JP2012048241A - Colored photosensitive resin composition, color filter and liquid crystal display device including the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored photosensitive resin composition having no pattern defect even with a low dose of exposure or having no decrease in transmittance, when the composition is used for a color filter, and thereby showing superior sensitivity.SOLUTION: The colored photosensitive resin composition includes a coloring material (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E). The photopolymerization initiator (D) includes a compound having at least two photo-active oxime ester skeletons in one molecule. The compound having at least two photo-active oxide ester skeletons in one molecule is a dimerized compound of a compound expressed by chemical formula 18 via R1 or R2.

Description

  The present invention relates to a colored photosensitive resin composition, a color filter, and a color filter, which are used for forming a colored layer including pixels of a color liquid crystal display device on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device. The present invention relates to a liquid crystal display device provided.

  Color filters are widely used in image sensors, liquid crystal display devices (LCDs), and the like, and their application range is rapidly expanding. A color filter used for a color liquid crystal display device or an image pickup device is usually a spin coating with a colored photosensitive resin composition containing pigments corresponding to red, green and blue colors on a substrate on which a black matrix is patterned. The coating film formed by heating and drying (hereinafter sometimes referred to as “pre-baking”) is exposed and developed, and further heat-cured as necessary (hereinafter referred to as “post-baking”). This operation is sometimes repeated for each color to form pixels of each color.

  As such a colored photosensitive resin composition, a composition containing a photopolymerizable compound and a photopolymerization initiator together with a pigment and a binder resin is often used, and a photosensitive resin containing a black pigment also in forming a black matrix. A composition is utilized.

  Recently, colored photosensitive resin compositions have been required to have excellent sensitivity due to high transmittance and excellent adhesiveness even with a small exposure amount in order to improve the yield in the process.

  For this reason, in the prior art, an attempt was made to improve the sensitivity by increasing the content of the polyfunctional monomer in the colored photosensitive resin composition to increase the degree of cross-linking. Residues remain in the exposed area, or the development type proceeds to the peeling type, which causes display defects due to development in which the pattern is missing.

  Recently, a photopolymerization initiator containing a photoactive oxime ester group having excellent sensitivity in a colored photosensitive resin composition, that is, a compound containing one photoactive oxime ester skeleton in one molecule is introduced to increase sensitivity. I was trying to improve. However, when the content of the photopolymerization initiator containing the photoactive oxime ester group exceeds an appropriate amount, there is a problem in that the brightness is lowered, the color characteristics are poor, and the exposure machine is contaminated. Is required.

  Accordingly, an object of the present invention is to provide a colored photosensitive resin composition exhibiting excellent sensitivity when applied to a color filter, since there is no lack of pattern even at a low exposure amount and there is no decrease in transmittance.

  Another object of the present invention is to provide a color filter produced using the colored photosensitive resin composition.

  Still another object of the present invention is to provide a liquid crystal display device having the color filter.

  In order to achieve the above object, the present invention includes a coloring material (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E). The initiator (D) provides a colored photosensitive resin composition comprising a compound having at least two photoactive oxime ester skeletons in one molecule.

  The present invention also provides a color filter including a color layer formed by forming the colored photosensitive resin composition according to the present invention into a predetermined pattern, and then exposing and developing.

  The present invention also provides a liquid crystal display device comprising the color filter according to the present invention.

  When the colored photosensitive resin composition according to the present invention is applied to a color filter, an excellent high-quality color filter exhibiting excellent sensitivity is obtained because there is no pattern loss even at a low exposure amount and there is no decrease in transmittance. An equipped liquid crystal display device can be provided.

It is sectional drawing which shows schematically the process of forming a color filter using the colored photosensitive resin composition by this invention. It is sectional drawing which shows schematically the process of forming a color filter using the colored photosensitive resin composition by this invention.

  Hereinafter, the present invention will be described in detail.

  The colored photosensitive resin composition according to the present invention includes a colored photosensitive resin containing a coloring material (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E). It is a composition, and the photopolymerization initiator (D) contains a compound having at least two photoactive oxime ester skeletons in one molecule.

[Coloring material (A)]
The coloring material (A) is usually a pigment, and is preferably an organic pigment or an inorganic pigment generally used for a pigment dispersion resist. The coloring material (A) may use a dye as necessary.

  Examples of inorganic pigments include metal compounds such as metal oxides and metal complex salts, such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, barium, and calcium. Examples thereof include metal oxides and composite metal oxides. Carbon black may also be included.

Specific examples of the organic pigment and the inorganic pigment include compounds classified by pigments according to a color index (published by The Society of Dyer's and Colorists). More specifically, the following color index ( CI)) pigments are mentioned, but not necessarily limited thereto.
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, 242, 254, 255 and 264
C. I. Pigment Violet 14, 19, 23, 29, 32, 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, 5, 25, 36, 47 and 58
C. I. Pigment Brown 28
C. I. Pigment Black 1 and 7 etc.

  These coloring materials (A) may be used alone or in combination of two or more.

  Content of the said coloring material (A) is 5-60 mass% by mass fraction with respect to solid content in a colored photosensitive resin composition, Preferably, it is 10-50 mass%. If the content of the coloring material (A) is in the range of 5 to 60% by mass on the basis of the above, the color density of the pixel is sufficient even if a thin film is formed, and the non-pixel portion lacks during development. It is preferable because it does not decrease and a residue is hardly generated.

  In the present invention, the solid content in the colored photosensitive resin composition means the total of components from which the solvent has been removed.

  When the coloring material is a pigment, a pigment dispersion in a state where the pigment is uniformly dispersed in the solution can be obtained by carrying out a dispersion treatment by containing a pigment dispersant.

  As the pigment dispersant, for example, surfactants such as silicon-based, fluorine-based, polyester-based, polyamine-based, polyacryl-based, positive ion-based, negative ion-based, non-ionic, and positive may be used. These may be used alone or in combination of two or more.

  When a pigment dispersant is used, the amount used is preferably 1 part by mass or less, more preferably 0.05 parts by mass to 0 parts by mass per 1 part by mass of the coloring material (A) in the colored photosensitive resin composition. .5 parts by mass. If the amount of the pigment dispersant used is within the above range, a pigment in a uniform dispersion state can be obtained. Therefore, the pigment dispersant is preferably used within the above range.

[Binder resin (B)]
The binder resin (B) usually has reactivity and alkali solubility due to the action of light and heat, and acts as a dispersion medium for the coloring material. The binder resin (B) contained in the colored photosensitive resin composition of the present invention acts as a binder resin for the coloring material (A) and is used for the alkaline development used in the development stage for producing a color filter. Any binder resin that can be dissolved in the liquid can be used.

（前記化学式１において、ｎは０又は１であり、Ｒ_１及びＲ_２は、それぞれ独立に、水素、ヘテロ原子を含むか含まない炭素原子数１〜１２の脂肪族又は芳香族炭化水素であり、Ｒ_３，Ｒ_４，Ｒ_５及びＲ_６は、それぞれ独立に、水素、ヘテロ原子を含むか含まない炭素原子数１〜３０の脂肪族又は芳香族炭化水素であり、Ｒ_３，Ｒ_４，Ｒ_５及びＲ_６のうちから２つが選択されて連結された鎖状又は連結されない枝状である。） The binder resin (B) includes a norbornene skeleton compound (B1) represented by the following chemical formula 1, an aromatic vinyl compound or an N-substituted maleimide compound (B2), and a compound (B3) having an unsaturated bond with a carboxyl group. It is preferable that it is a copolymer obtained by copolymerization reaction of the compound containing, and it is obtained by further reacting the obtained copolymer with a compound (B4) having an unsaturated bond and an epoxy group in one molecule. More preferably, it is an unsaturated group-containing resin.

(In the chemical formula 1, n is 0 or 1, and R ₁ and R ₂ are each independently hydrogen, an aliphatic or aromatic hydrocarbon having 1 to 12 carbon atoms, which may or may not contain a hetero atom. , R ₃ , R ₄ , R ₅ and R ₆ are each independently hydrogen, an aliphatic or aromatic hydrocarbon having 1 to 30 carbon atoms, which may or may not contain heteroatoms, and R ₃ , R ₄ , Two of R ₅ and R ₆ are selected to be linked or branched or unlinked.)

  The colored photosensitive resin composition containing a binder resin containing the norbornene skeleton compound (B1) represented by the chemical formula 1 exhibits excellent thermal and chemical resistance characteristics.

More specifically, the norbornene skeleton compound (B1) represented by the chemical formula 1 may be at least one selected from compounds having structural formulas represented by the following chemical formulas 2 to 17.

  On the other hand, the (meth) acrylate described in the present specification means acrylate and / or methacrylate.

  Specific examples of the compound that can be used as the aromatic vinyl compound or the N-substituted maleimide compound (B2) include the following. First, aromatic vinyl compounds include styrene, vinyl toluene, α-methyl styrene, p-chlorostyrene, o-methoxy styrene, m-methoxy styrene, p-methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl. Examples include methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and indene. Among them, vinyl toluene is preferable because of its excellent developability and processability. . Examples of N-substituted maleimide compounds include N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, and Np-hydroxyphenylmaleimide. N-o-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, N-o-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenylmaleimide, etc. Among them, N-benzylmaleimide is preferable because it is excellent in developability and processability. These may be used alone or in combination of two or more.

  The compound (B3) having a carboxyl group and an unsaturated bond is not particularly limited as long as it is a carboxylic acid compound having a polymerizable unsaturated double bond, and specific examples include acrylic acid and methacrylic acid. Is mentioned. Acrylic acid and methacrylic acid may be used alone or in combination of two or more. In addition to these acrylic acid and methacrylic acid, one or more other acids may be used. Specific examples of the other acid include one or more selected from other unsaturated carboxylic acids such as crotonic acid, itaconic acid, maleic acid, and fumaric acid. Moreover, you may use together the monomer containing a hydroxyl group and a carboxyl group in the same molecule, such as (alpha)-(hydroxymethyl) acrylic acid.

According to the present invention, a copolymer obtained by copolymerizing the (B1), (B2) and (B3) (a monomer other than B1, B2 and B3 is further contained and copolymerized). In the present invention, the ratio of the components derived from each of (B1), (B2) and (B3) is a mole fraction relative to the total number of moles of the components constituting the copolymer. It is preferable to be in the following range.
Structural units derived from (B1): 2 to 30 mol%
Structural units derived from (B2): 2 to 95 mol%
Structural units derived from (B3): 2 to 70 mol%

In particular, the proportions of the components derived from (B1), (B2), and (B3) are within the following ranges in terms of mole fraction with respect to the total number of moles of the components constituting the copolymer. More preferably it is.
Structural units derived from (B1): 5-30 mol%
Structural units derived from (B2): 5 to 80 mol%
Structural units derived from (B3): 5 to 65 mol%

  As described above, if the ratio of the components derived from (B1), (B2), and (B3) is within the above range, the balance between developability, solubility, and heat resistance is good, which is preferable. A polymer can be obtained.

  In one embodiment of the present invention, when the copolymer is obtained by copolymerizing (B1), (B2) and (B3), the copolymer may be produced by copolymerization by the following method. .

  In a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, 0.5 to 0.5 on a mass basis relative to the total mass of (B1) and (B1), (B2) and (B3). 20 times the amount of solvent is introduced together and the atmosphere in the flask is replaced by nitrogen from air. Next, after raising the temperature of the solvent to 40 to 140 ° C., the predetermined amount of (B2) and (B3) and 0 to 20 on a mass basis with respect to the total mass of (B1), (B2) and (B3). Double the amount of solvent and a polymerization initiator such as azobisisobutyronitrile or t-butylperoxy 2-ethylhexyl carbonate with respect to the total number of moles of (B1), (B2) and (B3). A solution with 0.1 to 10 mol% added in a fraction (stirred and dissolved at room temperature or under heating) was dropped from the dropping funnel into the flask over 0.1 to 8 hours, and the solution was added at 40 to 140 ° C for 1 hour to 10 hours. Stir further for hours.

  In the said process, a part or whole quantity of a polymerization initiator may be put into a flask, and a part or whole quantity of (B1), (B2) and (B3) may be put into a flask. When (B4) is polymerized to the copolymer obtained by copolymerizing (B1), (B2) and (B3), the remaining amount of (B1), (B2) and (B3) is added in this process May be.

  As the solvent used in the above step, a solvent used in a normal radical polymerization reaction may be used. Specifically, tetrahydrofuran, dioxane, ethylene glycol dimethylethyl, diethylene glycol dimethylethyl, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl nitrate, butyl nitrate, propylene glycol monomethyl ethyl acetate, 3-methoxybutyl acetate, methanol, ethanol, Examples include propanol, n-butanol, ethylene glycol monomethyl ether, propyl glycol monomethyl ether, toluene, xylene, ethylbenzene, chloroform, dimethyl sulfoxide and the like. These solvents may be used alone or in combination of two or more.

  Moreover, it does not specifically limit as a polymerization initiator used for the said process, You may add the polymerization initiator used normally. Specifically, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, benzoyl peroxide, t-butyl peroxyisopropyl carbonate, t-amyl peroxy-2-ethylhexanoate, t-butyl peroxy- Organic peroxides such as 2-ethylhexyl carbonate, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis And nitrogen compounds such as (2-methylpropionate). These may be used alone or in combination of two or more.

  The copolymer obtained by copolymerizing (B1), (B2) and (B3) is a chain transfer of α-methylstyrene dimer or mercapto compound in order to control the molecular weight and molecular weight distribution during the polymerization process. It may be used as an agent. The usage-amount of (alpha) -methyl styrene dimer and a marker pto compound is 0.005-5 mass% in a mass fraction with respect to the total mass of (B1), (B2), and (B3). In addition, the polymerization conditions may be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

  According to one embodiment of the present invention, the binder resin has an unsaturated bond with the norbornene skeleton compound (B1), the aromatic vinyl compound or the N-substituted maleimide compound (B2) represented by Chemical Formula 1 and the carboxyl group. Photo / thermosetting properties were imparted by adding a compound (B4) having an unsaturated bond and an epoxy group in one molecule to a copolymer obtained by a copolymerization reaction of a compound containing the compound (B3) having It may be a binder resin.

  Specific examples of the compound (B4) having an unsaturated bond and an epoxy group in one molecule include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and 3,4-epoxycyclohexane. Hexylmethyl (meth) acrylate, methyl glycidyl (meth) acrylate, etc. are mentioned. Of these, glycidyl (meth) acrylate is preferably used. These may be used alone or in combination of two or more.

  The compound (B4) having an unsaturated bond and an epoxy group in one molecule is moles relative to the number of moles of the component derived from the compound (B3) having a carboxyl group and an unsaturated bond in the copolymer. It is preferable to carry out the reaction at a fraction of 5 to 80 mol%, particularly 10 to 80 mol%. If the compound (B4) having an unsaturated bond and an epoxy group is within the above range, it is preferable because sufficient photocurability and thermosetting can be obtained, and sensitivity and pencil hardness are compatible and excellent in reliability.

  In one embodiment of the present invention, the binder resin (B) is obtained by copolymerizing (B4) with a copolymer obtained by copolymerizing the above (B1), (B2) and (B3), for example, by the following method. You may manufacture by making it react.

  When the copolymer of (B1), (B2) and (B3) is obtained by the above-described method, the atmosphere in the flask is replaced with nitrogen to air, and the carboxyl group and the unsaturated bond in the copolymer are removed. For example, trisdimethylaminomethylphenol is used as a reaction catalyst of a carboxyl group and an epoxy group (B4) having a mole fraction of 5 to 80 mol% with respect to the number of moles of the component derived from the compound (B3) having (B4). B1), (B2), (B3) and (B4) as a mass fraction in a mass fraction of 0.01 to 5% by mass, and a polymerization inhibitor, for example, hydroquinone (B1), (B2), (B3) and 0.001-5 mass% in a mass fraction with respect to the total mass of (B4) are put in a flask and reacted at 60-130 ° C. for 1-10 hours. React B4) It may be. In addition, the charging method and the reaction temperature may be appropriately adjusted in consideration of the production equipment and the amount of heat generated by the polymerization in the same manner as the polymerization conditions.

  In one embodiment of the present invention, the binder resin (B) preferably has a polystyrene-equivalent weight average molecular weight in the range of 3,000 to 100,000, and in the range of 5,000 to 50,000. Is more preferable. When the weight average molecular weight of the binder resin (B) is in the range of 3,000 to 100,000, it is preferable that the film is not easily reduced during development and the non-pixel portion lackability is good.

  The acid value of the binder resin (B) is preferably in the range of 30 to 150 mgKOH / g based on the solid content. If the acid value is less than 30 mgKOH / g, the developability with respect to alkaline water may be reduced, and a residue may be left on the substrate. If the acid value exceeds 150 mgKOH / g, pattern desorption is likely to occur. .

  The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the binder resin (B) is preferably 1.5 to 6.0, and more preferably 1.8 to 4.0. preferable. A molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of 1.5 to 6.0 is preferable because of excellent developability.

  The content of the binder resin (B) is usually 5 to 90% by mass, preferably 10 to 70% by mass, based on the solid content in the colored photosensitive resin composition. If the content of the binder resin (B) is 5 to 90% by mass on the basis of the above, the solubility in the developer is sufficient and a development residue is hardly generated on the non-pixel portion of the substrate. This is preferable because the film of the pixel portion is less likely to be reduced and the non-pixel portion has good omissibility.

[Photopolymerizable compound (C)]
The photopolymerizable compound (C) contained in the colored photosensitive resin composition of the present invention is a compound that can be polymerized by the action of light and a photopolymerization initiator described later, and is a monofunctional monomer or a bifunctional monomer. And other polyfunctional monomers.

  The photopolymerizable compound (C) used in the present invention is different in the structure of the functional group and the number of functional groups in order to improve the developability, sensitivity, adhesion, surface problems, etc. of the colored photosensitive resin composition. Two or more photopolymerizable compounds may be mixed and used, and the range is not limited.

  Specific examples of monofunctional monomers include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl pyrrolidone, and the like. Can be mentioned.

  Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (meth). Examples thereof include acrylate, bis (acryloyloxyethyl) ether of bisphenol A, and 3-methylpentanediol di (meth) acrylate.

  Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and pentaerythritol. Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, dipentaerythritol Examples include hexa (meth) acrylate.

  Of these, polyfunctional monomers having two or more functions are preferably used.

  A photopolymerizable compound (C) is 1-60 mass% normally by mass fraction with respect to solid content in a coloring photosensitive resin composition, Preferably, it is used in 5-50 mass%. It is preferable that the photopolymerizable compound (C) is in the range of 1 to 60% by mass on the basis of the above because the strength and smoothness of the pixel portion are improved.

[Photopolymerization initiator (D)]
The photopolymerization initiator (D) contained in the colored photosensitive resin composition according to the present invention contains a compound having two or more photoactive oxime ester skeletons in one molecule. The compound having two or more photoactive oxime ester skeletons in one molecule is preferably a compound obtained by dimerizing a compound represented by the following chemical formula 18 via R ₁ or R ₂ .

（前記式において、Ｒ_１，Ｒ_２及びＲ_３はそれぞれ独立に、Ｒ_１１，ＯＲ_１１，ＣＯＲ_１１，ＳＲ_１１，ＣＯＮＲ_１２Ｒ_１３又はＣＮを示し、Ｒ_４及びＲ_５はそれぞれ独立に、Ｒ_１１，ＯＲ_１１，ＳＲ_１１，ＣＯＲ_１１，ＣＯＮＲ_１２Ｒ_１３，ＮＲ_１２ＣＯＲ_１１，ＯＣＯＲ_１１，ＣＯＯＲ_１１，ＳＣＯＲ_１１，ＯＣＳＲ_１１，ＣＯＳＲ_１１，ＣＳＯＲ_１１，ＣＮ，ハロゲン原子又は水酸基を示し、ａ及びｂはそれぞれ独立に、０〜３である。）

(In the above formula, R ₁ , R ₂ and R ₃ each independently represent R ₁₁ , OR ₁₁ , COR ₁₁ , SR ₁₁ , CONR ₁₂ R ₁₃ or CN, and R ₄ and R ₅ each independently represent R ₁₁ , OR ₁₁ , SR ₁₁ , COR ₁₁ , CONR ₁₂ R ₁₃ , NR ₁₂ COR ₁₁ , OCOR ₁₁ , COOR ₁₁ , SCOR ₁₁ , OCSR ₁₁ , COSR ₁₁ , CSOR ₁₁ , CN, a halogen atom or a hydroxyl group b is independently 0-3.)

R ₁₁ , R ₁₂ and R ₁₃ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or the number of carbon atoms. 2 to 20 heterocyclic groups, wherein the hydrogen atoms of the alkyl group, aryl group, arylalkyl group and heterocyclic group are R ₂₁ , OR ₂₁ , COR ₂₁ , SR ₂₁ , NR ₂₂ R ₂₃ , CONR _{22. R 23, -NR 22 -OR 23,} -NCOR 22 -OCOR 23, -C (= N-OR 21) -R 22, -C (= N-OCOR 21) -R 22, CN, halogen atom, -CR _{21 = CR 22 R 23, -CO} -CR 21 = CR 22 R 23, OCO-CR 21 = CR 22 R 23, O-C 1-6 alkylene _-OCOR 21, COOR ₂₁ or an epoxy group may be substituted, and R ₂₁ , R ₂₂ and R ₂₃ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a carbon atom. An arylalkyl group having a number of 7 to 30 or a heterocyclic group having a number of carbon atoms of 2 to 20, and the alkylene part of the substituent represented by R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ and R ₂₃ The methylene group may be interrupted 1 to 5 times by unsaturated bond, ether bond, thioether bond, ester bond, thioester bond, amide bond or urethane bond, and the alkyl part of the substituent has a branched side chain. may be, may be a cyclic alkyl, alkyl-terminus of said substituents may be unsaturated bond and, R ₁₂ and R ₁₃ and R ₂₂ and R ₂₃ it Together may form a ring, R ₃ may form a ring together with the adjacent benzene ring. R ₄ and R ₅ are each independently R ₁₁ , OR ₁₁ , SR ₁₁ , COR ₁₁ , CONR ₁₂ R ₁₃ , NR ₁₂ COR ₁₁ , OCOR ₁₁ , COOR ₁₁ , SCOR ₁₁ , OCSR ₁₁ , COSR ₁₁ , CSOR ₁₁ , CN, a halogen atom or a hydroxyl group is shown, and a and b are each independently 0 to 3. )

Preferably, examples of the alkyl group represented by R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ and R ₂₃ in the chemical formula 18 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and s-butyl. , T-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, Icosyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, vinyl, allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propoxyethyl, pentyloxyethyl, octyloxyethyl, methoxyethoxyethyl, ethoxyethoxy Examples include ethyl, propoxyethoxyethyl, methoxypropyl, 2-methoxy-1-methylethyl and the like. Examples of the aryl group represented by R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ and R ₂₃ include phenyl, tolyl, xylyl, ethylphenyl, chlorophenyl, naphthyl, anthryl, phenanthrenyl, and the above alkyl group. One or more substituted phenyl, biphenylyl, naphthyl, anthryl and the like can be mentioned. Examples of the arylalkyl group represented by R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ and R ₂₃ include benzyl, chlorobenzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl, phenyl And ethenyl. Examples of the heterocyclic group represented by R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ and R ₂₃ include pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzoxazol-2-yl, tetrahydro Preferable examples include 5- to 7-membered heterocyclic rings such as pyranyl, pyrrolidyl, imidazolidyl, pyrazolidyl, thiazolidyl, isothiazolidyl, oxazolidyl, isoxazolidyl, piperidyl, piperazyl, morpholinyl and the like. Examples of the ring that R ₁₂ and R ₁₃ can form together, the ring that R ₂₂ and R ₂₃ can form together, and the ring that R ₃ can form together with the adjacent benzene ring include, for example, a cyclopentane ring, a cyclohexane ring, Examples thereof include 5- to 7-membered rings such as cyclopentene ring, benzene ring, piperidine ring, morpholine ring, lactone ring, and lactam ring. In addition, examples of the halogen atom which may be substituted for R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ and R ₂₃ and the halogen atom represented by R ₄ and R ₅ include fluorine, chlorine, bromine and iodo. It is done.

  The methylene group of the alkylene part of the substituent may be interrupted 1 to 5 times by an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond or a urethane bond. 1 or 2 or more types of groups may be used, and two or more groups may be continuously interrupted as long as they can be interrupted continuously. The alkyl part of the substituent may have a branched side chain, may be a cyclic alkyl, and the alkyl terminal of the substituent may be an unsaturated bond.

Among the oxime ester compounds according to the present invention, in the chemical formula 18, R ₁ is an alkyl group having ₁₁ to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, carbon A heterocyclic group having 2 to 20 atoms, OR ₁₁ , COR ₁₁ , SR ₁₁ , CONR ₁₂ R ₁₃ or CN, or the number of carbon atoms in which R ₃ is interrupted 1 to 5 times by an ether bond or an ester bond An alkyl group having 1 to 12 carbon atoms, an alkyl group having 13 to 20 carbon atoms, an OR ₁₁ , COR ₁₁ , SR ₁₁ , CONR ₁₂ R ₁₃ or CN, particularly R ₁ is an alkyl group having ₁₁ to 20 carbon atoms or An aryl group having 6 to 30 carbon atoms, or a methylene group of an alkylene part in which R ₃ is an alkyl group is an ether bond or an ester bond. A branched alkyl group having 8 or more carbon atoms which may be interrupted 5 times, or a methylene group in the alkylene part of the alkyl group may be interrupted 1 to 5 times by an ether bond or an ester bond. Easy to synthesize, wherein R ₃ is an alkyl group interrupted 1 to 5 times by an ether bond, and R ₃ is an alkyl group interrupted 1 to 5 times by an ester bond In addition, when used as a photopolymerization initiator, it is dissolved in propylene glycol-1-monomethyl ether-2-acetate or cyclohexanone as a solvent in an amount of 1% by mass or more and satisfies the requirements as a photopolymerization initiator. Therefore, it is preferable.

The oxime ester compound according to the present invention is preferably a compound obtained by dimerizing the compound represented by the chemical formula 18 via R ₁ or R ₂ as represented by the following chemical formula 19 and chemical formula 20.

（前記化学式１９及び化学式２０において、Ｒ_１，Ｒ_２，Ｒ_３，Ｒ_４，Ｒ_５，ａ及びｂは、前記化学式１８で定義されたものと同義である。）

(In the chemical formula 19 and chemical formula 20, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , a, and b have the same meanings as defined in the chemical formula 18.)

  Preferable specific examples of the oxime ester compound represented by the chemical formula 18 according to the present invention include compounds represented by the following chemical formulas 21 to 27. However, the present invention is not limited by the following compounds.

Preferable specific examples of the oxime ester compound represented by the chemical formula 20 according to the present invention include a compound represented by the following chemical formula 28. However, the present invention is not limited by the following compounds.

  A compound that is commercially available as a compound having two or more photoactive oxime ester skeletons in one molecule may be used. Specifically, NCI-831 ( ADEKA Co., Ltd.).

  The compound having two or more photoactive oxime ester skeletons in one molecule is preferably 10% by mass or more by mass fraction with respect to the photopolymerization initiator in the colored photosensitive resin composition based on the solid content. Is 20-80 mass%. When the photopolymerization initiator contains 10% by mass or more of a compound having two or more photoactive oxime ester skeletons in one molecule according to the present invention, the photopolymerization initiator exhibits high sensitivity to light and is crosslinked even at a low exposure amount. It is preferable because of its high density, excellent adhesion to the substrate, no peeling of the pattern during the development process, and excellent thermal stability.

  The photopolymerization initiator (D) contained in the colored photosensitive resin composition according to the present invention is not limited to compounds other than those having two or more photoactive oxime ester skeletons in one molecule, but a triazine compound, One or more compounds selected from the group consisting of acetophenone compounds, biimidazole compounds and oxime compounds may be used together. The colored photosensitive resin composition containing the photopolymerization initiator (D) has high sensitivity, and the film formed using this composition has good strength and surface smoothness of the pixel portion.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1.3.5-triazine, 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-methylph Nyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like. .

  Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4-2 (-hydroxyethoxy). ) Phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2 -Oligomer of dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one It is done.

Further, examples of acetophenone compounds that can be used other than the acetophenone compounds described above include compounds represented by the following chemical formula 29.

In the chemical formula 29, R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group which may be substituted with an alkyl group having 1 to 12 carbon atoms, a carbon atom A benzyl group which may be substituted with an alkyl group having 1 to 12 carbon atoms or a naphthyl group which may be substituted with an alkyl group having 1 to 12 carbon atoms is shown.

  Specific examples of the compound represented by the chemical formula 29 include 2-methyl-2-amino (4-morpholinophenyl) ethane-1-one and 2-ethyl-2-amino (4-morpholinophenyl). Ethane-1-one, 2-propyl-2-amino (4-morpholinophenyl) ethane-1-one, 2-butyl-2-amino (4-morpholinophenyl) ethane-1-one, 2-methyl- 2-Amino (4-morpholinophenyl) propan-1-one, 2-methyl-2-amino (4-morpholinophenyl) butan-1-one, 2-ethyl-2-amino (4-morpholinophenyl) Propan-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propane 1-one, 2-methyl-2-dimethylamino (4-morpholinophenyl) propane-1-one, 2-methyl-2-dimethylamino (4-morpholinophenyl) propane-1-one and the like.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl). -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 or the phenyl group at the 4,4', 5,5 'position is substituted by a carboalkoxy group Examples include imidazole compounds. Of these, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole or 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5 5,5′-Tetraphenylbiimidazole is preferably used.

Examples of the oxime compound include O-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one and compounds represented by the following chemical formulas 30 to 32.

  Moreover, as long as the effect of the present invention is not damaged, other photopolymerization initiators usually used in this field may be used in combination. Examples of other photopolymerization initiators include benzoin compounds, benzophenone compounds, thioxanthone compounds, and anthracene compounds. These may be used alone or in combination of two or more.

  Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of the benzophenone compounds include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfate, 3,3 ′, 4,4′-tetra (tert-butyl). Peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

  Examples of the anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. .

  In addition, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenyl phenyloxylate, titanocene compound And the like as other photopolymerization initiators.

  Moreover, you may use it combining a photoinitiator (D) with a photoinitiator auxiliary agent (D-1). When the photopolymerization initiator (D-1) is used in combination with the photopolymerization initiator (D), the colored photosensitive resin composition containing them becomes more sensitive, and a color filter is formed using this composition. This is preferable because productivity is improved.

  As the photopolymerization initiation auxiliary agent (D-1), amine compounds and carboxylic acid compounds are preferably used.

  Among the photopolymerization initiation aid (D-1), specific examples of amine compounds include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, 4-dimethylamino. Ethyl benzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) Aromatic amine compounds such as benzophenone (common name: Michler's ketone) and 4,4′-bis (diethylamino) benzophenone are exemplified. As the amine compound, an aromatic amine compound is preferably used.

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

  The amount of the photopolymerization initiator (D) used is usually 0.1 to 40% by mass with respect to the total amount of the binder resin (B) and the photopolymerizable compound (C) based on the solid content. The amount of the photopolymerization initiation auxiliary (D-1) used is usually 0.1 to 50% by mass, preferably 1 to 40% by mass based on the above standard.

  If the amount of the photopolymerization initiator (D) used is within the above range, the colored photosensitive resin composition is enhanced in sensitivity, and the strength of the pixel portion formed using this composition, the surface of the pixel portion, and the like. Since the smoothness in is good, it is preferable. Moreover, if the usage-amount of photoinitiator adjuvant (D-1) exists in the said range, the sensitivity of a colored photosensitive resin composition will become still higher, and the production of the color filter formed using this composition will be carried out. This is preferable because of improved properties.

[Solvent (E)]
The solvent (E) contained in the colored photosensitive resin composition according to the present invention is not particularly limited, and various organic solvents used in the field of the colored photosensitive resin composition may be used. Specific examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoalkyl ethers such as ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, Diethylene glycol dialkyl ethers such as diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether Alkylene glycol alkyl ether acetates such as teracetate, 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 esters such as γ-butyrolactone, etc. Can be mentioned.

  Among the above solvents, in view of coating property and drying property, an organic solvent having a boiling point of 100 ° C. to 200 ° C. is preferable, and more preferably, alkylene glycol alkyl ether acetates, ketones, 3-ethoxypropionic acid. And esters such as ethyl and methyl 3-methoxypropionate, and more preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, etc. Is mentioned. These solvents (E) may be used alone or in admixture of two or more.

  The content of the solvent (E) in the colored photosensitive resin composition according to the present invention is usually 60 to 90% by mass, preferably 70 to 70% by mass with respect to the total amount of the colored photosensitive resin composition containing the solvent. It is 85 mass%. If the content of the solvent (E) is in the range of 60 to 90% by mass based on the above standard, coating is performed with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as a die coater), or an inkjet. Is preferable because the coating property is improved.

[Additive (F)]
Addition of a filler, other polymer compound, a curing agent, a pigment dispersant, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-aggregation agent, etc., to the colored photosensitive resin composition according to the present invention as necessary Agent (F) can also be used in combination.

  Specific examples of the filler include glass, silica, alumina and the like.

  Specific examples of other polymer compounds include curable resins such as epoxy resins and maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. Etc.

  The curing agent is used for increasing the depth curing and the mechanical strength, and examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.

  Examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolac epoxy resin, and other aromatic epoxies. Resins, alicyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, or brominated derivatives of such epoxy resins, epoxy resins and aliphatic, alicyclic or aromatic epoxy compounds other than brominated derivatives thereof Butadiene (co) polymer epoxidized product, isoprene (co) polymer epoxidized product, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate and the like.

  In the curing agent, examples of the oxetane compound include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and bisoxetane cyclohexanedicarboxylate.

  The curing agent may contain an auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound together with the curing agent. Examples of the curing auxiliary compound include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, and acid generators.

  As the carboxylic acid anhydride, a commercially available epoxy resin curing agent may be used. As the epoxy resin curing agent, for example, a trade name (ADEKA HARDNER EH-700) (manufactured by ADEKA INDUSTRY CO., LTD.), A trade name (RIKACID HH) (manufactured by Shin Nippon Rika Co., Ltd.), and a trade name (MH-700). ) (New Nippon Rika Co., Ltd.). You may use the said hardening | curing agent individually or in mixture of 2 or more types.

  As the pigment dispersant, commercially available surfactants may be used. For example, silicon-based, fluorine-based, polyester-based, polyamine-based, polyacryl-based, positive-ion-based, negative-ion-based, non-ionic-based ones. , And positive surfactants. These may be used alone or in combination of two or more. 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, and polyethyleneimines. Other than this, trade names KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (POLYFLOW) (manufactured by Kyoeisha Chemical Industry Co., Ltd.), EFTOP (manufactured by Tochem Products), MegaFac (MEGAFAC) ) (Manufactured by Dainippon Ink & Chemicals, Inc.), Florad (manufactured by Sumitomo 3M), Asahi guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Solsperse (S) LSPERSE) (Zeneca Co., Ltd. production), EFKA (EFKA Chemicals Co., Ltd. production), PB821 (Ajinomoto Co., Inc., and the like manufacturing).

  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-epoxycyclohexene) Xylyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane , 3 isocyanatepropyltriethoxysilane and the like.

  These adhesion promoters may be used alone or in combination of two or more. An adhesion promoter is 0.01-10 mass% normally by mass fraction with respect to solid content of a coloring photosensitive resin composition, Preferably, 0.05-2 mass% is contained.

  Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol.

  Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone.

  Specific examples of the anti-aggregation agent include sodium polyacrylate.

  The colored photosensitive resin composition according to the present invention may be produced, for example, by the following method. The coloring material (A) is preliminarily mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle size of the coloring material becomes about 0.2 μm or less. At this time, a pigment dispersant is used as necessary, and a part or all of the binder resin (B) may be blended. The remaining amount of the binder resin (B), the photopolymerizable compound (C) and the photopolymerization initiator (D), and other used as necessary in the obtained dispersion (hereinafter sometimes referred to as mill base) These components and, if necessary, an additional solvent are further added so as to have a predetermined concentration to obtain a desired colored photosensitive resin composition.

  The present invention provides a color filter including a color layer formed by exposing and developing the above-described colored photosensitive resin composition according to the present invention in a predetermined pattern, and a liquid crystal display device including the color filter. .

  A process of forming a color filter using the colored photosensitive resin composition according to the present invention will be described below with reference to FIGS.

  When manufacturing a color filter by the COA (Color Filter on Array) method using the colored photosensitive resin composition according to the present invention, a glass substrate having a TFT layer 31 on which a SiNx (protective layer) coating film 21 is formed. The red, green, and blue pixel patterns 11, 12, and 13 are directly formed on 41. The pixel patterns 11, 12, and 13 are formed on the SiNx coating film 21 (FIG. 1a).

  In the process for forming an electrical conduction path between the TFT layer 31 and the electrode (IZO layer), the positive photosensitive resin film 51 is patterned using a mask for removing the SiNx (protective layer) coating film 21. (FIG. 1b).

  The SiNx (protective layer) coating film 21 located on the lower surface (electric conduction path) of the positive photosensitive resin film 51 is dry-etched (dry etching) to form an electrical conduction path (FIG. 1c).

  In order to remove the positive photosensitive resin film 51 remaining on the pixel patterns 11, 12, and 13 of FIG. 1c, the positive photosensitive resin film 51 layer is removed using a stripper developer (FIG. 1d).

  An IZO layer 61 to be used as a common electrode (IZO layer) 61 with the TFT layer 31 is deposited (FIG. 2e).

  In order to form the common electrode (IZO layer) 61 layer, a positive photosensitive resin film 51 is formed on the common electrode (IZO layer) 61 layer (FIG. 2f).

  The exposed portion (portion where the IZO layer 61 is exposed) of the formed positive photosensitive resin film 51 is removed by wet etching (wet etching) (FIG. 2g).

  In order to remove the positive photosensitive resin film 51 remaining on the common electrode (IZO layer) 61 of FIG. 2g, the positive photosensitive resin film 51 layer is removed using a stripper developer (FIG. 2h).

  Since the color filter manufactured as described above does not lack a pattern even at a low exposure amount, an excellent quality liquid crystal display device can be provided at a high yield.

  In the following, the present invention will be described in more detail based on examples, but the embodiments of the present invention disclosed below are merely examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is defined by the terms of the claims, and also includes all modifications within the meaning and scope equivalent to the terms of the claims. In the following examples and comparative examples, “%” and “part” indicating the content mean mass% or mass part relative to the colored photosensitive resin composition unless otherwise specified.

<Synthesis Example of Binder Resin: Binder Resin (B)>
In a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube, 90 g of propylene glycol monomethyl ether acetate, 90 g of propylene glycol monomethyl ether and 11.0 g of 2-norbornene (0.10 mol) ) Was mixed and introduced, and the atmosphere in the flask was changed from air to nitrogen, and then the temperature was raised to 80 ° C., 70.5 g (0.4 mol) of benzyl methacrylate, 45.0 g (0.5 mol) of methacrylic acid And a solution containing 136 g of propylene glycol monomethyl ether acetate to which 3.2 g of t-butylperoxy 2-ethylhexyl carbonate was added dropwise to the flask over 2 hours from the dropping funnel, and further stirred at 100 ° C. for 5 hours. Continued. Next, the atmosphere in the flask was changed from nitrogen to air, 30 g of glycidyl methacrylate [0.2 mol (40 mol% with respect to the carboxyl group of methacrylic acid used in this reaction)], 0.9 g of trisdimethylaminomethylphenol and Hydroquinone (0.145 g) was charged into the flask, and the reaction was continued at 110 ° C. for 6 hours to obtain Resin B having a solid acid value of 100 mgKOH / g. The polystyrene-reduced weight average molecular weight measured by GPC was 31,000, and the molecular weight distribution (Mw / Mn) was 2.3.

  At this time, an HLC-8120GPC (manufactured by Tosoh Corp.) apparatus was used to measure the weight average molecular weight (Mw) and number average molecular weight (Mn) of the binder resin, and the columns were TSK-GELG4000HXL and TSK-. GELG2000HXL is used in series, the column temperature is 40 ° C., the mobile phase solvent is tetrahydrofuran, the flow rate is 1.0 ml / min, the injection volume is 50 μl, and the detector RI is used. Was 0.6% by mass (solvent = tetrahydrofuran), and TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation) was used as the fixing standard substance.

<Examples 1-4 and Comparative Examples 1-5>
Among the components listed in Table 1 below, the total amount of (A) the pigment as the coloring material and (F) the pigment dispersant as the other additive is a mixture of the pigment, the pigment dispersant and propylene glycol monomethyl ether acetate. Is mixed so that the mass fraction is 20% by mass with respect to the total amount, and the bead mill is used to sufficiently disperse the pigment, and then the bead mill is separated, and the remaining amount including the remaining amount of propylene glycol monomethyl ether acetate is contained. Components were further added and mixed to obtain a colored photosensitive resin composition.

In Table 1, each component is as follows.
Coloring material (A1): Blue pigment dispersion (CI Pigment Green 58)
Coloring material (A2): Yellow pigment dispersion (CI Pigment Yellow 150)
Photopolymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Initiator (D1): Chemical formula 28 [NCI-831 <manufacturer: ADEKA Corporation>]
Initiator (D2): Ethanone-1- [9-ethyl-6- (2-methyl-4tetrahydropyranyloxybenzoyl) -9H-cabazol-3-yl] -1- (0-acetyloxime) (Irgacure OXE02 ; Ciba Specialty Chemical manufactured)
Initiator (D3): 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (Irgacure 369; manufactured by Ciba Specialty Chemical)
Initiator (D4): 4.4'-bis (diethylamino) benzophenone (EAB-F; manufactured by Hodogaya Chemical Co., Ltd.)
Solvent (E): Propylene glycol monomethyl ether acetate Additive (F1): Acrylic pigment dispersant (Disperbyk-2009; manufactured by BYK)
Additive (F2): 3-Methacryloxypropyltrimethoxysilane

<Production of measurement specimen>
A 2 square inch glass substrate (manufactured by Corning, # 1737) was washed with a neutral detergent, water and alcohol in that order and then dried. When the colored photosensitive resin composition (Table 1) is exposed on this glass substrate at an exposure amount (365 nm) of 100 mJ / cm ² and the development step is omitted, the film thickness after post-baking is 3 Spin coated to 2 μm, then pre-dried at 100 ° C. for 3 minutes in a clean oven. After cooling, a substrate coated with this colored photosensitive resin composition and a quartz glass photomask (pattern for changing the transmittance in a stepped manner within a range of 1 to 100%, and a line / space pattern from 1 μm to 50 μm And having an exposure of 100 mJ / cm ^{2 in} an air atmosphere (365 nm) using an ultrahigh pressure mercury lamp (trade name USH-250D) manufactured by Ushio Electric Co., Ltd. . Next, the coating film is immersed in an aqueous developer containing 0.12% nonionic surfactant and 0.06% potassium hydroxide at 26 ° C. for a predetermined time, developed, washed with water, and then washed at 230 ° C. And dried for 60 minutes. In the obtained pixel portion, the surface roughness could not be found. In the non-pixel portion, no development residue was generated on the substrate.

＊１：現像した後、Ｌ／Ｓにパターンの欠けが発生しないようにするために必要な最低必要露光量が２０ｍＪ以下である場合は○、２０ｍＪ超過である場合は×とした。
＊２：実施例及び比較例の組成が、同じ（ｘ，ｙ）色座標上で実施例１組成の透過率（Ｙ）を１００％とした場合、透過率が５％未満に落ちる場合は○、５％以上である場合は×とした。

* 1: After development, when the minimum required exposure required to prevent L / S from lacking a pattern is 20 mJ or less, ◯, and when it exceeds 20 mJ, it was marked as x.
* 2: When the transmittance of the composition of Example 1 and the comparative example is 100% on the same (x, y) color coordinate and the transmittance (Y) of Example 1 is 100%, the transmittance falls below 5%. When it was 5% or more, it was set as x.

  As shown in Table 2, in the case of Examples 1 to 4 including D1 which is a compound containing two or more photoactive oxime ester skeletons in one molecule as a photopolymerization initiator according to the present invention, this is included. Compared to Comparative Examples 1 to 5, it was confirmed that there was no chipping of patterns and a decrease in transmittance even at a low exposure amount.

  11, 12, 13 ... R / G / B pixel pattern, 21 ... SiNx (protective layer) coating film, 31 ... TFT layer, 41 ... glass substrate, 51 ... positive photosensitive resin film, 61 ... IZO layer (common electrode) ).

Claims (6)

A coloring material (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E), wherein the photopolymerization initiator (D) is contained in one molecule In the colored photosensitive resin composition comprising a compound having at least two photoactive oxime ester skeletons,
The compound having at least two photoactive oxime ester skeletons in one molecule is a compound obtained by dimerizing a compound represented by the following chemical formula 18 via R ₁ or R _2. Resin composition.

(In the chemical formula 18, R ₁ , R ₂ , and R ₃ each independently represent R ₁₁ , OR ₁₁ , COR ₁₁ , SR ₁₁ , CONR ₁₂ R ₁₃ or CN,
R ₄ and R ₅ are each independently R ₁₁ , OR ₁₁ , SR ₁₁ , COR ₁₁ , CONR ₁₂ R ₁₃ , NR ₁₂ COR ₁₁ , OCOR ₁₁ , COOR ₁₁ , SCOR ₁₁ , OCSR ₁₁ , COSR ₁₁ , CSOR ₁₁ , CN, a halogen atom or a hydroxyl group,
a and b are each independently 0-3.
R ₁₁ , R ₁₂ and R ₁₃ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a carbon atom. indicates 2-20 heterocyclic group, wherein the alkyl group, an aryl group, a hydrogen atom of the arylalkyl group and heterocyclic _{group, R 21, oR 21, COR} 21, SR 21, NR 22 R 23, CONR _{22 R 23, -NR 22 -OR 23} , -NCOR 22 -OCOR 23, -C (= N-OR 21) -R 22, -C (= N-OCOR 21) -R 22, CN, halogen atom, - _{CR 21 = CR 22 R 23,} -CO-CR 21 = CR 22 R 23, OCO-CR 21 = CR 22 R 23, O-C 1-6 alkylene _-OCOR 21, COO It may be substituted by ₂₁ or an epoxy group,
R ₂₁ , R ₂₂ and R ₂₃ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a carbon atom. Represents a heterocyclic group of formula 2 to 20,
The methylene group of the alkylene moiety of the substituent represented by R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ and R ₂₃ is an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond or The substituent may be interrupted 1 to 5 times, the alkyl part of the substituent may have a branched side chain, may be a cyclic alkyl, and the alkyl terminal of the substituent is an unsaturated bond. You can,
R ₁₂ and R ₁₃ and R ₂₂ and R ₂₃ may each form a ring, and R ₃ may form a ring with an adjacent benzene ring. ) The colored photosensitive resin composition according to claim 1, wherein the compound dimerized via R ₁ or R ₂ is a compound represented by the following chemical formula 19 or 20.

(In the chemical formula 19 and chemical formula 20, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , a, and b have the same meanings as defined in the chemical formula 18.) The colored photosensitive resin composition according to claim 1, wherein the compound dimerized via R ₁ or R ₂ is a compound represented by the following chemical formula 28:

Content of the said photoinitiator (D) is 0.1-40 by mass fraction with respect to the total amount of the said binder resin (B) and the said photopolymerizable compound (C) on the basis of solid content. Mass%,
The compound having at least two photoactive oxime ester skeletons in the one molecule is contained in a mass fraction of 10% by mass or more based on the solid content with respect to the photopolymerization initiator (D). The colored photosensitive resin composition according to claim 1.   A color comprising a color layer formed by forming the colored photosensitive resin composition according to any one of claims 1 to 4 in a predetermined pattern on a substrate, and then exposing and developing the color layer. filter.   A liquid crystal display device comprising the color filter according to claim 5.

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