JP7128087B2 - Photosensitive coloring composition, black matrix, and organic electroluminescent display device - Google Patents

Description

TECHNICAL FIELD The present invention relates to a photosensitive coloring composition used for forming a black matrix of an organic electroluminescence display device comprising a silicon substrate, a color filter and a black matrix formed on the silicon substrate.

In recent years, in electronic devices such as mobile phones and personal digital assistants, organic EL, which is a self-luminous element, has been developed in order to meet the demand for further thinning and weight reduction and curved surface display, which was difficult for current mainstream liquid crystal display devices. Development and mass production of display devices using (organic electroluminescence) are progressing. Among them, in order to take advantage of thinness and lightness, it is expected to be applied to high-definition and small displays of about 0.5 inches (hereinafter referred to as microdisplays) such as head-mounted displays and electronic viewfinders.

In the display method of the organic EL display, there is a method in which a white light-emitting layer is formed and a color filter and a black matrix are used to express colors such as RGB. There are two main methods for doing this. Since microdisplays have fine pixels, it is very difficult to selectively form RGB light-emitting layers. Therefore, a system using a color filter and a black matrix for the white light emitting layer is actively adopted for the microdisplay.

Since the pixel size of microdisplays is as small as 1 μm to 10 μm, conventional methods of fabricating organic EL elements, color filters, and black matrices on separate substrates and bonding them together would result in reduced precision and color shifts. end up Therefore, a method of forming a color filter and a black matrix on an organic EL element has been proposed.

Color filters and black matrices are produced by ink-jet methods, photolithography methods, and the like, and the photolithography method, which enables the formation of fine pixels, is increasingly being adopted. However, since the organic light-emitting layer has low heat resistance, it needs to be baked at a low temperature in order to form a color filter on the organic EL element. Specifically, in the conventional photolithography method, baking is performed at a very high temperature of 230° C., but baking at about 100° C. is required. However, if the baking temperature of the colored pixels is lowered, curing becomes insufficient, and problems such as peeling of the colored pixels and surface roughening due to the solvent contained in the applied coloring composition occur during pixel formation in the next step. On the other hand, when the exposure amount is increased, the reaction of the cross-linking component contained in the colored pixels progresses and curing progresses, but it is very difficult to form pixels of any size.

In order to solve the above-mentioned problems, for example, Patent Document 1 proposes a method of increasing curability at low temperature by using a colored composition containing an alkali-soluble resin containing an epoxy group and an amine compound. However, the addition of an amine compound to the coloring composition may reduce the transmittance of the color filter. Further, Patent Document 2 proposes a method of curing at a low temperature by using an oxetane compound and a benzophenone-based compound having a peroxide skeleton.

In order to improve the light-shielding properties of the black matrix, it is necessary to increase the content of dye in the photosensitive black composition or increase the film thickness. However, in the method of increasing the content of the dye, problems such as a decrease in sensitivity and deterioration in developability and resolution occur. In the method of increasing the thickness of the film, exposure light does not reach the bottom of the film, resulting in problems such as poor pattern shape. In order to solve such problems, it is necessary to increase the sensitivity of the photosensitive black composition. Alternatively, the amount is increased. However, there is a limit to how much the sensitivity can be improved by simply selecting or increasing the amount of the photopolymerization initiator, sensitizer, and monomer. In particular, when the amount of the photopolymerization initiator is increased, coloring due to the color peculiar to the photopolymerization initiator, deterioration in heat resistance, reduction in light transmittance, deterioration in resolution, and the like occur. Further, when the amount of the monomer is increased, problems such as tackiness arise.

In order to solve the above-mentioned problems, for example, Patent Document 3 proposes a method of using two or more kinds of organic pigments and a highly sensitive photopolymerization initiator to achieve high light shielding properties and to improve patterning characteristics with high sensitivity. .

JP 2012-063745 A JP-A-2003-255531 JP 2013-207124 A

A cured film of a colored composition containing carbon black (CB) is widely used as a black matrix used in color filters of liquid crystal display devices and the like. However, in a colored composition containing CB, it was difficult for the photocuring reaction to proceed deep into the coating film due to the light absorption of the CB. Therefore, the black matrix had to be post-baked at a high temperature (eg, 230° C.). In the organic electroluminescence display device, since the heat resistance of the light-emitting element is low, the method of forming the color filter and the black matrix on the organic EL element as described above cannot be post-baked at a high temperature, and the curing reaction does not occur. could not be promoted enough. On the other hand, when the intensity of light irradiation is increased, there is a problem that a pattern with a good shape cannot be formed due to excessive exposure.
In Patent Documents 1 and 2 described above, the curing temperature of the composition is 150° C. or higher, and further low-temperature curability is required in consideration of the heat resistance of the organic EL device. Also, in order to achieve high color reproducibility with a thin film, it is necessary to increase the colorant density of the color filter. With the methods of Patent Documents 1 to 3, it is very difficult to achieve sufficient sensitivity for patterning when the colorant concentration is high.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a photosensitive coloring composition which has high sensitivity, excellent patterning properties (resolution) and solvent resistance even when the concentration of the coloring agent is high.

That is, the present invention provides a photosensitive coloring composition used for forming a black matrix of an organic electroluminescence display device comprising a silicon substrate, a color filter and a black matrix formed on the silicon substrate,
containing a coloring agent (A), a photopolymerization monomer (B), a photopolymerization initiator (C), and a resin (D),
The coloring agent (A) contains at least a blue pigment, a yellow pigment and a purple pigment,
The photopolymerizable monomer (B) contains a compound represented by the following general formula (1),
The resin (D) is composed of a hydroxyl group of a compound (a) having two hydroxyl groups and one thiol group in the molecule and an acid anhydride group of pyromellitic anhydride and/or trimellitic anhydride. In the presence of a reaction product, a hydroxyl group of a hydroxyl group-containing polymer obtained by polymerizing an ethylenically unsaturated monomer (c) containing a hydroxyl group-containing ethylenically unsaturated monomer (b), one isocyanate group and one A resin obtained by reacting an isocyanate group of a compound (d) having one or more (meth)acryloyl groups, wherein the content of structural units derived from the hydroxyl group-containing ethylenically unsaturated monomer (b) is , a photosensitive coloring composition containing a photosensitive acrylic resin (E) that is 35% by mass or more and 80% by mass or less with respect to the total amount of structural units derived from the ethylenically unsaturated monomer (c).
General formula (1)
[ _CH2 =CHC(=O)-( _OCmH2m ) _{n - OCH2} ] _{3 - CCH2CH3}
(In general formula (1), m represents an integer of 1 to 3, n represents an integer of 0 to 2, and multiple m and n may be the same or different.)

In one embodiment of the photosensitive coloring composition, the blue pigment is Pigment Blue 15:6, the yellow pigment is Pigment Yellow 139, and the violet pigment is Pigment Violet 23.

One embodiment of the photosensitive coloring composition, relative to the total amount of the coloring agent (A), 32 to 45% by weight of the blue pigment, 30 to 40% by weight of the yellow pigment, and 20 to 30% by weight of the purple pigment include.

In one embodiment of the photosensitive coloring composition, the photopolymerization initiator (C) contains an oxime ester photopolymerization initiator represented by the following general formula (2).

（一般式（２）中、Ｚは直接結合、又は－Ｃ（＝Ｏ）－基を表し、Ｒ^１は置換基を有してもよい炭素数１～２０のアルキル基を表し、Ｒ^２は置換基を有してもよい炭素数１～２０のアルキル基、又は置換基を有してもよいアリール基を表し、Ｒ^３～Ｒ^１０はそれぞれ独立して、水素原子、置換基を有してもよい炭素数１～２０のアルキル基、置換基を有してもよいアリール基、ニトロ基、又はＲ^１１－Ｃ（＝Ｏ）－基を表す。Ｒ^１１は置換基を有してもよいアリール基を表す。）

(In general formula (2), Z represents a direct bond or a -C(=O)- group, R ¹ represents an optionally substituted alkyl group having 1 to 20 carbon atoms, and R ² represents represents an optionally substituted alkyl group having 1 to 20 carbon atoms or an optionally substituted aryl group, wherein each of R ³ to R ¹⁰ independently has a hydrogen atom and a substituent; represents an alkyl group having ¹ to ²⁰ carbon atoms which may be represents a good aryl group.)

The present invention relates to a black matrix formed from the photosensitive coloring composition.

The present invention also relates to an organic electroluminescence display comprising the black matrix.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a photosensitive coloring composition which has high sensitivity and excellent patterning properties (resolution) and solvent resistance even when the concentration of the coloring agent is high.

FIG. 4 is a schematic cross-sectional view showing an example of a black matrix; FIG. 4 is a schematic plan view showing an example of a black matrix; 1 is a schematic cross-sectional view showing an example of an organic EL display device; FIG.

Each constituent component of the photosensitive coloring composition of the present invention is described below.
In the present application, when "(meth)acryloyl", "(meth)acryl", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide""acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate", or "acrylamide and/or methacrylamide", respectively, unless shall be represented. Moreover, "C.I." mentioned in this specification means a color index (C.I.).

1. Photosensitive coloring composition The photosensitive coloring composition of the present invention is a photosensitive coloring composition used for forming a black matrix of an organic electroluminescent display device comprising a silicon substrate, a color filter and a black matrix formed on the silicon substrate. There is
containing a coloring agent (A), a photopolymerization monomer (B), a photopolymerization initiator (C), and a resin (D),
The coloring agent (A) contains at least a blue pigment, a yellow pigment and a purple pigment,
The photopolymerizable monomer (B) contains a compound represented by the following general formula (1),
Reaction of the hydroxyl group of the compound (a) in which the resin (D) has two hydroxyl groups and one thiol group in the molecule and the acid anhydride group of pyromellitic anhydride and/or trimellitic anhydride. In the presence of the product, the hydroxyl group of the hydroxyl group-containing polymer obtained by polymerizing the ethylenically unsaturated monomer (c) containing the hydroxyl group-containing ethylenically unsaturated monomer (b), one isocyanate group and one It is a resin obtained by reacting the above (meth)acryloyl group-containing compound (d) with an isocyanate group, and the content of structural units derived from the hydroxyl group-containing ethylenically unsaturated monomer (b) is ethylenic It is characterized by containing a photosensitive acrylic resin (E) in an amount of 35% by mass or more and 80% by mass or less based on the total amount of structural units derived from the unsaturated monomer (c).

General formula (1)
[ _CH2 =CHC(=O)-( _OCmH2m ) _{n - OCH2} ] _{3 - CCH2CH3}
(In general formula (1), m represents an integer of 1 to 3, n represents an integer of 0 to 2, and multiple m and n may be the same or different.)

<Colorant (A)>
The coloring agent (A) in the present invention contains at least blue pigments, yellow pigments and violet pigments, and various organic pigments can be used as long as the effects of the present invention are not impaired. In the present invention, a black photosensitive coloring composition that can be applied to a black matrix can be obtained by combining the above pigments as colorants. In addition, since the photosensitive resin composition allows light to easily reach deep portions of the coating film during light irradiation, the obtained cured film is excellent in solvent resistance and adhesiveness.

(organic pigment)
Examples of blue pigments include C.I. I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like. Among these, C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, or 15:6, more preferably C.I. I. Pigment Blue 15:3, C.I. I. Pigment Blue 15:6.

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

Examples of purple pigments include C.I. I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like. Among these, C.I. I. Pigment Violet 19 or 23, more preferably C.I. I. Pigment Violet 23.

In particular, the coloring agent (A) in the present invention is C.I. I. A combination of Pigment Blue 15:6 with Pigment Yellow 139 and Pigment Violet 23 is preferred.
Further, the ratio of the coloring agent (A) is preferably 32 to 45% by mass of blue pigment, 30 to 40% by mass of yellow pigment, and 20 to 30% by mass of violet pigment.

(Refinement of pigment)
When a pigment is used as the colorant (A), it is preferable to use the pigment in a fine form. Examples of the refinement method include salt milling treatment and the like.

The salt milling process involves milling a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent while heating using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, and sand mill. In this method, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water after kneading thoroughly. It is believed that the water-soluble inorganic salt acts as a crushing aid, and the high hardness of the inorganic salt is used during salt milling to crush the pigment, thereby generating an active surface and causing crystal growth. Therefore, during kneading, crushing and crystal growth of the pigment occur at the same time, and the primary particle size of the pigment obtained differs depending on the kneading conditions.

A heating temperature of 40 to 150° C. is preferable for promoting crystal growth by heating. If the heating temperature is less than 40° C., crystal growth does not occur sufficiently, and the shape of the pigment particles becomes nearly amorphous, which is not preferable. On the other hand, if the heating temperature exceeds 150° C., crystal growth may proceed excessively and the primary particle size of the pigment may increase. The kneading time for the salt milling treatment is preferably 2 to 24 hours from the viewpoint of the balance between the particle size distribution of the primary particles of the salt milling pigment and the cost required for the salt milling treatment.

By optimizing the conditions for the salt milling treatment of the pigment, a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution can be obtained.

The particle size of the pigment is determined by TEM (transmission electron microscope). The average primary particle size of the pigment is preferably 20-100 nm. If it is smaller than 20 nm, it becomes difficult to disperse in an organic solvent. Also, when the thickness is larger than 100 nm, a sufficient contrast ratio may not be obtained. The average primary particle size of the pigment is particularly preferably 25-85 nm.

Examples of water-soluble inorganic salts used in salt milling include sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like. Among them, sodium chloride (salt) is preferable from the point of price.

The amount of the water-soluble inorganic salt to be used is preferably 50 to 2000 parts by mass, more preferably 300 to 1000 parts by mass, based on 100 parts by mass of the pigment, in terms of both processing efficiency and production efficiency.

The water-soluble organic solvent has the function of moistening the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (miscible in) water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point solvent having a boiling point of 120° C. or higher is preferable from the viewpoint of safety. Water-soluble organic solvents include, for example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. mentioned.

The water-soluble organic solvent is preferably 5 to 1,000 parts by mass, more preferably 50 to 500 parts by mass, per 100 parts by mass of the pigment.

The salt milling process may add resin as needed. Examples of the types of resins include natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like. The resin is preferably solid at room temperature (25° C.) and water-insoluble. Furthermore, it is preferable that the polymer is partially soluble in the above organic solvent.
The amount of the resin used is preferably 5 to 200 parts by mass with respect to 100 parts by mass of the pigment.

<Photopolymerization monomer (B)>
The photopolymerizable monomer (B) contains at least a compound represented by the following general formula (1).
General formula (1)
[ _CH2 =CHC(=O)-( _OCmH2m ) _{n - OCH2} ] _{3 - CCH2CH3}
(In general formula (1), m represents an integer of 1 to 3, n represents an integer of 0 to 2, and multiple m and n may be the same or different.)

The content of the photopolymerizable monomer (B) is preferably 5 to 30% by weight with respect to the total non-volatile matter in the photosensitive coloring composition. When the thickness is within the above range, peeling does not occur when forming a fine pattern, and the tapered portion of the pattern is prevented from being elongated, so that a fine pixel pattern with high definition can be formed. Furthermore, the content of the compound represented by the general formula (1) contained in the photopolymerization monomer (B) is preferably 50 to 100% by mass with respect to the total amount of the photopolymerization monomer (B), and 60 % or more by mass is more preferable. By setting the amount within the above range, excellent adhesion of the coating film to the substrate during development and chemical resistance can be obtained.

(Other photopolymerizable monomers)
Moreover, the photopolymerizable monomer (B) may contain other photopolymerizable monomers. Other photopolymerizable monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxy Ethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, pentaerythritol tri(meth) Acrylates, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipenta Erythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, ester acrylate, methylolated melamine (meth)acrylate, epoxy (meth)acrylate and other acrylic acid esters and methacrylic acid ester, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, acrylonitrile etc., but not limited to these.
These photopolymerizable monomers may be used singly or as a mixture of two or more at any ratio as required.

<Photoinitiator (C)>
In the present invention, the photopolymerization initiator (C) is cured by ultraviolet irradiation and used for preparation in the form of a solvent-developable or alkali-developable photosensitive coloring composition capable of forming filter segments by photolithography. A photosensitive coloring composition having excellent properties and chemical resistance and good patterning properties can be obtained. In the present invention, the photopolymerization initiator (C) preferably contains an oxime ester photopolymerization initiator.

(Oxime ester photopolymerization initiator)
In the oxime ester photopolymerization initiator, upon absorption of ultraviolet rays, the N—O bond of the oxime is cleaved to generate iminyl radicals and alkyloxy radicals. Since these radicals are further decomposed to generate highly active radicals, a pattern can be formed with a small amount of exposure. When the colorant concentration of the photosensitive coloring composition is high, the ultraviolet transmittance of the coating film may be low and the degree of curing of the coating film may be low, but the oxime ester photopolymerization initiator is suitable because it has a high quantum efficiency. is. Among them, an oxime ester photopolymerization initiator represented by the following general formula (2) or (3) is preferable, and an oxime ester photopolymerization initiator represented by general formula (2) is more preferable.

[Oxime ester photopolymerization initiator represented by formula (2)]

(In general formula (2), Z represents a direct bond or a -C(=O)- group, R ¹ represents an optionally substituted alkyl group having 1 to 20 carbon atoms, and R ² represents represents an optionally substituted alkyl group having 1 to 20 carbon atoms or an optionally substituted aryl group, wherein each of R ³ to R ¹⁰ independently has a hydrogen atom and a substituent; represents an alkyl group having ¹ to ²⁰ carbon atoms which may be represents a good aryl group.)

Substituents that may be present include, for example, halogen groups such as fluorine, chlorine, bromine and iodine atoms; alkoxy groups such as methoxy, ethoxy and tert-butoxy groups; phenoxy and p-tolyloxy groups. alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group; acetyl group, benzoyl group, isobutyryl group, acryloyl group, acyl groups such as methacryloyl group and methoxalyl group; alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group; arylsulfanyl groups such as phenylsulfanyl group and p-tolylsulfanyl group; alkyl groups such as methylamino group and cyclohexylamino group Amino group; dimethylamino group, diethylamino group, morpholino group, dialkylamino group such as piperidino group; phenylamino group, arylamino group such as p-tolylamino group; methyl group, ethyl group, tert-butyl group, dodecyl group, cyclo Alkyl groups such as propyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclooctadecyl group; phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group aryl groups such as furyl group, heterocyclic group such as thienyl group, etc., hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammoniumyl group, dimethylsulfoniumyl group, triphenylphenacylphosphoniumyl group and the like.
One or more or more than one of these substituents may be present, and hydrogen atoms of these substituents may be further substituted with other substituents.

R ¹ is preferably an optionally substituted alkyl group having 1 to 20 carbon atoms. R ² is preferably an optionally substituted alkyl group having 1 to 20 carbon atoms or an optionally substituted aryl group. R ³ to R ¹⁰ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted aryl group, a nitro group, or R ¹¹ —CO - group is preferred, among which R ³ to R ⁹ are more preferably hydrogen atoms, R ¹⁰ is preferably a hydrogen atom or R ¹¹ -CO- group, and R ¹¹ -CO- group is more preferred. R ¹¹ is preferably an optionally substituted aryl group.

Examples of the oxime ester photopolymerization initiator represented by the general formula (2) include compounds represented by the following chemical formulas (2-1) and (2-2).

[Oxime ester photopolymerization initiator represented by general formula (3)]

（一般式（３）において、Ｒ^２１及びＲ^２２は、それぞれ独立して、水素原子、置換基を有してもよい炭素数１～２０のアルキル基、又は置換基を有してもよいアリール基であり、Ｒ^２３及びＲ^２４は、それぞれ独立して、水素原子、置換基を有してもよい炭素数１～２０のアルキル基、又は置換基を有してもよいアリール基であり、Ｒ^２５は、水素原子、置換基を有してもよい炭素数１～２０のアルキル基、置換基を有してもよいアリール基、又はＲ^２６－ＣＯ－基であり、Ｒ^２６は、置換基を有してもよい炭素数１～２０のアルキル基、置換基を有してもよいアリール基、又は複素環基である。）

(In general formula (3), R ²¹ and R ²² are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted aryl and R ²³ and R ²⁴ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted aryl group, R ²⁵ is a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted aryl group, or an R ²⁶ —CO— group, and R ²⁶ is a substituted an alkyl group having 1 to 20 carbon atoms which may have a group, an aryl group which may have a substituent, or a heterocyclic group.)

The alkyl group having 1 to 20 carbon atoms for R ²¹ to R ²⁶ can be the same as the alkyl group having 1 to 20 carbon atoms for R ¹ to R ¹⁰ .
The aryl groups for R ²¹ to R ²⁶ can be the same as the aryl groups for R ² to R ¹¹ above.

Examples of the heterocyclic ring in the heterocyclic group represented by R ²⁶ include furan, thiophene, pyrrole, oxazole, thiazole, imidazole, pyrazole, pyran, pyrone, pyridine, pyrone, pyridazine, pyrimidine, pyrazine, benzofuran, thionaphthene, indole, carbazole, coumarin, quinoline, phthalazine, quinoxaline and the like.
Further, the substituents that the alkyl group and the aryl group may have may be the same as the substituents in the general formula (2).

In the oxime ester photopolymerization initiator represented by the general formula (3), R ²¹ is an optionally substituted aryl group, and R ²² is a C 1-20 optionally substituted aryl group. It is preferably an alkyl group, R ²³ and R ²⁴ are hydrogen atoms, R ²⁵ is a hydrogen atom, or an R ²⁶ —CO— group.

Examples of the oxime ester photopolymerization initiator represented by the general formula (3) include photopolymerization initiators represented by the following chemical formula (3-1).

(Other photopolymerization initiators)
Moreover, the photopolymerization initiator (C) in the present invention may contain other photopolymerization initiators. Other photopolymerization initiators include, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1- one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl) Acetophenone compounds such as methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone or 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4- Benzophenone compounds such as benzoyl-4′-methyldiphenyl sulfide or 3,3′,4,4′-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone , 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine , 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl- 4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl) )-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or Triazine compounds such as 2,4-trichloromethyl-(4′-methoxystyryl)-6-triazine; bis(2,4,6-trimethylbenzoyl)phenylphosphine oxy or phosphine compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds Compounds; titanocene-based compounds and the like.
These photopolymerization initiators can be used singly or as a mixture of two or more at any ratio.

Moreover, you may use a commercial item. As acetophenone-based compounds, "IRGACURE 907" (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one) and "IRGACURE 369" (2-( dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone), “IRGACURE 379” 2-benzyl-2-dimethylamino-1-( 4-morpholinophenyl)-butan-1-one and phosphine-based compounds are all manufactured by BASF and include "IRGACURE 819" (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide) and "IRGACURE TPO" ( 2,4,6-trimethylbenzoyldiphenylphosphine oxide), and the like.

The content of the photopolymerization initiator (C) is preferably 2 to 50 parts by mass, more preferably 2 to 30 parts by mass with respect to 100 parts by mass of the colorant, from the viewpoint of photocurability and developability. If it is less than 2 parts by mass, the adhesion of the formed pattern to the base material will be poor, and if it exceeds 50 parts by mass, a problem in resolution may occur.

<Sensitizer>
Furthermore, the photosensitive coloring composition of the present invention may contain a sensitizer.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone; 1,2-diketone derivatives such as benzyl and camphorquinone; benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene. derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, sub- phthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler ketone derivatives, α-acyloxyesters, acylphosphine oxides, methyl phenyl glyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butyl per oxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone and the like.

Among the above sensitizers, thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives are exemplified as sensitizers that are particularly suitable for sensitization. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4′-bis (Dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- Examples include N-ethylcarbazole and the like.

Commercially available products include "KAYACURE DETX-S" (2,3-diethylthioxanthone, manufactured by Nippon Kayaku Co., Ltd.) and "EAB-F" (4,4'-bis(diethylamino)benzophenone, manufactured by Hodogaya Chemical Industry Co., Ltd.). be done.

More specifically, edited by Shin Okawara et al., "Dye Handbook" (1986, Kodansha), edited by Shin Okawara et al., "Chemistry of Functional Dyes" (1981, CMC), Chuzaburo Ikemori et al. Special Functional Materials" (1986, CMC), but are not limited to these. In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region may also be used.
These sensitizers can be used singly or as a mixture of two or more at any ratio.

The content when using a sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator contained in the photosensitive coloring composition from the viewpoint of photocurability and developability, and 5 to 50 parts by mass is more preferable.

<Resin (D)>
In the present invention, the resin (D) is a resin having a transmittance of preferably 80% or more, more preferably 95% or more, in the entire wavelength region of 400 to 700 nm in the visible light region. In the present invention, the resin (D) contains at least a specific photosensitive acrylic resin (E) described later, and may contain other resins. In terms of functions, the resin (D) can be used as a resin-type dispersant and a binder resin. The resin (D) is preferably used as a resin-type dispersant. Moreover, the resin (D) includes a photosensitive acrylic resin, and in terms of properties, thermoplastic resins, thermosetting resins, photosensitive resins, and the like can be mentioned.
As for the resin (D), other resins will be described first, and then the photosensitive acrylic resin (E) will be described.

Examples of thermoplastic resins include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. , acrylic resins, alkyd resins, polystyrene, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, polybutadiene, polyimide resins, and the like.

Examples of thermosetting resins include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenolic resins.

As a photosensitive acrylic resin different from the photosensitive acrylic resin (E), a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, an amino group, etc. is reacted with an isocyanate group, an aldehyde group, an epoxy group, etc. Resins obtained by reacting a (meth)acrylic compound or cinnamic acid having a functional substituent to introduce photocrosslinkable groups such as (meth)acryloyl groups and styryl groups into the linear polymer, and styrene-maleic anhydride copolymers. Polymers and linear polymers containing acid anhydrides such as α-olefin-maleic anhydride copolymers are half-esterified with (meth)acrylic compounds having hydroxyl groups such as hydroxyalkyl (meth)acrylates. .

The photosensitive acrylic resin preferably has an ethylenically unsaturated double bond and a carboxyl group. In particular, by using a resin into which an ethylenically unsaturated double bond is introduced by the method (i) or (ii) shown below, the resin is three-dimensionally crosslinked when exposed to active energy rays to form a coating film. This increases the crosslink density and improves chemical resistance.

[Method (i)]
As method (i), for example, a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and one or more other monomers, The carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond is subjected to an addition reaction, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to introduce an ethylenically unsaturated double bond and a carboxyl group. There is a way.

Ethylenically unsaturated monomers having an epoxy group include, for example, glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate. , and 3,4-epoxycyclohexyl (meth)acrylate, which may be used alone or in combination of two or more. Glycidyl (meth)acrylate is preferred from the viewpoint of reactivity with the unsaturated monobasic acid in the next step.

Examples of unsaturated monobasic acids include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted (meth)acrylic acid. and the like, and these may be used alone or in combination of two or more.

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. These may be used alone or in combination of two or more. may In order to increase the number of carboxyl groups, if necessary, use a tricarboxylic anhydride such as trimellitic anhydride, or use a tetracarboxylic dianhydride such as pyromellitic dianhydride to remove the remaining anhydride. A hydrolyzed group may be used. In addition, when a polybasic acid anhydride having an ethylenically unsaturated double bond, such as tetrahydrophthalic anhydride or maleic anhydride, is used, the number of ethylenically unsaturated double bonds can be further increased.

As a method similar to method (i), for example, the side chain carboxyl of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and one or more other monomers There is a method in which an ethylenically unsaturated monomer having an epoxy group is added to a part of the group to introduce an ethylenically unsaturated double bond and a carboxyl group.

[Method (ii)]
As method (ii), an ethylenically unsaturated monomer having a hydroxyl group is used, and an unsaturated monobasic acid monomer having another carboxyl group, or obtained by copolymerizing other monomers There is a method of reacting the side chain hydroxyl group of the copolymer with the isocyanate group of an ethylenically unsaturated monomer having an isocyanate group.

Ethylenically unsaturated monomers having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, glycerol Hydroxyalkyl methacrylates such as mono(meth)acrylates and cyclohexanedimethanol mono(meth)acrylates may be mentioned, and these may be used alone or in combination of two or more. In addition, polyether mono(meth)acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide, etc. to the above hydroxyalkyl (meth)acrylate, poly γ-valerolactone, poly ε-caprolactone, and/or Polyester mono(meth)acrylates added with poly-12-hydroxystearic acid or the like can also be used. 2-Hydroxyethyl methacrylate or glycerol mono(meth)acrylate is preferred from the viewpoint of suppressing coating film foreign substances. From the viewpoint of sensitivity, it is preferable to use one having 2 to 6 hydroxyl groups, and glycerol mono(meth)acrylate is more preferable.

Examples of the ethylenically unsaturated monomer having an isocyanate group include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, 1,1-bis[methacryloyloxy]ethyl isocyanate and the like. , but not limited to. The ethylenically unsaturated monomer having the isocyanate group can be used alone or in combination of two or more.

Monomers constituting the photosensitive acrylic resin include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, ) acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate , phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethyleneglycol (meth)acrylate, methoxypolypropyleneglycol (meth)acrylate, or ethoxypolyethyleneglycol (meth)acrylate (meth)acrylates (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or (meth)acrylamide such as acryloylmorpholine Styrenes such as styrene and α-methylstyrene; Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether; Fatty acid vinyls such as vinyl acetate or vinyl propionate, etc. ;

Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide coumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4- Phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimide N-substituted maleimides such as hexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine;
Compounds represented by the following general formula (4), specifically EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, phenolic ethylene oxide (EO)-modified (meth)acrylate , EO- or propylene oxide (PO)-modified (meth)acrylates of paracumylphenol, EO-modified (meth)acrylates of nonylphenol, and PO-modified (meth)acrylates of nonylphenol.

（一般式（４）中、Ｒ^１２は、水素原子、又はメチル基であり、Ｒ^１３は、炭素数２～３のアルキレン基であり、Ｒ^１４は、ベンゼン環を有していてもよい炭素数１～２０のアルキル基であり、ｎは１～１５の整数である。）

(In general formula (4), R ¹² is a hydrogen atom or a methyl group, R ¹³ is an alkylene group having 2 to 3 carbon atoms, and R ¹⁴ is a carbon atom optionally having a benzene ring. is an alkyl group of numbers 1 to 20, and n is an integer of 1 to 15.)

A carboxyl group-containing ethylenically unsaturated monomer may also be used. Carboxyl group-containing ethylenically unsaturated monomers include, for example, acrylic acid, methacrylic acid, ε-caprolactone-added acrylic acid, ε-caprolactone-added methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid.

Moreover, you may use a hydroxyl-containing ethylenically unsaturated monomer. Examples of hydroxyl group-containing ethylenically unsaturated monomers include 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3-, or 4-hydroxybutyl (meth)acrylate, cyclohexane Hydroxyalkyl (meth)acrylates such as dimethanol mono(meth)acrylate can be mentioned. In addition, polyether mono(meth)acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide, etc. to the above hydroxyalkyl (meth)acrylate, (poly)γ-valerolactone, (poly)ε-caprolactone , and/or (poly)ester mono(meth)acrylate to which (poly)12-hydroxystearic acid or the like is added.

Phosphate ester group-containing ethylenically unsaturated monomers may also be used. Examples of the phosphate ester group-containing ethylenically unsaturated monomer include, for example, monomers obtained by reacting the hydroxyl group of the hydroxyl group-containing ethylenically unsaturated monomer with a phosphate esterifying agent such as phosphorus pentoxide and polyphosphoric acid. is mentioned.

In the present invention, the resin (D) preferably contains a photosensitive acrylic resin. The photosensitive acrylic resin improves the chemical resistance and solvent resistance after curing the colored composition. The photosensitive acrylic resin is preferably a photosensitive acrylic resin (E). The photosensitive acrylic resin (E) will be described below.

<Photosensitive acrylic resin (E)>
The photosensitive acrylic resin (E) is composed of the hydroxyl group of the compound (a) having two hydroxyl groups and one thiol group in the molecule, and the acid anhydride groups of pyromellitic anhydride and/or trimellitic anhydride. , In the presence of the reaction product, the hydroxyl group of the hydroxyl group-containing polymer obtained by polymerizing the ethylenically unsaturated monomer (c) containing the hydroxyl group-containing ethylenically unsaturated monomer (b), and one isocyanate group and the isocyanate group of the compound (d) having one or more (meth)acryloyl groups, the content of structural units derived from the hydroxyl group-containing ethylenically unsaturated monomer (b) is 35% by mass or more and 80% by mass or less based on the total amount of structural units derived from the ethylenically unsaturated monomer (c).
By including the photosensitive acrylic resin (E), the chemical resistance and solvent resistance after curing the photosensitive coloring composition are further improved.

Photosensitive acrylic resin (E) is a reaction product of a hydroxyl group of compound (a) having two hydroxyl groups and one thiol group and an acid anhydride group of pyromellitic anhydride and/or trimellitic anhydride. followed by an ethylenically unsaturated monomer (c ) is radically polymerized to produce a hydroxyl group-containing polymer into which a vinyl polymer moiety having a hydroxyl group is introduced, and a compound (d) having one isocyanate group and one or more (meth)acryloyl groups. It is obtained by going through the third step, which is a reaction with A plurality of carboxyl group moieties in the photosensitive acrylic resin (E) function as pigment adsorption moieties, and vinyl polymer moieties function as solvent affinity moieties.

The photosensitive acrylic resin (E) undergoes multiple reactions such as reaction between hydroxyl groups and acid anhydride groups, radical polymerization reaction using residual thiol groups as chain transfer agents, and reaction between residual hydroxyl groups and isocyanate groups. It has a complicated structure obtained by the following method, and it is impossible or almost unrealistic to express it with a general formula (structure), so it is described by the manufacturing method.

(Compound (a) having two hydroxyl groups and one thiol group in the molecule)
As the compound (a) having two hydroxyl groups and one thiol group in the molecule, 3-mercapto-1,2-propanediol (also known as 1-thioglycerol) can be preferably used.

A known catalyst can be used as a catalyst for reacting the acid anhydride group of pyromellitic anhydride and/or trimellitic anhydride with the hydroxyl group. For example, triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo-[5.4.0]-7-undecene, 1,5-diazabicyclo-[4.3.0 ]-5-nonene, monobutyltin oxide and the like.

Next, the thiol group remaining in the reaction product of the hydroxyl group of compound (a) having two hydroxyl groups and one thiol group and the acid anhydride group of pyromellitic anhydride and/or trimellitic anhydride. as a chain transfer agent, a hydroxyl group-containing ethylenically unsaturated monomer (c) containing a hydroxyl group-containing ethylenically unsaturated monomer (b) is radically polymerized to introduce a hydroxyl group-containing ethylenically unsaturated monomer The second step of producing the polymer will be explained. By copolymerizing the hydroxyl-containing ethylenically unsaturated monomer (b) in the second step, a hydroxyl group can be introduced into the vinyl polymer portion of the dispersant, and in the third step, one isocyanate group and a compound (d) having one or more (meth)acryloyl groups.

(Hydroxyl group-containing ethylenically unsaturated monomer (b))
The hydroxyl group-containing ethylenically unsaturated monomer (b) is a monomer having a hydroxyl group and an ethylenically unsaturated double bond. As the hydroxyl group-containing ethylenically unsaturated monomer (b), for example, a (meth)acrylate monomer having a hydroxyl group, a (meth)acrylamide monomer having a hydroxyl group, a vinyl ether monomer having a hydroxyl group, a hydroxyl group Allyl ether-based monomers having
(Meth)acrylate monomers having a hydroxyl group include, for example, 2-hydroxyethyl (meth)acrylate, 2 (or 3)-hydroxypropyl (meth)acrylate, 2 (or 3 or 4)-hydroxybutyl (meth) ) acrylate, hydroxyalkyl (meth)acrylate such as cyclohexanedimethanol mono(meth)acrylate; alkyl-α-hydroxyalkyl acrylate such as ethyl-α-hydroxymethyl acrylate, and the like.
(Meth)acrylamide-based monomers having a hydroxyl group include, for example, N-(2-hydroxyethyl)(meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, N-(2-hydroxybutyl) N-(hydroxyalkyl)(meth)acrylamide such as (meth)acrylamide and the like.
Vinyl ether monomers having a hydroxyl group include, for example, hydroxyalkyl vinyl ethers such as 2-hydroxyethyl vinyl ether, 2-(or 3-) hydroxypropyl vinyl ether, 2-(or 3- or 4-) hydroxybutyl vinyl ether, and the like. mentioned.
Examples of allyl ether monomers having a hydroxyl group include 2-hydroxyethyl allyl ether, 2-(or 3-) hydroxypropyl allyl ether, 2-(or 3- or 4-) hydroxybutyl allyl ether and hydroxyalkyl allyl ethers such as

(Other ethylenically unsaturated monomers)
The ethylenically unsaturated monomer (c) may contain other ethylenically unsaturated monomers other than the hydroxyl group-containing ethylenically unsaturated monomer (b). Other ethylenically unsaturated monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2,2,4-trimethylcyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate , Alkyl (meth)acrylates such as isobornyl (meth)acrylate;
aromatic (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and phenoxydiethylene glycol (meth)acrylate;
Heterocyclic (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate;
Alkoxypolyalkylene glycol (meth)acrylates such as methoxypolypropylene glycol (meth)acrylate and ethoxypolyethylene glycol (meth)acrylate;
(N-substituted) such as (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, diacetone (meth)acrylamide, acryloylmorpholine ( meth) acrylamides;
N,N-dimethylaminoethyl (meth)acrylate, amino group-containing (meth)acrylates such as N,N-diethylaminoethyl (meth)acrylate;
Nitriles such as (meth)acrylonitrile;
styrenes such as styrene, α-methylstyrene and indene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl ether;
Fatty acid vinyls such as vinyl acetate and vinyl propionate;
Examples include carboxyl group-containing ethylenically unsaturated monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid. These monomers can be used singly or in combination of two or more.

The content of the hydroxyl group-containing ethylenically unsaturated monomer (b) is preferably 35% by mass or more and 80% by mass or less with respect to the total amount of the ethylenically unsaturated monomers (c).

Next, the third step of reacting the hydroxyl group-containing polymer with the compound (d) having one isocyanate group and one or more (meth)acryloyl groups will be described. The photosensitive acrylic resin (E) is obtained by reacting the hydroxyl groups in the hydroxyl group-containing polymer with the isocyanate groups in the compound (d) having one isocyanate group and one or more (meth)acryloyl groups. Thereby, a (meth)acryloyl group can be arbitrarily introduced mainly into the vinyl polymer portion in the photosensitive acrylic resin (E), and functions as a curable dispersant having curable properties at the solvent affinity portion.

(Compound (d) having one isocyanate group and one or more (meth)acryloyl groups)
The compound (d) having one isocyanate group and one or more (meth)acryloyl groups used in the third step can have an isocyanate group and one or more (meth)acryloyl groups. , and other structures are not particularly limited. Among them, compounds having one isocyanate group and one or two (meth)acryloyl groups are preferred, and 2-methacryloyloxyethyl isocyanate and 2-acryloyloxyethyl isocyanate are more preferred. Compound (d) having one isocyanate group and one or more (meth)acryloyl groups may be used alone or in combination of two or more.

A resin having an oxetane group may also be used as the resin (D). A resin having an oxetane group can be obtained, for example, by copolymerizing an ethylenically unsaturated monomer having an oxetane group. Ethylenically unsaturated monomers having an oxetane group include (3-methyl-3-oxetanyl)methyl (meth)acrylate, (3-ethyl-3-oxetanyl)methyl (meth)acrylate, (3-butyl-3 -oxetanyl)methyl (meth)acrylate, (3-hexyltyl-3-oxetanyl)methyl (meth)acrylate and the like.
Examples of commercially available ethylenically unsaturated monomers having an oxetane group include ETERNACOLL OXMA (manufactured by Ube Industries, Ltd.), OXE-10, and OXE-30 (manufactured by Osaka Organic Chemical Industry Co., Ltd.). Since the resin has an oxetane group, the colored composition containing the resin has excellent heat resistance after curing.

The content of the resin (D) is 1-400 parts by mass, preferably 1-300 parts by mass, per 100 parts by mass of the colorant (A) in the photosensitive coloring composition.

<Antioxidant>
The photosensitive coloring composition of the present invention may contain an antioxidant. Antioxidants prevent the photopolymerization initiators and thermosetting compounds contained in the photosensitive coloring composition from yellowing due to oxidation during heating processes such as thermal curing and ITO annealing, resulting in coating films with high transmittance. can get.

In the present invention, the "antioxidant" includes compounds having ultraviolet absorption function, radical scavenging function and peroxide decomposition function. Specifically, antioxidants include hindered phenol, hindered amine, phosphorus, sulfur, benzotriazole, benzophenone, hydroxylamine, salicylate, and triazine compounds. Ultraviolet absorbers, antioxidants, and the like can be used.

Among these antioxidants, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant or a sulfur antioxidant is preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. and more preferably a hindered phenol antioxidant, a hindered amine antioxidant, or a phosphorus antioxidant.

Hindered phenol antioxidants include 2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di -t-butylanilino)-1,3,5-triazine, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,6-di-t-butyl-4- nonylphenol, 2,2'-isobutylidene-bis-(4,6-dimethyl-phenol), 4,4'-butylidene-bis-(2-t-butyl-5-methylphenol), 2,2'-thio- Bis-(6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2' thiodiethylbis-(3,5-di-t-butyl-4-hydroxyphenyl )-propionate, 1,1,3-tris-(2′-methyl-4′-hydroxy-5′-t-butylphenyl)-butane, 2,2′-methylene-bis-(6-(1-methyl -cyclohexyl)-p-cresol), 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol, N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydro cinnamamide) and the like. In addition, oligomer type and polymer type compounds having a hindered phenol structure may also be used.

Hindered amine antioxidants include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine, 2-methyl-2-(2,2,6,6-tetramethyl-4 -piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)(1,2,3, 4-butanetetracarboxylate, poly[{6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl}{(2,2,6,6 -tetramethyl-4-piperidyl)imino}hexamethyl{(2,2,6,6-tetramethyl-4-piperidyl)imino}], poly[(6-morpholino-1,3,5-triazine-2,4 -diyl) {(2,2,6,6-tetramethyl-4-piperidyl)imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl)imino}], dimethyl succinate and 1- Polycondensate with (2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N -(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine and the like. In addition, oligomer type and polymer type compounds having a hindered amine structure may also be used.

Phosphorus antioxidants include tris(isodecyl)phosphite, tris(tridecyl)phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi(tridecyl)phosphite, diphenylisooctylphosphite, diphenylisodecyl phosphite, diphenyltridecylphosphite, triphenylphosphite, tris(nonylphenyl)phosphite, 4,4' isopropylidenediphenol alkylphosphite, trisnonylphenylphosphite, trisdinonylphenylphosphite, tris(2 ,4-di-t-butylphenyl)phosphite, tris(biphenyl)phosphite, distearylpentaerythritol diphosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di(nonyl phenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 1,1,3- Tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, sodium bis(4-t-butylphenyl) Phosphite, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, ethyl bis(2, 4-di-tert-butyl-6-methylphenyl) and the like. In addition, oligomer type and polymer type compounds having a phosphite structure may also be used.

Sulfur antioxidants include 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]- o-cresol, 2,4-bis[(laurylthio)methyl]-o-cresol and the like. In addition, oligomer type and polymer type compounds having a thioether structure may also be used.

Benzotriazole-based antioxidants include oligomer-type and polymer-type compounds having a benzotriazole structure.

Benzophenone antioxidants include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4 -octadecyloxybenzophenone, 2,2'dihydroxy-4-methoxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4 -methoxy-5 sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-chlorobenzophenone and the like. In addition, oligomer type and polymer type compounds having a benzophenone structure may also be used.

Triazine-based antioxidants include 2,4-bis(allyl)-6-(2-hydroxyphenyl)1,3,5-triazine and the like. In addition, oligomer type and polymer type compounds having a triazine structure may also be used.

Salicylic acid ester-based antioxidants include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate, and the like. In addition, oligomer type and polymer type compounds having a salicylic acid ester structure may also be used.

These antioxidants can be used singly or as a mixture of two or more at any ratio.

The content of the antioxidant is preferably 0.5 to 5.0 mass % based on the non-volatile mass of the photosensitive coloring composition. Within the above range, the brightness and sensitivity are improved.

<Adhesion improver>
The photosensitive coloring composition of the present invention may contain an adhesion improver such as a silane coupling agent in order to improve adhesion to the substrate. By improving the adhesion, fine line reproducibility is improved and the resolution is improved.

Examples of adhesion improvers include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane; 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, (Meth)acrylsilanes such as methacryloxypropyltriethoxysilane and 3-acryloxypropyltrimethoxysilane; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3 - epoxysilanes such as glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane; N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane; Silane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl- butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, and other aminosilanes; 3-mercaptopropylmethyldimethoxy; mercaptos such as silane and 3-mercaptopropyltrimethoxysilane; styryls such as p-styryltrimethoxysilane; ureides such as 3-ureidopropyltriethoxysilane; sulfides such as bis(triethoxysilylpropyl)tetrasulfide and silane coupling agents such as isocyanates such as 3-isocyanatopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, per 100 parts by weight of the colorant in the coloring composition. Within this range, the effect is large, and the balance between adhesion, resolution and sensitivity is good.

<Leveling agent>
The photosensitive coloring composition of the present invention may contain a leveling agent in order to improve the leveling properties of the composition on the transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in its main chain is preferred. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Dow Corning Toray Co., Ltd. and BYK-333 manufactured by BYK Chemie. Specific examples of dimethylsiloxane having a polyester structure include BYK-310 and BYK-370 manufactured by BYK-Chemie. A dimethylsiloxane having a polyether structure in the main chain and a dimethylsiloxane having a polyester structure in the main chain may be used in combination. The content of the leveling agent is usually preferably 0.003 to 0.5% by mass based on the total mass of the coloring composition (100% by mass).

Especially preferred as a leveling agent is a type of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a hydrophilic group but has low solubility in water, and when added to a coloring composition, the surface tension It is useful to have a low ability to lower the surface tension and good wettability to the glass plate despite the low ability to lower the surface tension. can be preferably used. Dimethylpolysiloxane having polyalkylene oxide units is preferred as a leveling agent having such preferred properties. Examples of polyalkylene oxide units include polyethylene oxide units and polypropylene oxide units, and dimethylpolysiloxane may have both polyethylene oxide units and polypropylene oxide units.

An anionic, cationic, nonionic, or amphoteric surfactant may be added to the leveling agent. Surfactants can be used singly or in combination of two or more.
Examples of the anionic surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, sodium alkyldiphenyl ether disulfonate, and monoethanol lauryl sulfate. amine, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate, and the like.

Examples of the cationic surfactant include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate. , polyethylene glycol monolaurate; alkylbetaines such as alkyldimethylaminoacetic acid betaine; amphoteric surfactants such as alkylimidazoline; and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Moreover, the photosensitive coloring composition may contain a curing agent, a curing accelerator, etc., as necessary, in order to assist the curing of the thermosetting resin. Examples of curing agents include phenol-based resins, amine-based compounds, acid anhydrides, active esters, carboxylic acid-based compounds, sulfonic acid-based compounds and the like, but are not particularly limited to these, and thermosetting resins and Any curing agent that can be reacted will suffice. Among these, compounds having two or more phenolic hydroxyl groups in one molecule and amine curing agents are preferred. Examples of the curing accelerator include amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl -N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives bicyclic amidine compounds and salts thereof (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2- ethyl-4-methylimidazole, etc.), phosphorus compounds (e.g., triphenylphosphine, etc.), guanamine compounds (e.g., melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (e.g., 2,4-diamino-6 -methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6- methacryloyloxyethyl-S-triazine/isocyanuric acid adduct, etc.). These may be used individually by 1 type, and may use 2 or more types together. The content of the curing accelerator is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the thermosetting resin.

<Other additive ingredients>
The photosensitive coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity over time. In addition, an adhesion improver such as a silane coupling agent may be contained in order to improve adhesion to the transparent substrate.

Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine; organic acids such as lactic acid and oxalic acid and their methyl ethers; t-butylpyrocatechol, tetraethylphosphine, tetraphenylphosphine and the like. organic phosphines; phosphites; The storage stabilizer is usually used in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the colorant.

Examples of adhesion improvers include vinylsilanes such as vinyltris(β-methoxyethoxy)silane, vinylethoxysilane and vinyltrimethoxysilane; (meth)acrylsilanes such as γ-methacryloxypropyltrimethoxysilane; 4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)methyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane; N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino ethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-amino silane coupling agents such as aminosilanes such as propyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane; and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The amount of the adhesion improver is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, per 100 parts by weight of the colorant in the coloring composition.

<Solvent>
The photosensitive coloring composition of the present invention is obtained by sufficiently dispersing and permeating a coloring agent in a coloring agent carrier, and coating a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm to form a colored film. It preferably contains a solvent to facilitate the formation of the The solvent is selected in consideration of good applicability of the photosensitive coloring composition, solubility of each component of the photosensitive coloring composition, and safety.

Examples of solvents include 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1, 4-butanediol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5- trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3- methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone , ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol Monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate , diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol Methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol Diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate , benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid esters, and the like.
These solvents can be used alone or as a mixture of two or more at any ratio.

Among them, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol diacetate, and ethylene glycol monomethyl ether are preferred because they have good dispersibility and permeability of colorants and good applicability of photosensitive compositions. Acetates such as acetate, ethylene glycol monoethyl ether acetate, 1,3-butylene glycol diacetate, cyclohexanol acetate, 1,4-butanediol diacetate, butanediol diacetate; benzyl alcohol, diacetone alcohol, 1-methoxy alcohols such as 2-propanol and 3-methoxybutanol; ketones such as cyclohexanone; and ethyl 3-ethoxypropionate.

The content of the solvent is 500 to 4,000 parts by mass with respect to 100 parts by mass of the colorant, in order to adjust the viscosity of the photosensitive coloring composition to an appropriate level and form a colored film having the desired uniform thickness. preferable.

<Method for producing a photosensitive coloring composition>
The photosensitive coloring composition in the present invention is obtained by dispersing a coloring agent in a resin and/or solvent, preferably together with a dispersing aid, through a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, It can be produced by finely dispersing it using various dispersing means such as an annular bead mill or an attritor (colorant dispersion). At this time, the colorant dispersion may be obtained by mixing the colorant (A) and other colorants or the like, or the colorant dispersion may be obtained by dispersing the colorants of each color and then mixing them. In addition, when the coloring agent has high solubility, specifically, when the coloring agent has high solubility in the solvent to be used and is in a state in which no foreign matter is confirmed by dissolution by stirring, it is necessary to finely disperse and manufacture as described above. no.

Moreover, when using a photosensitive coloring composition as a resist material, it can be prepared as a solvent development type or alkali development type coloring composition. The solvent-developable or alkali-developable colored composition can be obtained by mixing the colorant dispersion, a photopolymerization monomer and/or a photopolymerization initiator, and optionally a solvent and other components. can. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

[Dispersing aid]
When dispersing the colorant, a dispersing aid such as a pigment derivative, a resin-type dispersant, or a surfactant may be added as appropriate. Since the dispersing aid has a great effect of preventing reaggregation of the colorant after dispersion, the photosensitive coloring composition containing the dispersing aid has good brightness and viscosity stability.

(dye derivative)
Examples of dye derivatives include organic pigments, anthraquinones, acridones or triazines into which a basic substituent, an acidic substituent, or a phthalimidomethyl group optionally having a substituent is introduced. 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-2001-335717, JP-A-2003- 128669, JP 2004-091497, JP 2007-156395, JP 2008-094873, JP 2008-094986, JP 2008-095007, JP 2008-195916 Those described in publications, Japanese Patent No. 4585781 and the like can be used. These can be used alone or in combination of two or more.

From the viewpoint of improving the dispersibility, the content of the pigment derivative is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and still more preferably 3 parts by mass or more with respect to 100 parts by mass of the colorant. From the viewpoint of heat resistance and light resistance, the amount is preferably 40 parts by mass or less, more preferably 35 parts by mass or less.

(resin type dispersant)
The resin-type dispersant has a colorant-affinity site that has the property of adsorbing to the colorant and a site that is compatible with solvents and resins, and acts to adsorb to the colorant to stabilize the dispersion of the colorant. It is intended to Resin-type dispersants include polycarboxylic acid esters such as polyurethanes and polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes. , long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly(lower alkyleneimine) with polyesters having free carboxyl groups, and oily salts thereof Water-soluble resins such as dispersants, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone, and water-soluble soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide/propylene oxide adducts, phosphoric acid esters, and the like. These can be used alone or in combination of two or more.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by BYK-Chemie Japan. , 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK -P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, SOLSPERSE manufactured by Nippon Lubrizol Co., Ltd.-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 241000, 2 ,26000,27000,28000,31845,32000,32500,32550,33500,32600,34750,35100,36600,38500,41000,41090,53095,55000,76500 etc. EFKA-486, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. Ajinomoto Fine-Techno Co., Ltd. Ajisper PA111, PB711, PB821, PB822, PB824, etc. is mentioned.

(Surfactant)
Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenylether disulfonate. , monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, anionic surfactants such as polyoxyethylene alkyl ether phosphate; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; cationic surfactants such as quaternary ammonium salts and ethylene oxide adducts thereof; alkylbetaines such as alkyldimethylaminoacetic acid betaine; and amphoteric surfactants such as alkylimidazoline. These can be used alone or in combination of two or more.

When a dispersing aid is added, the blending amount is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass, per 100 parts by mass of the colorant. When the content of the dispersing aid is less than 0.1 parts by mass, the effect of the addition is difficult to obtain, and when the content is more than 55 parts by mass, the dispersing aid becomes excessive.

<Removal of coarse particles>
The photosensitive coloring composition after dispersion is separated into coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more by means of centrifugation, filtration with a sintered filter or membrane filter, or the like. Removal of particles and entrained dust is preferred. The photosensitive coloring composition preferably contains substantially no particles of 0.5 μm or more, more preferably no particles of 0.3 μm or more.

2. Black Matrix The black matrix according to the present invention is characterized by being formed from the photosensitive coloring composition of the present invention. Since the black matrix of the present invention is formed using the photosensitive coloring composition, it has low visible light transmittance and is excellent in solvent resistance and adhesiveness.

A black matrix of the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of a substrate provided with a black matrix of the present invention. FIG. 2 is a schematic plan view showing an example of a substrate provided with the black matrix of the present invention. In the example of FIGS. 1 and 2, the black matrix 2 of the present invention is formed in a pattern having openings 3 on a substrate 1 to constitute a black matrix substrate 10. FIG. A colored layer of a color filter, which will be described later, is formed in the opening 3 . 1 and 2 show an example in which the black matrix 2 is formed on the substrate 1, but in an organic electroluminescent display device described later, instead of the substrate 1, an organic EL layer or an organic EL layer It is preferably formed on a flat layer formed thereon. The photosensitive coloring composition of the present invention can form a sufficiently cured black matrix without post-baking at a high temperature, even when formed directly on an organic EL layer or a laminate containing an organic EL layer. Even so, the deterioration of the organic EL element during the formation of the black matrix is suppressed.

The pattern of the black matrix is not particularly limited, and may be adjusted according to the arrangement of the colored layers described below. Although the thickness of the black matrix is not particularly limited, it is usually 0.2 to 2 μm. Although the line width of the black matrix is not particularly limited, it is preferably a fine line, specifically 0.4 to 1.0 μm.

The black matrix of the present invention is formed on the organic EL layer or on a flat layer provided as necessary. The flattening layer is a layer for flattening the fine uneven surface of the organic EL layer. A well-known curable resin can be used for the flat layer, preferably an ultraviolet curable resin, and if necessary, a thermosetting resin may be used together. Although the ultraviolet curable resin is not particularly limited, an acrylic resin exhibiting sensitivity to the i-line (wavelength of 365 nm) is preferable.

A method for forming the black matrix is not particularly limited, but for example, the following method can be used. First, the photosensitive coloring composition described above is applied by a known coating method such as spray coating, dip coating, bar coating, call coating, spin coating, or the like to form a coating film.
Next, after drying the coating film as necessary, it is exposed through a mask of a predetermined pattern to photopolymerize a photopolymerizable monomer or a photosensitive acrylic resin to form a cured coating film. do. Light sources used for exposure include, for example, ultraviolet light from low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, electron beams, and the like. The amount of exposure may be appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
Moreover, in order to accelerate the polymerization reaction after exposure, heat treatment may be performed. Since the photosensitive composition has low-temperature curability, it can be sufficiently cured even by heat treatment at 100° C. or less.

3. Organic Electroluminescence Display Device An organic EL display device of the present invention is characterized by comprising the black matrix of the present invention.
The configuration of the organic EL display device will be described with reference to FIG. FIG. 3 is a schematic cross-sectional view of the organic EL display device of this embodiment. An organic EL display device 11 of this embodiment has an organic EL layer 5 and a color filter 6 having a black matrix 2 on a silicon substrate 4 on which drive elements are formed. A sealing layer 7 and a cover glass 8 may be provided on the color filter 6, and the flat layer (planar) may be provided between the organic EL layer 5 and the color filter 6 (Fig. not shown).
Details of each configuration of the organic EL display device will be described below.

[Color filter]
A color filter 6 is formed on the organic EL layer 5 and normally comprises red pixels, green pixels and blue pixels (6a, 6b, 6c). In this implementation, the color filter may further have magenta pixels, cyan pixels, yellow pixels, or other pixels.

<Manufacturing method of color filter>
In this embodiment, the color filters 6 are formed on the organic EL layer 5 on which the black matrix 2 is formed, or on the flat layer.

Although the method of forming the pixels constituting the color filter is not particularly limited, the following method can be used, for example.
First, a photosensitive coloring composition for each color pixel is prepared. The photosensitive coloring composition can be appropriately selected from known ones. Moreover, in the photosensitive coloring composition for the black matrix, the coloring agent may be changed for pixels.

The prepared photosensitive coloring composition for pixels is applied to the organic EL layer or flat layer using a coating method such as a spray coating method, a dip coating method, a bar coating method, a call coating method, a spin coating method, and a coating film to form
Next, after drying the coating film as necessary, it is exposed through a mask of a predetermined pattern to photopolymerize a photopolymerizable monomer or a photosensitive acrylic resin to form a cured coating film. and Light sources used for exposure include, for example, ultraviolet light from low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, electron beams, and the like. The amount of exposure may be appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
Moreover, in order to accelerate the polymerization reaction after exposure, heat treatment may be performed. By using the same composition as the photosensitive composition for the black matrix except for the colorant, the composition can be sufficiently cured even by heat treatment at 100° C. or lower. The film thickness of the pixels forming the color filter is usually 1.0 μm to 2.0 μm.

[Organic EL layer]
The organic EL layer 5 can be formed of an organic light emitting single layer or multiple layers containing a light emitting material. When formed in multiple layers, for example, a general three-layer structure in which a hole transport layer, an electron transporting organic light-emitting layer, and an electron transport layer are sequentially stacked, a hole (electron) injection layer, a hole ( A multi-layer structure may be employed in which an electron) transport layer and a layer having separate injection and transport functions are provided, or a layer for blocking hole (electron) transport is provided.

An example of the organic EL layer is a structure in which an anode, an organic layer, and a cathode are laminated in order from the silicon substrate side, and airtightly covered with a sealing layer.

The anode is provided on the silicon substrate and made of a conductive material with a large work function. Examples of conductive materials with a large work function include nickel, silver, gold, platinum, palladium, selenium, rhodium, ruthenium, iridium, rhenium, tungsten, molybdenum, chromium, tantalum, niobium, alloys thereof, and tin oxide ( SnO ₂ ), indium tin oxide (ITO), zinc oxide, titanium oxide, and the like.

The cathode is constructed using a conductive material with a small work function. As such a conductive material, for example, an alloy of an active metal such as Li, Mg, or Ca and a metal such as Ag, Al, or In, or a structure in which these are laminated can be used. Alternatively, a thin compound layer of active metal such as Li, Mg or Ca and halogen such as fluorine or bromine or oxygen may be inserted between the organic layer.

The anode and cathode are patterned into a suitable shape according to the driving method of the display device. For example, when the drive system of the organic EL display device is a simple matrix type, the anode and the cathode are formed in stripes that intersect with each other, and the intersection of these stripes becomes the organic EL element.

The organic layer has at least a white light-emitting layer, and is usually composed of a plurality of layers of organic layers. It may have a charge transport layer such as a hole transport layer that transports holes and an electron transport layer that transports electrons to the white light emitting layer. The organic layer can be of any known configuration having a white light-emitting layer.

A known layer that emits white light can be used as the light-emitting layer. Emission characteristics of white color should include emission in at least three regions of red region (600 nm to 780 nm), green region (475 nm to 600 nm), and blue region (380 nm to 475 nm). The number of emission peaks does not necessarily need to be three or more. For example, two emission peaks may be used as long as they emit light in the above region. However, in order to obtain wide color reproducibility, it is preferable to use a white light-emitting layer having three or more emission peaks, and one or more of the above three color regions preferably has an emission peak.

A material constituting such a white light-emitting layer is not particularly limited as long as it emits fluorescence or phosphorescence. Moreover, the light-emitting material may have a hole-transport property or an electron-transport property. Examples of light-emitting materials include dye-based materials, metal complex-based materials, and polymer-based materials.

Examples of the dye-based materials include cyclopentamine derivatives, tetraphenylbutadiene derivatives, triphenylamine derivatives, oxadiazole derivatives, pyrazoloquinoline derivatives, distyrylbenzene derivatives, distyrylarylene derivatives, silole derivatives, thiophene ring compounds, pyridine. Ring compounds, perinone derivatives, perylene derivatives, oligothiophene derivatives, trifmanylamine derivatives, oxadiazole dimers, pyrazoline dimers, and the like.

Examples of the metal complex-based materials include aluminum quinolinol complexes, benzoquinolinol beryllium complexes, benzoxazole zinc complexes, benzothiazole zinc complexes, azomethyl zinc complexes, porphyrin zinc complexes, and europium complexes, or Al, Zn, and Be as central metals. or a metal complex having a rare earth metal such as Tb, Eu, Dy, etc., and a ligand having an oxadiazole, thiadiazole, phenylpyridine, phenylbenzimidazole, quinoline structure, or the like.

Examples of the polymer materials include polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyfluorene derivatives, polyvinylcarbazole derivatives, and the dye materials and metal complex materials described above. Molecularized ones and the like can be mentioned.

Examples of the method for forming the white light-emitting layer include a vapor deposition method, a printing method, an inkjet method, a spin coating method, a casting method, a dipping method, a bar coating method, a blade coating method, a roll coating method, a gravure coating method, and flexographic printing. method, spray coating method, self-assembly method (alternate adsorption method, self-assembled monolayer method), and the like. In particular, it is preferable to use a vapor deposition method, a spin coating method, and an inkjet method. The film thickness of the white light-emitting layer is usually about 5 nm to 5 μm.

The organic EL layer may also include a hole injection layer between the white light emitting layer and the anode. By providing the hole-injection layer, the injection of holes into the white light-emitting layer is stabilized, and the light emission efficiency can be increased. As a material for forming the hole injection layer, a material generally used for the hole injection layer of an organic EL element can be used. Further, the material for forming the hole injection layer may be any material that has either hole injection properties or electron blocking properties.

Specifically, materials for forming the hole injection layer include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, polysilane-based, aniline-based copolymers, and conductive polymer oligomers such as thiophene oligomers.

Furthermore, examples of materials for forming the hole injection layer include porphyrin compounds, aromatic tertiary amine compounds, and styrylamine compounds. The film thickness of the hole injection layer is usually about 5 nm to 1 μm.

The organic EL layer may also comprise an electron injection layer formed between the white light emitting layer and the cathode. By providing the electron injection layer, the injection of electrons into the white light emitting layer can be stabilized and the luminous efficiency can be improved.

Materials for forming the electron injection layer include, for example, nitro-substituted fluorene derivatives, anthraquinodimethane derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, heterocyclic tetracarboxylic acid anhydrides such as naphthalene perylene, carbodiimides, and fluorenylidene methane derivatives. , anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, thiazole derivatives in which the oxygen atom of the oxadiazole ring of the oxadiazole derivative is substituted with a sulfur atom, and quinoxaline derivatives having a quinoxaline ring known as an electron-withdrawing group. , metal complexes of 8-quinolinol derivatives such as tris(8-quinolinol)aluminum, phthalocyanines, metal phthalocyanines, and distyrylpyrazine derivatives.

The following examples illustrate the invention. "Parts" and "%" in the examples represent "parts by mass" and "% by mass", respectively. "PGMAc" means propylene glycol monomethyl ether acetate.

First, prior to Examples, methods for producing a resin-type dispersant, a binder resin solution, a colorant, a pigment dispersion, and a photosensitive coloring composition will be described. Moreover, the method for measuring the weight average molecular weight (Mw) and acid value of the resin is as follows.

(Weight average molecular weight)
The weight-average molecular weight (Mw) of the resin is measured using a TSKgel column (manufactured by Tosoh Corporation) with a GPC (manufactured by Tosoh Corporation, HLC-8320GPC) equipped with an RI detector, using THF as a developing solvent. Weight average molecular weight (Mw).

(acid number)
The resin acid value is a value obtained by converting the measured acid value (mgKOH/g) into the non-volatile content according to the potentiometric titration method of JIS K 0070.

<Production of acrylic resin solution>
(Acrylic resin solution 1)
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer, 8 parts of 3-mercapto-1,2-propanediol, 12 parts of pyromellitic anhydride, 80 parts of propylene glycol monomethyl ether acetate (PGMAc), a catalyst 0.2 part of monobutyltin oxide was charged as a solution, and after purging with nitrogen gas, the reaction was carried out at 120° C. for 5 hours (first step). It was confirmed by acid value measurement that 95% or more of the acid anhydride was half-esterified. Then, 15 parts of methyl methacrylate (MMA), 10 parts of t-butyl acrylate (tBA), 10 parts of ethyl acrylate (EA), 5 parts of methacrylic acid (MAA), 10 parts of benzyl methacrylate (BzMA), 2-hydroxyethyl methacrylate 50 parts of (HEMA) was charged, the inside of the reaction vessel was heated to 80° C., 1 part of 2,2′-azobis(2,4-dimethylvaleronitrile) was added, and the mixture was reacted for 12 hours (second step). It was confirmed by measuring the non-volatile content that 95% had reacted. Next, the inside of the flask was replaced with air, 54.0 parts of 2-methacryloyloxyethyl isocyanate (MOI) and 0.1 part of hydroquinone were charged, and a reaction was carried out at 70° C. for 4 hours (third step). After confirming the disappearance of the peak at 2270 cm ⁻¹ based on the isocyanate group by IR, the reaction solution was cooled and the nonvolatile content was adjusted with PGMAc to obtain acrylic resin solution 1, which is a photosensitive acrylic resin having a nonvolatile content of 40%. Obtained. The obtained acrylic resin had an acid value of 36 and a weight average molecular weight of 12,000.

(Acrylic resin solution 2)
30 parts of ethyl acrylate, 20 parts of tert-butyl acrylate and 40 parts of 2-methyl methacrylate were charged into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer, and the contents were purged with nitrogen gas. The inside of the reaction vessel was heated to 80° C., and a solution of 6 parts of 3-mercapto-1,2-propanediol and 0.1 part of 2,2′-azobisisobutyronitrile dissolved in 45.7 parts of cyclohexanone was prepared. was added and reacted for 10 hours. It was confirmed by measuring the non-volatile content that 95% had reacted. At this time, the weight average molecular weight was 4,000. Next, add 9.7 parts of pyromellitic dianhydride, 70 parts of PGMAc, and 0.20 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst, and react at 120° C. for 7 hours. let me It was confirmed by acid value measurement that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. After completion of the reaction, a PGMAc solution (acrylic resin solution 2) of an acrylic resin having a weight average molecular weight of 8,100, an acid value of 50 mgKOH/g, and a glass transition temperature of the vinyl polymerization site of 22.5°C was prepared to have a nonvolatile content of 40% by mass. got

(Acrylic resin solution 3)
196 parts of cyclohexanone was charged into a reaction vessel equipped with a separable 4-necked flask, a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirring device, heated to 80°C, and after replacing the inside of the reaction vessel with nitrogen, dropwise. From the tube, 20.0 parts of benzyl methacrylate, 17.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (manufactured by Toagosei Co., Ltd. " Aronix M110”) 20.7 parts and 1.1 parts of 2,2′-azobisisobutyronitrile were added dropwise over 2 hours. After completion of dropping, the reaction was continued for 3 more hours to obtain an acrylic resin solution.
After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the nonvolatile content. Acrylic resin solution 3 was prepared by adding ether acetate. The weight average molecular weight (Mw) was 26,000.

<Production of colorant (A)>
(Micronized blue pigment (B1))
phthalocyanine blue pigment C.I. I. Pigment Blue 15:6 (“LIONOL BLUE ES” manufactured by Toyocolor Co., Ltd., specific surface area 60 m ² /g) 200 parts, 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), The mixture was kneaded at 80°C for 6 hours. Next, this kneaded product is put into 8000 parts of hot water and stirred for 2 hours while heating to 80°C to form a slurry, which is repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 85°C for a day and night. , to obtain a phthalocyanine-based finely divided blue pigment (B1).

(Micronized yellow pigment (Y1))
yellow pigment C.I. I. 200 parts of Pigment Yellow 139 (“Pariotol Yellow D1819” manufactured by BASF), 1400 parts of sodium chloride and 360 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80° C. for 6 hours. Next, this kneaded product is put into 8000 parts of hot water and stirred for 2 hours while heating to 80°C to form a slurry, which is repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 85°C for a day and night. , to obtain a finely divided yellow pigment (Y1).

(Micronized yellow pigment (Y2))
azo yellow pigment C.I. I. Pigment Yellow 150 (PY150, LANXESS "E-4GN") 100 parts, pulverized salt 500 parts, and diethylene glycol 250 parts were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70°C for 4 hours. This mixture is poured into 5000 parts of warm water, heated to about 80°C and stirred with a high-speed mixer for about 1 hour to form a slurry, which is repeatedly filtered and washed with water to remove salt and solvent, then heated at 80°C for 24 hours. It was dried to obtain 490 parts of a yellow finely divided pigment (Y2).

(Miniaturized purple pigment (V1))
dioxazine-based purple pigment C.I. I. Pigment Violet 23 (“LIONOGEN VIOLET RL” manufactured by Toyocolor Co., Ltd.) 200 parts, sodium chloride 1400 parts, and diethylene glycol 360 parts were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80° C. for 6 hours. Next, this kneaded product is put into 8000 parts of hot water and stirred for 2 hours while heating to 80°C to form a slurry, which is repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 85°C for a day and night. , a dioxazine-based finely divided purple pigment (V1) was obtained.

<Production of pigment dispersion>
(Pigment Dispersion (BP-1))
After stirring and mixing the following mixture uniformly, using zirconia beads with a diameter of 0.5 mm, after dispersing for 3 hours with an Eiger mill (manufactured by Eiger Japan Co., Ltd. "Mini Model M-250 MKII"), 5.0 μm to prepare a pigment dispersion (BP-1) having a non-volatile content of 20% by mass.
Micronized blue pigment (B1): 14.0 parts Acrylic resin solution 1: 11.0 parts Acrylic resin solution 3: 8.0 parts Propylene glycol monomethyl ether acetate: 67.0 parts

(Production of pigment dispersions (BP-2, YP1-4, VP-1-2))
Pigment dispersions (BP-2, YP1 to 4, VP-1 to 2) in the same manner as the pigment dispersion (BP-1) except that the composition and the amount (parts by mass) were changed to those shown in Table 1. got

黒色顔料Ｃ１：カーボンブラック
（ＣＡＢＯＴ社製「Ｒｅｇａｌ２５０Ｒ」）

Black pigment C1: carbon black ("Regal250R" manufactured by CABOT)

[Example 1]
(Production of photosensitive coloring composition (BLK-1))
The following mixture (total of 100 parts) was uniformly stirred and mixed, and filtered through a 1.0 μm filter to obtain a photosensitive coloring composition (BLK-1).
Pigment dispersion (BP-1): 22.5 parts C.I. I. Pigment Blue PB15:6
Pigment dispersion (YP-1): 24.4 parts C.I. I. Pigment Yellow PY139
Pigment dispersion (VP-1): 18.3 parts C.I. I. Pigment Violet PV23
Photopolymerization monomer (B-1): 4.2 parts Toagosei Co., Ltd. "Aronix M-309"
Photopolymerization initiator (C-2): 0.7 parts BASF "Irgacure OXE-02"
(ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime))
Leveling agent solution: 1.0 part Dow Corning Toray Co., Ltd. "FZ-2122"
(Solution obtained by diluting 1 part (non-volatile content 100% by mass) with 99 parts of cyclohexanone)
Solvent: 28.9 parts propylene glycol monomethyl ether acetate

[Examples 2 to 13, Comparative Examples 1 to 6]
(Production of photosensitive coloring composition (BLK-2 to 19))
A photosensitive coloring composition (BLK-2 to 19) was obtained in the same manner as the photosensitive coloring composition (BLK-1) except that the composition and the blending amount (parts by mass) were changed to those shown in Table 2. .

Abbreviations in Table 2 are shown below.
<Photopolymerization monomer (B)>
Photopolymerizable monomer B-1: trimethylolpropane triacrylate (“Aronix M-309” manufactured by Toagosei Co., Ltd.) (m = 1, n = 0 in general formula (1))
Photopolymerizable monomer (B-2): trimethylolpropane EO-modified triacrylate ("Aronix M-350" manufactured by Toagosei Co., Ltd.) (in general formula (1), m = 2, n = 1)
Photopolymerizable monomer (B-3): dipentaerythritol hexaacrylate ("Aronix M-402" manufactured by Toagosei Co., Ltd.)
<Photoinitiator (C)>
Photopolymerization initiator (C-1): compound represented by general formula (3)/1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime)] (manufactured by BASF) "IRGACURE OXE 01")
Photopolymerization initiator C-2: compound represented by chemical formula (2)/ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime) (“IRGACURE OXE 02” manufactured by BASF)
Photopolymerization initiator (C-3): a compound represented by the following chemical formula (2-2)

光重合開始剤（Ｃ－４）：２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１（ＢＡＳＦ社製「ＩＲＧＡＣＵＲＥ ３６９」）

Photopolymerization initiator (C-4): 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (manufactured by BASF "IRGACURE 369")

<Evaluation of photosensitive coloring composition>
[Evaluation of light transmittance measurement]
Each of the resulting photosensitive coloring compositions was applied onto a glass substrate of 100 mm×100 mm and 0.7 mm thick using a spin coater, and prebaked by heat treatment on a hot plate at 70° C. for 1 minute. Further, after heating on a hot plate at 100° C. for 15 minutes and cooling, a coated substrate having a film thickness of 1.2 μm was obtained. For the resulting coated substrate, the light transmittance at a wavelength of 400 to 1000 nm was measured using a spectrophotometer ("U-3900" manufactured by Hitachi High-Tech Science Co., Ltd.), and the maximum light transmittance at a wavelength of 400 to 650 nm ( Tmax (400 to 650 nm)) and the maximum value of light transmittance (Tmax (650 to 730 nm)) in the wavelength range of 650 to 730 nm were determined and evaluated in the following two stages. Table 3 shows the results. The photosensitive coloring compositions of Comparative Examples 1 to 3 were not subjected to evaluation other than measurement of light transmittance, since a black film was not obtained. As for the evaluation criteria, ◯ to △ are in the practical range, and × is not practical (the same applies hereinafter).

Evaluation of the maximum value of light transmittance (Tmax (400 to 650 nm)) in the wavelength range of 400 to 650 nm:
○: Tmax is less than 3% ×: Tmax is 3% or more

Evaluation of the maximum light transmittance (Tmax (650-730 nm)) in the wavelength range of 650-730 nm:
○: Tmax is less than 13% ×: Tmax is 13% or more

[Solvent resistance evaluation]
An 8-inch silicon wafer was coated with a flattening film resist solution (HL-18s: manufactured by Nippon Steel Chemical Co., Ltd.) by spin coating, and pre-baked by heating on a hot plate at 70° C. for 1 minute. Further, the coated film was cured by heat treatment on a hot plate at 100° C. for 15 minutes to form a 0.2 μm flattening film, thereby obtaining a wafer with a flattening film.

The photosensitive coloring composition (BLK-1) was applied onto a silicon wafer with a flattening film by a spin coater and pre-baked by heating on a hot plate at 70° C. for 1 minute. Then, using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.), an exposure dose of 300 mJ through a photomask for forming a thin line filter segment of 2.4 μm square and 100 μm line width at a wavelength of 365 nm. Pattern exposure was performed at 1/cm ² .

The exposed coating film was puddle-developed with an organic alkaline developer for 1 minute. After the puddle development, it was rinsed with pure water for 20 seconds using a spin shower, and then washed with pure water for 20 seconds. Thereafter, water droplets remaining on the wafer were blown off with high-pressure air, the substrate was naturally dried, and heat-treated on a hot plate with a surface temperature of 100° C. for 15 minutes to form a square pixel pattern. The film thickness of the black pattern after heat treatment was 1.2 μm. The film thickness of the coating film was measured using Dektak 3030 (manufactured by Nippon Vacuum Engineering Co., Ltd.) on a thin line pattern portion with a line width of 100 μm.

After the patterned substrate formed by the above method was immersed in propylene glycol monomethyl ether acetate for 5 minutes, the film thickness of the coating film was measured using Dektak 3030 (manufactured by Nippon Vacuum Engineering Co., Ltd.). compared with the film thickness. The rank of evaluation is as follows. Table 3 shows the results.
○: film thickness difference is within 3% △: film thickness difference is greater than 3%, within 5% ×: film thickness difference is greater than 5%

[Resolution evaluation]
The 2.4 μm square pixel pattern of the coating film formed by the above method at 2000 to 4000 J/m ² was observed and evaluated using a scanning electron microscope (“S-3000N” manufactured by Hitachi High-Tech). gone. The rank of evaluation is as follows. Table 3 shows the results.
◯: Pixels of less than 2.8 μm can be formed Δ: Pixels of 2.8 μm or more and less than 3.2 μm can be formed ×: Pixels of 3.2 μm or more can be formed

[Adhesion evaluation]
The resulting 2.4 μm square pixel pattern was observed with a microscope, and the number of patterns in close contact per 100 pixel patterns was counted to evaluate adhesion. The rank of evaluation is as follows. Table 3 shows the results.
○: 98 or more out of 100 patterns are in close contact △: 95 or more but less than 98 out of 100 patterns are in close contact ×: Out of 100 patterns, close less than 95 patterns

Reference Signs List 1 substrate 2 black matrix 3 opening 4 silicon substrate 5 organic EL layer 6 color filters 6a, 6b, 6c pixel 7 sealing layer 8 cover glass 10 black matrix substrate 11 organic EL display device

Claims (6)

A photosensitive coloring composition used for forming a black matrix of an organic electroluminescence display device comprising a silicon substrate, a color filter and a black matrix formed on the silicon substrate,
containing a coloring agent (A), a photopolymerization monomer (B), a photopolymerization initiator (C), and a resin (D),
The coloring agent (A) contains at least a blue pigment, a yellow pigment and a purple pigment,
The photopolymerizable monomer (B) contains a compound represented by the following general formula (1),
The resin (D) is composed of a hydroxyl group of a compound (a) having two hydroxyl groups and one thiol group in the molecule and an acid anhydride group of pyromellitic anhydride and/or trimellitic anhydride. In the presence of a reaction product, a hydroxyl group of a hydroxyl group-containing polymer obtained by polymerizing an ethylenically unsaturated monomer (c) containing a hydroxyl group-containing ethylenically unsaturated monomer (b), one isocyanate group and one A resin obtained by reacting an isocyanate group of a compound (d) having one or more (meth)acryloyl groups, wherein the content of structural units derived from the hydroxyl group-containing ethylenically unsaturated monomer (b) is , A photosensitive coloring composition comprising a photosensitive acrylic resin (E) in an amount of 35% by mass or more and 80% by mass or less relative to the total amount of structural units derived from the ethylenically unsaturated monomer (c).
General formula (1)
[ _CH2 =CHC(=O)-( _OCmH2m ) _{n - OCH2} ] _{3 - CCH2CH3}
(In general formula (1), m represents an integer of 1 to 3, n represents an integer of 0 to 2, and multiple m and n may be the same or different.) 2. The photosensitive coloring composition of claim 1, wherein said blue pigment is Pigment Blue 15:6, said yellow pigment is Pigment Yellow 139, and said violet pigment is Pigment Violet 23. 32 to 45% by mass of the blue pigment, 30 to 40% by mass of the yellow pigment, and 20 to 30% by mass of the purple pigment, based on the total amount of the coloring agent (A), photosensitive according to claim 1 or 2 coloring composition. The photosensitive coloring composition according to any one of claims 1 to 3, wherein the photopolymerization initiator (C) comprises an oxime ester photopolymerization initiator represented by the following general formula (2).

(In general formula (2), Z represents a direct bond or a -C(=O)- group, R ¹ represents an optionally substituted alkyl group having 1 to 20 carbon atoms, and R ² represents represents an optionally substituted alkyl group having 1 to 20 carbon atoms or an optionally substituted aryl group, wherein each of R ³ to R ¹⁰ independently has a hydrogen atom and a substituent; represents an alkyl group having ¹ to ²⁰ carbon atoms which may be represents a good aryl group.) A black matrix formed from the photosensitive coloring composition according to any one of claims 1 to 4. An organic electroluminescent display comprising the black matrix according to claim 5.

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