JP7848465B2 - Photosensitive composition, optical filter, image display device, and solid-state image sensor - Google Patents

Description

This invention relates to a photosensitive composition used in the formation of optical filters such as color filters.

Optical filters, such as color filters used in image display devices and solid-state image sensors, often have fine patterns formed using photolithography.
As image display devices and solid-state image sensors become smaller and have higher pixel counts, the area per pixel tends to decrease, which is being addressed by increasing the concentration of dyes in the photosensitive composition. At the same time, it becomes necessary to increase the resolution of the patterns.

Patent Document 1 discloses a photosensitive composition containing polyalkylene oxides and alkylene oxide adducts of glycerin.

Japanese Patent Publication No. 2007-058192

However, conventional photosensitive compositions tended to produce patterns with widths exceeding the aperture width of the photomask. Furthermore, the adhesion between the pattern and the substrate, as well as the chemical resistance, were not at a satisfactory level.

The present invention aims to provide a photosensitive composition that can form a coating with excellent adhesion and chemical resistance while having a line width of pattern close to that of the aperture width of a photomask.

The photosensitive composition of the present invention comprises a dye (A), a dispersant (B), an alkali-soluble resin (C), a polymerizable compound (D), and a photopolymerization initiator (E).
The polymerizable compound (D) comprises a monomer (D1) containing one hydroxyl group and one carboxyl group, a hydrocarbon ring, and one polymerizable unsaturated group.

According to the present invention described above, it is possible to provide a photosensitive composition that can form a coating with excellent adhesion and chemical resistance while having a line width of a pattern close to that of the aperture width of a photomask. Furthermore, the present invention can provide optical filters, image display devices, and solid-state image sensors.

Figure 1 is a schematic cross-sectional view of an image display device.

The following describes each component of the photosensitive composition of the present invention.
In this application, when "(meth)acryloyl,""(meth)acrylic,""(meth)acrylicacid,""(meth)acrylate," or "(meth)acrylamide" are used, unless otherwise specified, they shall represent "acryloyl and/or methacryloyl,""acrylic and/or methacrylic,""acrylic acid and/or methacrylic acid,""acrylate and/or methacrylate," or "acrylamide and/or methacrylamide," respectively.
Furthermore, as used herein, "C.I." refers to Color Index (C.I.).

The photosensitive composition of the present invention comprises a dye (A), a dispersant (B), an alkali-soluble resin (C), a polymerizable compound (D), and a photopolymerization initiator (E).
The polymerizable compound (D) contains a monomer (D1) (hereinafter also referred to as monomer (D1)) which contains one hydroxyl group and one carboxyl group, a hydrocarbon ring, and one polymerizable unsaturated group. The photosensitive composition of the present invention is used by forming a film. The film is preferably used as an optical filter.

The film formed from the photosensitive composition of the present invention is such that the polymerizable unsaturated group in the monomer (D1), which contains either a hydroxyl group or a carboxyl group, a hydrocarbon ring, and one polymerizable unsaturated group, is adjusted so that the photocurability is not excessive, thereby enabling the formation of a line width pattern close to the aperture width of the photomask by photosolivation.
Furthermore, the hydroxyl or carboxyl groups derived from the monomer (D1) in the film can improve the formation of hydrogen bonds and intermolecular forces with the substrate interface, significantly improving adhesion. In addition, the hydrocarbon rings derived from the monomer (D1) suppress affinity with the alkaline developer used in the development process, making it less likely for the pattern to peel off the substrate during the development process.

<Pigment A>
The photosensitive composition of the present invention includes pigments, dyes, and near-infrared absorbing dyes as the dye (A). Pigments include inorganic pigments and organic pigments.
Red pigments include, for example, C.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 ,64,64:1,68,69,81,81:1,81:2,81:3,81:4,83,88,90:1,101,101:1,104,108,108:1,109,112,113,114,122,123,144,146,147,149,151,166,168,169,170,172,173,174,175,176,177,178,179,181,1 84, 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 Examples include pigments described in JP 2014-134712, JP 6368844, JP 262, JP 263, JP 264, JP 265, JP 266, JP 267, JP 268, JP 269, JP 270, JP 271, JP 272, JP 273, JP 274, JP 275, JP 276, JP 277, JP 278, JP 279, JP 280, JP 281, JP 282, JP 283, JP 284, JP 285, JP 286, JP 287, JP 291, JP 295, JP 296, pigments described in JP 2014-134712, pigments described in JP 6368844, etc. Among these, C.I. is considered to have the most heat resistance, light resistance, and transmittance. Pigment red 48: 1,122,177,224,242,269,254,291,295,296, the pigment described in Japanese Patent Publication No. 2014-134712, and the pigment described in Japanese Patent Publication No. 6368844 are preferred, and C.I. Pigment red 177,254,291,295,296, the pigment described in Japanese Patent Publication No. 2014-134712, and the pigment described in Japanese Patent Publication No. 6368844 are particularly preferred.

Examples of orange pigments include C.I. Pigment Orange 36, 38, 43, 64, 71, and 73.

Yellow pigments include, for example, C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 1 Examples include pigments described in 27, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, and Japanese Patent Publication No. 2012-226110. Among these, C.I. Pigments described in Pigment Yellow 138, 139, 150, 185, 231, 233 and Japanese Patent Publication No. 2012-226110 are preferred.

Examples of green pigments include C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, and 63. Among these, C.I. Pigment Green 7, 36, 58, 59, 62, and 63 are preferred.

Examples of blue pigments include C.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, and 79. Among these, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6 are preferred.

Examples of purple pigments include C.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, and 50. Among these, C.I. Pigment Violet 19 and 23 are preferred.

Examples of black pigments that can be used in this invention include C.I. Pigment Black 1, 6, 7, 12, 20, and 31.

Examples of inorganic pigments include titanium dioxide, barium sulfate, zinc oxide, lead sulfate, lead yellow, zinc yellow, red iron oxide (iron(III) oxide), cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, amber, and synthetic iron black.

Near-infrared absorbing dyes are compounds that have maximum absorption in the wavelength range of 700 to 2,000 nm. Examples of near-infrared absorbing dyes include pigments (also called near-infrared absorbing pigments) or dyes (also called near-infrared absorbing dyes). Near-infrared absorbing pigments and near-infrared absorbing dyes may also be used in combination. However, from the viewpoint of heat resistance, near-infrared absorbing pigments are preferred.
The solubility of the near-infrared absorbing pigment in 100 g of propylene glycol monomethyl ether acetate at 25°C is preferably less than 2 g, more preferably less than 1 g, and even more preferably 0.5 g or less.

Examples of near-infrared absorbing dyes include cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, indigo compounds, immonium compounds, anthraquinone compounds, pyrrolopyrrol compounds, squarylium compounds, and crokonium compounds. Among these, naphthalocyanine compounds, pyrrolopyrrol compounds, and squarylium compounds are preferred from the viewpoint of heat resistance, with naphthalocyanine compounds and squarylium compounds being more preferred.

Cyanine compounds are described in International Publication WO2006/006573, International Publication WO2010/073857, Japanese Patent Publication No. 2013-241598, Japanese Patent Publication No. 2016-113501, Japanese Patent Publication No. 2016-113504, etc.; Phthalocyanine compounds are described in Japanese Patent Publication No. Hei 4-23868, Japanese Patent Publication No. Hei 06-192584, Japanese Patent Publication No. 2000-63691 Japanese Patent Publication No. 11-152414, Japanese Patent Publication No. 2000-86919, Japanese Patent Publication No. 2009-29955, Japanese Patent Publication No. WO2018/186490, etc.; Japanese Patent Publication No. 2013-230412, etc.; Japanese Patent Publication No. 2005-3361 Japanese Patent Publication No. 50, Japanese Patent Publication No. 2007-197492, Japanese Patent Publication No. 2008-88426, etc.; for anthraquinone compounds, Japanese Patent Publication No. Sho 62-903, Japanese Patent Publication No. Hei 1-172458, etc.; for pyrrolopyrrol compounds, Japanese Patent Publication No. 2009-263614, Japanese Patent Publication No. 2010-90313, Japanese Patent Publication No. 2011-068731; for squarylium compounds Examples of croconium compounds include those described in Japanese Patent Publication No. 2011-132361, Japanese Patent Publication No. 2016-142891, International Publication WO2017/135359, International Publication WO2018/225837, Japanese Patent Publication No. 2019-001987, International Publication WO2020/054718, etc. Croconium compounds include those described in International Publication WO2019/021767, etc.

(Squallium compounds)
The preferred squarylium compound is one represented by the following general formula (1).

General formula (1)

(In general formula (1), ^R1 to ^R4 each independently represent a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, -OR ¹⁰ , -COR ¹¹ , -COOR ¹² , -OCOR ¹³ , -NR ¹⁴ R ¹⁵ , -NHCOR ¹⁶ , -CONR ¹⁷ R ¹⁸ , -NHCONR ^{19 R 20, -NHCOOR 21, -SR 22, -SO₂ R 23 , -SO₂OR 24} _, ^-NHSO₂ _{R 25} ^, _-SO₂NR ²⁶ R ²⁷ , -B(OR ²⁸ ) ₂ , and -NHBR ²⁹ R ³⁰ . ^R10 to ^R30 each independently represent a hydrogen atom, an optionally substituted alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, and an aralkyl group. Note that when ^R12 in -COOR ¹² is hydrogen (i.e., a carboxyl group), the hydrogen atom may dissociate (i.e., a carbonate group), or it may exist in a salt state. Also, when ^R24 in _-SO2OR ²⁴ is a hydrogen atom (i.e., a sulfo group), the hydrogen atom may dissociate (i.e., a sulfonate group), or it may exist in a salt state. Furthermore, ^R1 and ^R2 , and ^R3 and ^R4 may bond to each other to form a ring.

Examples of "substituents" include halogen atoms, cyano groups, nitro groups, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, aralkyl groups, -OR ¹⁰⁰ , -COR ¹⁰¹ , -COOR ¹⁰² , -OCOR ¹⁰³ , -NR ^{104R 105} , -NHCOR ¹⁰⁶ , -CONR ^{107R 108} , -NHCONR ^{109R 110} , -NHCOOR ¹¹¹ , -SR ¹¹² , _-SO₂R ¹¹³ , _-SO₂OR ¹¹⁴ , _-NHSO₂R ¹¹⁵ , or _-SO₂NR ^{116R 117} .
R ¹⁰⁰ to R ¹¹⁷ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aralkyl group. Note that when R ¹⁰² in -COOR ¹⁰² is hydrogen (i.e., a carboxyl group), the hydrogen atom may dissociate (i.e., a carbonate group), or the product may exist in a salt state. Similarly, when R ¹¹⁴ in _-SO₂OR ¹¹⁴ is a hydrogen atom (i.e., a sulfo group), the hydrogen atom may dissociate (i.e., a sulfonate group), or the product may exist in a salt state.

Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.
The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 8 carbon atoms. The alkyl group may be linear, branched, or cyclic.
The number of carbon atoms in the alkenyl group is preferably 2 to 20, more preferably 2 to 12, and even more preferably 2 to 8. The alkenyl group may be linear, branched, or cyclic.
The number of carbon atoms in the alkynyl group is preferably 2 to 20, more preferably 2 to 12, and even more preferably 2 to 8. The alkynyl group may be linear, branched, or cyclic.
The number of carbon atoms in the aryl group is preferably 6 to 25, more preferably 6 to 15, and even more preferably 6 to 10.
The alkyl portion of the aralkyl group is the same as that of the alkyl group described above. The aryl portion of the aralkyl group is the same as that of the aryl group described above. The number of carbon atoms in the aralkyl group is preferably 7 to 40, more preferably 7 to 30, and even more preferably 7 to 25.
The heteroaryl group is preferably a monocyclic or fused ring, more preferably a monocyclic or fused ring with 2 to 8 fused rings, and even more preferably a monocyclic or fused ring with 2 to 4 fused rings. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The heteroatoms constituting the ring of the heteroaryl group are preferably nitrogen atoms, oxygen atoms, or sulfur atoms. The heteroaryl group is preferably a 5-membered or 6-membered ring. The number of carbon atoms constituting the ring of the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12.
Alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, and aralkyl groups may have substituents or may be unsubstituted. Examples of substituents include the "substituents" mentioned above.

From the viewpoint of light resistance and heat resistance, the compound represented by the following general formula (2) is more preferable among the squarylium compounds.

General formula (2)

(In general formula (2), R ⁵ to R ⁸ each independently represent a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, -OR ⁵⁰ , -COR ⁵¹ , -COOR ⁵² , -OCOR ⁵³ , -NR ⁵⁴ R ⁵⁵ , -NHCOR ⁵⁶ , -CONR ⁵⁷ R ⁵⁸ , -NHCONR ⁵⁹ R ⁶⁰ , -NHCOOR ⁶¹ , -SR ⁶² , _-SO₂ R ⁶³ , _-SO₂ OR ⁶⁴ , -NHSO₂ R ⁶⁵ or _-SO₂ ^{NR 66} _R ⁶⁷ , -B(OR ⁶⁸ ) _₂ , and -NHBR ⁶⁹ R ⁷⁰ . ^R50 to ^R70 each independently represent a hydrogen atom, an optionally substituted alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, and an aralkyl group. Note that when ^R52 in -COOR ⁵² is hydrogen (i.e., a carboxyl group), the hydrogen atom may dissociate (i.e., a carbonate group), or the product may exist in a salt state. Similarly, when ^R64 in _-SO2OR ⁶⁴ is a hydrogen atom (i.e., a sulfo group), the hydrogen atom may dissociate (i.e., a sulfonate group), or the product may exist in a salt state. Furthermore, ^R5 and ^R6 , and ^R7 and ^R8 may bond to each other to form a ring.

The term "substituent" has the same meaning as the term "substituent" described above.

The following are specific examples of squarylium compounds. However, the present invention is not limited to these examples.

(Pyrrolopyrrole compounds)
The pyrrolopyrrol compound is preferably a compound represented by the following general formula (3).

General formula (3)

(In general formula (3), R ^1X and R ^1Y each independently represent an alkyl group, an aryl group, or a heteroaryl group; R ² and R ³ each independently represent a hydrogen atom or a substituent; R ² and R ³ may be bonded to each other to form a ring; R ⁴ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR ^4X R ^4Y , or a metal atom; R ⁴ may be covalently or coordinately bonded with at least one selected from the group consisting of R ^1X , R ^1Y , and R ³ ; and R ^4X R ^4Y each independently represent a substituent. Compounds represented by general formula (3) are described in Japanese Patent Publication No. 2009-263614, Japanese Patent Publication No. 2011-68731, and International Publication No. 2015/166873.

R ^1X and R ^1Y are each independently preferably aryl groups or heteroaryl groups, with aryl groups being more preferred. Furthermore, the alkyl groups, aryl groups, and heteroaryl groups represented by R ^1X and R ^1Y may be substituted or unsubstituted. Examples of substituents include alkoxy groups, hydroxyl groups, halogen atoms, cyano groups, nitro groups, -OCOR ¹¹ , -SOR ¹² , and _-SO₂R ^13. R ¹¹ to R ¹³ each independently represent a hydrocarbon group or a heteroaryl group. Examples of substituents include those described in paragraphs 0020 to 0022 of Japanese Patent Application Publication No. 2009-263614. Among these, alkoxy groups, hydroxyl groups, halogen atoms, cyano groups, nitro groups, -OCOR ¹¹ , -SOR ¹² , and _-SO₂R ¹³ are preferred substituents. The groups represented by R ^1X and R ^1Y are preferably alkoxy groups having a branched alkyl group, or aryl groups having a group represented by -OCOR ¹¹ as a substituent. The number of carbon atoms in the branched alkyl group is preferably 3 to 30, and more preferably 3 to 20.

At least one of ^R2 and ^R3 is preferably an electron-withdrawing group, more preferably ^R2 represents an electron-withdrawing group and ^R3 represents a heteroaryl group. The heteroaryl group is preferably a five-membered ring or a six-membered ring. The heteroaryl group is also preferably a monoring or a fused ring, preferably a monoring or a fused ring with 2 to 8 fused rings, and more preferably a monoring or a fused ring with 2 to 4 fused rings. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, more preferably 1 to 2. Examples of heteroatoms include nitrogen atoms, oxygen atoms, and sulfur atoms. The heteroaryl group preferably has one or more nitrogen atoms. The two ^R2s in general formula (3) may be the same or different. The two ^R3s in general formula (3) may be the same or different.

R ⁴ is preferably a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, or a group represented by -BR ^4X R ^{4Y ,} more preferably a hydrogen atom, an alkyl group, an aryl group, or a group represented by -BR ^{4X R 4Y} , and even more preferably a group represented by -BR ^4X R 4Y. The substituent represented by R 4X R ^4Y is preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a heteroaryl group, more preferably an alkyl group, an aryl group, or a heteroaryl group, and even more preferably an aryl group. These groups may have further substituents. The two R ^4s in general formula (3) may be the same or different.

The following are specific examples of pyrrolopyrrol compounds. In the following structural formulas, ME represents a methyl group and PH represents a phenyl group. Examples of pyrrolopyrrol compounds include those described in paragraphs 0016-0058 of Japanese Patent Publication No. 2009-263614, paragraphs 0037-0052 of Japanese Patent Publication No. 2011-68731, paragraphs 0014-0027 of Japanese Patent Publication No. 2014-130343, and paragraphs 0010-0033 of International Publication No. 2015/166873. However, the present invention is not limited to these.

(Naphthalocyanine compounds)
The naphthalocyanine compound is preferably a compound represented by the following general formula (4).

General formula (4)

In general formula (4), ^R1 to ^R24 each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 4 to 20 carbon atoms, ^-OR25 or ^-SR26 , and ^R25 and ^R26 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms,
This represents an aryl group having 6 to 20 carbon atoms, either substituted or unsubstituted.

Examples of halogen atoms represented by ^R1 to ^R24 in general formula (4) include fluorine, chlorine, bromine, and iodine atoms.

The alkyl groups having 1 to 20 carbon atoms represented by ^R1 to ^R24 in formula (4) are not particularly limited as long as they are saturated aliphatic hydrocarbon groups having 1 to 20 carbon atoms. The alkyl groups may be branched or may form a ring.
Specific examples of alkyl groups having 1 to 20 carbon atoms represented by ^R1 to ^R24 in general formula (4) include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, n-pentyl group, iso-pentyl group, neo-pentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, sec-hexyl group, n-heptyl group, iso-heptyl group, s Examples include ec-heptyl group, n-octyl group, 2-ethylhexyl group, 3-methyl-1-isopropylbutyl group, 1-t-butyl-2-methylpropyl group, n-nonyl group, 3,5,5-trimethylhexyl group, n-decyl group, n-dodecyl group, cyclohexyl group, cyclopentyl group, cyclohexylmethyl group, cyclohexylethyl group, cyclopentylmethyl group, and cyclopentylethyl group.
The alkyl groups having 1 to 20 carbon atoms represented by ^R1 to ^R24 in general formula (4) are preferably linear or branched alkyl groups having 1 to 12 carbon atoms, and more preferably linear or branched alkyl groups having 1 to 8 carbon atoms.

The alkyl groups having 1 to 20 carbon atoms represented by ^R1 to ^R24 in general formula (4) may have substituents. Examples of such substituents include, but are not limited to, alkoxy groups, halogen groups, amino groups, cyano groups, and nitro groups.
In this invention, the phrase "substituted" in a C1 to C20 alkyl group having substituents means that one or more hydrogen atoms of a saturated aliphatic hydrocarbon group having C1 to C20 are substituted with substituents such as the alkoxy group, halogen group, amino group, cyano group, or nitro group. The phrase "unsubstituted" means that the hydrogen atoms of a saturated aliphatic hydrocarbon group having C1 to C20 are not substituted with substituents such as the alkoxy group, halogen group, amino group, cyano group, or nitro group. In this invention, "substituted" and "unsubstituted" are used hereafter with the same meanings as described herein.

The aryl groups having 6 to 20 carbon atoms represented by ^R1 to ^R24 in general formula (4) are not particularly limited as long as they are residues obtained by removing one hydrogen atom from an aromatic ring consisting of 6 to 20 carbon atoms. Specific examples include phenyl group, phenethyl group, o-, m- or p-tolyl group, 2,3- or 2,4-xylyl group, mesityl group, naphthyl group, anthryl group, phenanthryl group, biphenylyl group, benzhydryl group, trityl group, and pyrenyl group. The phenyl group is particularly preferred.
The aryl groups having 6 to 20 carbon atoms represented by ^R1 to ^R24 in general formula (4) may have substituents. Examples of such substituents are the same as those that may be present on alkyl groups having 1 to 20 carbon atoms represented by ^R1 to ^R24 in formula (4).

The heterocyclic groups having 4 to 20 carbon atoms represented by ^R1 to ^R24 in general formula (4) are not particularly limited as long as they are residues obtained by removing one hydrogen atom from a heterocyclic ring having 4 to 20 carbon atoms. Specific examples include pyridyl group, pyrrolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, imidazolyl group, oxadiazolyl group, thiadiazolyl group, triazolyl group, tetrazolyl group, pyrazolyl group, pyrimidinyl group, pyridadinyl group, pyrazinyl group, triazinyl group, indolyl group, isoindolyl group, benzimidazolyl group, benzoxazolyl group, benzothiazolyl group, quinolyl group, isoquinolyl group, purinyl group, carbazolyl group, acridinyl group, phenoxazinyl group, and phenothiazinyl group. The pyridyl group is particularly preferred.
The heterocyclic groups having 4 to 20 carbon atoms represented by ^R1 to ^R24 in general formula (4) may have substituents. Examples of such substituents are the same as those that may be present on alkyl groups having 1 to 20 carbon atoms represented by ^R1 to ^R24 in general formula (4).

The alkyl groups having 1 to 20 carbon atoms represented by R ²⁵ and R ²⁶ in general formula (4) are the same as the alkyl groups having 1 to 20 carbon atoms represented by R ¹ to R ²⁴ in general formula (4).
The alkyl groups having 1 to 20 carbon atoms represented by ^R25 and ^R26 of general formula (4) may have substituents. Examples of such substituents are the same as those that may be present on the alkyl groups having 1 to 20 carbon atoms represented by ^R1 to ^R24 of general formula (4).

The aryl groups having 6 to 20 carbon atoms represented by R ²⁵ and R ²⁶ in general formula (4) are the same as the aryl groups having 6 to 20 carbon atoms represented by R ¹ to R ²⁴ in general formula (4).
The aryl groups having 6 to 20 carbon atoms represented by ^R25 and ^R26 in general formula (4) may have substituents. Examples of such substituents are the same as those that may be present on the alkyl groups having 1 to 20 carbon atoms represented by ^R1 to ^R24 in general formula (4).

In general formula (4), ^R1 to ^R24 are preferably each independently a hydrogen atom or an aryl group having 6 to 20 carbon atoms, either substituted or unsubstituted. It is preferable that all of ^R1 to ^R24 are hydrogen atoms, or that ^R1 , ^R2 to ^R5 , ^R7 , ^R8 to ^R11 , ^R13 , ^R14 to ^R17 , R19 ^{and R20} to ^R23 are hydrogen atoms and ^R6 , ^R12 , ^R18 and ^R24 are unsubstituted C6 to C20 aryl groups, or more preferably that ^R2 to ^R5 , ^R6 , ^R8 to ^R11 , ^R12 , ^R14 to ^R17 , ^R18 , ^R20 to ^R23 and ^R24 are hydrogen atoms and ^R1 , ^R7 , ^R13 and ^R19 are unsubstituted C6 to C20 aryl groups. It is more preferable that all of ^R1 to ^R24 are hydrogen atoms, or that ^R1 , ^R2 to ^R5 , ^R7 , ^R8 to ^R11 , ^R13 , ^R14 to ^R17 , R19 and ^R20 to ^R23 are hydrogen atoms and ^R6 , ^R12 , ^R18 and ^R24 are phenyl groups, or that ^R2 to ^R5 , ^R6 , ^R8 to ^R11 , ^R12 , ^R14 to ^R17 , ^R18 , ^R20 to ^R23 and ^R24 are hydrogen atoms and ^R1 , ^R7 , ^R13 and ^R19 are phenyl ^groups .

In general formula (4), M represents two hydrogen atoms, a metal atom, a metal oxide, or a metal halide. When M represents two hydrogen atoms, the N-M-N portion of general formula (4) is represented as two N-H structures.
Examples of metal atoms represented by M in general formula (4) include iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, and tin.
Examples of metal oxides represented by M in general formula (4) include titanyl and vanadyl.
Examples of metal halides represented by M in general formula (4) include aluminum chloride, indium chloride, germanium chloride, tin(II) chloride, tin(IV) chloride, and silicon chloride.
In formula (1), M is preferably copper, zinc, cobalt, nickel, iron, vanadyl, titanyl, indium chloride, or tin(II) chloride, more preferably copper, zinc, vanadyl, or titanyl, and particularly preferably vanadyl.

Specific examples of compounds represented by general formula (4) are shown below, but the present invention is not limited to these.

Naphthalocyanine compounds represented by general formula (4) can be used individually or in combination of multiple types.
The naphthalocyanine compound represented by general formula (4) is preferably one having a maximum absorption wavelength in the wavelength region of 750 to 1500 nm, and more preferably one having a maximum absorption wavelength in the wavelength region of 780 to 1000 nm.

Furthermore, the naphthalocyanine compound is preferably one represented by the following general formula (5).

General formula (5)

(In general formula (5), ^R1 to ^R24 each independently represent a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted cycloalkyl group, an optionally substituted alkoxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted arylthio group, an optionally substituted alkylamino group, an optionally substituted arylamino group, or an optionally substituted sulfamoyl group.
Z is a polymer moiety containing the monomer unit shown in general formula (6), or a phosphorus compound moiety represented by general formula (7).

(In general formula (6), X represents ^an alkylene or ^arylene group ^{in which carbon atoms may be linked by -O-, -CO-, -COO-, -OCO-, -CONH-, or -NHCO- between carbon atoms. R 25 to R 28 represent a hydrogen} atom or a methyl group. ⁿ is 0 or an integer from 1 to 10. * represents a bond with Al.)
(In general formula (7), R ²⁹ and R ³⁰ each independently represent a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxyl group, or an optionally substituted aryloxy group, and R ²⁹ and R ³⁰ may be bonded to each other to form a ring. * represents a bond with Al.)

The following are specific examples of compounds represented by general formula (5). However, the present invention is not limited to these examples.

Near-infrared absorbing dyes can be used individually or in combination of two or more types. When using two or more types in combination, it is preferable to use at least two compounds with different maximum absorption wavelengths. This broadens the waveform of the absorption spectrum compared to using a single near-infrared absorbing dye, allowing for absorption of near-infrared light across a wider wavelength range.

(dye)
Examples of dyes include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, and sulfur dyes. In addition, derivatives of these dyes, or lake pigments obtained by lake-forming dyes, can also be used.

Acid dyes preferably have acidic groups such as sulfonic acid or carboxylic acid. Direct dyes preferably form salt compounds with an inorganic salt of the acid dye, or with an acid dye and a nitrogen-containing compound such as a quaternary ammonium salt compound, tertiary amine compound, secondary amine compound, or primary amine compound. Salt compounds that are salts of a resin component having these functional groups and an acid dye are also preferred. Furthermore, by sulfonamidating the salt compound to a sulfonic acid amide compound, it is easy to obtain a photosensitive composition with excellent resistance (lightfastness, solvent resistance).
Furthermore, salt-forming compounds of acid dyes and compounds containing an onium base are also preferred due to their excellent resistance (light resistance and solvent resistance). The compound containing the onium base is preferably a resin having a cationic group.

Basic dyes can be used as is, but salt compounds formed by chlorinating with organic acids, perchloric acid, or their metal salts are preferred. Salt compounds of basic dyes are preferred because they have excellent resistance (lightfastness, solvent resistance) and affinity with pigments. Furthermore, preferred salt compounds of basic dyes contain anionic components that act as counterions, such as organic sulfonic acids, organic sulfuric acids, fluorine-containing phosphorus anionic compounds, fluorine-containing boron anionic compounds, cyano-containing nitrogen anionic compounds, anionic compounds having a conjugate base of an organic acid with a halogenated hydrocarbon group, and acid dyes. Note that the resistance of the salt compound is further improved if it contains polymerizable unsaturated groups in its molecule.

The chemical structures of dyes include, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), and azi Examples of pigment structures derived from dyes selected from the following: lin-based dyes, polymethine-based dyes (oxonol-based dyes, merocyanine-based dyes, arylidene-based dyes, styryl-based dyes, cyanine-based dyes, squarylium-based dyes, croconium-based dyes, etc.), quinophthalone-based dyes, phthalocyanine-based dyes, subphthalocyanine-based dyes, perinone-based dyes, indigo-based dyes, thioindigo-based dyes, quinoline-based dyes, nitro-based dyes, nitroso-based dyes, rhodamine-based dyes, and metal complex dyes thereof.

Among these, from the viewpoint of color characteristics such as hue, color separation, and color unevenness, a pigment structure derived from a dye selected from azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes is preferred, and a pigment structure derived from a dye selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyromethene dyes, and phthalocyanine dyes is more preferred.

Dye (A) can be used alone or in combination of two or more types.

The content of dye (A) is preferably 0.5 to 80% by mass, and more preferably 1 to 60% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

(Fine milling of organic pigments)
Organic pigments are preferably used after being finely milled. The milling method is not particularly limited, and for example, wet milling, dry milling, or dissolution milling can all be used. Among these, salt milling by the kneader method, which is a type of wet milling, is preferred. The average primary particle size of the finely milled pigment, as determined by TEM (transmission electron microscope), is preferably 5 to 90 nm. More preferably, from the viewpoint of dispersibility and contrast ratio, the average primary particle size is 10 to 70 nm.

Resin may be added to the salt milling process as needed. Adding resin coats the pigment, improving stability, lightfastness, and other properties. The type of resin is not particularly limited and includes natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. Among these, it is preferable that the resin is solid at room temperature, water-insoluble, and partially soluble in the organic solvent. The amount of resin added is preferably 2 to 200 parts by mass per 100 parts by mass of pigment.

<Dispersant (B)>
The dispersant (B) can be any known resin-type dispersant. The resin-type dispersant has a colorant affinity site that adsorbs to the colorant (A), and a relaxation site that has high affinity for components other than the colorant and causes steric repulsion between dispersed particles.
Examples of dispersants (B) include urethane-based dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial)amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof; amides and salts thereof formed by the reaction of poly(lower alkyleneimines) with polyesters having free carboxyl groups; (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone, etc.; polyesters, modified polyacrylates, ethylene oxide/propylene oxide adduct compounds, phosphate esters, etc.
Furthermore, polymeric dispersants having basic functional groups include nitrogen atom-containing graft copolymers, nitrogen atom-containing acrylic block copolymers and urethane polymeric dispersants having functional groups in their side chains that include tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles, etc.

Commercially available resin-type dispersants include, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2050, 2070, 2095, 2150, 2050, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2050, 2010, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 201 155, 2163, 2164 or Anti-Terra-U, 203, 204 or BYK-P104, P104S, 220S, LPN6919, LPN21116, LPN21324 or Lactimon, Lactimon-WS or Bykumen, etc., manufactured by Nippon Lubrisol Co., Ltd. SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21 000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., and EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 408 manufactured by BASF Japan. Examples include 0, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., as well as Ajispa PA111, PB711, PB821, PB822, PB824, etc., manufactured by Ajinomoto Fine Techno Co., Ltd.

The photosensitive composition preferably uses a resin-type dispersant having carboxyl groups. Examples of resin-type dispersants having carboxyl groups include comb-type resin-type dispersants and linear resin-type dispersants.

[A comb-shaped resin dispersant containing carboxyl groups]
Comb-shaped resin dispersants having carboxyl groups can be manufactured by known methods such as those described in WO2008/007776, JP 2008-029901, JP 2009-155406, and JP 2011-157416.
For example, a resin-type dispersant is a reaction product of the hydroxyl group of a polymer having a hydroxyl group and the acid anhydride group of a tetracarboxylic dianhydride; a resin-type dispersant is a polymer obtained by polymerizing monomers in the presence of the reaction product of the hydroxyl group of a compound having a hydroxyl group and the acid anhydride group of a tetracarboxylic dianhydride; or a resin-type dispersant having a side chain obtained by polymerizing monomers having a hydroxyl group, a t-butyl group, or an oxetane skeleton, a blocked isocyanate, or other thermal crosslinking group, in the presence of the reaction product of the hydroxyl group of a compound having a hydroxyl group and the acid anhydride group of a tetracarboxylic dianhydride, and further reacting a ethylene unsaturated monomer having an isocyanate group on the hydroxyl group of the side chain.

[Linear resin-type dispersant containing carboxyl groups]
Linear resin-type dispersants having carboxyl groups can be manufactured by known methods such as those described in Japanese Patent Publication No. 2009-251481, Japanese Patent Publication No. 2007-23195, and Japanese Patent Publication No. 1996-143651. As an example of a method for manufacturing linear dispersants, a dispersant having carboxyl groups can be manufactured by using a vinyl polymer having one hydroxyl group at one end as a raw material and adding a tricarboxylic acid anhydride to the hydroxyl group.

The amount of dispersant (B) used is preferably about 3 to 200% by mass relative to the dye (A), and more preferably about 5 to 100% by mass. Using an appropriate amount improves film formation.

<Alkali-soluble resin (C)>
Alkali-soluble resins (C) can be classified into alkali-soluble resins containing polymerizable unsaturated groups and alkali-soluble resins not containing polymerizable unsaturated groups. Examples of alkali-soluble groups in alkali-soluble resins (C) include carboxyl groups, phosphate groups, sulfonic acid groups, hydroxyl groups, and phenolic hydroxyl groups. Among these, carboxyl groups are preferred.

Examples of alkali-soluble resins (C) include acrylic resins having acidic groups, α-olefin/(anhydride) maleic acid copolymers, styrene/styrene sulfonic acid copolymers, ethylene/(meth)acrylic acid copolymers, or isobutylene/(anhydride) maleic acid copolymers. Among these, acrylic resins having acidic groups and styrene/styrene sulfonic acid copolymers are preferred in terms of developability, heat resistance, and transparency, and acrylic resins having acidic groups are more preferred.
Furthermore, the alkali-soluble resin (C) may contain thermosetting groups such as epoxy groups or oxetanyl groups.

[Alkali-soluble resin containing polymerizable unsaturated groups]
An alkali-soluble resin containing polymerizable unsaturated groups is a resin to which polymerizable unsaturated groups have been added. In this specification, the alkali-soluble resin containing polymerizable unsaturated groups is preferably a resin synthesized by the methods of (i) or (ii) below. This further improves the crosslinking density of the film formed from the photosensitive colored composition upon light irradiation.

[Method (i)]
Method (i) is, for example, to first synthesize polymers of epoxy group-containing monomers and other monomers. Then, a monocarboxyl group-containing monomer is added to the epoxy group of the polymer, and a polybasic acid anhydride is reacted with the resulting hydroxyl group to obtain an alkali-soluble resin (C1) containing polymerizable unsaturated groups.

Examples of epoxy group-containing monomers include glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity.

Other monomers include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, or ethoxypolyethylene glycol (meth)acrylate.
Alternatively, examples include (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or styrenes such as acryloylmorpholine, or styrenes such as α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, and vinyl fatty acid compounds such as vinyl acetate or vinyl propionate.

Also, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane, 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidediphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide Examples include midobenzoates, N-succinimidyl-3-maleimide propionate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-[4-(2-benzimidazol)phenyl]maleimide, 9-maleimide acridine, and other N-substituted maleimides; EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol.
Another example is a phosphate ester group-containing monomer obtained by reacting the hydroxyl group of a hydroxyl group-containing monomer with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphate.

Examples of monocarboxyl group-containing monomers include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, and monocarboxylic acids such as α-haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted derivatives of (meth)acrylic acid.

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. Note that polybasic acid anhydrides may also contain carboxyl groups that do not form acid anhydrides.

Another method similar to method (i) involves, for example, synthesizing polymers of monocarboxyl group-containing monomers and other monomers. Then, epoxy group-containing monomers are added to some of the carboxyl groups of the polymer to obtain an alkali-soluble resin (C1) containing polymerizable unsaturated groups.

[Method (ii)]
Method (ii) involves, for example, synthesizing a polymer by combining a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other monomers. Then, a resin is synthesized by reacting the hydroxyl group of the polymer with the isocyanate group of an isocyanate group-containing monomer.

Examples of hydroxyl group-containing monomers include hydroxyalkyl methacrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, or cyclohexanedimethanol mono(meth)acrylate. Also included are polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide to hydroxyalkyl (meth)acrylate, and polyester mono(meth)acrylates obtained by addition of polyγ-valerolactone, polyε-caprolactone, and/or poly12-hydroxystearic acid. Among these, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferred, with glycerol mono(meth)acrylate being more preferred.

Examples of isocyanate group-containing monomers include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, or 1,1-bis[methacryloyloxy]ethyl isocyanate.

Other monomers that can be used besides the monomers mentioned above include the other monomers exemplified in method (i) above.

The weight-average molecular weight (Mw) of the alkali-soluble resin (C) is preferably 2,000 to 40,000, more preferably 3,000 to 300,000, and particularly preferably 5,000 to 25,000. Furthermore, the Mw/Mn (number-average molecular weight) value is preferably 10 or less.

The acid value of the alkali-soluble resin (C) is preferably 20 to 200 mg KOH/g, and more preferably 30 to 180 mg KOH/g.

Alkali-soluble resin (C) can be used alone or in combination of two or more types.

The content of alkali-soluble resin (C) is preferably 20 to 400 parts by mass, and more preferably 30 to 250 parts by mass, per 100 parts by mass of dye (A).

<Polymerizable compound (D)>
Polymerizable compound (D) is a monomer or oligomer containing polymerizable unsaturated groups. Polymerizable compound (D) contributes to the film formation of the photosensitive composition. Polymerizable compound (D) may include, for example, a monomer (D1) containing one hydroxyl group or a carboxyl group, a hydrocarbon ring, and one polymerizable unsaturated group, or a monomer (D2) containing three or more polymerizable unsaturated groups (hereinafter referred to as monomer (D2)). Monomer (D2) may also contain acidic groups or urethane bonds. The inclusion of acidic groups improves affinity to alkaline developers, and urethane bonds improve solvent resistance. In this specification, monomer (D1) is included as an essential component. The inclusion of monomer (D1) improves the adhesion of the photosensitive composition. The molecular weight of the oligomer is 1000 or more.

Monomer (D1), which contains one hydroxyl group, one carboxyl group, a hydrocarbon ring, and one polymerizable unsaturated group, suppresses the photocurability of the composition due to the presence of one polymerizable unsaturated group. This allows for the formation of a pattern line width close to that of the photomask aperture. Furthermore, the hydroxyl or carboxyl group of monomer (D1) can improve hydrogen bonding and intermolecular forces with the substrate interface, significantly enhancing adhesion. Additionally, the hydrocarbon ring derived from monomer (D1) suppresses affinity with the alkaline developer used in the development process, making it less likely for the pattern to peel off the substrate during development.

Examples of monomers (D1) include 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethylhexahydrophthalic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl-2-hydroxyethyl phthalic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxypropyl phthalic acid, 2-acryloyloxypropyl hexahydrophthalic acid, methacryloyloxyethyl phthalic acid, methacryloyloxypropyl phthalic acid, and methacryloyloxypropyl hexahydrophthalic acid.

Commercially available monomers (D1) include epoxy ester M-600A, light acrylate HOA-HH(N), HOA-MPL(N), and HOA-MPE(N) manufactured by Kyoeisha Chemical Co., Ltd., and ACB-3, ACB-21, ACB-23, CB-1, CB-3, CB-21, and CB-23 manufactured by Shin-Nakamura Chemical Co., Ltd.

Monomer (D2) is a monomer other than monomer (D1) and is a monomer containing three or more polymerizable unsaturated groups.

Monomer (D2) is a monomer other than monomer (D1), and examples include trimethylolpropane triacrylate, trimethylolpropanepropylene oxide-modified triacrylate, trimethylolpropaneethylene oxide-modified triacrylate, isocyanurate ethylene oxide-modified triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropanetetraacrylate, dipentaerythritol hexaacrylate, and diglycerin ethylene oxide-modified acrylate. However, the structure is not limited to these, as long as it contains three or more polymerizable unsaturated groups.

Suitable commercially available products include Aronics M-305, M-306, M-309, M-310, M-321, M-350, M-313, M-315, M-400, M-402, M-403, M-404, M-405, M-406, M-408, M-450, M-471, M-460 from Toagosei Co., Ltd., and NK Ester A-9300 from Shin Nakamura Chemical Co., Ltd.

(Polymerizable compounds containing acidic groups)
By using a photopolymerizable compound having an acidic group as monomer (D2), the solubility of the formed coating film in the alkaline developer can be increased when the photosensitive composition of the present invention is alkaline developed, thereby improving the development speed and reducing residue. Examples of acidic groups include sulfonic acid groups, carboxyl groups, and phosphate groups.
These commercially available products include, and suitably, Aronics M-510, M-520, M-521, etc., manufactured by Toagosei Co., Ltd.

(Polymerizable compounds containing urethane bonds)
The monomer (D2) contains a photopolymerizable compound having a urethane bond, which suppresses the precipitation of colorants when the formed coating film is heated, thereby improving solvent resistance and adhesion to the substrate.

Suitable commercially available products include AH-600, AT-600, UA-306H, UA-306T, UA-306I, and UA-510H from Kyoeisha Chemical Co., Ltd., and UA-1100H, UA-33H, U-10HA, U-10PA, and U-15HA from Shin-Nakamura Chemical Industry Co., Ltd.

Examples of polymerizable compounds (D) that do not belong to monomer (D2) or monomer (D1) include polymerizable compounds containing two polymerizable unsaturated groups and polymerizable compounds containing one polymerizable unsaturated group that does not contain a hydrocarbon ring.

Examples of commercially available products include A-DCP, ABE-300, and A-SA manufactured by Shin-Nakamura Chemical Industry Co., Ltd., and EA-200 and EA-300 manufactured by Osaka Gas Chemical Co., Ltd.

Polymerizable compound (D) can be used alone or in combination of two or more types.

The polymerizable compound (D) is preferably present in an amount of 1 to 50 parts by mass per 100 parts by mass of the nonvolatile content of the photosensitive composition. The mass ratio of monomer (D1) to monomer (D2) is preferably 0.5:9.5 to 8:2, more preferably 0.5:9.5 to 6:4, and even more preferably 0.5:9.5 to 4:6.
Furthermore, the monomer (D1) content is preferably 100% by mass of polymerizable compound (D), 5 to 80% by mass, more preferably 5 to 65% by mass, and even more preferably 5 to 45% by mass.

[Photopolymerization initiator (E)]
The photopolymerization initiator (E) is a photoradical polymerization initiator.
The photopolymerization initiator (E) is, for example, an acetophenone compound such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone;
Triazine compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine;
Oxime compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyl oxime)], or etanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime);
Acylphosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide;
Examples include quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds.

Commercially available photopolymerization initiators (E) include, as acetophenone compounds, Omnirad 907, 369, 379EG from IGM Resins; as acylphosphine compounds, Omnirad 819, TPO from IGM Resins; as oxime compounds, IRGACURE OXE-01, 02, 03, 04 from BASF Japan, N-1919, 730, 831, 930 from ADEKA, and TRONLY TR-PBG-301, 304, 305, 309, 345, 346, 358, 3054, 3057 from Changzhou Strong New Materials Co., Ltd. Other examples include OMNIRAD1312, 1314, and 1316 from Resins, SPI-02, 03, 04, 05, 06, and 07 from Samyang Corporation, DFI-020, 036, and EOX-01 from Daito Chemix, as well as initiators described in Japanese Patent Publication No. 2021-076846. Furthermore, oxime compounds described in Japanese Patent Publication No. 2005-215378, Japanese Patent Publication No. 2011-105713, Japanese Patent Publication No. 2017-523465, Japanese Patent Publication No. 2007-210991, Japanese Patent Publication No. 2009-179619, Japanese Patent Publication No. 2010-037223, Japanese Patent Publication No. 2010-215575, Japanese Patent Publication No. 2011-020998, International Publication No. 2015/036910, etc., can also be cited.

The photopolymerization initiator (E) can be used alone or in combination of two or more types.

From the viewpoint of adhesion and pattern shape, the content of the photopolymerization initiator (E) is preferably 1 to 15% by mass, more preferably 1 to 10 parts by mass, and even more preferably 1 to 5% by mass, in the nonvolatile content of the photosensitive composition.

[Sensitizer (F)]
The photosensitive composition of the present invention may contain a sensitizer (F).

The sensitizer (F) is, for example, a polymethine dye such as chalcone derivatives, unsaturated ketones represented by dibenzalacetone, 1,2-diketone derivatives represented by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, acridine derivatives, azine derivatives, thiaidine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyra Examples include din derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxaliloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrillium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospilopyran derivatives, metal allene complexes, organoruthenium complexes, or Mihler-ketone derivatives, α-acyloxyesters, acyl oxides, methylphenylglyoxylates, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone, etc.

Among these, thioxanthone derivatives, Mihler-ketone derivatives, and carbazole derivatives are preferred. Specific compounds that are preferred include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, and 3,6-dibenzoyl-N-ethylcarbazole.

The sensitizer (F) can be used alone or in combination of two or more types.

The sensitizer (F) content is preferably 3 to 60 parts by mass, and more preferably 5 to 50 parts by mass, per 100 parts by mass of the photopolymerization initiator (E). An appropriate amount improves photocurability and developability.

[Thermosetting compound (G)]
The photosensitive composition of the present invention may contain a thermosetting compound (G). This allows the thermosetting compound (G) to react during the heating process, increasing the crosslinking density and thus improving the heat resistance of the coating.

The thermosetting compound (G) may be a low-molecular-weight compound or a high-molecular-weight compound such as a resin. Examples of thermosetting compounds (G) include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenolic compounds. Among these, epoxy compounds and oxetane compounds are preferred.

(Epoxy compound (G1))
Epoxy compounds (G1) include, for example, polycondensates of bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnolbornene, tetrahydroindene, divinylbenzene) and phenols. Examples include polymers of phenols (such as divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), polycondensates of phenols and ketones (such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (such as benzenedimethanol, α,α,α',α'-benzenedimethanol, biphenyldimethanol, α,α,α',α'-biphenyldimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (such as α,α'-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine epoxy resins, and glycidyl ester epoxy resins obtained by glycidylating alcohols, etc.

Examples of commercially available products include Epicote 807, 815, 825, 827, 828, 190P, and 191P from Shell Epoxy Oil & Epoxy Corporation, and TECHMORE from Mitsui Chemicals. Examples include VG3101L, EPPN-201, 501H, 502H, EOCN-102S, 103S, 104S, 1020 (manufactured by Nippon Kayaku Co., Ltd.), Epicote 1004, 1256, JER1032H60, 157S65, 157S70, 152, 154 (manufactured by Japan Epoxy Resin Co., Ltd.), Celoxide 2021, EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.), Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 (manufactured by Nagase ChemteX Corporation), and TEPIC-L, H, S (manufactured by Nissan Chemical Industries, Ltd.).

From the viewpoint of heat resistance of the cured film, the content of epoxy compound (G1) is preferably 0.5 to 50% by mass, and more preferably 1 to 40% by mass, based on 100% by mass of the non-volatile content of the photosensitive composition.

(Oxetane compound (G2))
Oxetane compounds (G2) are known compounds having an oxetane group. Examples of oxetane compounds include monofunctional oxetane compounds, difunctional oxetane compounds, and trifunctional or multifunctional oxetane compounds.

Examples of monofunctional oxetane compounds include (3-ethyloxetane-3-yl)methyl acrylate, (3-ethyloxetane-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyl oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, and 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane.

Examples of commercially available products include OXE-10 and 30 manufactured by Osaka Organic Chemical Industry Co., Ltd., and OXT-101 and 212 manufactured by Toagosei Co., Ltd.

Difunctional oxetane compounds include, for example, 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3-oxetanyl)]methyl ether 3-ethyl-3-hydroxymethyloxetane, 3- Ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxanonanane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycos(3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl(3-ethyl- 3-Oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) modified bis(3-ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) modified bis(3-ethyl-3-oxetanylmethyl) ether Examples include sphenol A bis(3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, and EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether.

Examples of commercially available products include OXBP and OXTP manufactured by Ube Industries, and OXT-121 and OXT-221 manufactured by Toagosei Co., Ltd.

Examples of oxetane compounds with three or more functionalities include pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, and caprolactone-modified dipenta Examples include erythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis(3-ethyl-3-oxetanylmethyl) ether, resins containing oxetane groups (for example, the oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462), and polymers obtained by radical polymerization of (meth)acrylic monomers such as the aforementioned OXE-30.

The content of the oxetane compound (G2) is preferably 0.5 to 50% by mass, and more preferably 1 to 40% by mass, based on 100% by mass of the non-volatile content of the photosensitive composition.

Melamine compounds are compounds having a melamine ring structure. Methylol-type and ether-type melamine compounds are preferred, and melamine compounds with an average of 5.0 or more methylol and/or ether groups per melamine ring are more preferred. Having a moderate number of methylol and ether groups makes it easier to obtain adequate heat resistance.

Examples of commercially available products include Nikarac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS-001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, MX-410 from Sanwa Chemical Co., Ltd., and Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, 370 from Nippon Cytec Industries Co., Ltd.

Among these, Nikarac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MX-45 from Sanwa Chemical Co., Ltd., and Cymel 232, 235, 236, 238, 300, 301, 303, 350 from Nippon Cytec Industries Co., Ltd., which have an average of 5.0 or more methylol groups and/or ether groups per melamine ring, are preferred in terms of increasing crosslinking density.

Thermosetting compound (G) can be used alone or in combination of two or more types.

[Hardening agent (hardening accelerator)]
The photosensitive composition of the present invention may be used in combination with a curing agent (curing accelerator) to assist in the curing of the thermosetting compound (G). Examples of curing agents include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, etc. Examples of curing agents include amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and their salts (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, Examples include 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.), phosphorus compounds (e.g., triphenylphosphine), S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid adduct, etc.).

The hardening agent can be used alone or in combination of two or more types.

The curing agent content is preferably 0.01 to 15 parts by mass per 100 parts by mass of thermosetting compound (G).

[Thiol chain transfer agent (H)]
The photosensitive composition of the present invention may contain a thiol-based chain transfer agent (H). When the thiol-based chain transfer agent (H) is used in combination with a photopolymerization initiator (E), thiyl radicals that are less susceptible to polymerization inhibition by oxygen are generated during radical polymerization after light irradiation, thereby improving the photosensitivity of the photosensitive composition.

The thiol-based chain transfer agent (H) is preferably a polyfunctional thiol having two or more thiol groups (SH groups). More preferably, the thiol-based chain transfer agent has four or more SH groups. Increasing the number of functional groups facilitates photocuring from the surface to the deepest part of the film.

Polyfunctional thiols include, for example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, and pentaerythritol. Examples include lysritol tetraxythiopropionate, tris(2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine. Preferably, examples include ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetraxythiopropionate.

Thiol-based chain transfer agents (H) can be used alone or in combination of two or more types.

The content of the thiol-based chain transfer agent (H) is preferably 0.1 to 10% by mass, and more preferably 0.2 to 8% by mass, based on 100% by mass of the non-volatile content of the photosensitive composition. An appropriate amount improves photosensitivity and reduces the likelihood of wrinkles forming on the pattern surface.

[Polymerization inhibitor (I)]
The photosensitive composition of the present invention may contain a polymerization inhibitor (I).

Polymerization inhibitor (I) is, for example, alkylcatechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-t-butylcatechol, 3-t-butylcatechol, 4-t-butylcatechol, 3,5-di-t-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n Examples include alkylresorcinol compounds such as -butylresorcinol, 4-n-butylresorcinol, 2-t-butylresorcinol, and 4-t-butylresorcinol; alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butylhydroquinone, and 2,5-di-t-butylhydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and tripenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphine and trisnonylphenylphosphine; pyrogallol and phloroglucin.

The content of polymerization inhibitor (I) is preferably 0.01 to 0.4% by mass, based on 100% by mass of the non-volatile content of the photosensitive composition.

[UV absorber (J)]
The photosensitive composition of the present invention may contain an ultraviolet absorber (J).

UV absorbers (J) are organic compounds that have UV absorption properties, and include benzotriazole organic compounds, triazine organic compounds, benzophenone organic compounds, salicylate ester organic compounds, cyanoacrylate organic compounds, and salicylate organic compounds.

The content of the ultraviolet absorber (J) is preferably 5 to 70% by mass of the total mass of the photopolymerization initiator (E) and the ultraviolet absorber (J).

[Antioxidant (K)]
The photosensitive composition of the present invention may contain an antioxidant (K). The antioxidant (K) prevents yellowing due to oxidation caused by the photopolymerization initiator (E) and thermosetting compound (H) contained in the photosensitive composition during the thermal process of thermosetting and ITO aneeling. In particular, when the dye (A) concentration of the photosensitive composition is high, the content of polymerizable compound (D) decreases relatively, so if the amount of photopolymerization initiator (E) or thermosetting compound (H) is increased to compensate, the cured film is prone to yellowing. Therefore, by including an antioxidant, yellowing of the cured film due to oxidation during the heating process is prevented.

Antioxidant (K) can be, for example, hindered phenol, hindered amine, phosphorus, sulfur, or hydroxylamine compounds. In this invention, the antioxidant is preferably a compound that does not contain halogen atoms.

Among these, hinderedphenol antioxidants, hinderedamine antioxidants, phosphorus antioxidants, and sulfur antioxidants are preferred.

Antioxidants (K) can be used alone or in combination of two or more types.

The antioxidant (K) content is preferably 0.5 to 5.0% by mass of 100% by mass of the non-volatile content of the photosensitive composition. An appropriate amount improves transmittance, spectral characteristics, and sensitivity.

[Leveling agent (L)]
The photosensitive composition of the present invention may contain a leveling agent (L). This further improves the wettability and drying properties to the substrate during coating. Examples of leveling agents (L) include silicon-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

Silicone-based surfactants include, for example, linear polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals.

Examples of commercially available products include BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, 3570 from Bic Chemie, and FZ-7002, 211 from Toray Dow Corning. Examples include 0, 2122, 2123, 2191, 5609, and Shin-Etsu Chemical Co., Ltd.'s X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341, etc.

Examples of fluorinated surfactants include surfactants or leveling agents having fluorocarbon chains.

Examples of commercially available products include AGC Seimi Chemical's Surflon S-242, 243, 420, 611, 651, 386; DIC's Megafac F-253, 477, 551, 552, 555, 558, 560, 570, 575, 576, R-40-LM, R-41, RS-72-K, DS-21; Sumitomo 3M's FC-4430, 4432; Mitsubishi Materials Electronic Chemicals' EF-PP31N09, EF-PP33G1, EF-PP32C1; and Neos's Futergent 602A.

Nonionic surfactants include, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristelle ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrenated phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate Examples include sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitan tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl alkanolamide, alkylimidazoline, etc.

Commercially available products include, for example, Kao's Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS. -106, LS-110, LS-114, MS-110, A-60, A-90, B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD-450, Leodor SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V, SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V TW-L120, TW-L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40 Examples include CH-60(K), Ami-to 102, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA's Adekapluronic (registered trademark) L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R, and Kyoeisha Chemical's (meth)acrylic acid copolymer Polyflow No. 75, No. 90, No. 95.

Cationic surfactants include, for example, alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and their ethylene oxide adducts.

Examples of commercially available products include Kao Corporation's Acetamine 24, Cortamin 24P, 60W, and 86P Concentrate.

Examples of anionic surfactants include polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate esters.

Examples of commercially available products include Neos's Futegent 100 and 150, and ADEKA's Adeka Hope YES-25, Adeka Call TS-230E, PS-440E, and EC-8600.

Examples of amphoteric surfactants include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyldimethylaminoacetic acid betaine, and alkylamine oxides such as lauryldimethylamine oxide.

Examples of commercially available products include Kao Corporation's Anchitol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, and 20N.

Leveling agent (L) can be used alone or in combination of two or more types.

The leveling agent (L) content is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, based on 100% by mass of the non-volatile content of the photosensitive composition. Within this range, the balance between the applicability and adhesion of the photosensitive composition is further improved.

[Storage stabilizer (M)]
The photosensitive composition of the present invention may contain a storage stabilizer (M). This stabilizes the viscosity of the photosensitive composition over time. Examples of storage stabilizers (M) include benzyltrimethyl chloride, quaternary ammonium chlorides such as diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine, and tetraphenyl, and phosphates.

The storage stabilizer (M) content is preferably 0.1 to 10 parts by mass per 100 parts by mass of dye (A).

[Adhesion enhancer (N)]
The photosensitive composition of the present invention may contain an adhesion enhancer (N). This improves the adhesion between the cured film and the substrate. It also makes it easier to form narrow patterns using photolithography.

Examples of adhesion enhancers (N) include silane coupling agents.

Adhesion enhancers (N) can be used alone or in combination of two or more types.

The content of the adhesion enhancer (N) is preferably 0.01 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the pigment (A).

[Organic solvent (O)]
The photosensitive composition of the present invention may contain an organic solvent (O).

Organic solvents (O) include, for example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, 3-ethyl ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl Alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotolen, o-diethylbenzene, o-dichlorobenzene, p-chlorotolen, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether Ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol Examples include propyl monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters. Among these, from the viewpoint of pigment dispersibility and alkali-soluble resin solubility, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone are preferred.

Organic solvents (O) can be used alone or in combination of two or more types.

[Method for manufacturing a photosensitive composition]
The photosensitive composition of the present invention can be produced by manufacturing a dispersion by adding, for example, a dye (A), a dispersant (B), an alkali-soluble resin (C), an organic solvent (O), etc., and performing a dispersion treatment. Subsequently, a polymerizable compound (D) and a photopolymerization initiator (E) are added to the dispersion and mixed. The timing of adding each material is arbitrary. Furthermore, the dispersion process can be performed multiple times.

Distributed processing machines include, for example, two-roll mills, three-roll mills, ball mills, horizontal sand mills, vertical sand mills, annular bead mills, or attritors.

The average dispersed particle size (secondary particle size) of the dye (A) in the dispersion is preferably 30 to 200 nm, and more preferably 40 to 200 nm. Having an appropriate particle size makes it easier to obtain a photosensitive composition with high dispersion stability.

The measurement method for the average dispersed particle diameter (secondary particle diameter) uses, for example, Nikkiso's Microtrac UPA-EX150, which employs dynamic light scattering (FFT power spectrum method). The particle permeability is set to absorption mode, the particle shape to non-spherical, and the D50 particle diameter is defined as the average diameter. The diluent for measurement is the same organic solvent used for dispersion. Measurement immediately after sample preparation of ultrasonically treated samples is preferable as it tends to yield results with less variation.

The photosensitive composition is preferably subjected to filtration by means of centrifugal separation, sintering filters, or membrane filters to remove coarse particles of 5 μm or larger, preferably 1 μm or larger, more preferably 0.5 μm or larger, and any impurities such as dust. The photosensitive composition of the present invention preferably contains substantially no particles of 0.5 μm or larger, and more preferably contains no particles of 0.3 μm or smaller.

<Optical Filters>
The optical filter of the present invention comprises a substrate and a coating formed from the photosensitive composition of the present invention. The coating can be used as various optical filters by appropriately selecting the type of dye (A) used. For example, it can be used as a red filter segment, a green filter segment, and a blue filter segment for color filter applications using an organic pigment. Alternatively, it can be used as a magenta filter segment, a cyan filter segment, and a yellow filter segment. Furthermore, it can be used as a near-infrared transmission filter or a near-infrared cut-off filter using a near-infrared absorbing dye.

Examples of substrates include transparent substrates and reflective substrates. Transparent substrates include, for example, glass substrates. Reflective substrates include, for example, substrates that use aluminum electrodes or thin metal films as reflective surfaces.

[Manufacturing method for optical filters]
The method for manufacturing an optical filter is not limited, but photolithography is preferred. For example, it can be manufactured by a step of applying a photosensitive composition to a substrate to form a film (1), exposing the film to light in a patterned manner through a mask (2), alkaline developing the unexposed areas to form a patterned cured film (3), and heat-treating the pattern (post-bake) (4).

The manufacturing method of optical filters will be described in detail below.
(Step (1))
The film formation step (1) involves applying the photosensitive composition onto a substrate by methods such as rotary coating, roll coating, slit coating, casting coating, or inkjet coating, and then drying (pre-baking) it for 10 to 120 seconds at a temperature of 50 to 120°C using an oven, hot plate, etc., if necessary.
Examples of the substrate include glass substrates and silicon substrates. For example, an image sensor such as a CCD or CMOS may be formed on the surface of the silicon substrate. Furthermore, if necessary, an undercoat layer may be provided on the substrate to improve adhesion with the upper layer, prevent diffusion of materials, and flatten the substrate surface.
The layer thickness is preferably 0.05 to 10.0 μm after drying, and more preferably 0.3 to 5 μm.

(Step (2))
In the exposure process, the film obtained in step (1) is exposed to a specific pattern through a mask using an exposure device such as a stepper. This results in a cured film.
Examples of radiation used in exposure include ultraviolet rays such as g-rays, h-rays, and i-rays.

(Step (3))
The cured film obtained in step (2) is subjected to alkaline development treatment, which causes the unexposed portions of the film to dissolve in the alkaline aqueous solution, leaving only the cured portions and resulting in a patterned cured film.
Examples of developing solutions include alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrol, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene.
The concentration of the developer is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass.
The pH of the alkaline developer is preferably 11 to 13, and more preferably 11.5 to 12.5. Using an appropriate pH suppresses pattern roughness and peeling, and improves the residual film rate after development.

Development methods include, for example, the dip method, spray method, and padre method. The development temperature is preferably 15 to 40°C. Furthermore, it is preferable to wash with pure water after alkaline development.

(Step (4))
The heat treatment (post-bake) is used to thoroughly harden the patterned cured film obtained in step (3) by heating. The heating temperature for post-bake is preferably 100 to 300°C, and more preferably 150 to 250°C. The heating time is preferably 2 minutes to 1 hour, and more preferably 3 minutes to 30 minutes.

<Image display device>
The image display device of the present invention includes an optical filter.
The form used in the image display device is not particularly limited, as long as it functions as an image display device. For example, the configuration described in "Next-Generation Liquid Crystal Display Technology" (by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994) is one such example.
For definitions of image display devices and details of various image display devices, see, for example, "Electronic Display Devices" (by Akio Sasaki, Kogyo Chosakai Co., Ltd., published in 1990) and "Display Devices" (by Junsho Ibuki, Sangyo Tosho Co., Ltd., published in 1989).

Examples of image display devices include liquid crystal displays and organic EL displays. Liquid crystal displays will be described below.
The image display device 10 shown in Figure 1 comprises a pair of transparent substrates 11 and 21 arranged opposite each other at a distance from one another, with a liquid crystal (LC) sealed between them.

A TFT (thin-film transistor) array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of, for example, ITO is formed on top of it. An orientation layer 14 is provided on top of the transparent electrode layer 13. A polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

On the other hand, the optical filter 22 of the present invention is formed on the inner surface of the second transparent substrate 21. The red, green, and blue filter segments constituting the optical filter 22 are separated by a black matrix (not shown).

A transparent protective film (not shown) is formed over the optical filter 22 as needed. Furthermore, a transparent electrode layer 23, made of, for example, ITO, is formed on top of this, and an alignment layer 24 is provided covering the transparent electrode layer 23.

Furthermore, a polarizing plate 25 is formed on the outer surface of the transparent substrate 21. A backlight unit 30 is provided below the polarizing plate 15.

<Solid-state image sensor>
The solid-state image sensor of the present invention includes an optical filter.
The form used for the solid-state image sensor is not particularly limited, but for example, it may have a substrate on which a plurality of photodiodes constituting the light-receiving area of the solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) and transfer electrodes made of polysilicon or the like are provided, a light-shielding film with an opening only for the light-receiving portion of the photodiode is provided on the photodiode and transfer electrodes, a device protective film made of silicon nitride or the like is provided on the light-shielding film so as to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiode, and an optical filter on the device protective film. Furthermore, it may have a configuration in which a light-gathering means (e.g., a microlens, etc.; the same applies hereinafter) is provided on the device protective film and below the optical filter (on the side closer to the substrate), or a configuration in which the light-gathering means is provided on the optical filter. In addition, the optical filter may have a structure in which a hardened film forming each colored pixel is embedded in a space partitioned, for example, in a grid pattern by partitions. In this case, a low refractive index is preferable for each colored pixel of the partitions.
The imaging device equipped with the solid-state image sensor of the present invention can be used in digital cameras, electronic devices with imaging functions (mobile phones, smartphones, etc.), as well as in-vehicle cameras and surveillance cameras.

The present invention will be described more specifically below with reference to examples. However, the present invention is not limited to these examples. Note that "parts" refers to "parts by mass," and "%" refers to "mass percent."

Prior to the examples, each measurement method will be described.
The weight-average molecular weight (Mw), number-average molecular weight (Mn), acid value (mgKOH/g), and amine value (mgKOH/g) of the resin are as follows:

(Average molecular weight of alkali-soluble resins and dispersion resins)
The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of alkali-soluble resins and dispersed resins were measured by gel permeation chromatography (GPC) equipped with an RI detector. An HLC-8220GPC (Tosoh Corporation) was used, with two separation columns connected in series. Both columns were packed with two TSK-GEL SUPER HZM-N columns. Measurements were performed at an oven temperature of 40°C, using tetrahydrofuran (THF) solution as the eluent, and a flow rate of 0.35 ml/min. The sample was dissolved in a solvent consisting of 1% by mass of the above eluent, and 20 microliters were injected. Molecular weights are expressed on a polystyrene basis.

(Acid value of alkali-soluble resins and dispersion resins)
0.5 to 1 g of alkali-soluble resin and dispersion resin solution were mixed with 80 ml of acetone and 10 ml of water and stirred to dissolve uniformly. A 0.1 mol/L aqueous KOH solution was used as the titrant, and the solution was titrated using an automatic titrator ("COM-555," manufactured by Hiranuma Sangyo Co., Ltd.) to measure the acid value (mg KOH/g). The acid value per unit of non-volatile content of the resin was then calculated from the acid value of the resin solution and the non-volatile content concentration of the resin solution.

(Amine value of dispersion resin)
The amine value of the dispersion resin is calculated by converting the total amine value (mgKOH/g), which was measured according to the ASTM 2074 method, into a non-volatile content value.

<Manufacturing of pigment (A)>
(Manufacturing of micronized pigment A-1)
500 parts of anthraquinone-based red pigment C.I. Pigment Red 177 (Synirex Red SR3C, manufactured by Synirex), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 120°C for 8 hours. Next, this mixture was added to 5 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeated filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight to obtain finely ground pigment (A-1).

(Manufacturing of micronized pigment A-2)
500 parts of diketopyrrolopyrrole-based red pigment C.I. Pigment Red 254 (BASF Japan's "Irgajin Red L 3630"), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 120°C for 8 hours. Next, this mixture was added to 5 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeated filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight to obtain finely ground pigment (A-2).

(Manufacturing of micronized pigment A-3)
100 parts of quinophthalone-based yellow pigment C.I. Pigment Yellow 138 (BASF Japan's "Pariotol Yellow K0960-HD"), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 80°C for 6 hours. This mixture was added to 2000 parts of warm water and stirred for 1 hour while heating to 80°C to form a slurry. After repeated filtration and washing with water to remove salt and solvent, it was dried at 80°C overnight to obtain finely ground pigment (A-3).

(Manufacturing of micronized pigment A-4)
100 parts of isoindoline yellow pigment C.I. Pigment Yellow 139 (BASF Japan's "Paliotoll Yellow D1819"), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader and kneaded at 60°C for 10 hours. Next, this mixture was added to 3 liters of warm water and stirred with a high-speed mixer for about 1 hour while heating to about 80°C to form a slurry. After repeated filtration and washing with water to remove sodium chloride and solvent, it was dried at 80°C for 24 hours to obtain finely ground pigment (A-4).

(Manufacturing of micronized pigment A-5)
100 parts of C.I. Pigment Green 58 (DIC Corporation's FASTOGEN Green A110), 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70°C for 6 hours. This mixture was added to 3,000 parts of warm water and stirred in a high-speed mixer for 1 hour while heating to 70°C to form a slurry. After repeated filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight and then pulverized to obtain fine pigment (A-5).

(Manufacturing of micronized pigment A-6)
100 parts of C.I. Pigment Green 63, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60°C for 6 hours. Next, the kneaded mixture was added to warm water and stirred in a high-speed mixer for 1 hour while heating to approximately 80°C to form a slurry. After filtering and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight and then pulverized to obtain fine pigment (A-6).

(Manufacturing of micronized pigment A-7)
100 parts of C.I. Pigment Blue 15:6 (Toyo Color Co., Ltd. "Lionol Blue ES"), 1,000 parts of sodium chloride, and 100 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 50°C for 12 hours. 3,000 parts of this mixture were added to warm water and stirred in a high-speed mixer for about 1 hour while heating to about 70°C to form a slurry. After repeated filtration and washing to remove salt and solvent, the mixture was dried at 80°C for 24 hours and then pulverized to obtain finely ground pigment (A-7).

(Manufacturing of micronized pigment A-8)
100 parts of C.I. Pigment Blue 15:3 (Toyo Color Co., Ltd. "Lionol Blue FG7351"), 1,000 parts of sodium chloride, and 100 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 50°C for 12 hours. 3,000 parts of this mixture were added to warm water and stirred in a high-speed mixer for about 1 hour while heating to about 70°C to form a slurry. After repeated filtration and washing to remove salt and solvent, the mixture was dried at 80°C for 24 hours and then pulverized to obtain finely ground pigment (A-8).

(Manufacturing of micronized pigment A-9)
C.I. Pigment Violet 23 (Toyo Color Co., Ltd. "Lionogen Violet FG6140") was placed in a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) at 50°C for 12 hours. This mixture was added to 3,000 parts of warm water and stirred in a high-speed mixer for about 1 hour while heating to about 70°C to form a slurry. After repeated filtration and washing to remove salt and solvent, the mixture was dried at 80°C for 24 hours and then pulverized to obtain fine pigment (A-9).

<Manufacturing of micronized pigments>
The following near-infrared absorbing pigment (a) was prepared in accordance with the examples in Japanese Patent Publication No. 2011-132361.

Near-infrared absorbing pigment (a)

100 parts of infrared-absorbing pigment (a), 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70°C for 6 hours. This mixture was added to 3,000 parts of warm water and stirred in a high-speed mixer for 1 hour while heating to 70°C to form a slurry. After repeated filtration and washing to remove sodium chloride and diethylene glycol, the mixture was dried at 80°C overnight and then pulverized to obtain finely ground pigment (A-10).

<Manufacturing of Dispersant (B)>
(Dispersant (B-1) solution)
250 parts by mass of tetrahydrofuran (THF) and 5.81 parts by mass of the initiator dimethylketene methyltrimethylsilyl acetal were added to a 500 mL round-bottom, four-neck separable flask equipped with a condenser, dropping funnel, nitrogen inlet, mechanical stirrer, and digital thermometer via the dropping funnel, and the flask was thoroughly purged with nitrogen. 0.5 parts by mass of a 1 mol/L acetonitrile solution of the catalyst tetrabutylammonium m-chlorobenzoate was injected using a syringe, and 19.7 parts by mass of 2-hydroxyethyl methacrylate, 7.5 parts by mass of 2-ethylhexyl methacrylate, 12.9 parts by mass of n-butyl methacrylate, 10.7 parts by mass of benzyl methacrylate, and 30.9 parts by mass of methyl methacrylate were added dropwise over 60 minutes using the dropping funnel. The temperature was kept below 40°C by cooling the reaction flask in an ice bath. After 1 hour, 18.3 parts by mass of dimethylaminopropyl methacrylamide was added dropwise over 20 minutes. After reacting for 1 hour, 1 part by mass of methanol was added to stop the reaction. The resulting block copolymer THF solution was reprecipitated in hexane, and purified by filtration and vacuum drying.
Next, 15.0 parts by mass of the obtained block copolymer was dissolved in 35 parts by mass of propylene glycol monomethyl ether acetate (PGMAC) in a 100 mL round-bottom flask. 1.1 parts by mass of phenylphosphinic acid (0.5 molar equivalent relative to dimethylaminopropyl methacrylamide), which is a salt-forming component, was added, and the mixture was stirred at a reaction temperature of 30°C for 20 hours. PGMAC was then added to adjust the solution, and a dispersant (B-1) solution with 20% non-volatile content was obtained.

(Dispersant (B-2) solution)
In a reaction vessel equipped with a gas inlet tube, temperature control, condenser, and stirrer, 10 parts methacrylic acid, 100 parts methyl methacrylate, 70 parts i-butyl methacrylate, 20 parts benzyl methacrylate, and 50 parts PGMAC were charged and purged with nitrogen gas. The reaction vessel was heated to 50°C and stirred, and 12 parts 3-mercapto-1,2-propanediol were added. The temperature was raised to 90°C, and the reaction was carried out for 7 hours while adding a solution of 0.1 parts 2,2'-azobisisobutyronitrile added to 90 parts PGMAC. Non-volatile content measurement confirmed that 95% had reacted. Next, 19 parts pyromellitic anhydride, 50 parts PGMAC, 50 parts cyclohexanone, and 0.4 parts 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out at 100°C for 7 hours. After confirming that more than 98% of the acid anhydride had undergone half-esterification by measuring the acid value, the reaction was terminated. The solution was then diluted by adding PGMac to reduce the non-volatile content to 20%, yielding a dispersion resin (B-2) solution with an acid value of 70 mg KOH/g and a weight-average molecular weight of 8,500.

<Manufacturing of alkali-soluble resin (C)>
(Alkali-soluble resin (C-1) solution)
In a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube, 333 parts of PGMAc were introduced, and the atmosphere inside the flask was changed from air to nitrogen. After raising the temperature to 100°C, a solution consisting of 70.5 parts (0.40 mol) of benzyl methacrylate, 71.1 parts (0.50 mol) of glycidyl methacrylate, 22.0 parts (0.10 mol) of tricyclodecane skeleton monomethacrylate (FA-513M, Hitachi Chemical Co., Ltd.), and 164 parts of PGMAc, to which 5.0 parts of azobisisobutyronitrile was added, was added dropwise to the flask from the dropping funnel over 2 hours, and the mixture was then stirred at 100°C for 5 hours. Next, the atmosphere inside the flask was changed from nitrogen to air, and 43.0 parts [0.5 mol, (100 mol%) relative to the glycidyl groups of the glycidyl methacrylate used in this reaction)], 0.9 parts of trisdimethylaminomethylphenol, and 0.145 parts of hydroquinone were added to the flask. The reaction was continued at 110°C for 6 hours, and terminated when the non-volatile acid value reached 1 mg KOH/g. Next, 60.9 parts (0.40 mol) of tetrahydrophthalic anhydride and 0.8 parts of triethylamine were added, and the reaction was carried out at 120°C for 3.5 hours to obtain a resin solution with an acid value of 80 mg KOH/g. After cooling to room temperature, approximately 2 parts of the resin solution were sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. PGMac was added to adjust the non-volatile content to 20% by mass to prepare a photosensitive alkali-soluble resin (C-1) solution. The weight-average molecular weight (Mw) was 9,000.

(Alkali-soluble resin (C-2) solution)
In a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube, 333 parts of PGMAc were introduced, and the atmosphere inside the flask was changed from air to nitrogen. After raising the temperature to 100°C, a solution consisting of 70.5 parts (0.40 mol) of benzyl methacrylate, 71.1 parts (0.50 mol) of glycidyl methacrylate, 22.0 parts (0.10 mol) of tricyclodecane skeleton monomethacrylate (FA-513M, Hitachi Chemical Co., Ltd.), and 164 parts of PGMAc, to which 5.0 parts of azobisisobutyronitrile was added, was added dropwise to the flask from the dropping funnel over 2 hours, and the mixture was then stirred at 100°C for 5 hours. Next, the atmosphere inside the flask was changed from nitrogen to air, and 43.0 parts of methacrylic acid [0.5 mol, (100 mol%) relative to the glycidyl groups of the glycidyl methacrylate used in this reaction)], 0.9 parts of trisdimethylaminomethylphenol, and 0.145 parts of hydroquinone were added to the flask. The reaction was continued at 110°C for 6 hours until the non-volatile acid value reached 1 mg KOH/g, at which point the reaction was terminated. Next, 60.9 parts (0.40 mol) of succinic anhydride and 0.8 parts of triethylamine were added, and the mixture was reacted at 120°C for 3.5 hours to obtain a resin solution with an acid value of 100 mg KOH/g. After cooling to room temperature, approximately 2 parts of the resin solution were sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. PGMac was added to adjust the non-volatile content to 20% by mass to prepare a photosensitive alkali-soluble resin (C-2) solution. The weight-average molecular weight (Mw) was 8,000.

(Alkali-soluble resin (C-3) solution)
A reaction vessel was prepared by fitting a thermometer, condenser, nitrogen gas inlet, dropping tube, and stirrer into a separable four-neck flask. 207 parts of cyclohexanone were charged into this vessel, and the temperature was raised to 80°C. After purging the reaction vessel with nitrogen, a mixture of 20 parts methacrylic acid, 20 parts paracumylphenol ethylene oxide-modified acrylate (Aronics M110, manufactured by Toagosei Co., Ltd.), 45 parts methyl methacrylate, 8.5 parts 2-hydroxyethyl methacrylate, and 0.99 parts 2,2'-azobisisobutyronitrile was added dropwise over 2 hours via the dropping tube. After the dropwise addition was complete, the reaction was continued for another 3 hours to obtain a resin solution. Next, the resin solution obtained was stirred while injecting dry air for 1 hour after stopping the nitrogen gas supply, and then cooled to room temperature. A mixture of 6.5 parts 2-methacryloyloxyethyl isocyanate (Kalenz MOI, Showa Denko Co., Ltd.), 0.08 parts dibutyltin laurate, and 26 parts cyclohexanone was added dropwise at 70°C for 3 hours. After the dropwise addition was complete, the reaction was continued for another hour to obtain a resin solution. After cooling to room temperature, approximately 2 parts of the resin solution were sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. Cyclohexanone was added to adjust the non-volatile content to 20% to prepare an alkali-soluble resin (C-3) solution. The weight-average molecular weight (Mw) was 22,050.

(Alkali-soluble resin (C-4) solution)
In a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube, 182 parts of PGMAc were introduced, and the atmosphere inside the flask was changed from air to nitrogen. After raising the temperature to 100°C, a solution consisting of 70.5 parts (0.40 mol) of benzyl methacrylate, 43.0 parts (0.5 mol) of methacrylic acid, 22.0 parts (0.10 mol) of tricyclodecane skeleton monomethacrylate (FA-513M, Hitachi Chemical Co., Ltd.), and 136 parts of PGMAc, to which 3.0 parts of azobisisobutyronitrile was added, was added dropwise to the flask from the dropping funnel over 2 hours, and the mixture was then stirred at 100°C for 5 hours. Next, the atmosphere inside the flask was changed from nitrogen to air, and 35.5 parts of glycidyl methacrylate [0.25 mol, (50 mol% relative to the carboxyl groups of methacrylic acid used in this reaction)], 0.9 parts of trisdimethylaminomethylphenol, and 0.145 parts of hydroquinone were added to the flask. The reaction was continued at 110°C for 6 hours to obtain a resin solution. After cooling to room temperature, approximately 2 parts of the resin solution were sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. PGMac was added to prepare an alkali-soluble resin (C-4) solution so that the non-volatile content was 20% by mass. The weight-average molecular weight (Mw) was 14,960.

(Alkali-soluble resin (C-5) solution)
A reaction vessel was prepared by fitting a thermometer, condenser, nitrogen gas inlet, dropping tube, and stirrer into a separable four-neck flask. 196 parts of cyclohexanone were charged into this vessel, and the temperature was raised to 80°C. After purging the reaction vessel with nitrogen, a mixture of 37.2 parts n-butyl methacrylate, 12.9 parts 2-hydroxyethyl methacrylate, 12.0 parts methacrylic acid, 20.7 parts paracumylphenol ethylene oxide modified acrylate (Toagosei Co., Ltd. "Aronics M110"), and 2.0 parts 2,2'-azobisisobutyronitrile was added dropwise over 2 hours via the dropping tube. After the addition was complete, the reaction was continued for another 2 hours to obtain a resin solution. After cooling to room temperature, approximately two parts of the resin solution were sampled and heated and dried at 180°C for 20 minutes. The non-volatile content was measured, and propylene glycol monomethyl ether acetate (hereinafter also referred to as PGMAC) was added to prepare an alkali-soluble resin (C-5) solution so that the non-volatile content was 20%. The weight-average molecular weight (Mw) was 20,000.

<Dispersion Manufacturing>
(Dispersion 1)
After stirring and mixing the following raw materials until uniform, the mixture was dispersed for 3 hours using an Eiger mill (Eiger Japan's "Mini Model M-250 MKII") with a diameter of 0.5 mm, and then filtered through a 1.0 μm pore size filter to prepare dispersion 1. The organic solvent (O-1) is PGMAC.
Micronized pigment (A-1): 12.00 parts Dispersant (B-1) solution: 20.00 parts Dispersant (B-2) solution: 20.00 parts Organic solvent (O-1): 48.00 parts

Dispersions 1 to 10 were obtained by varying the types and amounts of the ingredients to achieve the composition ratios shown in Table 1.

<Manufacturing of photosensitive composition>
[Example 1]
(Photosensitive composition 1)
The following raw materials were mixed and stirred, and filtered through a filter with a pore size of 1.0 μm to obtain photosensitive composition 1.
Dispersion 1: 37.50 parts Alkali-soluble resin (C-1) solution: 20.25 parts Polymerizable compound (D1-1): 0.75 parts Polymerizable compound (D2-1): 2.25 parts Photopolymerization initiator (E-1): 0.45 parts Leveling agent (L): 1.00 part Organic solvent (O): 37.80 parts

[Polymerizable compound (D)]
・D-1: A-DCP (polymerizable unsaturated group number 2: manufactured by Shin Nakamura Chemical Co., Ltd.)
• D1-1: HOA-MPL (2-acryloyloxyethyl phthalate: manufactured by Kyoeisha Chemical Co., Ltd.)
• D1-2: HOA-MPE (2-acryloyloxyethyl-2-hydroxyethyl-phthalate: manufactured by Kyoeisha Chemical Co., Ltd.)
• D2-1: Arronix M-306 (3 polymerizable unsaturated groups: manufactured by Toagosei Co., Ltd.)
• D2-2: Arronix M-420 (6 polymerizable unsaturated groups: manufactured by Toagosei Co., Ltd.)
• D2-3: Arronix M-520 (5 polymerizable unsaturated groups: manufactured by Toagosei Co., Ltd.)
・D2-4: UA-306H (Number of polymerizable unsaturated groups: 6: manufactured by Kyoeisha Chemical)

[Photopolymerization initiator (E)]
• E-1: OXE-01 (manufactured by BASF Japan)
• E-2: OXE-02 (manufactured by BASF Japan)
• E-3: ADEKA Cruises NCI-831 (manufactured by ADEKA)
• E-4: ADEKA Cruises NCI-730 (manufactured by ADEKA)
• E-5: Ilgacure 907 (manufactured by BASF Japan)
• E-6: Irgacure 369 (manufactured by BASF Japan)
• E-7: The compound shown below. It was synthesized in accordance with Japanese Patent Publication No. 2021-076846.

[Leveling agent (L)]
One part each of BYK-330 (manufactured by Big Chemie) and Megafac F-551 (manufactured by DIC) were mixed and dissolved in 98 parts of PGMac to create a mixed solution which was used as the leveling agent (L).

[Organic solvent (O)]
80 parts of propylene glycol monomethyl ether acetate, 10 parts of cyclohexanone, and 10 parts of ethyl 3-ethoxypropionate were mixed to form an organic solvent (O).

[Examples 2-42, Comparative Example 1]
Except for changing the materials and proportions of Example 1 as shown in Tables 2 to 6, the same procedure was followed to obtain the photosensitive compositions of Examples 2 to 42 and Comparative Example 1.

<Evaluation of photosensitive compositions>
For Examples 1 to 42 and Comparative Example 1, the developability, adhesion, and chemical resistance were evaluated using the methods described below. The evaluation results are shown in Tables 7 and 8.

[Line width evaluation]
The obtained photosensitive composition was coated onto a 100 mm x 100 mm, 0.7 mm thick glass substrate (Corning Eagle 2000) using a spin coater to a dry film thickness of 2.0 μm, and dried on a hot plate at 70°C for 1 minute. Next, ultraviolet light was exposed using an ultra-high pressure mercury lamp at an illuminance of 30 mW/ ^cm² and 50 mJ/ ^cm² through a photomask with a 50 μm wide stripe pattern. Furthermore, after the substrate was cooled to room temperature, it was spray-developed with an organic alkaline developer, tetramethylammonium hydroxide (TMAH), at 23°C for 70 seconds, washed with deionized water, and air-dried to form a stripe pattern on the substrate. The pattern was observed with an optical microscope, and the line width was evaluated. The evaluation criteria are as follows, with a score of 3 or higher indicating practical usability.
5. The line width is -1 μm ≤ 1 μm from the mask opening.
4. From the mask opening, -3 μm ≤ line width < -1 μm or 1 μm < line width ≤ 3 μm.
3. From the mask opening, -5 μm ≤ line width < -3 μm or 3 μm < line width ≤ 5 μm.
2: From the mask opening, -7 μm ≤ line width < -5 μm or 5 μm < line width ≤ 7 μm.
1: The line width is -7 μm or 7 μm from the mask opening.

[Adhesion evaluation]
The obtained photosensitive composition was coated onto a 100 mm x 100 mm, 0.7 mm thick glass substrate (Corning Eagle 2000) by spin coating to a dry film thickness of 2.0 μm, and dried on a hot plate at 70°C for 1 minute. Next, after the substrate cooled to room temperature, it was exposed to light using a high-pressure mercury lamp through a photomask with a stripe pattern of 5 μm width intervals at an illuminance of 30 mW/ ^cm² and 50 mJ/ ^cm² . Subsequently, the substrate was spray developed using TMAH at 23°C, washed with deionized water, air-dried, and heated in a clean oven at 230°C for 30 minutes to obtain an evaluation substrate. Spray development was performed for the shortest time possible for pattern formation without any remaining development for each photosensitive composition, and this was defined as the appropriate development time.
Fine line patterns with a width of 5 to 25 μm on the evaluation substrate were observed with an optical microscope to confirm the minimum line width of the remaining fine line patterns. The evaluation criteria are as follows, with a score of 3 or higher indicating practical usability.
5: Fine lines measuring 5 to 10 μm remain.
4: Fine lines larger than 15 μm remain.
3: Fine lines larger than 20 μm remain.
2: Fine lines larger than 25 μm remain.
1: No thin lines remain.

[Chemical resistance evaluation]
The chromaticity ([L*(1), a*(1), b*(1)]) of a 100 μm wide stripe pattern on a substrate, prepared in the same manner as for adhesion evaluation, was measured using a micro-spectrophotometer (Olympus Optical Co., Ltd. "OSP-SP100"). After that, the substrate was immersed in N-methylpyrrolidone for 30 minutes, washed with deionized water, and air-dried. Next, the chromaticity ([L*(2), a*(2), b*(2)]) of the 100 μm stripe pattern on the substrate was measured using a C light source, and the color difference ΔE*a*b* was calculated using the following formula.
ΔE*a*b* = {(L*(2)-L*(1)) ² +(b*(2)-b*(1)) ² +(a*(2)-a*(1)) ² } ^0.5
The evaluation criteria are as follows, with a score of 3 or higher indicating practical usability.
5: ΔE*a*b* is less than 1. 4: ΔE*a*b* is 1 or greater and less than 3.
3: ΔE*a*b* is greater than or equal to 3 and less than 5.
2: ΔE*a*b* is 5 or greater and less than 10.
1: ΔE*a*b* is 10 or greater.

10 Liquid crystal display device 11 Transparent substrate 12 TFT array 13 Transparent electrode layer 14 Alignment layer 15 Polarizing plate 21 Transparent substrate 22 Optical filter 23 Transparent electrode layer 24 Alignment layer 25 Polarizing plate 30 Backlight unit 31 White LED light source LC Liquid crystal

Claims (6)

A photosensitive composition comprising a dye (A ), a dispersant (B), an alkali-soluble resin (C), a polymerizable compound (D), and a photopolymerization initiator (E),
The alkali-soluble resin (C) includes an alkali-soluble resin containing polymerizable unsaturated groups.
Furthermore, the alkali-soluble resin containing polymerizable unsaturated groups contains carboxyl groups as alkali-soluble groups,
A photosensitive composition comprising polymerizable compound (D), a monomer (D1) containing one hydroxyl group and one carboxyl group, a hydrocarbon ring, and one polymerizable unsaturated group, and a monomer (D2) containing three or more polymerizable unsaturated groups. The photosensitive composition according to claim 1, wherein the mass ratio of monomer (D1) to monomer (D2) is 0.5:9.5 to 8:2. The photosensitive composition according to claim 1 or 2, comprising 5 to 80% by mass of the monomer (D1) in 100% by mass of the polymerizable compound (D). An optical filter comprising a substrate and a coating formed from a photosensitive composition according to any one of claims 1 to 3. An image display device having the optical filter described in claim 4. A solid-state image sensor having the optical filter described in claim 4.