JP6604928B2 - Coloring composition, film and method for producing film - Google Patents

Description

  The present invention relates to a colored composition. The present invention also relates to a film using a colored composition and a method for producing the film.

  In recent years, with the spread of digital cameras, camera-equipped mobile phones and the like, the demand for solid-state imaging devices such as charge coupled device (CCD) image sensors has greatly increased. Color filters are used as key devices for displays and optical elements.

  The color filter is manufactured by applying a coloring composition containing a colorant, a resin, a curable compound, and a solvent to a support or the like.

  Patent Document 1 discloses a colored photosensitive resin composition containing a colorant, a binder polymer, a photopolymerizable compound, a photopolymerization initiator, a solvent, and a surfactant, and a colored photosensitive resin composition at 23 ° C. The viscosity of the product is 3.0 mPa · s or more and 6.5 mPa · s or less, and 10 μL of the colored photosensitive resin composition is dropped on the glass substrate, and the contact angle after 0.2 seconds and after 1 second is 10 A colored photosensitive resin composition having a degree of 20 ° to 20 ° is described.

Patent Document 2 discloses a resin composition for a colored layer used for a color filter for a liquid crystal display device comprising a substrate, a light shielding portion, a colored layer, and a spacer on the substrate. It is described that the spacer is a laminated column formed by laminating two or more colored layers on the light shielding portion, and the colored layer resin composition forming the laminated column satisfies the following conditions. ing.
(I) The 1st colored layer resin composition which forms a 1st layer on a light-shielding part has a contact angle of 4.0 degree | times or more with respect to a light-shielding part.
(II) The 2nd colored layer resin composition which forms a 2nd layer on a 1st layer has a contact angle of 4.0 degree | times or more with respect to a 1st layer.
Paragraph No. 0049 of Patent Document 2 describes a method for measuring a contact angle. In Patent Document 2, a droplet of a resin composition for a colored layer is dropped from a microsyringe onto a measurement substrate on which an underlayer film is formed. Then, the contact angle after 30 seconds is measured.

JP 2004-318111 A JP 2012-68512 A

  When a colored composition is applied on a support to produce a film, further improvement in coatability is desired in the colored composition. In particular, in the case where a colored composition is applied on a surface having steps such as unevenness, it has recently been desired to suppress the occurrence of radial streaks called striations.

  Moreover, when this inventor examined the coloring composition described in patent document 1, 2, it turned out that a striation is easy to generate | occur | produce.

  Accordingly, an object of the present invention is to provide a coloring composition, a film, and a film manufacturing method capable of suppressing the occurrence of coating unevenness and striation.

As a result of intensive studies on the applicability of the colored composition, the present inventor has found that striation tends to occur as the contact angle of the colored composition with respect to the support increases. As a result of intensive studies, the present inventors have found that the coloring composition having the contact angle characteristics described below can be applied without application unevenness when applied on various supports, and further, the occurrence of striations. The present inventors have found that it can be effectively suppressed and have completed the present invention. That is, the present invention is as follows.
<1> A coloring composition comprising a coloring agent A, a resin B, a curable compound C, a surfactant D, and a solvent E,
The content of the coloring agent A in the total solid content of the coloring composition is 40% by mass or less,
The coloring composition whose contact angle of the coloring composition measured by the method which consists of the following process 1 and process 2 is more than 0 degree and 5.5 degrees or less;
Step 1: 2 μL of 25 ° C. water is dropped on a glass substrate to form an organic layer having a contact angle of 60 to 80 degrees with respect to the organic layer measured after 5 seconds;
Process 2: After adjusting the temperature of an organic substance layer to 25 degreeC, 2 microliters of 25 degreeC coloring compositions are dripped at the surface of an organic substance layer, and the contact angle with respect to the organic substance layer of the coloring composition 5 seconds after is measured.
<2> The surfactant D is a fluorosurfactant, and the content of the surfactant D in the total solid content of the coloring composition is 0.001 to 0.20% by mass, according to <1>. Coloring composition.
<3> The solvent E includes a solvent E1 having a surface tension at 25 ° C. of 26.0 mN / m or more and a solvent E2 having a surface tension at 25 ° C. of less than 26.0 mN / m, <1> or <1. The coloring composition as described in 2>.
<4> The colored composition according to any one of <1> to <3>, which is for spin coating.
<5> A film formed by curing the colored composition according to any one of <1> to <4>.
<6> After adjusting the temperature of the film to 25 ° C., 2 μL of 25 ° C. water is dropped on the surface of the film, and the contact angle of water with respect to the film measured 5 seconds later is 70 degrees or less. Membrane.
<7> A method for producing a film, comprising a step of applying the colored composition according to any one of <1> to <4> to a support.
<8> The method for producing a film according to <7>, further comprising a step of forming a pattern.

  ADVANTAGE OF THE INVENTION According to this invention, it became possible to provide the coloring composition, the film | membrane, and the manufacturing method of a film | membrane which can manufacture the film | membrane in which generation | occurrence | production of application | coating nonuniformity and striation were suppressed.

It is a figure explaining the position of the level | step difference on the silicon wafer selected in the case of evaluation of the applicability | paintability in an Example.

Hereinafter, the contents of the present invention will be described in detail.
In the notation of a group (atomic group) in this specification, the notation which does not describe substitution and unsubstituted includes the group which has a substituent with the group which does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, “exposure” means not only exposure using light unless otherwise specified, but also exposure using particle beam such as electron beam and ion beam is included in exposure. The light used for the exposure generally includes an active ray or radiation such as an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, or electron beams.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In this specification, the total solid content refers to the total amount of components excluding the solvent from all the components of the composition.
In this specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, and “(meth) acryl” represents both and / or acrylic and “(meth) acrylic”. ") Allyl" represents both and / or allyl and methallyl, and "(meth) acryloyl" represents both and / or acryloyl and methacryloyl.
In this specification, the term “process” not only means an independent process, but also if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes, include.
In this specification, a weight average molecular weight (Mw) and a number average molecular weight (Mn) are defined as polystyrene conversion values measured by gel permeation chromatography (GPC).

<Coloring composition>
The coloring composition of the present invention is a coloring composition containing a coloring agent A, a resin B, a curable compound C, a surfactant D, and a solvent E,
The content of the coloring agent A in the total solid content of the coloring composition is 40% by mass or less,
The coloring composition whose contact angle of the coloring composition measured by the method which consists of the following process 1 and process 2 is more than 0 degree and 5.5 degrees or less;
Step 1: On a glass substrate, 2 μL of water at 25 ° C. is dropped, and an organic layer having a contact angle of 60 to 80 degrees with respect to the organic layer of water measured after 5 seconds is formed.
Process 2: After adjusting the surface temperature of an organic substance layer to 25 degreeC, 2 microliters of 25 degreeC coloring compositions are dripped at the surface of an organic substance layer, and the contact angle with respect to the organic substance layer of the coloring composition 5 seconds after is measured.

  According to the coloring composition of this invention, when apply | coating to various support bodies and forming a film | membrane, generation | occurrence | production of a coating nonuniformity and striation can be suppressed. Moreover, according to examination of this inventor, it became clear that striation is easy to generate | occur | produce as the density | concentration of the coloring agent in a coloring composition becomes low. However, according to the present invention, even if the content of the colorant in the total solid content of the colored composition is 40% by mass or less, the colored composition has the above-mentioned contact angle characteristics. Generation can be suppressed. In addition, since the concentration of the colorant in the total solid content of the colored composition can be lowered, when a color filter for a solid-state imaging device such as an image sensor is formed using the colored composition of the present invention, a high spectrum is obtained. Transmittance can be obtained and device sensitivity can be increased.

  In the colored composition of the present invention, the contact angle of the colored composition measured by the method comprising the above steps 1 and 2 is more than 0 degree and not more than 5.5 degrees. The lower limit value of the contact angle is preferably 1 degree or more, more preferably 2 degrees or more, and further preferably 2.5 degrees or more. The upper limit value of the contact angle is preferably 5 degrees or less, more preferably 4.8 degrees or less, and further preferably 4.5 degrees or less. If the contact angle of the coloring composition is within the above range, it is possible to effectively suppress the occurrence of coating unevenness and striation. The contact angle can be measured using a contact angle meter. Examples of the contact angle meter include Drop Master 701 manufactured by Kyowa Interface Science Co., Ltd. As an organic substance layer formed on a glass substrate in the process 1, it can form using resin compositions, such as CT-4000 (made by Fuji Film Electronics Materials), for example.

  The said contact angle of a coloring composition can be adjusted by changing suitably the kind and content of each component which are contained in a coloring composition. For example, the contact angle can be easily adjusted to the above-described range by appropriately changing the type and content of the solvent and / or surfactant. Among these, a fluorosurfactant is used as the surfactant, and the surfactant content in the total solid content of the colored composition is 0.001 to 0.20% by mass (preferably 0.0015 to 0.1). Mass%, more preferably 0.002 to 0.05 mass%), the contact angle can be easily adjusted to the above-described range.

  The film obtained by curing the colored composition of the present invention was prepared by adjusting the surface temperature of the film to 25 ° C., then dropping 2 μL of 25 ° C. water onto the film surface and contacting the water with the film measured 5 seconds later. The angle is preferably 70 degrees or less, more preferably 40 to 67 degrees, and still more preferably 50 to 65 degrees. According to this aspect, when forming a film | membrane using the coloring composition of this invention, generation | occurrence | production of striation can be suppressed more effectively. It is estimated that the reason why such an effect is obtained is as follows. That is, when the contact angle with respect to the water of the obtained film | membrane is low, it is thought that the surface tension (film | membrane / gas interfacial tension) when a coloring composition turns into a film | membrane becomes large. In this case, for example, when heat is applied during pre-baking or post-baking, the film surface tends to flow, and it is considered that surface irregularities such as striation are likely to disappear. For this reason, it is thought that generation | occurrence | production of striation was able to be suppressed effectively. The contact angle can be measured using a contact angle meter. Examples of the contact angle meter include Drop Master 701 manufactured by Kyowa Interface Science Co., Ltd.

  The colored composition of the present invention preferably has a viscosity at 25 ° C. of 1 to 3 mPa · s, more preferably 1.3 to 2.5 mPa · s, and more preferably 1.5 to 2.1 mPa · s. More preferably it is. If the viscosity of the coloring composition is in the above range, the occurrence of coating unevenness and striation can be more effectively suppressed. As a method for measuring the viscosity, for example, a viscometer RE85L (rotor: 1 ° 34 ′ × R24, measuring range 0.6 to 1200 mPa · s) manufactured by Toki Sangyo Co., Ltd. is used, and the temperature is adjusted to 25 ° C. Can be measured.

  The colored composition of the present invention preferably has a surface tension at 25 ° C. of 25 to 30 mN / m, more preferably 25.5 to 29 mN / m, and still more preferably 26 to 28 mN / m. . If the surface tension of the coloring composition is in the above range, the occurrence of coating unevenness and striation can be more effectively suppressed. The surface tension of the coloring composition is a value measured by a plate method using a platinum plate. The details of the plate method will be described in the solvent column described later.

  Hereinafter, each component of the coloring composition of the present invention will be described.

<< Colorant >>
The coloring composition of the present invention contains a colorant. The colorant may be a dye or a pigment, or both may be used in combination. Examples of the pigment include conventionally known various inorganic pigments or organic pigments. The average particle diameter of the pigment is preferably from 0.01 to 0.1 μm, more preferably from 0.01 to 0.05 μm. As the colorant, a pigment is preferable, and an organic pigment is more preferable. In the case of a coloring composition containing an organic pigment, there is a general tendency that striations are likely to occur, but in the present invention, even when a coloring composition containing an organic pigment is used, the generation of striations is effective. Can be suppressed.

  Examples of the inorganic pigment include black pigments such as carbon black and titanium black; metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony, and metal complex salts.

Examples of the organic pigment include the following.
Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 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, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 72,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214 (or more, and yellow pigments);
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73 ( Above, orange pigment);
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279 (above, red pigment) );
C. I. Pigment Green 7, 10, 36, 37, 58, 59 (above, green pigment);
C. I. Pigment Violet 1,19,23,27,32,37,42,58,59 (above, purple pigment);
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80 (above, blue pigment).
Further, as a green pigment, a halogenated zinc phthalocyanine pigment having an average number of halogen atoms in the molecule of 10 to 14, a bromine atom number of 8 to 12 and an average number of chlorine atoms of 2 to 5 It is also possible to use it. Specific examples thereof include compounds described in WO2015 / 118720.
Moreover, the aluminum phthalocyanine compound which has a phosphorus atom can also be used as a blue pigment. Specific examples include compounds described in paragraph numbers 0022 to 0030 of JP2012-247491A and paragraph number 0047 of JP2011-157478A.
These organic pigments can be used alone or in various combinations.

  Examples of the dye include JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, US Pat. No. 4,808,501 and US Pat. No. 505950. Examples thereof include dyes disclosed in US Pat. No. 5,667,920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-194828, and the like. It is done. When classified as chemical structure, pyrazole azo compounds, pyromethene compounds, anilinoazo compounds, triarylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, etc. Is mentioned.

  Moreover, you may use a pigment | dye multimer as a coloring agent. The dye multimer is preferably a dye used by being dissolved in a solvent, but may form particles. When the dye multimer is a particle, the dye multimer is dispersed in a solvent or the like. The dye multimer in the particle state can be obtained, for example, by emulsion polymerization. As a pigment | dye multimer of a particle state, the compound described in Unexamined-Japanese-Patent No. 2015-214682 is mentioned, for example. In addition, as the dye multimer, compounds described in JP2011-213925A, JP2013-041097A, JP2015-028144A, JP2015-030742A, and the like can also be used. .

  Further, as the yellow colorant, quinophthalone compounds described in paragraph numbers 0011 to 0034 of JP2013-54339A, quinophthalone compounds described in paragraph numbers 0013 to 0058 of JP2014-26228A, and the like can also be used. .

The content of the colorant is 40% by mass or less, preferably 39% by mass or less, more preferably 38% by mass or less, and 37% by mass with respect to the total solid content in the coloring composition. More preferably, it is as follows. The lower limit is preferably 5% by mass or more, more preferably 7% by mass or more, and further preferably 10% by mass or more.
The content of the pigment is 40% by mass or less, preferably 39% by mass or less, more preferably 38% by mass or less, and more preferably 37% by mass or less based on the total solid content in the coloring composition. More preferably. The lower limit is preferably 5% by mass or more, more preferably 7% by mass or more, and further preferably 10% by mass or more. The lower the content of the colorant in the total solid content of the coloring composition, the more likely it is to cause striations. According to the present invention, the striations are effectively suppressed even if the content of the colorant is small. it can.
1 type may be sufficient as the coloring agent contained in a coloring composition, and 2 or more types may be sufficient as it. When two or more colorants are included, the total amount is preferably within the above range.

<< Resin >>
The coloring composition of the present invention contains a resin. The resin is blended, for example, for the purpose of dispersing particles such as pigments in the composition and the use of a binder. In addition, a resin that is mainly used for dispersing particles such as pigment is also referred to as a dispersant. However, such use of the resin is an example, and the resin can be used for purposes other than such use.

  In the colored composition of the present invention, the resin content is preferably 1 to 95% by mass with respect to the total solid content of the colored composition. The lower limit is more preferably 5% by mass or more, and further preferably 10% by mass or more. The upper limit is more preferably 93% by mass or less, and still more preferably 90% by mass or less.

(Dispersant)
It is preferable that the coloring composition of this invention contains a dispersing agent as resin. In particular, when a pigment is used as the colorant, it is preferable to include a dispersant. Examples of the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin).

Here, the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups. The acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups occupies 70 mol% or more when the total amount of acid groups and basic groups is 100 mol%. A resin consisting only of acid groups is more preferred. The acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 5 to 105 mgKOH / g.
The basic dispersant (basic resin) represents a resin in which the amount of basic groups is larger than the amount of acid groups. The basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol% when the total amount of acid groups and basic groups is 100 mol%. The basic group possessed by the basic dispersant is preferably an amine.

  Examples of the dispersant include a polymer dispersant [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth). Acrylic copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine, alkanolamine and the like.

  The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof. The polymer dispersant acts to adsorb on the surface of the pigment and prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer having an anchor site to the pigment surface can be cited as preferred structures. In addition, a dispersant described in paragraph numbers 0028 to 0124 of JP2011-070156A and a dispersant described in JP2007-277514A are also preferably used. These contents are incorporated herein.

  As the resin (dispersant), a graft copolymer may be used. Details of the graft copolymer can be referred to the description of paragraph numbers 0025 to 0094 of JP2012-255128A, the contents of which are incorporated herein. Further, resins described in paragraph numbers 0072 to 0094 of JP 2012-255128 A can be mentioned, and the contents thereof are incorporated in the present specification.

  Moreover, as the resin (dispersant), an oligoimine dispersant containing a nitrogen atom in at least one of the main chain and the side chain can be used. The oligoimine-based dispersant has a repeating unit having a partial structure X having a functional group of pKa14 or less, a side chain containing a side chain Y having 40 to 10,000 atoms, and a main chain and a side chain. A resin having at least one basic nitrogen atom is preferred. The basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom.

  Regarding the oligoimine-based dispersant, the description in paragraphs 0102 to 0174 of JP 2012-255128 A can be referred to, and the above contents are incorporated in this specification. Specific examples of the oligoimine dispersant include, for example, resins described in paragraph numbers 0168 to 0174 of JP 2012-255128 A.

  A commercial item can also be used for a dispersing agent. For example, the product described in paragraph number 0129 of JP2012-137564A can also be used as a dispersant. In addition, resin demonstrated with the said dispersing agent can also be used for uses other than a dispersing agent. For example, it can be used as a binder.

  As for content of a dispersing agent, 1-200 mass parts is preferable with respect to 100 mass parts of pigments. The lower limit is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more. The upper limit is preferably 150 parts by mass or less, and more preferably 100 parts by mass or less.

(Alkali-soluble resin)
The coloring composition of this invention can contain alkali-soluble resin as resin. By containing an alkali-soluble resin, developability and pattern formability are improved. The alkali-soluble resin can also be used as a dispersant or a binder.

  The alkali-soluble resin can be appropriately selected from resins having a group that promotes alkali dissolution. Examples of the group that promotes alkali dissolution (hereinafter also referred to as an acid group) include a carboxyl group, a phosphate group, a sulfo group, and a phenolic hydroxyl group, and a carboxyl group is preferable. Only one type of acid group may be included in the alkali-soluble resin, or two or more types may be used.

  As for the weight average molecular weight (Mw) of alkali-soluble resin, 5000-100,000 are preferable. The number average molecular weight (Mn) of the alkali-soluble resin is preferably 1000 to 20,000.

  The alkali-soluble resin is preferably a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, or an acrylic / acrylamide copolymer resin from the viewpoint of heat resistance. From the viewpoint of control of developability, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable.

  The alkali-soluble resin is preferably a polymer having a carboxyl group in the side chain. For example, a copolymer having a repeating unit derived from a monomer such as methacrylic acid, acrylic acid, itaconic acid, crotonic acid, maleic acid, 2-carboxyethyl (meth) acrylic acid, vinyl benzoic acid, partially esterified maleic acid, Examples thereof include alkali-soluble phenol resins such as novolac resins, acidic cellulose derivatives having a carboxyl group in the side chain, and polymers obtained by adding an acid anhydride to a polymer having a hydroxyl group. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, etc. Is mentioned. Examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like. Examples of the other monomer include N-substituted maleimide monomers described in JP-A-10-300922, such as N-phenylmaleimide and N-cyclohexylmaleimide. Only one kind of these other monomers copolymerizable with (meth) acrylic acid may be used, or two or more kinds may be used.

  Examples of the alkali-soluble resin include benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, and benzyl (meth) acrylate. A multi-component copolymer composed of / (meth) acrylic acid / other monomers can be preferably used. Further, a copolymer obtained by copolymerizing 2-hydroxyethyl (meth) acrylate and another monomer, described in JP-A-7-140654, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / Methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer and the like can also be preferably used. Moreover, as a commercial item, FF-426 (made by Fujikura Kasei Co., Ltd.) etc. can also be used, for example.

  As the alkali-soluble resin, an alkali-soluble resin having a polymerizable group can also be used. Examples of the polymerizable group include a (meth) allyl group and a (meth) acryloyl group. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin having a polymerizable group in the side chain is useful. Commercially available products of the alkali-soluble resin having a polymerizable group include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (carboxyl group-containing polyurethane acrylate oligomer, manufactured by Diamond Shamrock Co., Ltd.), Biscote R-264. KS resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA230AA), Plaxel CF200 series (all manufactured by Daicel Corporation), Ebecryl 3800 (manufactured by Daicel UCB Corporation), Examples include ACRYCURE RD-F8 (manufactured by Nippon Shokubai Co., Ltd.) and DP-1305 (manufactured by Fuji Fine Chemicals Co., Ltd.).

  The alkali-soluble resin contains at least one compound selected from the compound represented by the following formula (ED1) and the compound represented by the formula (1) of JP 2010-168539 A (hereinafter referred to as “ether dimer”). It is also preferable to include a polymer obtained by polymerizing a monomer component including “.

In formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

  As a specific example of the ether dimer, for example, paragraph number 0317 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification. Only one type of ether dimer may be used, or two or more types may be used.

Examples of the polymer obtained by polymerizing a monomer component containing an ether dimer include polymers having the following structure.

式（Ｘ）において、Ｒ₁は、水素原子またはメチル基を表し、Ｒ₂は炭素数２〜１０のアルキレン基を表し、Ｒ₃は、水素原子またはベンゼン環を含んでもよい炭素数１〜２０のアルキル基を表す。ｎは１〜１５の整数を表す。 The alkali-soluble resin may contain a repeating unit derived from a compound represented by the following formula (X).

In the formula (X), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 10 carbon atoms, and R ₃ represents a hydrogen atom or a benzene ring that may contain a benzene ring. Represents an alkyl group. n represents an integer of 1 to 15.

In the formula (X), the number of carbon atoms of the alkylene group R ₂ is preferably 2-3. The number of carbon atoms in the alkyl group of R ₃ is from 1 to 10 are preferred. The alkyl group of R ₃ may contain a benzene ring. Examples of the alkyl group containing a benzene ring represented by R ₃ include a benzyl group and a 2-phenyl (iso) propyl group.

  As for the alkali-soluble resin, the description in paragraph Nos. 0558 to 0571 of JP 2012-208494 A (corresponding to paragraph Nos. 0687 to 0700 of the corresponding US Patent Application Publication No. 2012/0235099) can be referred to. Embedded in the book. Further, the copolymer (B) described in paragraphs 0029 to 0063 of JP2012-32767A and the alkali-soluble resin used in Examples, paragraphs 0088 to 0098 of JP2012-208474A The binder resin described in the description and the binder resin used in the examples, the binder resin described in paragraphs 0022 to 0032 of JP2012-137531A and the binder resin used in the examples, JP2013-024934A Binder resin described in paragraph Nos. 0132 to 0143 of the gazette and the binder resin used in the examples, paragraph numbers 0092 to 0098 of the gazette of JP2011-242752 and the binder resin used in the examples, and JP2012 Paragraph No. 0030 of Publication No. 032770 0072 can also be used a binder resin according to. These contents are incorporated herein.

  The acid value of the alkali-soluble resin is preferably 30 to 500 mgKOH / g. The lower limit is more preferably 50 mgKOH / g or more, and still more preferably 70 mgKOH / g or more. The upper limit is more preferably 400 mgKOH / g or less, still more preferably 200 mgKOH / g or less, still more preferably 150 mgKOH / g or less, and particularly preferably 120 mgKOH / g or less.

  As for content of alkali-soluble resin, 1-95 mass% is preferable with respect to the total solid of a coloring composition. The lower limit is more preferably 2% by mass or more, and further preferably 3% by mass or more. The upper limit is more preferably 93% by mass or less, and still more preferably 90% by mass or less. The coloring composition of the present invention may contain only one kind of alkali-soluble resin, or may contain two or more kinds. When two or more types are included, the total is preferably within the above range.

(Other resins)
The colored composition of the present invention may contain a resin other than the resin described above in the column of the dispersant and the alkali-soluble resin (also referred to as other resin). Examples of other resins include (meth) acrylic resin, (meth) acrylamide resin, ene / thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, and polyarylene ether. Examples thereof include phosphine oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, and siloxane resin. As for other resins, one kind of these resins may be used alone, or two or more kinds may be mixed and used.

<< Curable compound >>
The coloring composition of the present invention contains a curable compound. As the curable compound, known compounds that can be cross-linked by radicals, acids, and heat can be used. In the present invention, examples of the curable compound include a polymerizable compound and a compound having an epoxy group. Examples of the polymerizable compound include compounds having an ethylenically unsaturated bond group such as a vinyl group, a (meth) allyl group, and a (meth) acryloyl group. The polymerizable compound is more preferably a radical polymerizable compound.

  In the colored composition of the present invention, the content of the curable compound is preferably 0.1 to 50% by mass with respect to the total solid content of the colored composition. For example, the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. For example, the upper limit is more preferably 45% by mass or less, and still more preferably 40% by mass or less. One curable compound may be used alone, or two or more curable compounds may be used in combination. When using 2 or more types together, it is preferable that a total amount becomes the said range.

(Polymerizable compound)
The polymerizable compound may be any of chemical forms such as a monomer, a prepolymer, and an oligomer, but a monomer is preferable. The molecular weight of the polymerizable compound is preferably 100 to 3000. The upper limit is more preferably 2000 or less, and even more preferably 1500 or less. The lower limit is more preferably 150 or more, and further preferably 250 or more.

  The polymerizable compound is preferably a 3-15 functional (meth) acrylate compound, and more preferably a 3-6 functional (meth) acrylate compound. Specific examples of these compounds include those described in paragraph Nos. 0095 to 0108 of JP-A-2009-288705, paragraph 0227 of JP-A-2013-29760, and paragraph numbers 0254 to 0257 of JP-A 2008-292970. Compounds, the contents of which are incorporated herein.

Polymerizable compounds are dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; Nippon Kayaku Co., Ltd.) ), Dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial product, KAYARAD DPHA; Nippon Kayaku ( Co., Ltd., NK ester A-DPH-12E; Shin-Nakamura Chemical Co., Ltd.), and a structure in which these (meth) acryloyl groups are bonded via an ethylene glycol and / or propylene glycol residue (for example, SR454, commercially available from Sartomer, SR499) is preferred. These oligomer types can also be used. Moreover, KAYARAD RP-1040 and DPCA-20 (made by Nippon Kayaku Co., Ltd.) can also be used as a polymerizable compound.
In addition, as a polymerizable compound, trimethylolpropane tri (meth) acrylate, trimethylolpropane propyleneoxy modified tri (meth) acrylate, trimethylolpropane ethyleneoxy modified tri (meth) acrylate, isocyanuric acid ethyleneoxy modified tri (meth) acrylate It is also preferable to use a trifunctional (meth) acrylate compound such as pentaerythritol tri (meth) acrylate. As a commercial item of a trifunctional (meth) acrylate compound, Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305 , M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) Etc. Moreover, the following compound can also be used as a polymeric compound.

The polymerizable compound may have an acid group. By using the polymerizable compound having an acid group, the unexposed portion of the polymerizable compound is easily removed during development, and the generation of development residues can be suppressed. Examples of the acid group include a carboxyl group, a sulfo group, and a phosphate group, and a carboxyl group is preferable. Examples of the polymerizable compound having an acid group include the following compounds. Examples of commercially available products include Aronix M-510, M-520, Aronix TO-2349 (manufactured by Toagosei Co., Ltd.), and the like.

  A preferable acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g. If the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the solubility in the developer is good, and if it is 40 mgKOH / g or less, it is advantageous in production and handling. Furthermore, the photopolymerization performance is good and the curability is excellent.

  The polymerizable compound is also preferably a compound having a caprolactone structure. Polymerizable compounds having a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and examples thereof include DPCA-20, DPCA-30, DPCA-60, DPCA-120 and the like.

As the polymerizable compound, a polymerizable compound having an alkyleneoxy group can also be used. The polymerizable compound having an alkyleneoxy group is preferably a polymerizable compound having an ethyleneoxy group and / or a propyleneoxy group, more preferably a polymerizable compound having an ethyleneoxy group, and 3 to 4 having 4 to 20 ethyleneoxy groups. More preferred are hexafunctional (meth) acrylate compounds. Specific examples of the polymerizable compound having an alkyleneoxy group include the following compounds. Examples of commercially available polymerizable compounds having an alkyleneoxy group include SR-494, a tetrafunctional (meth) acrylate having four ethyleneoxy groups manufactured by Sartomer, and a trifunctional (meth) having three isobutyleneoxy groups. Examples thereof include KAYARAD TPA-330, which is an acrylate.

  Examples of the polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. It is also preferable to use a polymerizable compound having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. Commercially available products include urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA -306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (Kyoeisha Chemical Co., Ltd.) etc. are mentioned.

  As for content of a polymeric compound, 0.1-50 mass% is preferable with respect to the total solid of a coloring composition. The lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. The upper limit is more preferably 45% by mass or less, and still more preferably 40% by mass or less. One type of polymerizable compound may be used alone, or two or more types may be used in combination. When using 2 or more types together, it is preferable that a sum total becomes the said range.

(Compound having an epoxy group)
The compound having an epoxy group (hereinafter also referred to as an epoxy compound) preferably has 1 to 100 epoxy groups in one molecule. The lower limit is more preferably 2 or more. For example, the upper limit may be 10 or less, and may be 5 or less.

  The epoxy compound preferably has an epoxy equivalent (= molecular weight of epoxy compound / number of epoxy groups) of 500 g / equivalent or less, more preferably 100 to 400 g / equivalent, and 100 to 300 g / equivalent. Further preferred.

  The epoxy compound may be a low molecular compound (for example, a molecular weight of less than 1000) or a high molecular compound (for example, a molecular weight of 1000 or more, and in the case of a polymer, the weight average molecular weight is 1000 or more). The weight average molecular weight of the epoxy compound is preferably 200 to 100,000, and more preferably 500 to 50,000. The upper limit of the weight average molecular weight is more preferably 10,000 or less, still more preferably 5000 or less, and still more preferably 3000 or less.

  Examples of the epoxy compound are described in paragraph numbers 0034 to 0036 of JP2013-011869A, paragraph numbers 0147 to 0156 of JP2014043556A, and paragraphs 0085 to 0092 of JP2014089408A. Compounds can also be used. These contents are incorporated herein. As commercially available products, for example, as bisphenol A type epoxy resins, jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, jER1010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON860, EPICLON1050 , EPICLON 1051, EPICLON 1055 (above, manufactured by DIC Corporation) and the like. As bisphenol F type epoxy resin, jER806, jER807, jER4004, jER4005, jER4007, jER4010 (Mitsubishi Chemical Co., Ltd.), EPICLON830, EPICLON835 (above, DIC Corporation), LCE-21, RE-602S (Nippon Kayaku Co., Ltd.) and the like. Examples of the phenol novolac type epoxy resin include jER152, jER154, jER157S70, jER157S65 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, manufactured by DIC Corporation), etc. Is mentioned. As cresol novolac type epoxy resin, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, manufactured by DIC Corporation) ), EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.) and the like. As the aliphatic epoxy resin, ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (manufactured by ADEKA Corporation), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, PB 4700 (above, manufactured by Daicel Corporation), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, manufactured by Nagase ChemteX Corporation), and the like. In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), jER1031S (manufactured by Mitsubishi Chemical Corporation), and the like.

Moreover, the compound represented by a following formula (EP1) can also be used as an epoxy compound.

In the formula (EP1), R ^{EP1 to} R ^EP3 each independently represent a hydrogen atom, a halogen atom or an alkyl group. The alkyl group may be linear, branched or cyclic. Further, the alkyl group may be unsubstituted or may have a substituent. R ^EP1 and R ^EP2 , R ^EP2 and R ^EP3 may be bonded to each other to form a ring. ^QEP represents a single bond or an ^nEP- valent organic group. R ^EP1 to R ^EP3 is combined with Q ^EP may form a ring. n ^EP represents an integer of 1 or more, preferably an integer of 2 to 10, an integer of from 2 to 6 is more preferable. However, n ^EP is 2 when Q ^EP is a single bond. Details of R ^{EP1 to} R ^EP3 and Q ^EP can be referred to the description of paragraph numbers 0087 to 0088 of Japanese Patent Application Laid-Open No. 2014-089408, the contents of which are incorporated herein. Specific examples of the compound represented by the formula (EP1) include compounds described in paragraph No. 0090 of JP2014-089408A, the contents of which are incorporated herein.

  When the coloring composition of this invention contains an epoxy compound, 0.1-40 mass% is preferable with respect to the total solid of a coloring composition. For example, the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. For example, the upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less. One epoxy compound may be used alone, or two or more epoxy compounds may be used in combination. When using 2 or more types together, it is preferable that a sum total becomes the said range.

<< photopolymerization initiator >>
When the coloring composition of this invention contains a polymeric compound as a sclerosing | hardenable compound, it is preferable to contain a photoinitiator further. The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light in the ultraviolet region to the visible region is preferable. Moreover, the compound which produces | generates an active radical and some effect | action with a photoexcited sensitizer may be sufficient.

  Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton and compounds having an oxadiazole skeleton), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime derivatives, and the like. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone compounds, and the like. From the viewpoint of exposure sensitivity, trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, oniums A compound selected from the group consisting of a compound, a benzothiazole compound, a benzophenone compound, a hydroxyacetophenone compound, an aminoacetophenone compound, a cyclopentadiene-benzene-iron complex and a salt thereof, a halomethyloxadiazole compound, and a 3-aryl-substituted coumarin compound preferable. As specific examples of the photopolymerization initiator, for example, the description in paragraph Nos. 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

  As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be suitably used. For example, aminoacetophenone compounds described in JP-A-10-291969 and acylphosphine compounds described in Japanese Patent No. 4225898 can also be used. As the hydroxyacetophenone compound, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone compound, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone compound, a compound described in JP-A No. 2009-191179 whose absorption wavelength is matched with a light source of 365 nm or 405 nm can also be used. As the acylphosphine compound, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.

  More preferred examples of the photopolymerization initiator include oxime compounds. When the colored composition of the present invention is used for the production of a color filter, it is necessary to form a fine pattern with a sharp shape, so it is important that the unexposed area is developed with no residue as well as curability. It is. From such a viewpoint, it is preferable to use an oxime compound as the photopolymerization initiator.

  As the oxime compound, for example, compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166 can be used. Specific examples of the oxime compound include, for example, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentane-3- ON, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxy And carbonyloxyimino-1-phenylpropan-1-one.

  Examples of oxime compounds include J.M. C. S. Perkin II (1979) pp. 1653-1660, J. MoI. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. The compounds described in 202-232, JP-A 2000-66385, JP-A 2000-80068, JP-T 2004-534797, JP-A 2006-342166 can also be used. IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (above, manufactured by BASF) are also preferably used as commercial products. In addition, TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD), Adeka Arcles 30 Adekaoptomer N-1919 (photopolymerization initiator 2 of JP 2012-14052 A) (manufactured by ADEKA, Inc.) can also be used.

  Further, as oxime compounds other than the above, compounds described in JP-T 2009-519904, in which an oxime is linked to the N-position of the carbazole ring, and compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety A nitro group introduced into the dye moiety, a compound described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039, a ketoxime compound described in International Publication No. WO2009 / 131189, and a triazine skeleton identical to an oxime skeleton Even if the compound described in US Pat. No. 7,556,910 contained in the molecule, the compound described in JP2009-221114A having an absorption maximum at 405 nm and good sensitivity to a g-ray light source, etc. may be used. Good. Preferably, for example, paragraph numbers 0274 to 0306 in JP 2013-29760 A can be referred to, the contents of which are incorporated herein.

In the present invention, an oxime compound having a fluorene ring can also be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A No. 2014-137466. This content is incorporated herein.
In the present invention, an oxime compound having a benzofuran skeleton can also be used as a photopolymerization initiator. Specific examples thereof include compounds OE-01 to OE-75 described in International Publication WO2015 / 036910.

  In the present invention, an oxime compound having a fluorine atom can also be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in JP-A-2014-500852, and JP-A 2013-164471. (C-3) and the like. This content is incorporated herein.

  In the present invention, an oxime compound having a nitro group can be used as a photopolymerization initiator. The oxime compound having a nitro group is also preferably a dimer. Specific examples of the oxime compound having a nitro group include compounds described in JP-A No. 2013-114249, paragraph numbers 0031 to 0047, JP-A No. 2014-137466, paragraph numbers 0008 to 0012 and 0070 to 0079, and Japanese Patent No. 4223071. And the compounds described in paragraph Nos. 0007 to 0025 of the publication, Adeka Arcles NCI-831 (manufactured by ADEKA Corporation), and the like.

  Specific examples of the oxime compound preferably used in the present invention are shown below, but the present invention is not limited thereto.

  The oxime compound is preferably a compound having a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, and more preferably a compound having an absorption wavelength in a wavelength region of 360 nm to 480 nm. The oxime compound is preferably a compound having high absorbance at 365 nm and 405 nm.

From the viewpoint of sensitivity, the molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and 5,000 to 200,000. 000 is particularly preferred. The molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure with a UV-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L.
You may use a photoinitiator in combination of 2 or more type as needed.

  The content of the photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and still more preferably 1 to 20% by mass with respect to the total solid content of the colored composition. When the content of the photopolymerization initiator is within the above range, good sensitivity and good pattern formability can be obtained. The colored composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more photopolymerization initiators are included, the total amount is preferably within the above range.

<< Solvent >>
The coloring composition of the present invention contains a solvent. The solvent is preferably an organic solvent. The solvent is not particularly limited as long as it satisfies the solubility of each component and the coating property of the coloring composition. Various solvents such as an ester solvent, an ether solvent, a ketone solvent, and an aromatic hydrocarbon solvent can be used.

  In the present invention, the solvent includes a solvent E1 having a surface tension at 25 ° C. of 26.0 mN / m or more (hereinafter also referred to as solvent E1), and a solvent E2 having a surface tension at 25 ° C. of less than 26.0 mN / m. (Hereinafter also referred to as solvent E2). By using the solvent E1 and the solvent E2 in combination, the occurrence of striation can be effectively suppressed.

  In the present invention, the surface tension of the solvent is a value measured by a plate method using a platinum plate. Here, the measurement of the surface tension by the plate method is as follows. When the probe (plate) touches the surface of the liquid, the liquid wets the plate. At this time, the surface tension acts along the periphery of the plate and tries to draw the plate into the liquid. The pulling force is read and the surface tension of the liquid is measured. As a surface tension measuring device, a surface tension meter CBVP-Z manufactured by Kyowa Interface Science Co., Ltd. can be used.

  In the solvent, the ratio of the mass of the solvent E1 to the mass of the solvent E2 is preferably the mass of the solvent E1: the mass of the solvent E2 = 80: 20 to 30:70, and is 70:30 to 35:65. It is more preferable that the ratio is 60:40 to 40:60. Generation | occurrence | production of striation can be effectively suppressed by using together the solvent E1 and the solvent E2 in the ratio mentioned above. Furthermore, the drying property of the coloring composition is also good.

  The surface tension of the solvent E1 at 25 ° C. is preferably 26 mN / m or more and 35 mN / m or less. The upper limit is preferably 34 mN / m or less, more preferably 30 mN / m or less, and even more preferably 28 mN / m or less. The lower limit is preferably 26.5 mN / m or more. When the surface tension of the solvent E1 is in the above range, the wettability of the colored composition to the support, the drying property of the colored composition, and the like are good.

The boiling point of the solvent E1 is preferably 140 to 180 ° C. The upper limit is more preferably 175 ° C. or less, still more preferably 170 ° C. or less, and even more preferably 165 ° C. or less. The lower limit is more preferably 143 ° C. or higher, and more preferably 145 ° C. or higher. If the boiling point of the solvent E1 is in the above range, the drying property of the colored composition is good.
Further, the boiling point of the solvent E1 is preferably higher than the boiling point of the solvent E2, more preferably 5 ° C. or higher, more preferably 10 ° C. or higher than the boiling point of the solvent E2. According to this aspect, the occurrence of striation can be more effectively suppressed.

  The solvent E1 has a solubility in 100 g of water at 25 ° C. of preferably 30 g or less, more preferably 25 g or less, and even more preferably 20 g or less. By using a solvent having a low solubility in water as the solvent E1, the solubility of other components used in the coloring composition can be enhanced.

  Examples of the solvent E1 include ester solvents, ether solvents, and ketone solvents. Specific examples include compounds having an ester bond and an ether bond such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl 3-ethoxypropionate and ethyl lactate (ester solvent); diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether , Dipropylene Ether compound having no ester bond, such as recall dimethyl ether (ether solvent); methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and ketone solvents such as 3-heptanone. The solvent E1 is preferably an ester solvent from the viewpoints of the solubility of other components contained in the colored composition and the ease of handling, such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-ethoxy. More preferred is ethyl propionate. It is also preferable to use an ester solvent and a ketone solvent in combination. By further containing a ketone solvent, the solubility of other components contained in the colored composition can be improved.

  The content of the solvent E1 in the total mass of the solvent is preferably 15% by mass or more. The lower limit of the content of the solvent E1 is more preferably 20% by mass or more, further preferably 25% by mass or more, and further preferably 30% by mass or more. 90 mass% or less is preferable, as for the upper limit of content, 85 mass% or less is more preferable, and 80 mass% or less is still more preferable.

  The surface tension of the solvent E2 at 25 ° C. is preferably 25 mN / m or less, more preferably 24.8 mN / m or less, further preferably 24.6 mN / m or less, and 24.4 mN / m. It is particularly preferable that it is m or less. The lower limit is preferably 20 mN / m or more, more preferably 21 mN / m or more, and further preferably 22 mN / m or more. When the surface tension of the solvent E2 is in the above range, the wettability of the colored composition to the support and the drying property of the colored composition are good.

  The boiling point of the solvent E2 is preferably 50 to 135 ° C. The upper limit is more preferably 133 ° C. or less, further preferably 130 ° C. or less, and still more preferably 127 ° C. or less. The lower limit is more preferably 70 ° C. or higher, more preferably 90 ° C. or higher, and still more preferably 110 ° C. or higher.

  Solvent E2 has a solubility in 100 g of water at 25 ° C. of preferably 30 g or less, more preferably 10 g or less, and even more preferably 5 g or less. By using an organic solvent having a low solubility in water as the solvent E2, it is possible to enhance the solubility of other components used in the coloring composition. Moreover, mixing of the water | moisture content into a coloring composition can be suppressed, and the deterioration with time stability resulting from water can be suppressed.

The solvent E2 is preferably a compound (solvent) having an ester bond. The solvent E2 is preferably a compound (solvent) that does not have an ether bond, and more preferably a compound (solvent) that has an ester bond and does not have an ether bond. The solvent E2 is preferably a compound (solvent) represented by the following formula (E2-1).
R ^e1 —C (═O) —O—R ^e2 (E2-1)
In the formula, R ^e1 and R ^e2 each independently represent a hydrocarbon group.

The hydrocarbon group in R ^e1 and R ^e2 is a group consisting of only a carbon atom and a hydrogen atom. Specific examples of the hydrocarbon group represented by R ^e1 and R ^e2 include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. An alkyl group, an alkenyl group, and an alkynyl group are preferable, and an alkyl group is more preferable.
1-10 are preferable and, as for carbon number of an alkyl group, 1-5 are more preferable. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched, more preferably linear. The alkyl group is preferably an unsubstituted alkyl group.
2-10 are preferable and, as for carbon number of an alkenyl group, 2-5 are more preferable. The alkenyl group is preferably linear or branched, and more preferably linear. The alkenyl group is preferably an unsubstituted alkenyl group.
2-10 are preferable and, as for carbon number of an alkynyl group, 2-5 are more preferable. The alkynyl group is preferably linear or branched, and more preferably linear. The alkynyl group is preferably an unsubstituted alkenyl group.
6-20 are preferable and, as for carbon number of an aryl group, 6-12 are more preferable. The aryl group may be an unsubstituted aryl group, and may have an alkyl group, an alkenyl group, or an alkynyl group as a substituent.

  Specific examples of the solvent E2 include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, ethyl butyrate, ethyl propionate and the like, preferably methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate and butyl acetate. Propyl acetate, isopropyl acetate and butyl acetate are more preferred, and butyl acetate is more preferred.

  The content of the solvent E2 in the total mass of the solvent is preferably 10% by mass or more. The lower limit is more preferably 20% by mass or more, further preferably 30% by mass or more, and further preferably 40% by mass or more. The upper limit is preferably 90% by mass or less, more preferably 80% by mass or less, and still more preferably 70% by mass or less.

  The total content of the ester solvent E1 (hereinafter also referred to as ester solvent E1) and the solvent E2 in the total mass of the solvent is preferably 50% by mass or more. The lower limit is preferably 55% by mass or more, more preferably 60% by mass or more, and still more preferably 65% by mass or more. The upper limit is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less.

  The ratio of the mass of the ester solvent E1 and the mass of the solvent E2 in the solvent is preferably such that the mass of the ester solvent E1: the mass of the solvent E2 = 80: 20 to 30:70, and 70:30 to 35 : 65 is more preferable, and 60:40 to 40:60 is still more preferable. Generation | occurrence | production of striation can be effectively suppressed by using together the ester solvent E1 and the solvent E2 in the ratio mentioned above. Furthermore, the drying property of the coloring composition is also good.

上記式中、γ_iは、溶剤に含まれる溶剤Ｅ_iの表面張力の値（単位：ｍＮ／ｍ）であり、Ａ_iは、溶剤に含まれる溶剤Ｅ_iの質量分率である。ｎは２以上の整数である。 The surface tension at 25 ° C. of the solvent used in the present invention is preferably 22 mN / m or more and 29 mN / m or less. The upper limit is more preferably 27.5 mN / m or less, further preferably 27.2 mN / m or less, and further preferably 27.0 mN / m or less. The lower limit is more preferably 24 mN / m or more, further preferably 24.5 mN / m or more, and further preferably 25.0 mN / m or more. In addition, when the solvent contains two or more kinds of solvents, the surface tension of the solvent is a value of the surface tension in a mixed liquid of two or more kinds of solvents, and is defined by the following formula.

In the above formula, gamma _i is the surface tension of the solvent E _i contained in the solvent (unit: mN / m) is, A _i is the mass fraction of solvent E _i contained in the solvent. n is an integer of 2 or more.

  In the present invention, the solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide. Moreover, it is preferable to use the organic solvent with few metal contents as a solvent, for example, it is preferable that the metal content of an organic solvent is 10 mass ppb or less. If necessary, an organic solvent having a metal content of mass ppt may be used, and such a high-purity solvent is provided, for example, by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015). .

  It is preferable that the coloring composition of this invention contains 40-95 mass% of solvents. The lower limit of the content is more preferably 45% by mass or more, and further preferably 50% by mass or more. 90 mass% or less is more preferable, as for the upper limit of content, 85 mass% or less is further more preferable, and 80 mass% or less is still more preferable.

<< Curing accelerator >>
The colored composition of the present invention may contain a curing accelerator for the purpose of improving the hardness of the pattern or for decreasing the curing temperature. Examples of the curing accelerator include thiol compounds.

（式（Ｔ１）中、ｎは２〜４の整数を表し、Ｌは２〜４価の連結基を表す。） Examples of the thiol compound include polyfunctional thiol compounds having two or more mercapto groups in the molecule. The polyfunctional thiol compound may be added for the purpose of improving stability, odor, resolution, developability, adhesion and the like. The polyfunctional thiol compound is preferably a secondary alkanethiol, and more preferably a compound having a structure represented by the following formula (T1).
Formula (T1)

(In the formula (T1), n represents an integer of 2 to 4, and L represents a 2 to 4 valent linking group.)

  In the above formula (T1), L is preferably an aliphatic group having 2 to 12 carbon atoms. In the above formula (T1), n is preferably 2, and L is more preferably an alkylene group having 2 to 12 carbon atoms. Specific examples of the polyfunctional thiol compound include compounds represented by the following structural formulas (T2) to (T4), and a compound represented by the formula (T2) is preferable. One thiol compound may be used, or two or more thiol compounds may be used in combination.

  Further, the curing accelerator is a methylol compound (for example, a compound exemplified as a crosslinking agent in paragraph No. 0246 of JP-A-2015-34963), amines, phosphonium salts, amidine salts, amide compounds (above, for example, JP-A-2013-41165, curing agent described in paragraph No. 0186), base generator (for example, ionic compound described in JP-A-2014-55114), isocyanate compound (for example, JP-A-2012-150180). Compounds described in paragraph No. 0071 of the publication), alkoxysilane compounds (for example, alkoxysilane compounds having an epoxy group described in JP2011-255304A), onium salt compounds (for example, JP2015-34963A). The chemicals exemplified as acid generators in paragraph 0216 Things, compounds described in JP-A-2009-180949) or the like can be used.

  When the coloring composition of this invention contains a hardening accelerator, 0.3-8.9 mass% is preferable with respect to the total solid of a coloring composition, and 0.8-6 More preferably, 4% by mass.

<< Pigment derivative >>
The colored composition of the present invention preferably contains a pigment derivative. Examples of the pigment derivative include a compound having a structure in which a part of the chromophore is substituted with an acidic group, a basic group, or a phthalimidomethyl group.

  The chromophores constituting the pigment derivatives include quinoline skeleton, benzoimidazolone skeleton, diketopyrrolopyrrole skeleton, azo skeleton, phthalocyanine skeleton, anthraquinone skeleton, quinacridone skeleton, dioxazine skeleton, and perinone skeleton. Perylene skeleton, thioindigo skeleton, isoindoline skeleton, isoindolinone skeleton, quinophthalone skeleton, selenium skeleton, metal complex skeleton, etc., quinoline skeleton, benzimidazolone skeleton, diketopyrrolo A pyrrole skeleton, an azo skeleton, a quinophthalone skeleton, an isoindoline skeleton, and a phthalocyanine skeleton are preferable, and an azo skeleton and a benzimidazolone skeleton are more preferable. As an acidic group which a pigment derivative has, a sulfo group and a carboxyl group are preferable, and a sulfo group is more preferable. As a basic group which a pigment derivative has, an amino group is preferable and a tertiary amino group is more preferable. As specific examples of the pigment derivative, for example, the description of paragraph numbers 0162 to 0183 in JP 2011-252065 A can be referred to, and the contents thereof are incorporated in the present specification.

  When the coloring composition of this invention contains a pigment derivative, 1-30 mass parts is preferable with respect to 100 mass parts of pigments, and 3-20 mass parts is more preferable. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination.

<< Surfactant >>
The coloring composition of the present invention contains a surfactant. Various surfactants such as fluorosurfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used as surfactants, further improving coatability. A fluorosurfactant is preferable because it can be used.

  By containing the fluorosurfactant in the colored composition of the present invention, the liquid properties when prepared as a coating liquid can be improved, and the uniformity of the coating thickness can be further improved. That is, in the case of forming a film using a coating liquid to which a coloring composition containing a fluorosurfactant is applied, the interfacial tension on the surface of the coating film is lowered and drying uniformity is improved. For this reason, film formation with little coating nonuniformity can be performed more suitably.

  3-40 mass% is preferable, as for the fluorine content rate in a fluorochemical surfactant, More preferably, it is 5-30 mass%, Most preferably, it is 7-25 mass%. A fluorine-based surfactant having a fluorine content within the above range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in a colored composition.

  Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 (and above, DIC Corporation). Manufactured), FLORARD FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC -383, S-393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (above, manufactured by OMNOVA). As the fluorine-based surfactant, the compounds described in JP-A-2015-117327, paragraphs 0015 to 0158, and the compounds described in JP-A-2011-132503, paragraphs 0117 to 0132 can also be used. A block polymer can also be used as the fluorosurfactant, and specific examples thereof include compounds described in JP-A-2011-89090.

  The fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which the fluorine atom is volatilized by cleavage of the functional group containing the fluorine atom when heat is applied can be suitably used. . Examples of such a fluorosurfactant include Megafac DS series manufactured by DIC Corporation (Chemical Industry Daily, February 22, 2016) (Nikkei Sangyo Shimbun, February 23, 2016). -21, and these may be used.

上記の化合物の重量平均分子量は、好ましくは３，０００〜５０，０００であり、例えば、１４，０００である。 The fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group or propyleneoxy group) (meta). ) A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as the fluorine-based surfactant used in the present invention. In the following formula,% indicating the ratio of repeating units is mass%.

The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000.

  As the fluorosurfactant, a fluoropolymer having a group having an ethylenically unsaturated bond in the side chain can also be used. Specific examples thereof include compounds described in paragraph numbers 0050 to 0090 and paragraph numbers 0289 to 0295 of JP2010-164965A. Examples of commercially available products include Megafac RS-101, RS-102, RS-718-K, and RS-72-K manufactured by DIC Corporation.

  Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF ), Tetronic 304, 701, 704, 901, 904, 150R1 (BAS) ), Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), Pionein D-6112, D-6112-W, D -6315 (manufactured by Takemoto Yushi Co., Ltd.), Olphine E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.) and the like.

  Examples of the cationic surfactant include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.

  Examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Co., Ltd.), and the like.

  Examples of silicone-based surfactants include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torree Silicone SH28PA, Torree Silicone SH29PA, Torree Silicone SH30PA, Torree Silicone SH8400 (above, Toray Dow Corning Co., Ltd.) )), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4442 (above, manufactured by Momentive Performance Materials), KP341, KF6001, KF6002 (above, manufactured by Shin-Etsu Silicone Co., Ltd.) , BYK307, BYK323, BYK330 (above, manufactured by BYK Chemie) and the like.

The content of the surfactant is preferably 0.001 to 0.2% by mass, more preferably 0.0015 to 0.1% by mass, and more preferably 0.002 to 0.1% by mass with respect to the total solid content of the coloring composition. 05 mass% is still more preferable.
Moreover, 0.001-0.2 mass% is preferable with respect to the total solid of a coloring composition, and, as for content of a fluorochemical surfactant, 0.0015-0.1 mass% is more preferable, and 0.001. More preferably, it is 002 to 0.05% by mass.
If content of surfactant is the said range, the applicability | paintability of a coloring composition will be favorable, and generation | occurrence | production of a coating nonuniformity and striation can be suppressed more effectively.
Only one type of surfactant may be used, or two or more types may be combined. When two or more types are included, the total amount is preferably within the above range.

<< Silane coupling agent >>
The coloring composition of the present invention can contain a silane coupling agent. In the present invention, the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. The hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond by a hydrolysis reaction and / or a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and an acyloxy group.

  The silane coupling agent is composed of at least one group selected from a vinyl group, an epoxy group, a styryl group, a methacryl group, an amino group, an isocyanurate group, a ureido group, a mercapto group, a sulfide group, and an isocyanate group, and an alkoxy group. A silane compound having Specific examples of the silane coupling agent include, for example, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-602), N-β-aminoethyl-γ-aminopropyltri Methoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-603), N-β-aminoethyl-γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-602), γ-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) Industrial company KBM-903), γ-aminopropyltriethoxysilane (Shin-Etsu Chemical Co., KBE-903), 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., KBM-503), 3- Examples thereof include glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403). For details of the silane coupling agent, the description of paragraph numbers 0155 to 0158 in JP2013-254047A can be referred to, and the contents thereof are incorporated in the present specification.

  When the coloring composition of this invention contains a silane coupling agent, 0.001-20 mass% is preferable with respect to the total solid of a coloring composition, and, as for content of a silane coupling agent, 0.01- 10 mass% is more preferable and 0.1-5 mass% is especially preferable. The coloring composition of this invention may contain only 1 type of silane coupling agents, and may contain 2 or more types. When two or more silane coupling agents are included, the total amount is preferably within the above range.

<< Polymerization inhibitor >>
The coloring composition of the present invention preferably contains a polymerization inhibitor. As a polymerization inhibitor, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine salt (ammonium salt, primary cerium salt, etc.) and the like.
When the coloring composition of this invention contains a polymerization inhibitor, 0.01-5 mass% is preferable with respect to the total solid of a coloring composition. The coloring composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<< UV absorber >>
The coloring composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber is preferably a conjugated diene compound. As a commercial item of a ultraviolet absorber, UV-503 (Daito Chemical Co., Ltd. product) etc. are mentioned, for example. Further, as the ultraviolet absorber, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a triazine compound, or the like can be used. Specific examples thereof include compounds described in JP2013-68814A. Moreover, as a benzotriazole compound, you may use the MYUA series (Chemical Industry Daily, February 1, 2016) made from Miyoshi oil and fat.

  When the coloring composition of this invention contains a ultraviolet absorber, 0.1-10 mass% is preferable with respect to the total solid of a coloring composition, and, as for content of a ultraviolet absorber, 0.1-5 mass % Is more preferable, and 0.1 to 3% by mass is particularly preferable. Moreover, only 1 type may be used for an ultraviolet absorber and 2 or more types may be used for it. When using 2 or more types, it is preferable that a total amount becomes the said range.

<< Other additives >>
Various additives, for example, fillers, adhesion promoters, antioxidants, anti-aggregation agents, and the like can be blended with the colored composition of the present invention as necessary. Examples of these additives include additives described in JP-A No. 2004-295116, paragraph numbers 0155 to 0156, the contents of which are incorporated herein. As the antioxidant, for example, a phenol compound, a phosphorus compound (for example, a compound described in paragraph No. 0042 of JP 2011-90147 A), a thioether compound, or the like can be used. Examples of commercially available products include ADEKA Corporation's ADK STAB series (AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-80, AO- 330). Only one type of antioxidant may be used, or two or more types may be used. The coloring composition of the present invention can contain a sensitizer and a light stabilizer described in paragraph No. 0078 of JP-A No. 2004-295116 and a thermal polymerization inhibitor described in paragraph No. 0081 of the publication.

  Depending on the raw materials used, the colored composition may contain a metal element, but from the viewpoint of suppressing the occurrence of defects, the content of the Group 2 elements (calcium, magnesium, etc.) in the colored composition is 50 ppm by mass ( pers per million) or less, more preferably 0.01 to 10 ppm by mass. Moreover, it is preferable that the total amount of the inorganic metal salt in a coloring composition is 100 mass ppm or less, and 0.5-50 mass ppm is more preferable.

<Method for preparing colored composition>
The coloring composition of the present invention can be prepared by mixing the aforementioned components. In preparing the coloring composition, the respective components may be blended together, or may be blended sequentially after each component is dissolved and / or dispersed in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. For example, the composition may be prepared by dissolving and / or dispersing all the components in a solvent at the same time. If necessary, each component may be appropriately used as two or more solutions or dispersions at the time of use (application). May be prepared by mixing them.

  In preparation of the coloring composition, it is preferable to filter with a filter for the purpose of removing foreign substances or reducing defects. Any filter can be used without particular limitation as long as it is a filter that has been conventionally used for filtration. For example, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg nylon-6, nylon-6,6), polyolefin resins such as polyethylene and polypropylene (PP) (high density and / or super And a filter using a material such as a high molecular weight polyolefin resin). Among these materials, polypropylene (including high density polypropylene) and nylon are preferable.

  The pore size of the filter is suitably about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, more preferably about 0.05 to 0.5 μm.

  Moreover, it is also preferable to use the filter using a fiber-like filter medium as a filter. Examples of the fiber-shaped filter medium include polypropylene fiber, nylon fiber, and glass fiber. Specific examples of filters using fiber-shaped filter media include filter cartridges of SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) manufactured by Loki Techno. .

When using filters, different filters may be combined. In that case, filtration with each filter may be performed only once or may be performed twice or more.
For example, you may combine the filter of a different hole diameter within the range mentioned above. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, select from various filters provided by Nippon Pole Co., Ltd. (DFA4201NXEY, etc.), Advantech Toyo Co., Ltd., Japan Integris Co., Ltd. (formerly Nihon Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. can do.
Moreover, filtration with a 1st filter may be performed only with a dispersion liquid, and after mixing other components, it may filter with a 2nd filter. As the second filter, a filter formed of the same material as the first filter can be used.

  The water content of the colored composition of the present invention is usually 3% by mass or less, preferably 0.01 to 1.5% by mass, and more preferably 0.1 to 1.0% by mass. The water content can be measured by the Karl Fischer method.

<Use of colored composition>
The colored composition of the present invention can be preferably used as a composition for spin coating. The colored composition of the present invention can be preferably used for forming a colored layer in a color filter. For example, it can be preferably used for a solid-state imaging device such as a CCD (Charge Coupled Device) or CMOS (Complementary Metal Oxide Semiconductor) or a color filter such as an image display device.

  The film thickness of the color filter can be appropriately adjusted according to the purpose. The film thickness is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and further preferably 0.3 μm or more.

  When the colored composition of the present invention is used as a color filter for a liquid crystal display device, the voltage holding ratio of the liquid crystal display element provided with the color filter is preferably 70% or more, and more preferably 90% or more. . Known means for obtaining a high voltage holding ratio can be appropriately incorporated. Typical examples include the use of high-purity materials (for example, reduction of ionic impurities) and control of the amount of acidic functional groups in the composition. Is mentioned. The voltage holding ratio can be measured by, for example, the method described in paragraph 0243 of JP2011-008004A, paragraphs 0123 to 0129 of JP2012-224847A, and the like.

<Membrane>
The film of the present invention is a film formed by curing the colored composition of the present invention. In the membrane of the present invention, after adjusting the surface temperature of the membrane to 25 ° C., 2 μL of 25 ° C. water was dropped on the membrane surface, and the contact angle of water with respect to the membrane measured 5 seconds later was 70 degrees or less. Preferably, it is 40 to 67 degrees, more preferably 50 to 65 degrees. According to this aspect, when forming a film | membrane using the coloring composition of this invention, generation | occurrence | production of striation can be suppressed more effectively.

<Method for producing membrane>
The manufacturing method of the film | membrane of this invention includes the process of apply | coating the coloring composition of this invention to a support body.

  There is no limitation in particular as a support body, According to a use, it can select suitably. Examples thereof include a glass substrate, a substrate for a solid-state image sensor provided with a solid-state image sensor (light receiving element) such as a CCD or CMOS, a silicon substrate, and the like. In addition, an undercoat layer may be provided on these base materials, if necessary, for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the surface. The undercoat layer preferably contains an organic substance such as a resin. That is, the undercoat layer is preferably an organic layer. Conventionally, when a colored composition is applied on an organic material layer, striations tend to occur. However, according to the colored composition of the present invention, on a support on which an undercoat layer such as an organic material layer is formed. Even when a colored composition is applied to the coating, it is possible to effectively suppress the occurrence of coating unevenness and striation. Therefore, the present invention is particularly effective when a support having an undercoat layer such as an organic layer formed on the coating surface of the colored composition is used. Further, when there is a step on the coating surface of the colored composition on the support, striations tend to occur particularly easily, but according to the colored composition of the present invention, a support having such a step was used. Even if it is a case, generation | occurrence | production of striation can be suppressed effectively. For this reason, the present invention is particularly effective when a support having a step is used.

Examples of the method for applying the coloring composition include spin coating, slit coating, and ink jet. Conventionally, when applied by spin coating on a support having a step such as unevenness on the coated surface, striations tend to occur, but according to the present invention, when applied by spin coating. Even if it exists, generation | occurrence | production of striation can be suppressed. For this reason, a particularly remarkable effect can be obtained in the case of applying by spin coating.
In addition, the spin coating method is preferably performed by spin coating at 50 to 3000 rpm, and more preferably by spin coating at 500 to 2000 rpm. Moreover, 10-30 degreeC is preferable and the temperature of the support body at the time of spin coating has more preferable 15-25 degreeC. If it is said range, it will be easy to suppress generation | occurrence | production of striation more effectively.

  There is no limitation in particular as a coating film thickness. It can be appropriately adjusted depending on the application. The coating film thickness is preferably 0.2 to 50 μm. The lower limit is more preferably 0.5 μm or more, and further preferably 1.0 μm or more. The upper limit is more preferably 30 μm or less, and further preferably 10 μm or less.

  In the manufacturing method of the film | membrane of this invention, you may dry further with respect to the coloring composition (coloring composition layer) apply | coated on the support body. The drying conditions are not particularly limited. For example, the drying temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and even more preferably 110 ° C. or lower. The lower limit of the drying temperature can be, for example, 50 ° C. or higher, and can be 80 ° C. or higher. The drying time is preferably 10 seconds to 300 seconds, more preferably 40 to 250 seconds, and further preferably 80 to 220 seconds. Drying can be performed with a hot plate, oven, or the like.

  The method for producing a film of the present invention may further include a step of forming a pattern. In addition, when using the film | membrane obtained by the manufacturing method of the film | membrane of this invention as a flat film, the process of forming a pattern does not need to be performed. Examples of the pattern forming method include a photolithography method and a pattern forming method using a dry etching method.

  As a pattern forming method using a photolithography method, a patterning process is performed by exposing a colored composition layer formed on a support in a pattern (exposure process), and an unexposed portion of the colored composition layer is developed and removed. It is preferable that the process (development process) is formed. The pattern formation by the dry etching method includes a step of curing the colored composition layer formed on the support to form a cured product layer, a step of forming a photoresist layer on the cured product layer, exposure and It is preferable to include a step of patterning the photoresist layer by development to obtain a resist pattern and a step of forming a pattern by dry etching the cured product layer using the resist pattern as an etching mask.

  When the pattern forming step is performed, it is preferable that the film (pixel) after the pattern formation has high flatness. Specifically, the surface roughness Ra is preferably 100 nm or less, more preferably 40 nm or less, and even more preferably 15 nm or less. Although a minimum is not prescribed | regulated, it is preferable that it is 0.1 nm or more, for example. The surface roughness of the film can be measured using, for example, AFM (Atomic Force Microscope) Dimension 3100 manufactured by Veeco.

It is desirable that the pixel has a high volume resistance value. Specifically, the volume resistance value of the pixel is preferably 10 ⁹ Ω · cm or more, and more preferably 10 ¹¹ Ω · cm or more. The upper limit is not defined, for example, preferably not more than 10 ¹⁴ Ω · cm. The volume resistance value of the pixel can be measured using, for example, an ultrahigh resistance meter 5410 (manufactured by Advantest).

(Photolithography method)
When pattern formation is performed by photolithography, the colored composition layer formed on the support is exposed in a pattern. For example, the colored composition layer can be exposed in a pattern by exposing it through a mask having a predetermined mask pattern using an exposure apparatus such as a stepper. Thereby, an exposed part can be hardened.
As radiation (light) that can be used for exposure, ultraviolet rays such as g-line and i-line are preferable (particularly preferably i-line). Irradiation dose (exposure dose), for example, preferably ^{0.03~2.5J / cm 2, 0.05~1.0J / cm} 2 is more preferable.
The oxygen concentration at the time of exposure can be appropriately selected. In addition to being performed in the atmosphere, for example, in a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, substantially oxygen-free). ), Or in a high oxygen atmosphere (for example, 22% by volume, 30% by volume, 50% by volume) with an oxygen concentration exceeding 21% by volume. The exposure intensity is can be set appropriately, usually ^{1000W / m 2 ~100000W / m 2} ( ^{e.g., 5000W / m 2, 15000W /} m 2, 35000W / m 2) can be selected from the range of . Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / m ² at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20000W / m ^2.

  Next, the unexposed portion of the colored composition layer is developed and removed to form a pattern. The development removal of the unexposed part of the colored composition layer can be performed using a developer. The developer is preferably an organic alkali developer that does not damage the underlying solid-state imaging device or circuit. As for the temperature of a developing solution, 20-30 degreeC is preferable, for example. The development time is preferably 20 to 180 seconds. Moreover, in order to improve residue removability, the process of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.

  As the developer, an alkaline aqueous solution obtained by diluting an alkaline agent with pure water is preferably used. Examples of the alkaline agent include ammonia water, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxy. Organic alkaline compounds such as water, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, water Inorganic acids such as sodium oxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium metasilicate Potassium compounds may be mentioned. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. Further, the developer may further contain a surfactant. Examples of the surfactant include the surfactant described in the above-described coloring composition, and a nonionic surfactant is preferable. In addition, when the developing solution which consists of such alkaline aqueous solution is used, it is preferable to wash | clean (rinse) with a pure water after image development.

After the development, after drying, a heat treatment (post-bake) can be performed. Post-baking is a heat treatment after development for complete film curing. When performing post-baking, the post-baking temperature is preferably 100 to 240 ° C, for example. From the viewpoint of film curing, 200 to 230 ° C. is more preferable. The Young's modulus of the film after post-baking is preferably 0.5 to 20 GPa, more preferably 2.5 to 15 GPa. Further, when an organic electroluminescence (organic EL) element is used as the light source or when the photoelectric conversion film of the image sensor is composed of an organic material, the post-bake temperature is preferably 150 ° C. or lower, preferably 120 ° C. or lower. Is more preferable, 100 ° C. or lower is further preferable, and 90 ° C. or lower is particularly preferable. The lower limit can be, for example, 50 ° C. or higher.
Post-baking can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, etc., so that the film after development is in the above-mentioned condition. . Further, when a pattern is formed by a low temperature process, post baking is not necessary.

(When pattern is formed by dry etching method)
The pattern formation by the dry etching method includes a step of curing a colored composition layer formed on a support to form a cured product layer, a step of forming a photoresist layer on the cured product layer, and exposure and development. Preferably, the method includes a step of patterning the photoresist layer to obtain a resist pattern and a step of forming a pattern by dry etching the cured product layer using the resist pattern as an etching mask.

  The photoresist layer is preferably formed by applying a positive-type or negative-type radiation-sensitive composition on the cured product layer and drying it. As the radiation-sensitive composition used for forming the photoresist layer, a positive radiation-sensitive composition is preferably used. The positive radiation sensitive composition includes radiation sensitive to radiation such as ultraviolet rays (g rays, h rays, i rays), far ultraviolet rays including KrF rays, ArF rays, electron rays, ion beams and X rays. Is preferred. The above-mentioned positive radiation sensitive composition is preferably a radiation sensitive composition sensitive to KrF rays, ArF rays, i rays, X rays), and is sensitive to KrF rays from the viewpoint of fine workability. More preferred. As the positive photosensitive resin composition, positive resist compositions described in JP2009-237173A and JP2010-134283A are preferably used.

  In the formation of the photoresist layer, the exposure step of the radiation sensitive composition is preferably performed with KrF rays, ArF rays, i rays, X rays, etc., and more preferably with KrF rays, ArF rays, X rays, etc. More preferably, KrF line is used.

  Regarding the pattern formation by the dry etching method, the description of paragraph numbers 0010 to 0067 of JP2013-064993A can be referred to, and the contents thereof are incorporated in the present specification.

  A color filter, a solid-state image sensor, an image display device, etc. can also be manufactured using the film manufacturing method of the present invention.

  The configuration of the solid-state imaging device is not particularly limited as long as it is a configuration that functions as a solid-state imaging device, and examples thereof include the following configurations.

  A transfer electrode made of a plurality of photodiodes, polysilicon, and the like constituting a light receiving area of a solid-state imaging device (CCD (charge coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.)) on a support. Device protection consisting of silicon nitride, etc., which has a light-shielding film that opens only on the photodiode and the transfer electrode on the photodiode and the transfer electrode, and is formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part It has a film, and has a color filter on the device protective film. Further, a configuration having a light condensing means (for example, a microlens, etc., the same applies hereinafter) on the device protective film and below the color filter (on the side close to the support), a structure having the light condensing means on the color filter, etc. It may be. In addition, the color filter may have a structure in which a film forming each pixel is embedded in a space partitioned by a partition, for example, in a lattice shape. The partition in this case preferably has a low refractive index for each pixel. Examples of the solid-state imaging device having such a structure include apparatuses described in JP 2012-227478 A and JP 2014-179577 A.

  Examples of the image display device include a liquid crystal display device and an organic electroluminescence display device. For the definition of the image display device and details of each image display device, refer to, for example, “Electronic Display Device (Akio Sasaki, published by Kogyo Kenkyukai 1990)”, “Display Device (written by Junaki Ibuki, Sangyo Tosho Co., Ltd.) ) "Issued in 1989"). The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next-generation liquid crystal display technology”.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.

<Measurement of weight average molecular weight>
The weight average molecular weight of the resin was measured by the following method.
Column type: TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000 linked column developing solvent: Tetrahydrofuran Column temperature: 40 ° C.
Flow rate (sample injection amount): 1.0 μL (sample concentration: 0.1% by mass)
Device name: Tosoh HLC-8220GPC
Detector: RI (refractive index) detector Calibration curve Base resin: Polystyrene resin

ＰＧＭＥＡは、プロピレングリコールモノメチルエーテルアセテートの略称である。
ＥＥＰは、３−エトキシプロピオン酸エチルの略称である。
ＰＧＭＥはプロピレングリコールモノメチルエーテルの略称である。
ＰＥは、プロピレングリコールモノエチルエーテルの略称である。
ＰｎＰは、プロピレングリコールモノ−ｎ−プロピルエーテルの略称である。
ＰｎＢは、プロピレングリコールモノ−ｎ−ブチルエーテルの略称である。
ＤＭＭは、ジプロピレングリコールジメチルエーテルの略称である。 <Measurement of surface tension of solvent>
The surface tension of the solvent was measured by a plate method using a platinum plate using a surface tension meter CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.) as a measuring device. The surface tension at 25 ° C. of the following solvents measured by the above method is as follows.

PGMEA is an abbreviation for propylene glycol monomethyl ether acetate.
EEP is an abbreviation for ethyl 3-ethoxypropionate.
PGME is an abbreviation for propylene glycol monomethyl ether.
PE is an abbreviation for propylene glycol monoethyl ether.
PnP is an abbreviation for propylene glycol mono-n-propyl ether.
PnB is an abbreviation for propylene glycol mono-n-butyl ether.
DMM is an abbreviation for dipropylene glycol dimethyl ether.

[Preparation of Dispersion 1]
C. I. Pigment blue 15: 6, 10.2 parts by mass; I. 1.27 parts by mass of Pigment Violet 23, 24.42 parts by mass of propylene glycol monomethyl ether acetate (PGMEA), 14.62 parts by mass of cyclohexanone, 1.03 parts by mass of propylene glycol monomethyl ether, and resin P 1 is mixed with 2.54 parts by mass and mixed and dispersed for 3 hours with a bead mill (high-pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by Nippon BEE Co., Ltd.)). Prepared.
Resin P-1: Resin having the following structure (weight average molecular weight = 14000, the numerical values attached to the main chain are molar ratios)

[Preparation of colored composition]
The material shown in the following table | surface was mix | blended in the mass part as described in the following table | surface, and the coloring composition was manufactured. The content of the colorant and the content of the surfactant in the total solid content of the coloring composition are also described.

（光重合開始剤）
Ｉ−１：ＩＲＧＡＣＵＲＥ−ＯＸＥ０１（ＢＡＳＦ社製） The raw materials described in the above table are as follows.
(resin)
P-2: ACRYCURE RD-F8 (manufactured by Nippon Shokubai Co., Ltd.)
(Polymerizable compound)
M-1: Aronix TO-2349 (manufactured by Toagosei Co., Ltd.)
M-2: NK ester A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.)
(Surfactant)
S-1: The following mixture (Mw = 14000,% indicating the ratio of repeating units is% by mass)

(Photopolymerization initiator)
I-1: IRGACURE-OXE01 (manufactured by BASF)

<Measurement of contact angle (contact angle 1) with respect to organic layer of colored composition>
On the glass substrate, CT-4000 (manufactured by Fuji Film Electronics Materials) was applied and heated at 220 ° C. for 5 minutes to form an organic layer having a thickness of 0.1 μm. This organic layer had a contact angle of 60 to 80 degrees with respect to the organic layer measured 5 seconds after dropping 2 μL of water at 25 ° C.
Subsequently, after adjusting the surface temperature of the formed organic layer to 25 ° C., 2 μL of a colored composition at 25 ° C. was dropped on the surface of the organic layer. The contact angle of the colored composition with respect to the organic layer 5 seconds after dropping the colored composition on the surface of the organic layer was measured using a contact angle meter (Drop Master 701, manufactured by Kyowa Interface Science Co., Ltd.).

<Measurement of water contact angle (contact angle 2) with respect to the film formed using the colored composition>
The coloring composition was applied onto a silicon wafer and heated at 100 ° C. for 180 seconds to form a film having a thickness of 0.6 μm. After adjusting the surface temperature of this film to 25 ° C., 2 μL of 25 ° C. water was dropped on the surface of the film. The contact angle of water to the membrane 5 seconds after dropping water on the membrane surface was measured using a contact angle meter (Drop Master 701, manufactured by Kyowa Interface Science Co., Ltd.).

<Evaluation of striation and coating unevenness>
Using an etching method, a step (recess) pattern having a size of 3000 μm × 4000 μm and a depth of 1.5 μm is formed in a grid pattern on the entire surface of an 8-inch (1 inch = 2.54 cm) silicon wafer using the etching method. did. The gap between the steps was set to 100 μm.
The colored composition was applied onto the silicon wafer on which the step pattern was formed by spin coating, and heated at 100 ° C. for 120 seconds using a hot plate. Thereafter, it was further heated at 200 ° C. for 300 seconds using a hot plate.
Steps located at 1 to 28 shown in FIG. 1 were selected, and the corners of the steps were observed with an optical microscope (50 times). Of the four corners, the corner of the step that was farthest from the center of the silicon wafer was observed, and the striation and coating unevenness were evaluated according to the following criteria.
(Evaluation of striation)
A: No striation was observed in any part of 1 to 28 in FIG.
B: Striation was observed at any one of sites 1 to 28 in FIG.
(Evaluation of coating unevenness)
A: Coating unevenness was not observed in any part of 1 to 28 in FIG.
B: Coating unevenness was observed in any one of 1 to 28 in FIG.

<Evaluation of spectral characteristics>
The colored composition was applied onto a glass substrate by a spin coat method, and heated at 100 ° C. for 180 seconds using a hot plate. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at an exposure amount of 500 mJ / cm ² . Subsequently, it heated at 220 degreeC for 300 second using the hotplate, and the flat film | membrane with a film thickness of 0.6 micrometer was manufactured. About the obtained flat film, the transmittance | permeability of the light of the wavelength range of 400-700 nm was measured using the Otsuka Electronics Co., Ltd. multichannel spectrometer MCPD-3000. The case where the lowest value of the transmittance in the above range was 1.8% or more was designated as A, and the case where it was less than 1.8% was designated as B.

  From the above results, the examples had good coating properties and could suppress the occurrence of coating unevenness and striation. Furthermore, the spectral characteristics were also good.

Claims (10)

A coloring composition comprising a coloring agent A, a resin B, a curable compound C, a surfactant D, and a solvent E,
The content of the colorant A in the total solid content of the coloring composition is 40% by mass or less,
The solvent E includes a solvent E1 having a surface tension at 25 ° C. of 26.0 mN / m or more and 28.0 mN / m or less, and a solvent E2 having a surface tension at 25 ° C. of less than 26.0 mN / m,
The coloring composition whose contact angle of the coloring composition measured by the method which consists of the following process 1 and process 2 is more than 0 degree and 5.5 degrees or less;
Step 1: 2 μL of 25 ° C. water is dropped on a glass substrate to form an organic layer having a contact angle of 60 to 80 degrees with respect to the organic layer measured after 5 seconds;
Process 2: After adjusting the temperature of an organic substance layer to 25 degreeC, 2 microliters of 25 degreeC coloring compositions are dripped at the surface of an organic substance layer, and the contact angle with respect to the organic substance layer of the coloring composition 5 seconds after is measured.   The said surfactant D is a fluorine-type surfactant, and content of the said surfactant D in the total solid of the said colored composition is 0.001-0.20 mass%. Coloring composition. The coloring composition according to claim 1 or 2 , which is used for spin coating. The coloring composition according to any one of claims 1 to 3, wherein the colorant A contains a blue pigment. The colored composition according to any one of claims 1 to 4, wherein the solvent E2 is at least one selected from butyl acetate, propyl acetate, isopropyl acetate, ethyl acetate, and methyl acetate. The coloring composition of any one of Claims 1-4 whose said solvent E2 is butyl acetate. The coloring composition according to any one of claims 1 to 6, wherein the solvent E1 is at least one selected from propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether. The colored composition according to any one of claims 1 to 4, wherein the solvent E1 is at least one selected from propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether, and the solvent E2 is butyl acetate. The manufacturing method of a film | membrane including the process of apply | coating the coloring composition of any one of Claims 1-8 to a support body. Furthermore, the manufacturing method of the film | membrane of Claim 9 including the process of forming a pattern.

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