KR20090072221A - A colored photosensitive resin composition, color filter using the same, and flat panel display device comprising the color filter - Google Patents

Abstract

A coloured photosensitive resin composition, a color filter formed by using the composition, and a flat display device are provided to obtain a color filter having a low surface roughness and an excellent pencil hardness. A coloured photosensitive resin composition comprises a coloring material comprising C. I. pigment red 242; a binder resin; a photopolymerizable compound; a photopolymerization initiator; a thermal crosslinking agent comprising a novolac epoxy resin; and a solvent, wherein the binder resin comprises an unsaturated double bond per a molecule, and the content of the thermal crosslinking agent is 0.5 ~ 5 mass % to the solid part of the composition.

Description

A colored photosensitive resin composition, color filter using the same, and flat panel display device comprising the color filter}

The present invention relates to a colored photosensitive resin composition, a color filter using the same, and a flat panel display device including the color filter.

Color filters are widely used in flat panel display devices such as image pickup devices, liquid crystal display devices (LCDs), organic light emitting display devices (OLEDs), and the like, and their application ranges are rapidly expanding. The color filter used for a color liquid crystal display device, an image pick-up element, etc. is normally uniformly apply | coated by spin coating the coloring photosensitive resin composition containing the pigment corresponding to each color of red, green, and blue on the board | substrate with a black matrix patterned. Subsequently, an operation of exposing and developing the coating film formed by pre-baking (hereinafter sometimes referred to as heat drying or preliminary firing) and further baking (hereinafter sometimes referred to as heat curing or post-firing) as necessary is performed. It is manufactured by forming pixels of each color repeatedly for each color.

In particular, liquid crystal displays including color filters for notebook PCs and mobile devices have been required to have higher color purity and higher transmissive characteristics. As a color filter material, C.I. Patents using pigment 242 are known and are disclosed in Japanese Patent Application Laid-Open No. H11-14824. Also, Japanese Patent Application Laid-Open No. 2002-14463 discloses a coloring photosensitive resin composition having excellent transmittance and no residue on the substrate even after development. It is.

However, when the conventional technology as described above is introduced as it is, there is a problem in that the pencil hardness is insufficient in the composition in which the coloring material of high concentration is introduced and the surface roughness is high so that the transmittance is lowered.

An object of the present invention is a colored photosensitive resin composition which can provide a high quality color filter having excellent transmittance, low surface roughness and excellent pencil hardness, even if the pixel formed of the colored photosensitive resin composition includes a high concentration of coloring material. The present invention provides a color filter manufactured by the method, and a flat panel display device including the color filter.

The present invention for achieving the above object is (A) C.I. It comprises a coloring material containing pigment 242, (B) binder resin, (C) photopolymerizable compound, (D) photoinitiator, (E) thermal crosslinking agent containing novolak-type epoxy resin, and (F) solvent, The binder resin (B) contains an unsaturated double bond in one molecule, and the thermal crosslinking agent containing the (E) novolak-type epoxy resin is 0.5 to 5% by mass in terms of mass fraction with respect to the solid content in the colored photosensitive resin composition. It is providing the coloring photosensitive resin composition which is a range.

The present invention provides a color filter comprising a color layer formed by coating a colored photosensitive resin composition on a substrate and exposing and developing the film in a predetermined pattern, wherein the colored photosensitive resin composition is the colored photosensitive resin composition of the present invention. A color filter is provided.

The present invention provides a flat panel display device including the color filter.

According to the present invention, when forming a pixel using a high concentration of the coloring material in the coloring photosensitive resin composition of the present invention, it is possible to provide a high quality color filter having excellent transmittance, low surface roughness of the formed pixel and excellent pencil hardness. have.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

This invention provides the coloring photosensitive resin composition containing (A) coloring material, (B) binder resin, (C) photopolymerizable compound, (D) photoinitiator, (E) thermal crosslinking agent, and (F) solvent.

I. Coloring photosensitive resin composition

1. (A) Coloring material

The (A) coloring material is a red pigment C.I. Pigment Red 242 is included as a main pigment.

The (A) coloring material is optionally C.I. Pigments other than pigment 242 and other additives may be included. Hereinafter, the expression "other pigments" is referred to as C.I. Pigment Red 242 indicates a different pigment.

Specific examples of the other pigments include compounds classified as pigments in the color index (The Society of Dyers and Colourists), and more specifically, pigments having the following color index (CI) numbers. However, it is not necessarily limited to these.

C.I. Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 and 185

C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 254, 255 and 264

C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38

C.I. Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 28, 60, 64, and 76

C.I. Pigment Green 7, 10, 15, 25, 36, 47 and 58

C.I Pigment Brown 28

C.I pigment black 1 and 7, etc.

As said other pigment, they can be used individually or in combination of 2 or more types in the above-mentioned examples, respectively.

The coloring material (A) is C.I. If it further comprises pigments and other additives other than pigment 242, the C.I. Pigment 242 is 100: 0-30: 70 by mass ratio with another pigment, Preferably it is 90: 10-50: 50. If included in the above range, there is an advantage that the transmittance is improved.

The said (A) coloring material is 5-60 mass% in mass fraction with respect to solid content in colored photosensitive resin composition, Preferably it is 10-50 mass%. When included in the above-described range, there is an advantage that the transmittance is improved and the color concentration of the pixel is sufficient even when forming a thin film. In addition, there is an advantage that the residue hardly occurs because the omission of the non-pixel portion is not lowered during development.

2. (B) binder resin

The (B) binder resin typically serves to remove the non-exposed portion of the colored photosensitive resin layer formed by using the colored photosensitive resin composition, making it alkali-soluble, and to leave the non-exposed area. In addition, the (A) coloring material acts as a dispersion medium.

It is preferable that the said (B) binder resin is a polymer containing an unsaturated double bond in 1 molecule.

In addition, the binder resin (B) further reacts the compound obtained by copolymerizing the compounds (b-1), (b-2) and (b-3) with the compound (b-4) giving photocurability. It is preferable that it is a copolymer containing the unsaturated group obtained. The copolymer is excellent in crosslinking density and developability.

The compound (b-1) includes dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-hydroxypropyldehydroabietic acid acrylate, benzyl maleimide, and One or two or more compounds selected from the group consisting of N-vinylpyrrolidone compounds are included. When the compound (b-1) is used alone or in combination of two or more, surface roughness and transmittance are excellent.

The compound (b-2) is not limited as long as it is a compound having an unsaturated bond and a carboxylic acid group in one molecule, and may be used alone or in combination of two or more thereof. Specific examples thereof include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; And anhydrides of the dicarboxylic acids; and mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals, such as? -carboxypolycaprolactone mono (meth) acrylate. Acrylic acid and methacrylic acid among the compounds are preferred because of their excellent copolymerization reactivity and solubility in a developing solution.

The compound (b-3) is not limited as long as it has a compound having an unsaturated double bond which can be polymerized with the compounds (b-1) and (b-2). Specific examples thereof include unsaturated carboxylic acids such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and aminoethyl (meth) acrylate. Unsubstituted or substituted alkyl ester compound of; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclophene Tenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, isobornyl (meth) acrylic Unsaturated carboxylic ester compounds including alicyclic substituents such as late, pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, and pineneyl (meth) acrylate; 3-((meth) acryloyloxymethyl) oxetane, 3-((meth) acryloyloxymethyl) -3-ethyloxetane, 3-((meth) acryloyloxymethyl) -2-methyl Unsaturated carboxylic ester compounds containing thermosetting substituents such as oxetane and 3-((meth) acryloyloxymethyl) -2-trifluoromethyloxetane; Unsaturated carboxyl containing substituents having aromatic rings, such as monosaturated carboxylic acid ester compounds of glycols, such as oligoethylene glycol monoalkyl (meth) acrylate, benzyl (meth) acrylate, and phenoxy (meth) acrylate Acid ester compounds; Carboxylic acid vinyl esters, such as aromatic vinyl compounds, such as styrene and vinyltoluene (alpha) -methylstyrene, vinyl acetate, and a vinyl propionate; Vinyl cyanide compounds, such as (meth) acrylonitrile and the (alpha)-chloro acrylonitrile, etc. are mentioned. Among these, aromatic vinyl compounds are preferred for improving sensitivity and reducing outgassing. These can be used individually or in combination of 2 types or more, respectively.

Specific examples of the compound having an unsaturated bond and an epoxy group in the (b-4) 1 molecule include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl (Meth) acrylate, methylglycidyl (meth) acrylate, etc. are mentioned. Among these, glycidyl (meth) acrylate is preferably used. These can be used individually or in combination of 2 types or more, respectively.

As used herein, (meth) acrylate means acrylate and / or methacrylate.

When the (B) binder copolymer is a copolymer containing an unsaturated group obtained by further reacting the compound (b-4) with the copolymer obtained by copolymerizing the compounds (b-1) to (b-3), In the copolymer obtained by copolymerizing the compounds (b-1) to (b-3) with a comonomer, a proportion of the structural units derived from each of the compounds (b-1) to (b-3) is used for the copolymer. It is preferable that it is the following range in mole fraction with respect to the total mole number of the structural unit which comprises. In this case, the copolymer may further include other monomers in addition to the compounds (b-1) to (b-3).

Structural unit derived from the compound (b-1): 2 to 60 mol%,

Structural unit derived from the compound (b-2): 2 to 70 mol%,

Structural units derived from compound (b-3): 2 to 95 mol%.

In particular, it is more preferable that the ratio of said structural unit is the following ranges.

Structural unit derived from the compound (b-1): 10-50 mol%,

Structural unit derived from the compound (b-2): 5-65 mol%,

Structural units derived from compound (b-3): 5 to 80 mol%.

When said composition ratio satisfy | fills the said range, since the balance of developability, solubility, and heat resistance is favorable, a more preferable copolymer can be obtained.

The compound (b-4) is preferably reacted at 5 to 80 mol%, particularly preferably 10 to 80 mol%, based on the total moles of the structural units derived from the compound (b-2). It is preferable that the compound (b-4) is in the above range because it is excellent in sensitivity and developability.

Method for producing a copolymer comprising an unsaturated group obtained by further reacting the compound (b-4) with the copolymer obtained by copolymerizing the compound (b-1) to the compound (b-3). An example is as follows.

0.5 to 20 times the solvent was introduced to the flask equipped with the stirrer, the thermometer, the reflux condenser, the dropping lot and the nitrogen inlet tube, based on the total mass of the compounds (b-1) to (b-3). Substitute in nitrogen for air. Thereafter, the solvent was heated to 40 to 140 ° C., and then 0 with respect to a predetermined amount of the compounds (b-1) to (b-3) and the total mass of the compounds (b-1) to (b-3). A solution obtained by adding 0.1 to 10 mol% of a solvent having a ratio of 20 to 20 times and a polymerization initiator such as azobisisobutyronitrile or benzoyl peroxide to the total moles of the compounds (b-1) to (b-3) (room temperature Or stirring dissolution under heating) is added dropwise to the flask over 0.1 to 8 hours from the dropping lot, and further stirred at 40 to 140 ° C for 1 to 10 hours.

In this process, a part or the whole amount of the polymerization initiator may be put in the flask, or a part or the whole amount of the compounds (b-1) to (b-3) may be put in the flask. Moreover, in order to control molecular weight or molecular weight distribution, (alpha) -methylstyrene dimer or a mercapto compound can also be used as a chain transfer agent. The usage-amount of (alpha) -methylstyrene dimer or a mercapto compound is 0.005-5 mass% with respect to the gross mass of the said (b-1)-(b-3) compound. In addition, the said polymerization conditions can also adjust an input method and reaction temperature suitably in consideration of the amount of heat generation by a manufacturing facility, superposition | polymerization, etc ..

Thereby, the copolymer obtained by copolymerizing the said (b-1)-(b-3) compound is manufactured.

Subsequently, the atmosphere in the flask was replaced with nitrogen from air, and the molar fraction of the structural unit derived from the compound (b-2) in the copolymer obtained by copolymerizing the compounds (b-1) to (b-3). As a reaction catalyst of 80 mol% of the compound (b-4) and a carboxyl group and an epoxy group, for example, trisdimethylaminomethylphenol is 0.01-5 mass% with respect to the total mass of the compound (b-1)-(b-4). And as a polymerization inhibitor, for example, hydroquinone is added in an amount of 0.001 to 5% by mass based on the total mass of the compounds (b-1) to (b-4) in the flask and reacted at 60 to 130 ° C for 1 to 10 hours.

At this time, in the same manner as the polymerization conditions, the addition method and the reaction temperature may be appropriately adjusted in consideration of the amount of heat generated by the production equipment, polymerization, and the like.

Thereby, the said (B) binder copolymer manufactures the copolymer containing the unsaturated group obtained by making the said (b-4) compound further react with the copolymer obtained by copolymerizing the said (b-1)-(b-3) compound. do.

It is preferable that the weight average molecular weight converted into polystyrene of the said (B) binder resin and measured by the gel permeation chromatography exists in the range of 3,000-100,000, and it is more preferable that it exists in the range of 5,000-50,000. When the weight average molecular weight satisfies the above-mentioned range, film reduction is unlikely to occur at the time of development, and it is preferable because the missing property of the non-pixel portion at the time of development tends to be good.

The acid value of the (B) binder resin is preferably in the range of 30 to 150 mgKOH / g on a solid content basis. If the acid value is less than 30mgKOH / g, developability for alkaline water is low and there is a risk of leaving a residue on the substrate, if the acid value exceeds 150mgKOH / g is likely to desorption of the pattern.

It is preferable that it is 1.5-6.0, and, as for the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the said (B) binder resin, it is more preferable that it is 1.8-4.0. If the molecular weight distribution is 1.5 to 6.0, it is preferable because it is excellent in developability.

The amount of the binder resin (B) is usually in the range of 5 to 85% by mass, preferably 10 to 70% by mass, based on the mass fraction with respect to the solid content in the colored photosensitive resin composition. When the content of the binder resin (B) is 5 to 85% by mass based on the above criteria, the solubility in the developer is sufficient, and development residues are less likely to occur on the substrate of the non-pixel portion, and the film of the pixel portion of the exposed portion is reduced during development. Since the tendency to hardly occur and the missing property of a non-pixel part tends to be favorable, it is preferable.

3. (C) photopolymerizable compound

The said (C) photopolymerizable compound is a compound which can superpose | polymerize by the action of an active radical, an acid, etc. which generate | occur | produce by exposure alone or from the (D) photoinitiator mentioned later. Examples thereof include monofunctional monomers, bifunctional monomers, other polyfunctional monomers, and the like.

Specific examples of the monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate and N-vinylpyrrolidone Etc. can be mentioned.

Specific examples of the bifunctional monomer include 1,6-hexanedioldi (meth) acrylate, ethylene glycoldi (meth) acrylate, neopentylglycoldi (meth) acrylate, triethylene glycoldi (meth) acrylate, Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, etc. are mentioned.

Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and pentaerythritol tree. (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol Hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned.

Of these, bifunctional or higher polyfunctional monomers are preferably used. Especially preferably, it is a polyfunctional monomer more than 5-functional.

The said (C) photopolymerizable compound is used in 5-50 mass% normally with respect to solid content in colored photosensitive resin composition, Preferably it is used in the range of 7-45 mass%. Since the intensity | strength and smoothness of a pixel part tend to become favorable when (C) photopolymerizable compound is the range of 5-50 mass% on the said reference | standard, it is preferable.

4. (D) Photoinitiator

The photopolymerization initiator (D) plays a role of polymerizing the photopolymerizable compound (C) by generating an active radical or an acid by exposure. Moreover, the coloring photosensitive resin composition containing the said (D) photoinitiator is high sensitivity, and the film | membrane formed from the said composition becomes favorable intensity | strength and surface smoothness.

Although it does not specifically limit as a kind as said (D) photoinitiator, It is 1 type, or 2 or more types chosen from the group which consists of a triazine type compound, an acetophenone type compound, a biimidazole type compound, and an oxime compound.

Specific examples of the triazine-based compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6 -(4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2- Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

Specific examples of the acetophenone-based compound include diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2- Hydroxyethoxy) phenyl] -2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one , 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane- 1-one oligomer, the compound represented by following formula (1), etc. are mentioned.

<Formula 1>

In Formula 1, R ₁ to R ₄ are each independently hydrogen, a halogen, a hydroxyl group, a phenyl group unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms, a benzyl group unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms, or A naphthyl group unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms is represented.

Specific examples of the compound represented by Formula 2 include 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one and 2-ethyl-2-amino (4-morpholinophenyl) ethane-1 -One, 2-propyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-butyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-methyl-2 -Amino (4-morpholinophenyl) propane-1-one, 2-methyl-2-amino (4-morpholinophenyl) butan-1-one, 2-ethyl-2-amino (4-morpholino Phenyl) propane-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propan-1-one , 2-methyl-2-dimethylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-diethylamino (4-morpholinophenyl) propan-1-one, etc. may be mentioned. .

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichloro Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole , 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, phenyl group in 4,4', 5,5 'position And imidazole compounds substituted with groups. Among them, 2,2'bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole is preferably used.

Specific examples of the oxime compound include compounds represented by the following formulas (2) to (4).

<Formula 2>

<Formula 3>

<Formula 4>

The photopolymerization initiator (D) may further use other photopolymerization initiators or the like commonly used in this field as long as the effects of the present invention are not impaired. Examples of other photopolymerization initiators include benzoin compounds, benzophenone compounds, thioxanthone compounds, anthracene compounds, and polyfunctional thiol compounds containing two or more mercapto groups in the molecule. These can be used individually or in combination of 2 or more types, respectively.

Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like. Specific examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert -Butyl peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4,4'-di (N, N'-dimethylamino) -benzophenone, etc. are mentioned. Specific examples of the thioxanthone-based compound include 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4-propoxy thioxanthone, and the like. Can be mentioned. Specific examples of the anthracene-based compound include 9,10-dimethoxy cyanracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. Can be mentioned. Other 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclioxylic acid Methyl, titanocene compounds, etc. are mentioned as an example of another photoinitiator.

Specific examples of the multifunctional thiol compound include tris- (3-mercaptopropionyloxy) -ethyl-isocyanurate, trimethylolpropanetris-3-mercaptopropionate, pentaerythritol tetrakis-3- Mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, and the like. The polyfunctional thiol compounds are not limited to the above compounds but are all included in the present invention.

Moreover, the said (D) photoinitiator can also be used including the (D-1) photoinitiator adjuvant further. When the (D-1) photopolymerization initiation aid is further included, the colored photosensitive resin composition containing these is more sensitive, and thus the productivity at the time of forming a color filter using this composition is preferable.

As said (D-1) photoinitiator adjuvant, an amine compound and a carboxylic acid compound are used preferably.

Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine; 4-Dimethylaminobenzoic acid methyl, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4 Aromatic amine compounds, such as "-bis (dimethyl amino) benzophenone (common name: Michler's ketone) and 4,4'-bis (diethylamino) benzophenone, are mentioned. As an amine compound, an aromatic amine compound is used preferably.

Specific examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, And aromatic heteroacetic acids such as dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

The use amount of the photopolymerization initiator (D) is usually 0.1 to 40% by mass, preferably 1 to 30% by mass, based on the solid content, based on the total amount of the (B) binder resin and (C) the photopolymerizable compound, and photopolymerization. The usage-amount of a starting adjuvant (D-1) is 0.1-50 mass% normally on the said reference | standard, Preferably it is 1-40 mass%.

When the usage-amount of the said (D) photoinitiator exists in the said range, since the coloring photosensitive resin composition becomes high sensitivity and the intensity | strength of the pixel part formed using this composition and the smoothness in the surface of this pixel part tend to become favorable, it is preferable. Do. Moreover, when the usage-amount of a photoinitiator auxiliary (D-1) exists in the said range, since the sensitivity of a coloring photosensitive resin composition becomes higher and the productivity of the color filter formed using this composition tends to improve, it is preferable.

5. (E) Thermal crosslinking system

The thermal crosslinking agent (E) is used to increase the core hardening and mechanical strength, and particularly in the colored photosensitive resin composition of the present invention, it is possible to improve the surface roughness of the coating film. In order to obtain the outstanding surface roughness with the said (E) thermal crosslinking agent, it contains a noblock type epoxy resin.

Specific examples of the novolak-type epoxy resins include compounds represented by the following formula (5) (noblock epoxy resin, trade name: SUMI-EPOXY ESCN-195XL, manufacturer; Sumitomo Kagaku Kogyo Co., Ltd.).

<Formula 5>

The thermal crosslinking agent (E) may further include other compounds used as a thermal crosslinking agent in the field of colored photosensitive resin compositions within the scope of the present invention. As said other thermal crosslinking agent, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, etc. are mentioned. The said other compound may be used individually or in combination of 2 or more types with the said novolak-type epoxy resin.

Specific examples of the epoxy compound include bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, other aromatic epoxy resins, cycloaliphatic epoxy resins, and glycidyl esters. Resin, glycidyl amine resin, and the like. In addition, brominated derivatives of the above epoxy resins, aliphatic, cycloaliphatic or aromatic epoxy compounds other than the epoxy resins and their brominated derivatives, butadiene (co) polymer epoxides, isoprene (co) polymer epoxides, glycidyl (meth) acrylates (Co) polymer, triglycidyl isocyanurate, etc. are mentioned.

Specific examples of the oxetane compound include carbonate bis oxetane, xylene bis oxetane, adipate bis oxetane, terephthalate bis oxetane, and cyclohexane dicarboxylic acid bis oxetane.

The thermal crosslinking agent (E) may further include a curing aid capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. Specific examples of the curing aid include polyhydric carboxylic acids, polyhydric carboxylic anhydrides, acid generators, and the like.

As an example of carboxylic anhydrides, what is marketed can be used as an epoxy resin hardening | curing agent. As said epoxy resin hardening | curing agent, a brand name (Adekahadona EH-700) (made by Adeka Industrial Co., Ltd.), a brand name (Rikaditdo HH) (made by Nippon Ewha Co., Ltd.), a brand name (MH-700) ( New Nippon Ewha Co., Ltd.) etc. are mentioned.

The usage-amount of the said (E) heat crosslinking agent is 0.5-5 mass% normally with respect to solid content in colored photosensitive resin composition, Preferably it is 1-5 mass%. When the usage-amount of the said (E) thermal crosslinking agent exists in the said range, since the coloring photosensitive resin composition becomes highly sensitive and the intensity | strength of the pixel part formed using this composition and the smoothness in the surface of this pixel part tend to become favorable, it is preferable. Do.

6. (F) Solvent

The solvent (F) is not particularly limited as long as the colored photosensitive resin composition of the present invention has a suitable viscosity and can easily dissolve the remaining components, and various organic solvents used in the field of the colored photosensitive resin composition can be used.

Specific examples of the solvent (F) include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Propylene glycol dialkyl ethers such as ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, and propylene glycol monomethyl ether; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate; Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; Cyclic ester, such as (gamma) -butyrolactone, etc. are mentioned.

Among the solvents described above, organic solvents having a boiling point of 100 ° C. to 200 ° C. are preferable in terms of coating properties and drying properties, and more preferably alkylene glycol alkyl ether acetates, ketones, and 3-e. Ester, such as ethyl oxypropionate and methyl 3-methoxy propionate, is mentioned, More preferably, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3- Ethyl ethoxypropionate, methyl 3-methoxypropionate, and the like.

These (F) solvents can be used individually or in mixture of 2 or more types, respectively.

The content of the (F) solvent in the colored photosensitive resin composition of the present invention is usually 60 to 90% by mass, preferably 70 to 85% by mass, based on the mass fraction of the total amount of the colored photosensitive resin composition including the same. (F) When the content of the solvent is in the range of 60 to 90% by mass based on the above criteria, it is applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as die coater), inkjet, or the like. It is preferable because the coating property tends to be good at the time.

7. (G) Additives

The coloring photosensitive resin composition of this invention may further contain (G) additives, such as a filler, a polymer other than the said (B) binder resin, a pigment dispersing agent, an adhesion promoter, antioxidant, a ultraviolet absorber, and an aggregation inhibitor as needed. .

Specific examples of the filler include glass, silica, alumina and the like. Specific examples of the other polymers include thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, polyurethane, and the like.

Commercially available surfactants may be used as the pigment dispersant, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic and amphoteric. These can be used individually or in combination of 2 types or more, respectively. Specific examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, Polyethyleneimines and the like. In addition, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products Co., Ltd.), MEGAFAC (Die Nippon Inks Kagaku Kogyo Co., Ltd.), Florad (Sumitomo 3M Co., Ltd.), Asahi guard, Suflon (above, Asahi Glass Co., Ltd.), SOLSPERSE (Genesis) KK), EFKA (made by EFKA Chemicals Co., Ltd.), PB 821 (made by Ajinomoto Co., Ltd.), etc. are mentioned.

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N -(2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltri Methoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like. The said adhesion promoter can be used individually or in combination of 2 or more types, respectively, Usually 0.01-10 mass%, Preferably it is 0.05-2 mass% with respect to solid content in a coloring photosensitive resin composition.

Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol and the like. Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole, alkoxybenzophenone and the like. Specific examples of the aggregation inhibitor include sodium polyacrylate and the like.

The coloring photosensitive resin composition of this invention can be manufactured by the following methods, for example.

 The said (A) coloring material is previously contained in the (F) solvent, and it disperse | distributes using a bead mill until the average particle diameter of a coloring material becomes about 0.2 micrometer or less. Under the present circumstances, a pigment dispersant is used as needed, and some or all of said (B) binder resin may be mix | blended. The remainder of the (B) binder resin, the (C) photopolymerizable compound, (D) photopolymerization initiator, and (E) thermal crosslinking agent are used in the obtained dispersion (hereinafter sometimes referred to as mill base) as necessary. An additional solvent is further added so that it may become a predetermined density | concentration as needed, and a desired coloring photosensitive resin composition is obtained.

In addition, the coloring photosensitive resin composition of this invention can be manufactured by the following methods, for example.

The said (A) coloring material is previously contained in the (F) solvent, and it disperse | distributes using a bead mill until the average particle diameter of a coloring material becomes about 0.2 micrometer or less. At this time, a pigment dispersant is used as needed, and some or all of said (B) binder resin may be mix | blended. The remainder of the (B) binder resin, the (C) photopolymerizable compound and the (D) photopolymerization initiator, other components used as necessary, and, if necessary, added to the obtained dispersion (hereinafter sometimes referred to as a mill base). Solvent is further added to a predetermined concentration to obtain a desired colored photosensitive resin composition.

II. Pattern Forming Method Using Colored Photosensitive Resin Composition

The colored photosensitive resin layer using the colored photosensitive resin composition of this invention is formed on a base material. More specifically, first, the composition is applied to a substrate (not limited, usually glass or silicon wafer) or a layer containing the solids of the previously formed colored photosensitive resin composition to prebake and volatilize the solvent or the like. The component is removed to obtain a smooth coating film. The thickness of the coating film at this time is about 1-3 micrometers normally.

Subsequently, a partial region of the colored photosensitive resin layer is selectively exposed. More specifically, in order to obtain a desired pattern in the said colored photosensitive resin layer, a light ray is irradiated to a specific area | region through a mask. Under the present circumstances, it is preferable to use apparatuses, such as a mask aligner and a stepper, so that a parallel light beam may be irradiated uniformly to the whole exposure area | region, and a mask and a board | substrate exactly match.

The selectively exposed colored photosensitive resin layer is developed to remove the exposed area or the non-exposed area to form a pattern. More specifically, the desired pattern can be produced by contacting the colored photosensitive resin layer, which has been selectively exposed and cured, with an aqueous alkali solution to dissolve and develop the non-exposed areas. After development, postbaking may be performed at 150 to 230 ° C. for about 10 to 60 minutes as necessary.

The alkaline developer is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be either an inorganic or organic alkaline compound.

Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, ammonium dihydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, hydrogen carbonate Sodium, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like. Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethyl ammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine and the like. These inorganic and organic alkaline compounds can be used individually or in combination of 2 or more types, respectively. The concentration of the alkaline compound in the alkaline developer is in the range of 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.

The surfactant in the alkaline developer may be used either among nonionic surfactants, anionic surfactants or cationic surfactants. Specific examples of the non-ionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like. Specific examples of the anionic surfactants include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, Alkyl aryl sulfonates, such as sodium dodecyl naphthalene sulfonate, etc. are mentioned. Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride, or quaternary ammonium salts. These surfactant can be used individually or in combination of 2 or more types, respectively.

The density | concentration of surfactant in the said alkaline developing solution is 0.01-10 mass% normally, Preferably it is 0.05-8 mass%, More preferably, it is 0.1-5 mass%.

As an example, it can apply | coat on a base material as follows, and perform a photocuring and image development to form a pattern, and can be used as a black matrix or a colored pixel (colored image).

III. Color filter using colored photosensitive resin composition

The color filter according to the present invention is characterized by comprising a color layer formed by forming the colored photosensitive resin composition of the present invention in a predetermined pattern, followed by exposure and development.

The pattern formation method of a coloring photosensitive resin composition is based on the above-mentioned, and detailed description is abbreviate | omitted. As mentioned above, the pixel or black matrix corresponded to the color of the coloring material in the photosensitive resin composition is obtained through each operation of application | coating of a coloring photosensitive resin composition solution, a front baking, patterning exposure to the obtained dry coating film, and image development. In addition, a color filter can be obtained by repeating this operation by the number of colors required for the color filter. Since the configuration and manufacturing method of the color filter are well known in the art, detailed description thereof will be omitted.

The color filter manufactured using the coloring photosensitive resin composition of this invention has little in-plane film thickness difference, For example, it can make in-plane film thickness difference 0.15 micrometer or less and further 0.05 micrometer or less with the film thickness of 1-3 micrometers. . Therefore, the color filter obtained in this way is excellent in smoothness, and it can manufacture a liquid crystal display device of excellent quality by high yield by assembling this to a color liquid crystal display device.

Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by an Example. In addition, "%" and "part" which show an inclusion amount in a following example and a comparative example are a mass reference | standard unless there is particular notice.

Synthesis Example  1: Synthesis of Binder Resin B-1

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube was prepared. Meanwhile, as the monomer dropping lot, 11.1 parts (0.1 mole) of N-vinylpyrrolidone, 21.6 parts (0.3 mole) of acrylic acid, 70.8 parts (0.6 mole) of vinyltoluene, and t-butylperoxy-2-ethylhexanoate 4 In addition, 40 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") were added, followed by stirring and mixing. As a chain transfer agent dropping tank, 6 parts of n-dodecanethiol and 24 parts of PGMEA were put, and the thing which stirred and mixed was prepared. Thereafter, 395 parts of PGMEA was introduced into the flask, and the atmosphere in the flask was changed to nitrogen from air, and then the temperature of the flask was raised to 90 ° C. while stirring. The monomer and chain transfer agent were then started dropping from the dropping lot. The dropwise addition was carried out for 2 hours while maintaining 90 ° C, and after 1 hour, the temperature was raised to 110 ° C and maintained for 3 hours, and then a gas introduction tube was introduced to provide oxygen / nitrogen = 5/95 (v / v) mixed gas. Bubbling of was initiated. Next, 14.2 parts of glycidyl methacrylate (0.1 mol: 33 mol% with respect to the carboxyl group of methacrylic acid used for this reaction), 2,2'- methylenebis (4-methyl-6-t-butylphenol) 0.4 0.8 parts of triethylamine were added to the flask, and the reaction was continued at 110 ° C. for 8 hours to obtain binder resin B-1 having a solid acid value of 71 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 18,000, and molecular weight distribution (Mw / Mn) was 2.3.

Synthesis Example  2: Synthesis of Binder Resin B-2

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube was prepared. Meanwhile, as a monomer dropping lot, 22 parts (0.1 mole) of dicyclopentanyl methacrylate, 21.6 parts (0.3 mole) of acrylic acid, 105.6 parts (0.6 mole) of benzyl methacrylate, and t-butylperoxy-2-ethylhexano 4 parts of Eight and 40 parts of PGMEA were added, followed by stirring and mixing. As a chain transfer agent dropping tank, 6 parts of n-dodecanethiol and 24 parts of PGMEA were put, and the thing mixed with stirring was prepared. Thereafter, 395 parts of PGMEA was introduced into the flask, and the atmosphere in the flask was changed to nitrogen from air, and then the temperature of the flask was raised to 90 ° C. while stirring. The monomer and chain transfer agent were then started dropping from the dropping lot. The dropwise addition was carried out for 2 hours while maintaining 90 ° C, and after 1 hour, the temperature was raised to 110 ° C and maintained for 3 hours, and then a gas introduction tube was introduced to provide oxygen / nitrogen = 5/95 (v / v) mixed gas. Bubbling of was initiated. Next, 14.2 parts of glycidyl methacrylate (0.1 mol: 33 mol% with respect to the carboxyl group of methacrylic acid used for this reaction), 2,2'- methylenebis (4-methyl-6-t-butylphenol) 0.4 0.8 parts of triethylamine were added to the flask, and the reaction was continued at 110 ° C. for 8 hours to obtain binder resin B-2 having a solid acid value of 74 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 18,000, and molecular weight distribution (Mw / Mn) was 2.2.

Synthesis Example  3: Synthesis of Binder Resin B-3

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube was prepared. On the other hand, as a monomer dropping lot, 44.5 parts (0.1 mol) of 2-hydroxypropyl dehydroabiric acid acrylate, 21.6 parts (0.3 mol) acrylic acid, 105.6 parts (0.6 mol) benzyl methacrylate, t-butylperoxy- 4 parts of 2-ethylhexanoate and 40 parts of PGMEA were added, followed by stirring and mixing. As a chain transfer agent dropping tank, 6 parts of n-dodecanethiol and 24 parts of PGMEA were put, and the thing which stirred and mixed was prepared. Thereafter, 395 parts of PGMEA was introduced into the flask, and the atmosphere in the flask was changed to nitrogen from air, and then the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropwise addition was carried out for 2 hours while maintaining 90 ° C, and after 1 hour, the temperature was raised to 110 ° C and maintained for 3 hours, and then a gas introduction tube was introduced to provide oxygen / nitrogen = 5/95 (v / v) mixed gas. Bubbling of was initiated. Next, 14.2 parts of glycidyl methacrylate (0.1 mol: 33 mol% with respect to the carboxyl group of methacrylic acid used for this reaction), 2,2'- methylenebis (4-methyl-6-t-butylphenol) 0.4 0.8 parts of triethylamine were added to the flask, and the reaction was continued at 110 ° C for 8 hours to obtain a binder resin B-3 having a solid acid value of 73 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 18,500, and molecular weight distribution (Mw / Mn) was 2.3.

Synthesis Example  4: Synthesis of Binder Resin B-4

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube was prepared. Meanwhile, as a monomer dropping lot, 14.4 parts (0.2 mol) of acrylic acid, 140.8 parts (0.8 mol) of benzyl methacrylate, 4 parts of t-butylperoxy-2-ethylhexanoate and 40 parts of PGMEA were added, followed by stirring and mixing. It was. As a chain transfer agent dropping tank, 6 parts of n-dodecanethiol and 24 parts of PGMEA were put, and the thing mixed with stirring was prepared. Thereafter, 395 parts of PGMEA was introduced into the flask, and the atmosphere in the flask was changed to nitrogen from air, and then the temperature of the flask was raised to 90 ° C. while stirring. The monomer and chain transfer agent were then started dropping from the dropping lot. The dropwise addition was continued for 2 hours while maintaining 90 ° C, and after 1 hour, the temperature was raised to 110 ° C to continue the reaction for 8 hours to obtain a binder resin B-4 having a solid acid value of 80 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 19,200, and molecular weight distribution (Mw / Mn) was 2.3.

About the measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of said binder resin of B-1-B-4, it carried out on condition of the following using GPC method.

Equipment: HLC-8120GPC (Manufacturer: Toso Corporation)

Column: TSK-GELG4000HXL + TSK-GELG2000HXL (Serial Connection)

Column temperature: 40 ℃

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml / min

Injection volume: 50 μl

Detector: RI

Measurement sample concentration: 0.6 mass% (solvent = tetrahydrofuran)

Calibration standard: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufacturer: Tosoh Corporation)

The ratio of the weight average molecular weight and number average molecular weight obtained above was made into molecular weight distribution (Mw / Mn).

<Example 1>

In order to obtain a red pixel, the total amount of the pigment dispersant which is the pigment (A) coloring material and the additive (G) beforehand among each component shown in Table 1 is 20 with respect to the mixture of a pigment, a pigment dispersant, and a propylene glycol monomethyl ether acetate. The mixture was mixed up to the mass%, the pigment was sufficiently dispersed using the bead mill, the bead mill was separated, and the remaining components including the remaining amount of propylene glycol monomethyl ether acetate were further added and mixed to obtain a colored photosensitive resin composition.

(A) Coloring material C.I. Pigment Red 242 Part 5.28 C.I. Pigment Red 254 Part 2.97 (B) binder resin Binder Resin B-1 (Solid Powder) Part 4.56 (C) photopolymerizable compound Dipentaerythritol hexaacrylate (made by Nippon Kayaku Co., Ltd., "KAYARAD DPHA") Part 5.57 (D) photoinitiator Irgacure-369 (manufactured by CIBA-GEIGY) Part 1.21 TMMP (manufactured by Sakai Kagaku Co., Ltd.) 0.23 parts (E) Thermal crosslinking system Epoxy resin (SUMI-EPOXY ESCN-195XL; manufactured by Sumitomo Kagaku Kogyo Co., Ltd.) 0.30part (F) solvent Propylene Glycol Monomethyl Ether Acetate Part 78.18 (G) additive Pigment Dispersant (Polyester) Part 1.70

A 2 square inch glass substrate (# 1737, manufactured by Corning) was washed sequentially with a neutral detergent, water, and alcohol, and then dried. The coated photosensitive resin composition (Table 1) was exposed on the glass substrate at an exposure amount (365 nm) of 100 mJ / cm 2, and spin-coated so that the film thickness after post-firing when the developing step was omitted was 2.0 µm. Preliminary drying was carried out at 100 ° C for 3 minutes in a clean oven. After cooling, the gap between the substrate coated with the colored photosensitive resin composition and a quartz glass photomask (having a pattern for changing the transmittance stepwise in the range of 1 to 100% and a line / space pattern from 1 µm to 50 µm) Was made into 100 micrometers, and it irradiated with the exposure amount (365 nm) of 100 mJ / cm <2> in air | atmosphere using the ultrahigh pressure mercury lamp (brand name USH-250D) by Ushio Denki Corporation. Thereafter, the coating film was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.06% of potassium hydroxide at 26 ° C. for a predetermined time, and then dried at 220 ° C. for 30 minutes after washing with water. The pixel obtained at this time had low surface roughness and was excellent in transmittance.

<Example 2>

Operation similar to Example 1 was performed except changing binder resin B-1 to binder resin B-2. The evaluation results are shown in Table 2.

<Example 3>

Operation similar to Example 1 was performed except changing binder resin B-1 to binder resin B-3. The evaluation results are shown in Table 2.

Comparative Example 1

Operation similar to Example 1 was performed except changing binder resin B-1 to binder resin B-4. The evaluation results are shown in Table 2.

<Example 4>

The same operation as in Example 1 was carried out except that 0.3 part of the thermosetting agent (SUMI-EPOXY ESCN-195XL) was changed to 0.6 part and 5.57 part of the photopolymerizable compound (KAYARAD DPHA). The evaluation results are shown in Table 2.

Comparative Example 2

The same operation as in Example 1 was carried out except that 0.3 part of the thermosetting agent (SUMI-EPOXY ESCN-195XL) was changed to 1.20 part and 5.57 part of the photopolymerizable compound (KAYARAD DPHA). The evaluation results are shown in Table 2.

Comparative Example 3

The same operation as in Example 1 was carried out except that 0.3 part of the thermosetting agent (SUMI-EPOXY ESCN-195XL) was changed from 5.57 part to 5.87 parts of the photopolymerizable compound (KAYARAD DPHA). The evaluation results are shown in Table 2.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Pencil Hardness * 1 3H 3H 3H 3H 2H 2H 2H Surface Roughness * 2 ○ ○ ○ ○ × × ×

* 1: The cured coating film was produced like Example except having not used a photomask. Measurement of the pencil hardness is in accordance with JIS K5600-5-4.

* 2: Measured in contactless mode with AFM (XE-100, PSIA).

○: Ra: 3 nm or less, ×: 3 nm or more

From the said evaluation result, it turned out that the coloring photosensitive resin composition of Example 1, 2, 3, and 4 which concerns on this invention can obtain the color filter excellent in pencil hardness and surface roughness.

In contrast, in the case of the colored photosensitive resin compositions of Comparative Examples 1, 2, and 3, the surface roughness was poor and a high quality color filter could not be obtained.

Claims (6)

(A) C.I. It comprises a coloring material containing pigment 242, (B) binder resin, (C) photopolymerizable compound, (D) photoinitiator, (E) thermal crosslinking agent containing novolak-type epoxy resin, and (F) solvent, , The binder resin (B) includes unsaturated double bonds in one molecule, and the thermal crosslinking agent containing the (E) novolac epoxy resin ranges from 0.5 to 5% by mass in terms of mass fraction with respect to the solid content in the colored photosensitive resin composition. Phosphorus coloring photosensitive resin composition. The method according to claim 1, The binder resin (B) (b-1) dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-hydroxypropyldehydroabietic acid acrylate, benzylmaleimide and N-vinyl At least one compound selected from the group consisting of pyrrolidone compounds, (b-2) A compound having an unsaturated bond and a carboxylic acid group in 1 molecule, and (b-3) to a copolymer obtained by copolymerizing a compound having an unsaturated bond copolymerizable with the compounds (b-1) and (b-2), (b-4) The coloring photosensitive resin composition obtained by making the compound containing an unsaturated bond and an epoxy group react in 1 molecule. The method according to claim 2, In the copolymer by the polymerization of the compounds containing (b-1), (b-2) and (b-3), the constituent ratio of each of (b-1) to (b-3) is equal to 2 to 60 mol% of the structural units derived from (b-1), 2 to 70 mol% of the structural units derived from (b-2) and (b-3) in molar fractions relative to the total moles of the constituents constituting the coalescence. 2 to 95 mol% of a constitutional unit derived from the above), and the compound containing an unsaturated bond and an epoxy group in the (b-4) 1 molecule is a compound represented by (b-1), (b-2) and (b-3). The coloring photosensitive resin composition containing 5 to 80 mol% based on the number-of-moles of the compound which has an unsaturated bond and a carboxylic acid group in the molecule | numerator (b-2) 1 contained in the copolymer by superposition | polymerization of the containing compound. . A color filter comprising a color layer formed by applying a coloring photosensitive resin composition on a substrate and exposing and developing in a predetermined pattern, The said colored photosensitive resin composition is a colored photosensitive resin composition of any one of Claims 1-3, The color filter characterized by the above-mentioned. The method according to claim 4, Surface roughness Ra of the color filter is characterized in that 0 to 3. A flat panel display device comprising the color filter of claim 4.