of the present invention, the content of (a) the coloring agent is 23% by mass or less in the total solid content of the photosensitive coloring composition. (a) Since the coloring agent is a component that does not elastically deform, it is considered that the mechanical properties of the resulting colored spacer are improved by setting the content ratio to the above upper limit or less.
(a) The content of the coloring agent is not particularly limited as long as it is 23% by mass or less in the total solid content of the photosensitive coloring composition, but is preferably 22% by mass or less, more preferably 20% by mass or less, and 18% by mass. % or less, more preferably 16% by mass or less, particularly preferably 15% by mass or less, most preferably 14% by mass or less, preferably 1% by mass or more, more preferably 5% by mass or more, and 8% by mass. % or more is more preferable, 10% by mass or more is even more preferable, and 12% by mass or more is particularly preferable. (a) By setting the content of the colorant to the above upper limit or less, the mechanical properties are improved, and sufficient plate-making properties are likely to be obtained, and the electrical reliability tends to be excellent. With the above, there is a tendency that sufficient light shielding properties can be obtained.

The content of the pigment in the photosensitive coloring composition of the present invention is not particularly limited, but is not particularly limited as long as it is 23% by weight or less in the total solid content of the photosensitive coloring composition, preferably 22% by weight or less, and 20 % by mass or less is more preferable, 18% by mass or less is more preferable, 16% by mass or less is even more preferable, 15% by mass or less is particularly preferable, 14% by mass or less is most preferable, and 1% by mass or more is preferable. It is more preferably 8% by mass or more, even more preferably 10% by mass or more, and particularly preferably 12% by mass or more. When the content of the pigment is below the above upper limit, mechanical properties are improved, and sufficient plate-making properties are likely to be obtained, and electrical reliability tends to be excellent. , and there is a tendency to obtain sufficient light-shielding properties.

The content of the yellow pigment in the total solid content of the photosensitive coloring composition is preferably 1% by mass or more, more preferably 5% by mass or more, more preferably 8% by mass or more, even more preferably 10% by mass or more, 15 50% by mass or less is particularly preferable, 40% by mass or less is more preferable, 35% by mass or less is even more preferable, 30% by mass or less is even more preferable, 25% by mass or less is particularly preferable, and 20% by mass or less is particularly preferable. % by mass or less is most preferred. When it is equal to or higher than the lower limit, there is a tendency that the transmittance at a wavelength of 400 to 500 nm can be sufficiently suppressed, and when it is equal to or lower than the upper limit, it tends to be easy to obtain sufficient plate-making performance.

The total content of the red pigment and the orange pigment in the total solid of the photosensitive coloring composition is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 5% by mass or more, and 30% by mass. The following is preferable, 20% by mass or less is more preferable, 15% by mass or less is even more preferable, 10% by mass or less is even more preferable, and 8% by mass or less is particularly preferable. If it is above the lower limit, the optical density (OD) tends to increase, and if it is below the upper limit, there is a tendency that sufficient plate-making performance is likely to be obtained.

The content of the red pigment in the total solid of the photosensitive coloring composition is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 5% by mass or more, and preferably 30% by mass or less, 20% by mass % or less, more preferably 15 mass % or less, even more preferably 10 mass % or less, and particularly preferably 8 mass % or less. If it is above the lower limit, the optical density (OD) tends to increase, and if it is below the upper limit, there is a tendency that sufficient plate-making performance is likely to be obtained.

The content of the orange pigment in the total solid of the photosensitive coloring composition is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 5% by mass or more, and preferably 30% by mass or less, 20% by mass % or less, more preferably 15 mass % or less, even more preferably 10 mass % or less, and particularly preferably 8 mass % or less. If it is above the lower limit, there is a tendency that the optical density (OD) and the suppression of transmittance at a wavelength of 400 to 500 nm tend to be compatible, and if it is below the above upper limit, there is a tendency that sufficient plate-making performance is likely to be obtained.

The photosensitive coloring composition preferably has a low content of blue pigment and purple pigment in the total solid from the viewpoint of color tone, preferably 30% by mass or less, more preferably 25% by mass or less, and further 20% by mass or less. It is preferably 15% by mass or less, even more preferably 10% by mass or less, particularly preferably 5% by mass or less, and most preferably 0% by mass, that is, not contained.
On the other hand, from the viewpoint of light-shielding properties, it may contain a blue pigment and/or a purple pigment. More preferably 8% by mass or more, particularly preferably 10% by mass or more, most preferably 15% by mass or more, preferably 30% by mass or less, more preferably 25% by mass or less, 20% by mass % or less is more preferable. When the content is at least the lower limit, sufficient light-shielding properties tend to be obtained, and when the content is at most the upper limit, a color tone close to black tends to be obtained.

(b) The content of the alkali-soluble resin is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 30% by mass in the total solid content of the photosensitive coloring composition of the present invention. % or more, particularly preferably 35 mass % or more, usually 85 mass % or less, preferably 80 mass % or less, more preferably 70 mass % or less, even more preferably 60 mass % or less, still more preferably 50 mass % or less , particularly preferably 45% by mass or less. (b) By setting the content ratio of the alkali-soluble resin to the above lower limit or more, there is a tendency that the mechanical properties are improved and the developability is improved. Further, when the content is not more than the above upper limit, there is a tendency that appropriate sensitivity can be maintained, dissolution of the exposed portion by the developer can be suppressed, and a decrease in adhesion can be suppressed.

(c) the content of the photopolymerization initiator is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more in the total solid content of the photosensitive coloring composition of the present invention; More preferably 2% by mass or more, usually 15% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or less, even more preferably 7% by mass or less, particularly preferably 5% by mass or less. (c) When the content of the photopolymerization initiator is equal to or higher than the above lower limit, there is a tendency to suppress a decrease in sensitivity. , there is a tendency that poor development can be suppressed.

(c) When using a polymerization accelerator together with a photopolymerization initiator, the content of the polymerization accelerator is preferably 0.05% by mass or more, usually 10% by mass, in the total solid content of the photosensitive coloring composition of the present invention. %, preferably 5% by mass or less, and the polymerization accelerator is usually used in a proportion of 0.1 to 50 parts by mass and 0.1 to 20 parts by mass with respect to 100 parts by mass of the photopolymerization initiator (c). is preferred. By setting the content of the polymerization accelerator to the above lower limit or more, there is a tendency to suppress the decrease in sensitivity to exposure light, and by setting the content to the above upper limit or less, the decrease in the solubility of the unexposed portion in the developer is suppressed. and tend to be able to suppress poor development.
Further, (c) when using a sensitizing dye together with the photopolymerization initiator, the content of the sensitizing dye, from the viewpoint of sensitivity, in the total solid content in the photosensitive coloring composition, usually 20 wt% or less, preferably is 15% by mass or less, more preferably 10% by mass or less.

(d) The content of the ethylenically unsaturated compound is usually 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 10% by mass or more, in the total solid content of the photosensitive coloring composition of the present invention. It is 20% by mass or more, particularly preferably 30% by mass or more, and usually 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less. (d) By setting the content ratio of the ethylenically unsaturated compound to the above lower limit or more, there is a tendency that appropriate sensitivity can be maintained, dissolution of the exposed portion by the developer can be suppressed, and a decrease in adhesion can be suppressed, In addition, by making it equal to or less than the above upper limit, there is a tendency that it becomes easy to obtain a good image by suppressing an increase in the permeability of the developer to the exposed area.

On the other hand, the content ratio of the (b) alkali-soluble resin to 100 parts by mass of the (d) ethylenically unsaturated compound is not particularly limited, but is preferably 50 parts by mass or more, more preferably 80 parts by mass or more, and 100 parts by mass or more. More preferably, it is usually 700 parts by mass or less, preferably 500 parts by mass or less, more preferably 400 parts by mass or less, and even more preferably 300 parts by mass or less. When the content is at least the above lower limit, there is a tendency to achieve an appropriate developing state without peeling, etc., and when the content is at most the above upper limit, there is a tendency that an appropriate dissolution time in the developer can be achieved. The combination of the upper limit and the lower limit is preferably 50 to 700 parts by mass, more preferably 80 to 500 parts by mass, still more preferably 80 to 400 parts by mass, and particularly preferably 100 to 300 parts by mass.

Incidentally, the photosensitive coloring composition of the present invention, by using a solvent (e), the content of the total solid content is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more , and usually 50% by mass or less, preferably 30% by mass or less, more preferably 25% by mass or less.

When the photosensitive coloring composition of the present invention contains (f) a dispersant, the content of (f) the dispersant is usually 1% by mass or more in the total solid content of the photosensitive coloring composition, 2% by mass or more is preferably 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, and particularly preferably 5% by mass or less. (f) By setting the content ratio of the dispersant to the above lower limit or more, there is a tendency that sufficient dispersibility can be easily obtained, and by setting it to the above upper limit or less, the ratio of other components is relatively reduced. It tends to be possible to suppress deterioration in sensitivity, plate-making properties, and the like.

In addition, the content ratio of (f) dispersant to 100 parts by mass of (a) colorant is usually 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, and usually 50 parts by mass or less, especially It is preferably 30 parts by mass or less. (f) By setting the content ratio of the dispersant to the above lower limit or more, there is a tendency that sufficient dispersibility can be easily obtained, and by setting it to the above upper limit or less, the ratio of other components is relatively reduced. It tends to be possible to suppress deterioration in sensitivity, plate-making properties, and the like.

When using an adhesion improver, the content is usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, more preferably 0.4 to 5% by mass in the total solid content of the photosensitive coloring composition. It is 2% by mass. When the content of the adhesion improver is at least the above lower limit, there is a tendency that a sufficient effect of improving adhesion can be obtained. There is a tendency that it can be suppressed that it becomes a defect.

Further, when a surfactant is used, its content is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, more preferably 0.005 to 1% by mass, based on the total solid content in the photosensitive coloring composition. 01 to 0.5% by weight, most preferably 0.03 to 0.3% by weight. When the surfactant content is equal to or higher than the lower limit, the coating film tends to exhibit smoothness and uniformity, and when the content is equal to or lower than the upper limit, the coating film exhibits smoothness and uniformity. It tends to be easy and suppress the deterioration of other properties.

<Physical properties of photosensitive coloring composition>
The photosensitive coloring composition of the present invention can be suitably used for forming colored spacers. From the viewpoint of use as a colored spacer, the cured film preferably has a high optical density (OD) per 1 μm of film thickness. The colored spacer alone obtained by curing the photosensitive colored composition of the present invention is preferably 0.01 or more, more preferably 0.03 or more, further preferably 0.05 or more. , is more preferably 0.08 or more, particularly preferably 0.10 or more, and most preferably 0.15 or more. Here, the optical density (OD) per 1 μm of film thickness is a value measured by the method described in Examples below.

In the case of lamination with a blue color filter layer, the optical density (OD) of the two layers in which the colored spacer and the blue color filter layer are laminated is preferably 0.5 or more, preferably 1.0 or more. is more preferable. Here, the optical density (OD) of the laminated two layers is a value measured by the method described in Examples below.

In the photosensitive coloring composition of the present invention, the ratio of the average absorbance at a wavelength of 400 to 500 nm to the average absorbance at a wavelength of 500 to 700 nm is preferably 3.0 or more, more preferably 4.0 or more, and 5.0 More preferably 6.0 or more, particularly preferably 6.0 or more. Moreover, it is preferably 15.0 or less, more preferably 13.0 or less, still more preferably 11.0 or less, and particularly preferably 9.0 or less. When the content is at least the above lower limit, a color tone close to black can be obtained when laminated with a blue color filter layer, and there is a tendency that the transmittance of 400 to 500 nm can be suppressed. In addition, there is a tendency that the optical density (OD) can be increased by making it equal to or less than the above upper limit.

Here, the ratio of the average absorbance at a wavelength of 400 to 500 nm to the average absorbance at a wavelength of 500 to 700 nm of the photosensitive coloring composition is obtained by forming a cured film having a thickness of 2.5 μm using the photosensitive coloring composition, It can be specified by measuring the absorbance at wavelengths of 400 to 700 nm with a spectrophotometer every 1 nm.
Although detailed measurement conditions and the like are not particularly limited, measurement can be performed, for example, by the following method.
First, a spinner is used to apply a photosensitive coloring composition onto a glass substrate (“AN100” manufactured by AGC). Then, it is heated and dried on a hot plate at 90° C. for 90 seconds to form a coating film. The obtained coating film is irradiated with ultraviolet rays in the air. Ultraviolet rays having a wavelength of 365 nm and an intensity of 32 mW/cm ² are used, and the exposure dose is 70 mJ/cm ² . Subsequently, using a developer consisting of an aqueous solution containing 0.05% by mass of potassium hydroxide and 0.08% by mass of a nonionic surfactant (“A-60” manufactured by Kao Corporation), the water pressure was 0 at 25 ° C. After applying shower development at 15 MPa, the development is stopped with pure water, and washed with a washing spray. The shower development time is adjusted between 10 and 120 seconds and should be 1.5 times the time for the unexposed coating to dissolve away. The solid film substrate obtained by these operations is heated in an oven at 230° C. for 20 minutes to cure the pattern and obtain a substrate with a cured film having a thickness of 2.5 μm. Next, the absorbance of the substrate at a wavelength of 400 to 700 nm is measured at intervals of 1 nm using a UV-3150 spectrophotometer manufactured by Shimadzu Corporation, with a glass substrate not coated with the photosensitive coloring composition as a control. Calculate the average absorbance by averaging the measured values of the absorbance at 1 nm intervals at a wavelength of 400 to 500 nm, similarly calculate the average absorbance at a wavelength of 500 to 700 nm, and average the wavelength of 400 to 500 nm for the average absorbance at a wavelength of 500 to 700 nm Calculate the absorbance ratio.

In addition, the photosensitive coloring composition of the present invention is used for forming a colored spacer, particularly for forming the colored spacer of a liquid crystal display having a structure in which a blue color filter layer is provided in a portion facing the colored spacer in the frame portion. , the color tone is preferably close to black when superimposed on the blue color filter layer, and the color tone is more preferably x≧0.20 and y≧0.20, and x≧0. 25 and y≧0.25 are more preferred. This color tone can be measured by the procedure described in Examples.

<Method for producing a photosensitive coloring composition>
The photosensitive coloring composition of the invention is produced according to a conventional method.
Generally, (a) the colorant is preferably dispersed in advance using a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, or the like. Since the (a) colorant is finely divided by the dispersion treatment, the application properties of the photosensitive coloring composition are improved.

Dispersion treatment is usually preferably carried out in a system in which (a) a colorant, (e) a solvent, (f) a dispersant, and optionally (b) a part or all of an alkali-soluble resin are used in combination ( Hereinafter, the mixture subjected to the dispersion treatment and the composition obtained by the treatment may be referred to as "ink" or "pigment dispersion"). In particular, it is preferable to use a polymeric dispersant as (f) the dispersant, since the resulting ink and photosensitive coloring composition are prevented from thickening over time (excellent in dispersion stability).
Thus, in the process of producing the photosensitive coloring composition, it is preferable to produce a pigment dispersion containing at least (a) a colorant, (e) a solvent, and (f) a dispersant. As the (a) colorant, (e) solvent, and (f) dispersant that can be used in the pigment dispersion, those described as those that can be used in the photosensitive coloring composition can be preferably employed. can.

When a liquid containing all the components to be blended in the photosensitive coloring composition is subjected to dispersion treatment, heat generated during the dispersion treatment may denature highly reactive components. Therefore, it is preferable to carry out the dispersion treatment in a system that does not contain (c) a photopolymerization initiator or (d) an ethylenically unsaturated compound.
When dispersing (a) the colorant with a sand grinder, glass beads or zirconia beads having a particle size of about 0.1 to 8 mm are preferably used. As for the dispersion treatment conditions, the temperature is usually from 0°C to 100°C, preferably from room temperature to 80°C. Appropriate time for dispersing tends to vary depending on the composition of the liquid, the size of the dispersing apparatus, etc., and may be adjusted as appropriate. The aim of dispersion is to control the glossiness of the ink so that the 20° specular glossiness (JIS Z8741) is in the range of 50 to 300 when the pigment dispersion or photosensitive coloring composition is applied to the substrate. When the content is at least the lower limit, residual coarse pigment ((a) colorant) particles due to insufficient dispersion treatment can be suppressed, and developability, adhesion, resolution, etc. tend to be sufficient. . In addition, when the content is equal to or less than the above upper limit, it is possible to suppress the generation of a large number of ultrafine particles due to crushing of the pigment, and there is a tendency that the dispersion stability can be improved.

Further, the dispersed particle size of the pigment dispersed in the ink is usually 0.03 to 0.3 μm. The particle size is measured by a dynamic light scattering method or the like.
Next, the ink obtained by the dispersion treatment and the other components contained in the photosensitive coloring composition are mixed to form a uniform solution. In the manufacturing process of the photosensitive coloring composition, fine dust is often mixed in the liquid, so it is desirable to filter the obtained photosensitive coloring composition with a filter or the like.

[Cured product]
The cured product of the invention is obtained by curing the photosensitive coloring composition of the invention. A cured product obtained by curing a photosensitive coloring composition can be suitably used as a colored spacer.

[Colored spacer]
The colored spacer of the present invention, which is composed of the cured product of the present invention, will be described according to its manufacturing method.

(1) Support The material of the support for forming the colored spacer is not particularly limited as long as it has an appropriate strength. Transparent substrates are mainly used, and the materials used include, for example, polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, and epoxy. Thermosetting resin sheets such as resins, unsaturated polyester resins, and poly(meth)acrylic resins, and various types of glass can be used. Among these, glass and heat-resistant resin are preferable from the viewpoint of heat resistance. In some cases, a transparent electrode such as ITO or IZO is formed on the surface of the substrate. Besides the transparent substrate, it can also be formed on a TFT array.

In order to improve surface physical properties such as adhesiveness, the support may be subjected, if necessary, to corona discharge treatment, ozone treatment, silane coupling agent, thin film formation treatment of various resins such as urethane resins, and the like. .
The thickness of the transparent substrate is usually in the range of 0.05-10 mm, preferably 0.1-7 mm. When thin films of various resins are formed, the film thickness is usually in the range of 0.01 to 10 μm, preferably 0.05 to 5 μm.

(2) Colored Spacer The photosensitive colored composition of the present invention can be used for the same applications as known photosensitive colored compositions for color filters. Explain how.

Generally, the photosensitive coloring composition is applied in the form of a film or a pattern by a method such as coating onto a support on which colored spacers are to be provided, and the solvent is dried. Subsequently, a pattern is formed by a method such as a photolithography method in which exposure and development are performed. Thereafter, additional exposure or heat curing treatment is performed as necessary to form colored spacers on the support.

(3) Formation of Colored Spacer [1] Method of Supplying to Substrate The photosensitive coloring composition of the invention is usually supplied onto a support in a state of being dissolved or dispersed in a solvent. As the method of supply, conventionally known methods such as spinner method, wire bar method, flow coating method, die coating method, roll coating method and spray coating method can be used. Alternatively, it may be supplied in a pattern by an inkjet method, a printing method, or the like. Above all, according to the die coating method, the amount of coating liquid used is greatly reduced, and there is no effect of mist that adheres when using the spin coating method, and the generation of foreign matter is suppressed. preferable from this point of view.

The coating amount varies depending on the application, but in the case of a colored spacer, for example, the dry film thickness is usually in the range of 0.5 μm to 10 μm, preferably 1 μm to 9 μm, particularly preferably 1 μm to 7 μm. Also, it is important that the dry film thickness or the height of the finally formed spacers is uniform over the entire substrate. If the variation is large, display spots or the like may occur on the liquid crystal panel.

However, when using the photosensitive coloring composition of the present invention to collectively form colored spacers having different heights by photolithography, the finally formed colored spacers have different heights.

A known substrate such as a glass substrate can be used as the support. Moreover, it is preferable that the substrate surface is flat.

[2] Drying Method Drying after supplying the photosensitive coloring composition onto the support is preferably by a drying method using a hot plate, an IR oven, or a convection oven. Alternatively, a reduced pressure drying method, in which drying is performed in a reduced pressure chamber without raising the temperature, may be combined.

Drying conditions such as drying temperature and drying time can be appropriately selected according to the type of solvent component, the performance of the dryer to be used, and the like. Usually, the temperature is 40° C. to 130° C. for 15 seconds to 5 minutes, preferably 50° C. to 110° C. for 30 seconds to 3 minutes.

[3] Exposure method Exposure is carried out by overlaying a negative mask pattern on the coating film of the photosensitive coloring composition, and irradiating a light source of ultraviolet light or visible light through this mask pattern. When performing exposure using an exposure mask, a method of bringing the exposure mask close to the coating film of the photosensitive coloring composition, or placing the exposure mask at a position away from the coating film of the photosensitive coloring composition, the exposure A method of projecting exposure light through a mask may also be used. Alternatively, a scanning exposure method using a laser beam without using a mask pattern may be used. At this time, if necessary, in order to prevent the sensitivity of the photopolymerizable layer from decreasing due to oxygen, the exposure is performed in an oxygen-free atmosphere, or after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable layer. You can

As a preferred embodiment of the present invention, when simultaneously forming colored spacers having different heights by a photolithography method, for example, a light shielding portion (light transmittance of 0%) and a plurality of openings having the highest average light transmittance An exposure mask having apertures (perfectly transmissive apertures) and apertures with a low average light transmittance (intermediate transmissive apertures) is used. According to this method, the difference in the average light transmittance between the intermediate transmission opening and the complete transmission opening, that is, the difference in the amount of exposure, causes the difference in the residual film ratio.
For example, a method of forming the intermediate transmission aperture by a matrix-shaped light shielding pattern having minute polygonal light shielding units is known. Also known is a method of controlling the light transmittance by using a film of a chromium-based, molybdenum-based, tungsten-based, or silicon-based material as an absorber.

The light source used for the above exposure is not particularly limited. Examples of light sources include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps, argon ion lasers, YAG lasers, Examples include laser light sources such as excimer lasers, nitrogen lasers, helium-cadmium lasers, blue-violet semiconductor lasers, and near-infrared semiconductor lasers. An optical filter can also be used when using it by irradiating the light of a specific wavelength.

The optical filter may be, for example, a thin film type capable of controlling the light transmittance at the exposure wavelength. MoSi, Si, W, Al, etc. are mentioned.

The exposure dose is usually 1 mJ/cm ² or more, preferably 5 mJ/cm ² or more, more preferably 10 mJ/cm ² or more, and usually 300 mJ/cm ² or less, preferably 200 mJ/cm ² or less, more preferably. It is 150 mJ/cm ² or less.
In the case of the proximity exposure method, the distance between the exposure target and the mask pattern is usually 10 μm or more, preferably 50 μm or more, more preferably 75 μm or more, and usually 500 μm or less, preferably 400 μm or less, more preferably 400 μm or less. It is 300 μm or less.

[4] Development method After the above exposure, an image pattern can be formed on the substrate by development using an aqueous solution of an alkaline compound or an organic solvent. This aqueous solution may further contain surfactants, organic solvents, buffers, complexing agents, dyes or pigments.

Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate. , sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, inorganic alkaline compounds such as ammonium hydroxide, mono-, di- or triethanolamine, mono-, di- or trimethylamine , mono-, di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. compound. These alkaline compounds may be a mixture of two or more.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; Anionic surfactants such as acid salts, alkylnaphthalenesulfonates, alkylsulfates, alkylsulfonates, and sulfosuccinate ester salts; and amphoteric surfactants such as alkylbetaines and amino acids.

Examples of organic solvents include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. The organic solvent can be used alone or in combination with an aqueous solution.

The conditions for the development treatment are not particularly limited, and the development temperature is usually in the range of 10 to 50°C, especially 15 to 45°C, particularly preferably 20 to 40°C. Any method such as a development method or an ultrasonic development method can be used.

[5] Post-exposure and heat curing treatment If necessary, the substrate after development may be subjected to post-exposure by the same method as the above-described exposure method, or may be subjected to heat curing treatment. At this time, the heat curing treatment conditions are such that the temperature is selected in the range of 100° C. to 280° C., preferably 150° C. to 250° C., and the time is selected in the range of 5 minutes to 60 minutes.

The size, shape and the like of the colored spacer of the present invention are appropriately adjusted depending on the specifications of the color filter to which it is applied. It is useful for simultaneously forming colored spacers of different heights, in which case the spacer height is usually about 2 to 7 μm, and the sub-spacer is usually about 0.2 to 1.5 μm lower than the spacer. have.

[Color filter]
The color filter of the present invention comprises the colored spacer of the present invention as described above. are laminated to form a colored spacer, and then an alignment film is formed. Alternatively, the pixel colored layer and the colored spacer may be formed on the liquid crystal drive side substrate, or may be separately formed on the transparent substrate and the liquid crystal drive side substrate.
In addition, as described in Korean Patent Publication No. 10-2013-0015734, Korean Patent Publication No. 10-2015-0059026, and Korean Patent Publication No. 10-2017-0017447, a colored spacer is added to the non-display area. can be provided, and in this case, by laminating a color filter of a blue layer or a red layer on the facing side, leakage of light to the non-display area can be reduced. It is also possible to use only the blue layer, only the red layer, or only the green layer. Liquid crystal displays with LED backlights tend to have a strong LED blue light component. Therefore, the blue light component is easily transmitted. For example, in the case of only a single layer, particularly only a blue layer, there is a tendency for light leakage with a wavelength of 400 to 500 nm to easily occur. This light leakage can be adjusted by the laminated structure when the liquid crystal display is formed, or the material properties of the opposing colored spacers. For example, the colored spacers obtained by curing the photosensitive colored composition of the present invention can be used. preferred.

[Image display device]
The image display device of the present invention comprises the colored spacer of the present invention.
For example, a liquid crystal cell is formed by bonding a color filter having the colored spacer of the present invention described above and a substrate on the liquid crystal drive side, and liquid crystal is injected into the formed liquid crystal cell to obtain the colored spacer of the present invention. An image display device of the present invention such as a liquid crystal display device can be manufactured.

EXAMPLES Next, the present invention will be described in more detail with reference to examples, comparative examples, and reference examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
The constituent components of the photosensitive coloring compositions used in the following Examples, Comparative Examples and Reference Examples are as follows.

<Alkali-soluble resin-I>
145 parts by mass of propylene glycol monomethyl ether acetate was stirred under nitrogen substitution, and the temperature was raised to 120°C. Here, 10 parts by mass of styrene, 85.2 parts by mass of glycidyl methacrylate, and 66 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise, and 2,2'-azobis-2-methyl 8.47 parts by mass of butyronitrile was added dropwise over 3 hours, and the mixture was further stirred at 90°C for 2 hours. Next, the inside of the reaction vessel was changed to air exchange, 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 43.2 parts by mass of acrylic acid, and the reaction was continued at 100°C for 12 hours. After that, 56.2 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added and reacted at 100° C. for 3.5 hours. The polystyrene equivalent weight average molecular weight Mw measured by GPC of the alkali-soluble resin-I thus obtained was 8400, and the acid value was 80 mgKOH/g.

<Alkali-soluble resin-II>
A mixed liquid of 210.1 parts by mass of propylene glycol monomethyl ether acetate and 52.5 parts by mass of propylene glycol monomethyl ether was stirred under nitrogen substitution and heated to 120°C. Here, 3.52 parts by mass of benzyl methacrylate, 68.8 parts by mass of methacrylic acid, 39.7 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) and 2,2'-azobis-2- A mixed solution of 3.3 parts by mass of methylbutyronitrile was added dropwise over 3 hours, and the mixture was further stirred at 90° C. for 2 hours. Next, the inside of the reaction vessel was replaced with air, 38.4 parts by mass of glycidyl methacrylate, 0.8 parts by mass of trisdimethylaminomethylphenol and 0.1 part by mass of hydroquinone were added, and the reaction was continued at 100°C for 12 hours. The polystyrene equivalent weight average molecular weight Mw measured by GPC of the alkali-soluble resin-II thus obtained was 19100, and the acid value was 198 mgKOH/g.

<Alkali-soluble resin-III>
17 parts by weight of succinic anhydride and 350 parts by weight of dipentaerythritol polyacrylate (A-9550 manufactured by Shin-Nakamura Chemical Co., Ltd.), 1.8 parts by weight of triethylamine, and 0.12 parts by weight of 4-methoxyphenol, propylene glycol monomethyl ether acetate A polyfunctional acrylate (d-1) having one carboxyl group and two or more acryloyl groups per molecule was obtained by reacting at 85° C. for 6 hours in the presence of 91.8 parts by mass.
Subsequently, bisphenol A type epoxy resin (jER-828 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 186) 32.7 g, the polyfunctional acrylate (d-1) 460.7 g, 2,2,6,6-tetramethylpiperidine 1 0.2 g of oxyl, 8.0 g of triphenylphosphine, and 18.9 g of propylene glycol monomethyl ether acetate were stirred at 80° C. until the acid value became 2 mg KOH/g or less. Subsequently, 161.6 g of propylene glycol monomethyl ether acetate was added to 520.5 g of the obtained reaction product and dissolved, then 24.2 g of 1,2,3,6-tetrahydrophthalic anhydride was added, and the mixture was stirred at 90°C. Alkali-soluble resin-III was obtained by reacting for 4 hours. The obtained alkali-soluble resin-III had an acid value of 23 mgKOH/g, a polystyrene-equivalent weight average molecular weight Mw measured by GPC of 3000, and a double bond equivalent of 120 g/mol.

<Dispersant-I>
"BYK-LPN21116" manufactured by BYK Chemie (A block having a quaternary ammonium base and a tertiary amino group in the side chain, and a B block having no quaternary ammonium base and tertiary amino group, acrylic AB Block copolymer. Amine value: 70 mgKOH/g. Acid value: 1 mgKOH/g or less.)
The A block of Dispersant-I contains repeating units of the following formulas (1a) and (2a), and the B block contains repeating units of the following formula (3a). The content ratios of the repeating units of the following formulas (1a), (2a), and (3a) in the total repeating units of Dispersant-I are 11.1 mol%, 22.2 mol%, and 6.7 mol%, respectively. be.

<Solvent-I>
PGMEA: propylene glycol monomethyl ether acetate <solvent-II>
MB: 3-methoxybutanol

<Photoinitiator-I>
OXE-01 manufactured by BASF (oxime ester photopolymerization initiator)

<Photopolymerizable Monomer>
Nippon Kayaku DPHA (dipentaerythritol hexaacrylate)
<Additive-I>
Nippon Kayaku Co., Ltd. KAYAMER PM-21 (methacryloyl group-containing phosphate)
<Additive-II>
SH6040 (3-glycidoxypropyltrimethoxysilane) manufactured by Dow Corning Toray Co., Ltd.
<Surfactant>
DIC Megafac F-554

<Preparation of Pigment Dispersions 1 to 6>
A pigment, a dispersant, an alkali-soluble resin, and a solvent shown in Table 1 were mixed so as to have the mass ratio shown in Table 1. The amount of dispersant and alkali-soluble resin in Table 1 is the amount of solid content, and the amount of solvent includes the amount of solvent derived from the dispersant and alkali-soluble resin.
This solution was subjected to dispersion treatment for 3 hours in the range of 25 to 45° C. using a paint shaker. As the beads, 0.5 mmφ zirconia beads were used, and 2.5 times the mass of the dispersion liquid was added. After completion of dispersion, the beads and the dispersion liquid were separated by a filter to prepare pigment dispersion liquids 1 to 6.

<Preparation of photosensitive coloring compositions 1 to 13>
[Examples 1 to 3, Comparative Examples 1 to 4, and Reference Examples 1 to 6]
Using the pigment dispersions 1 to 4 and 6 prepared above, each component is added so that the ratio in the total solid content of the photosensitive coloring composition is the blending ratio in Tables 2 to 4, and the total solid content A solvent was added so that the content ratio was 22% by mass and PGMEA/MB=80/20 (mass ratio), and the mixture was stirred and dissolved to prepare photosensitive coloring compositions 1 to 13. Evaluation was performed by the method described later using each of the obtained photosensitive coloring compositions.

<Preparation of board for evaluation>
Each photosensitive coloring composition was applied onto a glass substrate (“AN100” manufactured by AGC) using a spinner so that the film thickness after heating and baking would be 2.5 μm. Then, it was heated and dried on a hot plate at 90° C. for 90 seconds to form a coating film.
The coating film thus obtained was exposed to light on the entire surface without using a mask. An ultraviolet ray having a wavelength of 365 nm and an intensity of 32 mW/cm ² was used, and the exposure amount was 70 mJ/cm ² . Moreover, the ultraviolet irradiation was performed in the air.

Subsequently, using a developer consisting of an aqueous solution containing 0.05% by mass of potassium hydroxide and 0.08% by mass of a nonionic surfactant (“A-60” manufactured by Kao Corporation), the water pressure was 0 at 25 ° C. After applying shower development at 15 MPa, the development was stopped with pure water and washed with a washing spray. The shower development time was 50 seconds.
The substrate was cured by heating in an oven at 230° C. for 20 minutes to obtain an evaluation substrate having a colored layer.

<Creation of blue board>
Using the pigment dispersion 5 prepared above, each component is added so that the ratio in the total solid content of the photosensitive coloring composition is the following mixing ratio, and the content ratio of the total solid content is 22% by mass. A photosensitive coloring composition 14 was prepared by adding PGMEA and stirring and dissolving.

Pigment dispersion liquid 5 41.67% by mass
Alkali-soluble resin-I 34.98 mass%
Photopolymerizable monomer 19.25% by mass
Photoinitiator-I 4.00 wt%
Surfactant 0.10% by mass

Next, a blue substrate having a blue layer was obtained in the same manner as in <Preparation of substrate for evaluation>, except that the film thickness after heating and baking was adjusted to 1.0 μm.

<Evaluation of Optical Density (OD)>
The optical density (OD) of each of the colored layer of the obtained evaluation substrate and the blue layer of the blue substrate was measured with a transmission densitometer ("D200-II" manufactured by Gretag Macbeth). From these measured values, the optical density in the state where the colored layer and the blue layer were laminated was calculated. Next, the optical density (OD/μm) per unit film thickness of only the colored layer of the substrate for evaluation was calculated. The results are shown in Tables 2-4, respectively.

<Evaluation of wavelength 400 to 500 nm transmittance, absorbance and color tone>
The light transmittance and absorbance of the obtained evaluation substrate and blue substrate at a wavelength of 380 to 780 nm were measured at intervals of 1 nm, and a glass substrate not coated with a photosensitive coloring composition was used as a control, and a spectrophotometer manufactured by Shimadzu Corporation UV- Measured using 3150.

Then, the average transmittance is calculated by averaging the measured values of the transmittance of each substrate at wavelengths of 400 to 500 nm every 1 nm, and then using these calculated values, the evaluation substrate and the blue substrate are superimposed. was calculated and evaluated according to the following criteria. Since the average transmittance at a wavelength of 400 to 500 nm is high when the blue substrate is used alone, it is preferable that the average transmittance value is lowered by further laminating a colored layer.
In the same procedure, the transmittance at a wavelength of 400 nm, the transmittance at a wavelength of 450 nm, and the transmittance at a wavelength of 500 nm were calculated, and the results are shown in Tables 2-4.

(Wavelength 400-500nm average transmittance)
○: 5% or less ×: Exceeds 5%

Next, the average absorbance was calculated by averaging the measured values of the absorbance of each substrate for evaluation at wavelengths of 400 to 500 nm at intervals of 1 nm. Similarly, the average absorbance at a wavelength of 500-700 nm was calculated, and the ratio of the average absorbance at a wavelength of 400-500 nm to the average absorbance at a wavelength of 500-700 nm was calculated. The results are shown in Tables 2-4.

Next, the chromaticity coordinates (x, y) in the xy chromaticity diagram in the XYZ color system in which the evaluation substrate and the blue substrate are superimposed are calculated at intervals of 1 nm at wavelengths of 380 to 780 nm for each evaluation substrate and the blue substrate. It was calculated from the transmittance and the profile (emission spectrum) of the light source in FIG. 1, and the color tone was evaluated.
The color tone results are Example 1 (x, y) = (0.255, 0.608), Example 2 (x, y) = (0.327, 0.631), Example 3 (x, y ) = (0.263, 0.437), Reference Example 1 (x, y) = (0.258, 0.581), Reference Example 2 (x, y) = (0.231, 0.614), Reference Example 3 (x, y) = (0.244, 0.617), Reference Example 4 (x, y) = (0.338, 0.594), Reference Example 5 (x, y) = (0. 319, 0.613) and Reference Example 6 (x, y) = (0.301, 0.633), both of which were found to be practically sufficient.

<Preparation of substrate for mechanical property evaluation>
Each photosensitive coloring composition of Examples 1 to 3 and Comparative Example 1 was applied onto a glass substrate (“AN100” manufactured by Asahi Glass Co., Ltd.) using a spinner. After drying in a vacuum, it was dried by heating on a hot plate at 90° C. for 90 seconds to form a coating film.
The obtained coating film was subjected to exposure treatment using an exposure mask having circular patterns of completely transparent apertures with various diameters of 5 to 50 μm (5 to 20 μm: every 1 μm, 25 μm to 50 μm: every 5 μm). . The exposure gap (distance between mask and coating surface) was 250 μm. As irradiation light, ultraviolet rays having a wavelength of 365 nm and an intensity of 32 mW/cm ² were used, and the exposure amount was 70 mJ/cm ² . Moreover, the ultraviolet irradiation was performed in the air.

Subsequently, using a developer consisting of an aqueous solution containing 0.05% by mass of potassium hydroxide and 0.08% by mass of a nonionic surfactant (“A-60” manufactured by Kao Corporation), the water pressure was 0 at 25 ° C. After applying shower development at .05 MPa, the development was stopped with pure water, and washed with a washing spray. The shower development time was adjusted between 10 and 120 seconds and was 1.3 times the time for the unexposed coating to dissolve away.
By these operations, a pattern from which unnecessary portions were removed was obtained. The substrate on which the pattern was formed was heated in an oven at 230° C. for 20 minutes to cure the pattern to obtain a substantially cylindrical spacer pattern with a height of 2.5 μm.

<Evaluation of mechanical properties>
Among the obtained spacer patterns, patterns having a bottom diameter of 27±2 μm were subjected to elastic recovery rate measurement according to the following procedure.
As a microhardness tester for load-unload test, Fischer Instruments Co. (FISCHERSCOPE H100C) is used, a measurement temperature is 23 ° C., a flat indenter with a diameter of 50 μm is used, and a load is applied to the spacer at a constant speed (5 mN / sec). In addition, when the load reached 150 mN, it was held for 5 seconds, then unloaded at the same speed, and when the load dropped to 0 mN, it was held for 5 seconds to obtain a load-displacement curve. From this load-displacement curve, the largest displacement value was calculated as the maximum displacement H [max], and the displacement after the load was kept at 0 mN for 5 seconds was calculated as the final displacement H [Last].
Next, the elastic recovery rate was calculated by the following formula, and the elastic recovery rate was evaluated as follows. The respective results are shown in Tables 2-4.

Elastic recovery rate (%) = {(maximum displacement H [max] - final displacement H [Last])
/ maximum displacement H [max]} × 100

(Elastic recovery rate)
○: 90% or more ×: less than 90%

In Table 2, from a comparison between Examples 1 and 2 and Comparative Example 1, by setting the content of the coloring agent in the total solid content of the photosensitive coloring composition to 23% by mass or less, the mechanical properties of the colored spacer It can be seen that the The content of the colorant in the total solid content is 23% by mass or less, that is, the content of the colorant that does not deform elastically does not become excessively high, so that plastic deformation when a load is applied to the colored spacer can be suppressed, and the elastic recovery rate is considered to be good.
In Tables 2 and 3, from a comparison of Examples 1, 3, and Reference Example 1 with Comparative Examples 2 and 3, a photosensitive coloring composition having a yellow pigment content of 40% by mass or more in all coloring agents. It can be seen that the average transmittance at a wavelength of 400 to 500 nm is sufficiently low by using . This is because the light having a wavelength of 400 to 500 nm, which is transmitted without being absorbed in the blue layer, is sufficiently blocked by containing the yellow pigment in an amount equal to or higher than the lower limit.
Furthermore, from a comparison between Example 1 and Comparative Example 4, when using a photosensitive coloring composition containing not only a yellow pigment but also a red pigment, the optical density (OD) in the state where the blue substrate was overlaid It can be seen that the light-shielding property is sufficient for practical use.

From the comparison of Example 1 in Table 2 and Reference Examples 2 and 3 in Table 4, regardless of the type of red pigment, the average transmittance at 400 to 500 nm is sufficiently low, and the optical density (OD ) is also sufficiently high.
Further, from a comparison between Example 1 in Table 2 and Reference Examples 4 to 6 in Table 4, even when an orange pigment is used instead of a red pigment, the average transmittance at a wavelength of 400 to 500 nm is sufficiently low, and the blue substrate It can be seen that the optical density (OD) in the state in which .

Claims (4)

(a) a coloring agent, (b) an alkali-soluble resin, (c) a photopolymerization initiator, and (d) a photosensitive coloring composition containing an ethylenically unsaturated compound,
The content of the (a) colorant is 10% by mass or more in the total solid content of the photosensitive coloring composition23
% by mass or less,
The (a) colorant comprises a yellow pigment and a red pigment and/or an orange pigment,
The content of the yellow pigment in the (a) colorant is 50% by mass or more and 90% by mass or less,
The yellow pigment is C.I. I. Pigment Yellow 138, C.I. I. pigment yellow 1
39, and C.I. I. including at least one selected from the group consisting of Pigment Yellow 150,
The total content of the red pigment and the orange pigment in the (a) colorant is 10% by mass or more and 50% by mass
% or less,
The photosensitive coloring composition, wherein the photopolymerization initiator (c) is an oxime ester compound. The red pigment is C.I. I. Pigment Red 177, C.I. I. pigment red 254
, and C.I. I. including at least one selected from the group consisting of Pigment Red 272,
The photosensitive coloring composition according to claim 1. The orange pigment is C.I. I. Pigment Orange 13, C.I. I. pigment orange 43
, C.I. I. Pigment Orange 64, and C.I. I. 3. The photosensitive coloring composition according to claim 1, comprising at least one selected from the group consisting of Pigment Orange 72. A cured product obtained by curing the photosensitive coloring composition according to any one of claims 1 to 3.

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