JP2013114249A - Black photosensitive resin composition and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a black photosensitive resin composition for forming, by using a general photo mask of proximity exposure system, a black matrix that has less variation in line width, no pattern deficit, high quality and 5 μm or less of line width.SOLUTION: A black photosensitive resin composition contains at least a black pigment, a binder resin, a photopolymerizable monomer, a photopolymerization initiator represented by the following formula (1), a polymerization inhibitor and a solvent.

Description

  The present invention relates to a color filter used for a television receiver, a computer, a mobile phone terminal, and the like, and a black photosensitive resin composition used for forming a black matrix of the color filter.

  A color filter is an indispensable component for colorization of a liquid crystal display device that has been applied in various fields in recent years. The color filter is obtained by providing colored pixels such as red, green, and blue on a transparent substrate such as glass. In general, a light-shielding portion (black matrix) is provided between the colored pixels in order to improve the contrast and to prevent malfunction caused by light of the TFT element provided on the counter substrate in the liquid crystal display device. .

  Various methods such as a printing method, an electrodeposition method, and an ink-jet method have been devised as methods for forming the colored pixels and the black matrix, and photolithography methods that are excellent in quality are widely used. In general, a color filter is produced by photolithography according to the following procedure. A black photosensitive resin composition is applied to the substrate and exposed and developed through a mask having a predetermined pattern to form a black matrix. As an exposure method, a proximity exposure (proximity exposure) method in which the distance between the substrate and the photomask (exposure gap) is maintained on the order of μm and irradiation light is irradiated is common. Subsequently, for example, a photosensitive resin composition in which a red pigment is dispersed is applied, and exposure and development are performed through a photomask corresponding to the black matrix opening in the display region, thereby forming a red pixel. By performing the same operation using a photosensitive resin composition in which green and blue pigments are dispersed, a color filter having red, green and blue colored pixels can be produced.

  In recent years, liquid crystal display devices used in mobile devices such as mobile phone terminals have been strongly demanded to have higher definition as the display content becomes more sophisticated. High definition of the liquid crystal display device requires high definition of both the TFT element and the color filter.

  If the pixel size of the color filter is made fine for high definition, the transmittance is lowered and the luminance of the liquid crystal display device is lowered. In order to achieve both high definition and high transmittance, it is essential to thin the black matrix of the color filter.

  Conventionally, the black matrix line width of a color filter for mobile devices has been about 6 μm, but the formation of fine lines of 5 μm and further 4 μm has been demanded.

  In order to make the black matrix thin, it is necessary to keep the exposure amount low and lengthen the development time. However, when the exposure amount is kept low, the black photosensitive resin composition is insufficiently cured, resulting in insufficient development resistance in the exposed area, large variations in line width in the substrate, and pattern defects. It becomes easy to do. Also, when the development time is lengthened, pattern shape defects or pattern defects are likely to occur.

Narrowing the opening width of the photomask used at the time of exposure is also an effective means for achieving thinning of the black matrix. However, when the opening width is narrowed, the influence of interference becomes stronger, the light intensity distribution actually irradiated to the coating film of the black photosensitive resin composition becomes broader, and the peak intensity is significantly reduced. As a result, the thinning effect as expected can not be obtained, and problems such as pattern surface peeling occur.

  By narrowing the exposure gap, it is possible to maintain a sharp light intensity distribution even when a photomask having a narrow aperture width is used. However, it is difficult to completely eliminate the distortion of the substrate stage of the exposure apparatus and the deflection of the photomask. If the gap is narrowed, there is a risk that the mask and the coating film of the photosensitive resin composition come into contact with each other and the same defect occurs. Rise. In the worst case, it may be assumed that the photomask is damaged.

  Although the above problem can be solved by using the projection exposure method, there are problems that the method is expensive and the throughput is low. The demand for cost reduction for liquid crystal display devices is increasing, and it is difficult to adopt a projection exposure method that goes against such a trend. Therefore, a method for forming a black matrix fine line pattern of 5 μm or less by a general proximity exposure method is required.

  In order to solve these problems, for example, in Patent Document 1 below, an auxiliary pattern that is narrower than the opening width and is not resolved after development processing is disposed on the photomask, so that the coating film of the photosensitive resin composition is actually provided. Proposals have been made to change the intensity distribution of the irradiated light to form a fine line pattern of a black matrix. However, in this proposal, the line width of the black matrix is only discussed up to a range of 6 μm ± 1 μm, and there is no description about 5 μm or less. In addition, the mask drawing work becomes complicated by providing the auxiliary pattern, and there is a concern that the lead time is delayed and the cost is increased.

  On the other hand, Patent Document 2 below proposes forming a fine line pattern of a black matrix by using an acidic group-containing monomer having a specific structure and a polymerization inhibitor in combination. However, in this proposal, there is a discussion about an increase in margin for variations in exposure conditions (exposure gap) and development conditions (development time) when using a photomask having an opening width of several tens of μm, and a black matrix having a line width of 5 μm or less. It did not provide a specific method of forming the fine line pattern.

JP 2007-148300 A JP 2007-34119 A

  The present invention has been made in view of such circumstances, and a high-quality line width of 5 μm or less using a general photomask in a proximity exposure method that has been widely used, with little variation in line width and no pattern defects. A black photosensitive resin composition for forming a black matrix is provided.

  The invention according to claim 1 of the present invention is a black photosensitive resin composition containing at least a black pigment, a binder resin, a photopolymerizable monomer, a photopolymerization initiator, a polymerization inhibitor, and a solvent, wherein the photopolymerization start The black photosensitive resin composition is characterized in that the agent is a compound represented by the following formula (1).

〔式（１）において、Ｘ^１・Ｘ^３・Ｘ^６は、それぞれ独立にＲ_１１、ＯＲ_１１、ＣＯＲ_１１、ＳＲ_１１、ＣＯＮＲ_１２Ｒ_１３又はＣＮを表し、Ｘ^２は置換基を有していてもよい
炭素原子数１〜２０のアルキル基、置換基を有していてもよい炭素原子数６〜３０のアリール基、置換基を有していてもよい炭素原子数７〜３０のアリールアルキル基又は置換基を有していてもよい炭素原子数２〜２０の複素環基を表し、Ｘ^４及びＸ^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、ＣＯＳＲ_１１、ＣＯＳＲ_１１、ＣＳＯＲ_１１、ＣＮ、ハロゲン原子又は水酸基を表す。Ｒ_１１、Ｒ_１２及びＲ_１３は、それぞれ独立に、水素原子、置換基を有していてもよい炭素原子数１〜２０のアルキル基、置換基を有していてもよい炭素原子数６〜３０のアリール基、置換基を有していてもよい炭素原子数７〜３０のアリールアルキル基又は置換基を有していてもよい炭素原子数２〜２０の複素環基を表す。ａ及びｂはそれぞれ独立に、０〜３である。〕

[In the formula (1), X ¹ , X ³ and X ⁶ each independently represent R ₁₁ , OR ₁₁ , COR ₁₁ , SR ₁₁ , CONR ₁₂ R ₁₃ or CN, and X ² has a substituent. An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms which may have a substituent, and an arylalkyl having 7 to 30 carbon atoms which may have a substituent Represents a heterocyclic group having 2 to 20 carbon atoms which may have a group or a substituent, and X ⁴ and X 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 , COSR ₁₁ , COSR ₁₁ , CSOR ₁₁ , CN, a halogen atom or a hydroxyl group. R ₁₁ , R ₁₂ and R ₁₃ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted carbon atom having 6 to 6 carbon atoms. It represents a 30 aryl group, an optionally substituted arylalkyl group having 7 to 30 carbon atoms, or an optionally substituted heterocyclic group having 2 to 20 carbon atoms. a and b are each independently 0-3. ]

  The invention according to claim 2 of the present invention is characterized in that the content of the photopolymerization initiator is 1 to 20% by weight based on the total solid content of the black photosensitive resin composition. Item 2. The black photosensitive resin composition according to Item 1.

  The invention according to claim 3 of the present invention contains at least one hydroquinone polymerization inhibitor as the polymerization inhibitor, wherein the black photosensitive resin composition according to claim 1 or 2 is characterized. It is a thing.

  The invention according to claim 4 of the present invention is characterized in that the content of the polymerization inhibitor is 0.01 to 0.5% by weight with respect to the total solid content of the black photosensitive resin composition. It is a black photosensitive resin composition in any one of Claims 1-3.

  The invention according to claim 5 of the present invention is a color filter comprising a black matrix formed using the black photosensitive resin composition according to any one of claims 1 to 4.

  The invention according to claim 6 of the present invention is the color filter according to claim 5, wherein the pattern line width of the black matrix is 5 μm or less.

  By using the black photosensitive resin composition of the present invention, a high-quality line width of 5 μm or less is obtained using a general photomask in a proximity exposure method that has been widely used, with little line width variation and no pattern defects. It is possible to form a black matrix.

It is the synthesis method of the photoinitiator of one Embodiment which concerns on this invention.

  The detailed contents of the present invention will be described below.

  Examples of the black pigment used in the black photosensitive resin composition of the present invention include organic pigments such as carbon black, graphite, aniline black and cyanine black, and inorganic pigments such as titanium oxide and iron oxide. Carbon black is particularly preferred.

  As content of the said black pigment, it is preferable that it is 35 to 60 weight% with respect to the total solid of a black photosensitive resin composition, More preferably, it is the range of 40 to 55 weight%. When the content of the black pigment is within this range, it is possible to achieve both high light shielding properties and good patterning characteristics (linearity, cross-sectional shape, etc.). When the content of the black pigment is 35% by weight or less, the heat flow property of the pattern is increased, and the line width shift amount in the post-baking process is increased, which is not suitable for forming a thin line. On the other hand, when the content of the black pigment is 60% by weight or more, the linearity of the pattern is deteriorated and a reverse taper shape tends to be obtained.

  As the binder resin, alkyl acrylate or alkyl methacrylate such as acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, cyclic cyclohexyl acrylate or methacrylate, hydroxyethyl acrylate or methacrylate, A resin having a molecular weight of about 5,000 to 100,000, which is synthesized using about 3 to 5 types of monomers such as styrene, can be preferably used.

  In addition, as a resin in which an unsaturated double bond is added to a part of an acrylic resin, a compound such as the above acrylic resin, isocyanate ethyl acrylate having at least one vinyl group and an isocyanate group, or methacryloyl isocyanate is reacted. The photosensitive copolymer having an acid value of 50 to 150 can be preferably used from the viewpoints of heat resistance, developability and the like. Furthermore, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin, polycarboxylic acid glycidyl ester, polyol polyglycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy resin, triphenolmethane type epoxy resin, Ordinary photopolymerizable resins such as epoxy (meth) acrylate obtained by reacting an epoxy resin such as a dihydroxybenzene type epoxy resin and (meth) acrylic acid, or a cardo resin can also be used.

  Examples of the photopolymerizable monomer include ethylene glycol (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and polypropylene. Glycol di (meth) acrylate, hexane di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, glycerin tetra (meth) acrylate, tetratrimethylolpropane tri (meth) ) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol pen (Meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like, these components are used alone or as a mixture. Various modified (meth) acrylates, urethane (meth) acrylates, and the like can also be used. Among these, pentafunctional / 6 functional monomers that can suppress the amount of line width shift in the post-baking process, specifically, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferably used.

  As content of a photopolymerizable monomer, it is preferable that it is 5 to 20 weight% with respect to the total solid of a black photosensitive resin composition, More preferably, it is the range of 10 to 15 weight%. When the content of the photopolymerizable monomer is within this range, the sensitivity and development speed of the black photosensitive resin composition can be adjusted to a level suitable for production. When the content of the photopolymerizable monomer is 5% by weight or less, the sensitivity of the black photosensitive resin composition is insufficient. On the other hand, when the content of the black pigment is 20% by weight or more, the linearity of the pattern is deteriorated, and an inversely tapered shape is easily obtained.

  The black photosensitive resin composition of this invention contains the compound represented by following formula (1) as a photoinitiator.

式（１）において、Ｘ^１・Ｘ^３・Ｘ^６は、それぞれ独立にＲ_１１、ＯＲ_１１、ＣＯＲ_１１、ＳＲ_１１、ＣＯＮＲ_１２Ｒ_１３又はＣＮを表し、Ｘ^２は置換基を有していてもよい炭素原子数１〜２０のアルキル基、置換基を有していてもよい炭素原子数６〜３０のアリー
ル基、置換基を有していてもよい炭素原子数７〜３０のアリールアルキル基又は置換基を有していてもよい炭素原子数２〜２０の複素環基を表し、Ｘ^４及びＸ^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、ＣＯＳＲ_１１、ＣＯＳＲ_１１、ＣＳＯＲ_１１、ＣＮ、ハロゲン原子又は水酸基を表す。Ｒ_１１、Ｒ_１２及びＲ_１３は、それぞれ独立に、水素原子、置換基を有していてもよい炭素原子数１〜２０のアルキル基、置換基を有していてもよい炭素原子数６〜３０のアリール基、置換基を有していてもよい炭素原子数７〜３０のアリールアルキル基又は置換基を有していてもよい炭素原子数２〜２０の複素環基を表す。ａ及びｂはそれぞれ独立に、０〜３である。

In Formula (1), X ¹ , X ^3, and X ⁶ each independently represent R ₁₁ , OR ₁₁ , COR ₁₁ , SR ₁₁ , CONR ₁₂ R _13, or CN, and X ² has a substituent. Or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms which may have a substituent, and an arylalkyl group having 7 to 30 carbon atoms which may have a substituent. Or an optionally substituted heterocyclic group having 2 to 20 carbon atoms, and X ⁴ and X 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 , COSR ₁₁ , COSR ₁₁ , CSOR ₁₁ , CN, a halogen atom or a hydroxyl group. R ₁₁ , R ₁₂ and R ₁₃ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted carbon atom having 6 to 6 carbon atoms. It represents a 30 aryl group, an optionally substituted arylalkyl group having 7 to 30 carbon atoms, or an optionally substituted heterocyclic group having 2 to 20 carbon atoms. a and b are each independently 0-3.

X ¹ is particularly preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n-, from the viewpoint of ease of synthesis, sensitivity, solubility, and storage stability when contained in a photosensitive coloring composition. Alkyl groups having 10 or less carbon atoms such as butyl group, isobutyl group, t-butyl group, n-amyl group, isoamyl group, t-amyl group, n-hexyl group, 2-ethylhexyl group, cyclopentyl group, cyclohexyl group, etc. A cyclic alkyl group, methoxymethyl group, ethoxymethyl group, ethoxyethyl group, 2- (1-methoxypropyl) group, 2- (1-ethoxypropyl) group and the like which may have a side chain having 10 or less carbon atoms, etc. It is an alkyl group having 10 or less carbon atoms and having one ether bond in the methylene chain.

X ³ is particularly preferably hydrogen, or a methyl group, an ethyl group, an n-propyl group, or an isopropyl group from the viewpoint of ease of synthesis, sensitivity, solubility, and storage stability when contained in a photosensitive coloring composition. , N-butyl group, isobutyl group, t-butyl group, n-amyl group, isoamyl group, t-amyl group, n-hexyl group and other alkyl groups having 6 or less carbon atoms, cyclopentyl group, cyclohexyl group, etc. 6 or less cyclic alkyl group, methoxymethyl group, ethoxymethyl group, ethoxyethyl group, 2- (1-methoxypropyl) group, 2- (1-ethoxypropyl) group and the like having 6 or less carbon atoms in the methylene chain An alkyl group having one ether bond.

X ⁶ is particularly preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n- group, from the viewpoint of ease of synthesis, sensitivity, solubility, and storage stability when contained in a photosensitive coloring composition. Alkyl groups having 6 or less carbon atoms such as butyl group, isobutyl group, t-butyl group, n-amyl group, isoamyl group, t-amyl group and n-hexyl group, and 6 or less carbon atoms such as cyclopentyl group and cyclohexyl group. It has 6 or less carbon atoms such as cyclic alkyl group, methoxymethyl group, ethoxymethyl group, ethoxyethyl group, 2- (1-methoxypropyl) group, 2- (1-ethoxypropyl) group and the like, and an ether bond is formed in the methylene chain. It is an alkyl group having one.

X ² is particularly preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-group, from the viewpoint of ease of synthesis, sensitivity, solubility, and storage stability when contained in a photosensitive coloring composition. Alkyl groups having 6 or less carbon atoms such as butyl group, isobutyl group, t-butyl group, n-amyl group, isoamyl group, t-amyl group and n-hexyl group, and 6 or less carbon atoms such as cyclopentyl group and cyclohexyl group. It has 6 or less carbon atoms such as cyclic alkyl group, methoxymethyl group, ethoxymethyl group, ethoxyethyl group, 2- (1-methoxypropyl) group, 2- (1-ethoxypropyl) group and the like, and an ether bond is formed in the methylene chain. It is an alkyl group having one.

X ⁴ and X ⁵ are particularly preferably hydrogen, a methyl group, an ethyl group, or an n-propyl group from the viewpoint of ease of synthesis, sensitivity, solubility, and storage stability when contained in a photosensitive coloring composition. , An isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-amyl group, an isoamyl group, a t-amyl group, an n-hexyl group, and the like.

  Preferable specific examples of the photopolymerization initiator represented by the formula (1) include compounds of the following formulas (2) to (10).

The method for synthesizing the photopolymerization initiator represented by the formula (1) is not particularly limited, but can be synthesized by the method shown in FIG.
<Step 1>
Synthesis of acyl body: Nitrocarbazole compound 1 and acid chloride 2 are reacted in the presence of aluminum chloride to obtain acyl body 3 of FIG.
<Step 2>
Synthesis of oxime compound 4: Acyl compound 3, hydroxylamine hydrochloride and dimethylformamide are charged, and heated and stirred to obtain oxime compound 4 of FIG.
<Step 3>
Synthesis of photopolymerization initiator: The oxime compound 4 and the acid anhydride 5 are heated and stirred, and after completion of the reaction, neutralized with an alkali to obtain a photopolymerization initiator represented by the formula (1).

  The photopolymerization initiator represented by the above formula (1) is excellent in matching with a high-pressure mercury lamp widely used as a light source of a proximity exposure apparatus, and is a main emission line i-line (365 nm), h-line (405 nm). ) Efficiently, the black photosensitive resin composition can be made highly sensitive. For this reason, even when the exposure amount is kept low for thinning, the pattern can be sufficiently cured, and it is possible to reduce line width variation and prevent occurrence of pattern defects. Further, since the sensitivity of the black photosensitive resin composition can be adjusted to a level that does not hinder the productivity with a small amount, the amount of the resin in the composition can be increased correspondingly, and the development margin can be expanded. .

  Moreover, it is preferable that content of the photoinitiator represented by the said Formula (1) is 1 to 20 weight% in solid content of the said black photosensitive resin composition, More preferably, it is 2 to 15 weight% Range. When the content of the photopolymerization initiator is within this range, it is possible to form a black matrix pattern having a line width of 5 μm or less with an exposure amount suitable for production. When the content of the photopolymerization initiator is 1% by weight or less, the sensitivity of the black photosensitive resin composition is insufficient. On the other hand, when the content of the photopolymerization initiator is 20% by weight or more, the pattern line width of the black matrix becomes too thick.

In the black photosensitive resin composition of the present invention, other photopolymerization initiators can be used in combination with the photopolymerization initiator represented by the formula (1). Other photopolymerization initiators include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Acetophenone compounds such as butan-1-one, benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenyl Benzophenone compounds such as benzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, thioxanthone, 2- Thioxanthone compounds such as chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6- Bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -S-triazine, -Piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6 Triazine, triazine compounds such as 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime) ], O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine, etc. Phosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, etc. A quinone compound, a borate compound, a carbazole compound, an imidazole compound, a titanocene compound, or the like is used. These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required. The content of the other photopolymerization initiator is preferably 0.1 to 5% by weight, more preferably 0.2 to 1% by weight in the solid content of the black photosensitive resin composition.

  The black photosensitive resin composition of this invention contains a polymerization inhibitor with the photoinitiator represented by said Formula (1). By adding a polymerization inhibitor, it is possible to significantly suppress the increase in line width due to diffracted light that becomes a barrier when forming a fine line by the proximity exposure method. In addition, since it is hardly affected by diffracted light, the curability of the pattern edge is excellent, and the line width change due to development variations can be reduced. By combining the effect of the photopolymerization initiator represented by the formula (1) and the effect of the polymerization inhibitor, it is possible to accurately form a black matrix pattern having a line width of 5 μm or less.

  The polymerization inhibitor contains at least one kind of hydroquinone polymerization inhibitor that is excellent in compatibility with the black photosensitive resin composition and the alkali developer and has a slight influence on the exposure sensitivity level itself. It is preferable. Specifically, hydroquinone, tert-butylhydroquinone, 2,5-bis (1,1-dimethylbutyl) hydroquinone, 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone, etc. are used. . In addition, catechol-based polymerization inhibitors such as catechol and tert-butylcatechol can also be used.

In addition to the monocyclic aromatic compound, a polycyclic aromatic compound can be used. Examples of the polycyclic aromatic compound include compounds represented by the following formulas (11) and (12).

  The addition amount of the polymerization inhibitor is preferably 0.01 to 0.5% by weight, more preferably 0.05 to 0.3% by weight in the solid content of the black photosensitive resin composition. . When the content of the photopolymerization inhibitor is within this range, it is possible to form a black matrix pattern having a line width of 5 μm or less with an exposure amount suitable for production. When the content of the photopolymerization inhibitor is 0.01% by weight or less, a sufficient effect cannot be obtained. On the other hand, when the content of the photopolymerization inhibitor is 0.5% by weight or more, the sensitivity of the black photosensitive resin composition is insufficient.

  Solvents include methanol, ethanol, ethyl cellosolve, ethyl cellosolve acetate, diglyme, cyclohexanone, ethylbenzene, xylene, isoamyl acetate, n amyl acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol mono Ethyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, triethylene glycol, Liethylene glycol monomethyl ether, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether, triethylene glycol monoethyl ether acetate, liquid polyethylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether , Dipropylene glycol monoethyl ether acetate, lactic acid ester, ethyl ethoxypropionate and the like.

  The colored pixels in the color filter of the present invention can be formed in the same manner as in the case of a black matrix using a photosensitive resin composition containing a red, green, or blue colorant. As the colorant, any known colorant used in conventional color filter production can be used. In addition, a plurality of colorants can be used in combination for spectral adjustment of the color filter.

  The black photosensitive resin composition of the present invention can be used in combination with a surfactant for further improving the coatability, a silane coupling agent for improving the adhesion to the substrate, and the like.

  Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates, and higher amines. Cationic surfactants such as halogenates and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and fatty acid monoglycerides, amphoteric surfactants, silicone surfactants Surfactants such as agents can be used, and these may be used in combination.

As the silane coupling agent, vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane, epoxy silanes such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 3-glycidoxypropyldimethoxysilane, Methacrylsilanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, N- Aminosilanes such as phenyl-3-aminopropyltrimethoxysilane, mercaptosilanes such as 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrieth Isocyanate silanes such as Shishiran like.

  Specifically, the color filter of the present invention can be produced as follows. First, a coating film of the black photosensitive resin composition of the present invention is formed on a substrate by a spin coating method or the like. Next, exposure is performed through a photomask corresponding to the pattern of the black matrix, and the exposed portion is photocured. Next, the black matrix is formed by removing the unexposed portion by alkali development and baking by heating. Next, the same process is repeated using a colored photosensitive resin composition containing red, green and blue colorants and a photomask corresponding to the opening of the black matrix, thereby forming the color filter of the present invention. be able to.

  EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated further in detail, this invention is not limited to these Examples.

<Example 1>
The following materials were added and stirred well to obtain a black photosensitive resin composition No. 1 was obtained.
Black pigment: 43.9 g of carbon black dispersion (solid content 77%)
(“ABK-2015” manufactured by Gokoku Color Co., Ltd.)
Binder resin: Bisphenol fluorene type epoxy resin 7.0g
(“V259-ME” manufactured by Nippon Steel Chemical Co., Ltd.)
・ Photopolymerizable monomer:
Dipentaerythritol penta / hexaacrylate mixture 2.2g
(“KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.)
-Photopolymerization initiator: 0.7 g of the same structure as formula (2)
("NCI-831" manufactured by ADEKA)
・ Polymerization inhibitor: (“Methylhydroquinone” manufactured by Wako Pure Chemical Industries, Ltd.) 0.01 g
・ Solvent: 46.2 g of propylene glycol monomethyl ether acetate

<Example 2>
A black photosensitive resin composition No. 1 was prepared in the same manner as in Example 1 except that the polymerization inhibitor was 0.02 g. 2 was obtained.

<Example 3>
A black photosensitive resin composition No. 1 was prepared in the same manner as in Example 1 except that 0.4 g of “NCI-831” manufactured by ADEKA and 0.4 g of “Irgacure 369” manufactured by BASF were used as the photopolymerization initiator. 3 was obtained.

<Example 4>
A black photosensitive resin composition No. 1 was prepared in the same manner as in Example 1 except that 0.01 g of “Kinopower MNT” manufactured by Kawasaki Kasei Kogyo Co., Ltd. having the same structure as the formula (11) was used as the polymerization inhibitor. 4 was obtained.

<Comparative Example 1>
In the same manner as in Example 1, except that the photopolymerization initiator was 0.4 g of “Irgacure OXE 02” manufactured by BASF Corporation represented by the following formula (13), the black photosensitive resin composition No. 5 was obtained.

<Comparative example 2>
Black as in Example 1 except that 0.4 g of “NCI-831” manufactured by ADEKA and 0.4 g of “Irgacure 369” manufactured by BASF are used as the photopolymerization initiator, and no polymerization inhibitor is used. Photosensitive resin composition No. 6 was obtained.

<Evaluation of black photosensitive resin composition>
Using the black photosensitive resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 and 2, a black matrix pattern was formed by the following method, the line width of the black matrix pattern was measured, and the appearance of the pattern Was observed with an optical microscope. In addition, the determination regarding the appearance of the pattern was evaluated as “◯” when there was no defect and good linearity, and “X” when the pattern defect and / or deterioration in linearity was observed. The results are shown in Table 1 below.
The above black photosensitive resin composition No. 1 was spin-coated on a glass substrate (“EAGLE XG” manufactured by Corning). 1 coating film was formed. After drying, it was pre-baked on a hot plate at 90 ° C. for 1 minute. Next, the coating film of the black photosensitive resin composition was irradiated with ultraviolet light through a photomask having an opening width of 6 μm using an ultrahigh pressure mercury lamp (illuminance 26 mW / cm ² ). After the exposure, development was performed with a 2.5% by weight aqueous sodium carbonate solution to form a black matrix pattern on the glass substrate. Each black photosensitive resin composition whose development time was 60 seconds, 70 seconds, and 80 seconds in a 230 ° C. clean oven for 30 minutes, then the width of the black matrix pattern was measured, and the appearance of the pattern was observed with an optical microscope. The evaluation was performed at two levels of development time of 60 seconds and 70 seconds.

<Comparison result>
Each of the products of the present invention obtained in Examples 1 to 4 was able to form a black matrix pattern having a good appearance with a line width of 5 μm or less, and the development margin was also good. On the other hand, the comparative product obtained in Comparative Examples 1 and 2 had a thick line width and poor appearance, and it was impossible to form a black matrix pattern having a good appearance with a line width of 5 μm or less.

  From the above results, it is possible to accurately form a black matrix pattern having a line width of 5 μm or less by using the black photosensitive resin composition of the present invention, and as a result, the aperture ratio of the color filter is improved. Therefore, high brightness can be achieved in a high-definition liquid crystal display device.

Claims (6)

A black photosensitive resin composition containing at least a black pigment, a binder resin, a photopolymerizable monomer, a photopolymerization initiator, a polymerization inhibitor, and a solvent, wherein the photopolymerization initiator is represented by the following formula (1). A black photosensitive resin composition, which is a compound.

[In the formula (1), X ¹ , X ³ and X ⁶ each independently represent R ₁₁ , OR ₁₁ , COR ₁₁ , SR ₁₁ , CONR ₁₂ R ₁₃ or CN, and X ² has a substituent. An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms which may have a substituent, and an arylalkyl having 7 to 30 carbon atoms which may have a substituent Represents a heterocyclic group having 2 to 20 carbon atoms which may have a group or a substituent, and X ⁴ and X 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 , COSR ₁₁ , COSR ₁₁ , CSOR ₁₁ , CN, a halogen atom or a hydroxyl group. R ₁₁ , R ₁₂ and R ₁₃ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted carbon atom having 6 to 6 carbon atoms. It represents a 30 aryl group, an optionally substituted arylalkyl group having 7 to 30 carbon atoms, or an optionally substituted heterocyclic group having 2 to 20 carbon atoms. a and b are each independently 0-3. ]   2. The black photosensitive resin composition according to claim 1, wherein the content of the photopolymerization initiator is 1 to 20 wt% with respect to the total solid content of the black photosensitive resin composition.   The black photosensitive resin composition according to claim 1 or 2, wherein the polymerization inhibitor contains at least one hydroquinone polymerization inhibitor.   The content of the polymerization inhibitor is 0.01 to 0.5 wt% with respect to the total solid content of the black photosensitive resin composition. Black photosensitive resin composition.   A color filter comprising a black matrix formed using the black photosensitive resin composition according to claim 1.   6. The color filter according to claim 5, wherein a pattern line width of the black matrix is 5 [mu] m or less.

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