JP6252039B2 - Color filter and liquid crystal display device - Google Patents

Description

The present invention relates to a color filter of a liquid crystal display device using a photosensitive resin composition having high sensitivity, excellent transparency, and little occurrence of unevenness during curing.

  As the functionality of image display devices increases, a wide viewing angle and high-speed response are required. For a wide viewing angle and a high-speed response, a display method in which lateral electrolysis is applied to a liquid crystal layer such as an IPS mode or a TBA mode is suitable. In a liquid crystal display device of a display type that applies a horizontal electric field, electrodes are not provided on a substrate provided with a filter layer such as a color filter, so that gas components and moisture generated from the filter layer enter the liquid crystal layer. As a result, the concentration of impurity ions in the liquid crystal layer increases, and there is a problem that bubbles in the liquid crystal and display defects are likely to occur.

  Therefore, on the side of the colored layer that is in contact with the liquid crystal layer, a transparent film layer for preventing gas, moisture, and impurity ions of the color filter composed of the light shielding layer and the colored layer from entering the liquid crystal layer and for the purpose of flattening the color filter. It is common to use a color filter in which the is formed.

  As a characteristic required for the transparent film layer of the color filter for liquid crystal display device described above, it is essential not to lower the transmittance of the colored layer serving as a base, and high transparency is required.

  Further, in the liquid crystal display device, the flatness of the color filter is caused by the existence of gap unevenness between Red, Green, and Blue pixels caused by the waviness of the transparent substrate surface of the color filter, or gap unevenness within each pixel. Damaged and causes color unevenness or contrast unevenness. As a result, since the image quality is lowered, the transparent film layer is required to have high flatness.

  Particularly in recent years, with the spread of smartphones and tablet-type terminals, image display devices have become higher in definition, and there is a strong demand for thinning color filters with narrowing gaps and thinning of image display devices. The demand for flattening the transparent film layer of the color filter is getting stronger.

  Moreover, the formation of the transparent film layer using the photo-curing resin is exposed and developed, and if the exposure is insufficient or unevenness occurs in the curing, the unevenness occurs during the development and the productivity is lowered. .

  In addition, after the transparent film is formed, post-process defects caused by uneven curing of the transparent film layer also occur during processes such as the photo spacer and alignment film formation, resulting in decreased productivity, and further variations in the height of the photo spacer. This causes the display quality of the liquid crystal display device to be greatly deteriorated, such as the occurrence of misalignment or the occurrence of alignment failure due to uneven coating of the alignment film. For this reason, the photosensitive resin composition for forming the transparent film layer is required to have high sensitivity and excellent curing uniformity.

  Conventionally, for the purpose of countermeasures for uneven curing of the transparent film layer and shortening the lead time during production, countermeasures have been taken by increasing the sensitivity of the photosensitive resin composition used for forming the transparent film layer. In order to increase the sensitivity of the photosensitive resin composition, it is common to increase the amount of the photopolymerizable monomer or the amount of the photopolymerization initiator.

However, when the amount of the photopolymerizable monomer is increased, the low molecular component in the photosensitive resin composition increases, so that there is a problem that the film easily flows and the flatness is lowered. Moreover, about the increase in the photoinitiator, there existed a problem that the transmittance | permeability will fall by coloring of a photoinitiator (patent document 1).

  For this reason, many studies have been conducted on binder polymers for the purpose of increasing sensitivity. However, when the sensitivity is increased with the binder polymer, problems such as deterioration in developability and storage stability are likely to occur, and there remains room for study (Patent Document 2).

JP 2001-106765 A JP 2001-064337 A

  The present invention has been made in consideration of the above-mentioned problems, and has a high sensitivity, excellent resolution, transparency, and storage stability, and a photosensitive resin composition that hardly causes uneven curing, and uses the same. The object is to provide a color filter and a liquid crystal display device.

As means for solving the above-mentioned problems, the invention described in claim 1 is a photopolymerization initiator containing a fluorene-based oxime ester compound represented by chemical formula 2, having a polystyrene-equivalent weight average molecular weight of 20,000 to A photosensitive resin composition containing a binder polymer, a photosensitive monomer, a surfactant, and a solvent, which is an acrylic polymer having an acid value of 40,000 and an acid value of 90 to 160, is used as a transparent film layer. A color filter laminated on a light shielding layer on a substrate and a colored pixel layer and fired at 230 ° C .;
And flattening index of the transparent film layer is a color filter, characterized in der Rukoto the range of 87.5 to 88.1%.

The invention according to claim 2 is a photopolymerization initiator containing a fluorene-based oxime ester compound represented by Formula 3, a polystyrene-equivalent weight average molecular weight of 20,000 to 40,000, and an acid A light-sensitive layer on a glass substrate, a colored pixel layer, using a photosensitive resin composition containing a binder polymer, a photosensitive monomer, a surfactant, and a solvent having a valence of 90 to 160 as a transparent film layer A color filter laminated on top and fired at 230 ° C.
And the flatness rate of the said transparent film layer is in the range of 87.8-88.1 %, It is a color filter characterized by the above-mentioned.

According to a third aspect of the present invention, there is provided a liquid crystal display device using the color filter according to the first or second aspect.

The present invention is a photopolymerization initiator containing a fluorene-based oxime ester compound represented by Formula 2 or Formula 3, a polystyrene equivalent weight average molecular weight of 20,000 to 40,000, and an acid value of 90 Use of a photosensitive resin composition containing a binder polymer, a photosensitive monomer, a surfactant, and a solvent, which is an acrylic polymer of ˜160, provides excellent transparency and flatness and excellent transparency in curing uniformity. A film layer can be formed, and a color filter with excellent display quality and a liquid crystal display device can be provided by using the film layer.

  Hereinafter, the present invention will be described in more detail with reference to embodiments, but the present invention is not limited only to these embodiments.

  The photosensitive resin composition of the present invention comprises (a) a photopolymerization initiator, (b) a binder polymer, (c) a photosensitive monomer, (d) a surfactant, (e) a solvent, and (f) an epoxy compound. Contains.

The (a) a photopolymerization initiator, and characterized in that it contains at least, of formula as fluorene oxime ester compound represented by 1, of Formula 2, or of formula fluorene oxime ester compound represented by 3 To do.

In Formula 1, X ¹ represents R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN, and X ² · X ³ has 1 to 1 carbon atoms which may have a substituent. 20 alkyl group, aryl group having 6 to 30 carbon atoms which may have a substituent, arylalkyl group having 7 to 30 carbon atoms which may have a substituent or a substituent. Represents an optionally substituted heterocyclic group having 2 to 20 carbon atoms, and X ⁴ represents R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ , NO ₂ , SO ₄ H, CN, halogen atom or hydroxyl group X ⁵ and X ⁶ 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 , COS R ¹¹ , COSR ¹¹ , CSOR ¹¹ , CN, a halogen atom or a hydroxyl group is represented. 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 black photosensitive resin composition. -Butyl group, isobutyl group, t-butyl group, n-amyl group, isoamyl group, t-amyl group, n-hexyl group, 2-ethylhexyl group and other alkyl groups having 10 or less carbon atoms, cyclopentyl group, cyclohexyl group, etc. An arylalkyl group having an aromatic ring such as a cyclic alkyl group, an aryl group, or a methylaryl group, which may have a side chain of 10 or less carbon atoms, a methoxymethyl group, an ethoxymethyl group, an ethoxyethyl group, 2- ( 1-methoxypropyl) group, 2- (1-ethoxypropyl) group and the like are alkyl groups having 10 or less carbon atoms and one ether bond in the methylene chain.

X ² and X ³ are particularly preferably a methyl group, an ethyl group, an n-propyl group, and isopropyl, from the viewpoints of ease of synthesis, sensitivity, solubility, and storage stability when contained in a black photosensitive resin composition. Group, 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 and other carbons A cyclic alkyl group having a number of 6 or less, a methoxymethyl group, an ethoxymethyl group,
It is an alkyl group having 6 or less carbon atoms and one ether bond in the methylene chain, such as an ethoxyethyl group, a 2- (1-methoxypropyl) group, and a 2- (1-ethoxypropyl) group.

X ⁴ 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, a nitro group, a sulfo group, a cyano group, a halogen atom, a hydroxyl group and the like.

X ⁵ and X ⁶ are particularly preferably 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, a cyano group, a halogen atom, a hydroxyl group and the like.

化式１で表される光重合開始剤の合成法は、特に制限は無いが以下の方法により合成できる。

The method for synthesizing the photopolymerization initiator represented by Formula 1 is not particularly limited, but can be synthesized by the following method.

  Synthesis of acyl body: The fluorene compound 1 and the acid chloride 2 are reacted in the presence of aluminum chloride to obtain the target acyl body 3.

オキシムエステル化合物の合成：アシル体３と、塩酸ヒドロキシルアミンと、ジメチルホルムアミドを仕込み、加熱攪拌し、オキシム化合物４を得る。オキシム化合物４と酸無水物５を加熱攪拌し、反応終了後、アルカリで中和し、オキシムエステル化合物６が得られる。

Synthesis of Oxime Ester Compound: Acyl compound 3, hydroxylamine hydrochloride and dimethylformamide are charged and heated and stirred to obtain oxime compound 4. The oxime compound 4 and the acid anhydride 5 are heated and stirred. After completion of the reaction, the oxime compound 4 is neutralized with an alkali to obtain the oxime ester compound 6.

オキシムエステル化合物の合成：オキシムエステル化合物６と酸クロライド７を塩化アルミニウムの存在下で反応し、目的物であるオキシムエステル化合物８を得る。

Synthesis of oxime ester compound: The oxime ester compound 6 and the acid chloride 7 are reacted in the presence of aluminum chloride to obtain the oxime ester compound 8 which is the target product.

オキシムエステル化合物の合成：オキシムエステル化合物６を硫酸酸性条件下で硝酸と
反応し、目的物であるオキシムエステル化合物９を得る。

Synthesis of oxime ester compound: The oxime ester compound 6 is reacted with nitric acid under sulfuric acid acidic conditions to obtain the oxime ester compound 9 which is the target product.

化式１で表される光重合開始剤は、近接露光装置の光源として広く用いられている高圧水銀ランプとのマッチングに優れ、主要な輝線であるｉ線（３６５ｎｍ）、ｈ線（４０５ｎｍ）の光を効率よく吸収するため、感光性樹脂組成物を高感度化することができる。

The photopolymerization initiator represented by the chemical formula 1 is excellent in matching with a high-pressure mercury lamp widely used as a light source of a proximity exposure apparatus, and has the main emission lines i-line (365 nm) and h-line (405 nm). In order to absorb light efficiently, the photosensitive resin composition can be highly sensitive.

  For this reason, since a coating film fully hardens | cures, it becomes a uniform cured film and leads to the reduction of the nonuniformity to a post process. In addition, since the sensitivity can be increased with a small amount, the heat resistance is hardly deteriorated by the initiator, and high transparency can be maintained. Furthermore, since it is highly sensitive, film fluidity hardly occurs and it has high flatness.

  The content of the photopolymerization initiator represented by Chemical Formula 1 is preferably 1 to 20% by weight, more preferably 2 to 15% by weight, based on the solid content of the photosensitive resin composition. When the content of the photopolymerization initiator is within this range, it is possible to form. When the content of the photopolymerization initiator is 1% by weight or less, the sensitivity of the photosensitive resin composition is insufficient. On the other hand, when the content of the photopolymerization initiator is 20% by weight or more, transparency is not maintained due to yellowing due to thermal decomposition of the initiator.

In addition to the photopolymerization initiator represented by Formula 1, another photopolymerization initiator can be used in combination with the photosensitive resin composition of the present invention.
Examples of acetophenone compounds include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one , Benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- [ An oligomer of 4- (1-methylvinyl) phenyl] propan-1-one and the like are preferable, and 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one and the like are preferable. A plurality of acetophenone-based and other photopolymerization initiators may be used in combination. Examples of photopolymerization initiators other than acetophenone are active radical generators and sensitizers that generate active radicals when irradiated with light. Examples of the active radical generator include benzoin compounds, benzophenone compounds, thioxanthone compounds, and triazine compounds.

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

  Examples of benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (t-butylperoxy). Carbonyl) benzophenone, 2,4,6-trimethylbenzophenone and the like.

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

Examples of triazine compounds include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4- Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 -[2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl]- 1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis ( Trichloromethyl)- - such as [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the active radical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′- Biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compounds, and the like can also be used.

  Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl methyl. Onium salts such as benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, Examples thereof include benzoin tosylate.

  Among the compounds described above as active radical generators, there are also compounds that generate an acid simultaneously with active radicals. For example, triazine photopolymerization initiators are also used as acid generators.

  The photopolymerization initiation assistant used in the present invention is a compound that is used in combination with a photopolymerization initiator and is used to promote polymerization of a photopolymerizable compound that has been polymerized by the photopolymerization initiator. The photopolymerization initiation assistant includes at least one amine system. Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminoethyl benzoate. 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4 ′ -Bis (ethylmethylamino) benzophenone is mentioned, among which 4,4'-bis (diethylamino) benzophenone is preferred. Further, a plurality of amines and other photopolymerization initiation assistants may be used in combination. Examples of other photopolymerization initiation assistants include alkoxyanthracene compounds and thioxanthone compounds.

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

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

A commercially available photopolymerization initiation assistant can also be used, and examples of the commercially available photopolymerization initiation assistant include EAB-F (Hodogaya Chemical Co., Ltd.).

  When using these photoinitiators, the usage-amount is 10 mol or less normally with respect to 1 mol of photoinitiators, Preferably it is 0.01 mol or more and 5 mol or less.

  As the binder polymer (b), an acrylic copolymer can be used, and examples thereof include a carboxyl group-containing monomer and a copolymer with another monomer copolymerizable therewith.

  Examples of the carboxyl group-containing monomer include an unsaturated carboxylic acid having at least one carboxyl group in a molecule such as an unsaturated monocarboxylic acid, an unsaturated polycarboxylic acid such as an unsaturated dicarboxylic acid, or an unsaturated tricarboxylic acid. Is mentioned. Here, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, and the like. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polyvalent carboxylic acid may be an acid anhydride thereof, specifically maleic anhydride, itaconic anhydride, citraconic anhydride and the like. The unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester such as succinic acid mono (2-acryloyloxyethyl) or succinic acid mono (2-methacryloyloxy). Ethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate, and the like. The unsaturated polycarboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both ends thereof, and may be, for example, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, or the like. These carboxyl group-containing monomers can be used alone or in admixture of two or more.

  Examples of other monomers copolymerizable with the carboxyl group-containing monomer include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl Aromatic vinyl compounds such as ether and indene, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i Propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, 2 -Hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxy Butyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl Acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate , Methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate , Isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate , Unsaturated carboxylic acid esters such as glycerol monomethacrylate, 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-amino Unsaturated carboxylic acid aminoalkyl esters such as propyl methacrylate, 3-dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate, unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate, vinyl acetate, vinyl propionate, Carboxylic acid vinyl esters such as vinyl butyrate and vinyl benzoate, unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether, cyanation of acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, etc. Vinyl compounds, acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, N-2-hydroxyethylmeta Unsaturated amides such as rilamide, unsaturated imides such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene, polystyrene, polymethyl acrylate, poly Examples thereof include macromonomers having a monoacryloyl group or a monomethacryloyl group at the end of the polymer molecular chain of methyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, or polysiloxane. These monomers can be used alone or in admixture of two or more.

  The content of the carboxyl group-containing monomer unit in the copolymer is usually 10 to 50% by weight, preferably 15 to 40% by weight, and particularly preferably 25 to 40% by weight. When the content of the carboxyl group-containing monomer unit is 10 to 50% by weight, the solubility in the developer is good, and the pattern tends to be formed accurately during development, which is preferable. Examples of the acrylic polymer include (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / 2-hydroxyethyl. (Meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / methyl (meth) acrylate / polymethyl (meth) acrylate Macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer, (meta Acrylic acid / 2-hydroxyethyl (Meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer, (Meth) acrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / succinic acid mono (2-acryloyloxyethyl) / styrene / benzyl (meth) acrylate / N- Phenylmaleimide copolymer, (meth) acrylic acid / succinic acid mono (2-acryloyloxyethyl) / styrene / allyl (meth) acrylate / N-phenylmaleimide copolymer (meth) acrylic acid / benzyl (meth) acrylate / N-phenylmaleimi / Styrene / such as glycerol mono (meth) acrylate copolymer. In addition, (meth) acrylate shows that it is an acrylate or a methacrylate.

Among them, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate / styrene copolymer, (meth) acrylic acid / methyl (meth) acrylate copolymer, (meta ) Acrylic acid / methyl (meth) acrylate / styrene copolymer is preferred.

  The acrylic polymer has a polystyrene-equivalent weight average molecular weight of usually 3,000 to 400,000, preferably 5,000 to 100,000, particularly preferably 20,000 to 40,000. When the above-mentioned polystyrene-equivalent weight average molecular weight is 3,000 to 400,000, the coating film hardness is improved, the residual film ratio is high, the solubility of the unexposed portion in the developer is good, and the resolution tends to be improved. And preferred. Moreover, an acid value is 30-250 normally, More preferably, it is 60-180, Especially preferably, it is 90-160.

  When the acid value is 30 to 250, the solubility in the developer is improved and the unexposed area is easily dissolved, and the sensitivity is increased so that the pattern of the exposed area remains during development and the remaining film ratio is improved. This is preferable. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the acrylic polymer, and can usually be obtained by titration with an aqueous potassium hydroxide solution. .

  The binder polymer is usually 5% by weight to 90% by weight, preferably 10% by weight to 80% by weight, particularly preferably 20% by weight to 70% by weight, based on the solid content of the colored photosensitive resin composition. Used in a range. When the content of the binder polymer is 5% by weight or more and 90% by weight or less, the pattern is less likely to be undercut, and the adhesion tends to be improved, and the resolution and the remaining film ratio tend to be improved. And preferred.

  The photosensitive monomer (c) used in the present invention is a monomer that can be polymerized by an active radical, an acid, or the like generated from a photopolymerization initiator when irradiated with light, and is, for example, a polymerizable carbon-carbon. Examples thereof include compounds having an unsaturated bond.

  The photosensitive monomer is preferably a trifunctional or higher polyfunctional photopolymerizable compound. Examples of the trifunctional or higher polyfunctional photosensitive monomer include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexamethacrylate. Can be mentioned. The said photosensitive monomer can be used individually or in combination of 2 or more types, respectively.

  (C) The content of the photosensitive monomer in the photosensitive resin composition is usually 5% by weight to 90% by weight, preferably 10% by weight to 80% by weight, particularly preferably 20% by weight to 70% by weight. It is used in the range. When the content of the photopolymerizable compound is 5% by weight or more and 90% by weight or less, the curing is sufficiently performed and the remaining film rate is improved, and the pattern is less likely to be undercut and the adhesion is good. This is preferable.

Examples of the surfactant (d) used in the present invention include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalene sulfonate, alkyl diphenyl ether disulfone. Anionic surfactants such as sodium lauryl sulfate monoethanolamine, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monosteaer Nonionic surfactants such as polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkylbetaines such as alkyldimethylaminoacetic acid betaines; alkylimidazolines Amphoteric surfactants can be mentioned, and these can be used alone or in admixture of two or more.

  The said surfactant can be used individually or in combination of 2 or more types.

  Examples of the (e) solvent used in the present invention include ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides and the like.

  Examples of ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol. Monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate Methyl cellosolve acetate, ethyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate, methoxybutyl acetate, methoxy pentyl acetate, anisole, phenetole, and the like methyl anisole. Examples of aromatic hydrocarbons include benzene, toluene, xylene, mesitylene and the like. Examples of ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, and cyclohexanone. Examples of alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin. Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate , Methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, 3-methoxy Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, 2-metho Methyl cypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, 2-oxy-2- Ethyl methyl propionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxobutane Examples include methyl acid, ethyl 2-oxobutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, and γ-butyrolactone. Examples of amides include N, N-dimethylformamide and N, N-dimethylacetamide. Examples of other solvents include N-methylpyrrolidone and dimethyl sulfoxide.

Among the solvents mentioned above, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, ethyl carbitol acetate, butyl carbitol Acetate, propylene glycol methyl ether acetate, 2-
Heptanone or the like is preferably used.

  The solvents can be used alone or in combination of two or more, and the content of the solvent in the photosensitive resin composition is usually from 50% by weight to 90% by weight, preferably from 60% by weight to 85%. % By weight or less. When the content of the solvent is 50% by weight or more and 90% by weight or less, the flatness is good and a color density sufficient for making a color filter is obtained, which is preferable.

  The photosensitive resin composition of the present invention includes additives such as fillers, polymer compounds other than binder polymers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, organic acids, organic amino compounds, and curing agents. May be contained.

  As a hardening | curing agent, the compound which can react with the carboxyl group in a binder polymer by heating and can bridge | crosslink a binder polymer is mentioned, for example. Moreover, the compound which can superpose | polymerize independently and harden a colored pattern is also mentioned. Examples of the compound include an epoxy compound and an oxetane compound.

  (F) Examples of the epoxy compound include bisphenol A-based epoxy resins, hydrogenated bisphenol A-based epoxy resins, bisphenol F-based epoxy resins, hydrogenated bisphenol F-based epoxy resins, novolac-type epoxy resins, and other aromatic epoxy resins. , Alicyclic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, epoxy resins such as epoxidized oil, brominated derivatives of these epoxy resins, epoxy resins and brominated derivatives thereof Aliphatic, cycloaliphatic or aromatic epoxy compounds, epoxidized butadiene (co) polymers, epoxidized isoprene (co) polymers, glycidyl (meth) acrylate (co) polymers, triglycidyl Examples include isocyanurate.

  Examples of the oxetane compound include carbonate bisoxetane, xylylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylate bisoxetane.

  When the photosensitive composition of the present invention contains an epoxy compound, an oxetane compound, or the like as a curing agent, it may contain a compound capable of ring-opening polymerization of the epoxy group of the epoxy compound or the oxetane skeleton of the oxetane compound. Examples of the compound include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, and acid generators.

  Examples of the polyvalent carboxylic acids include phthalic acid, 3,4-dimethylphthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3,3 Aromatic polycarboxylic acids such as', 4,4'-benzophenonetetracarboxylic acid, succinic acid, glutaric acid, adipic acid, 1,2,3,4-butanetetracarboxylic acid, maleic acid, fumaric acid, itaconic acid Aliphatic polycarboxylic acids such as hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2,4- Cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, etc. Such as alicyclic polycarboxylic acids and the like.

Examples of the polyvalent carboxylic acid anhydrides include aromatic polyvalent carboxylic acids such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride. Polyhydrides such as acid anhydrides, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride Carboxylic anhydrides, hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic anhydride, cyclo Pentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, anhydrous hymic acid, anhydrous nadi Alicyclic polycarboxylic acid anhydrides such as acid, ethylene glycol bis trimellitate acid, an ester group-containing carboxylic acid anhydrides such as glycerin tris trimellitate anhydride.

  As the carboxylic acid anhydrides, those commercially available as an epoxy resin curing agent may be used. Examples of the epoxy resin curing agent include ADEKA HARDNER EH-700 (manufactured by Asahi Denka Kogyo Co., Ltd.), Rikacid HH (manufactured by Shin Nippon Rika Co., Ltd.), MH-700 (manufactured by Shin Nippon Rika Co., Ltd.), and the like.

  The said hardening | curing agent can be used individually or in combination of 2 types or more, respectively.

  EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

<Formation of light shielding layer> (Preparation of photosensitive black composition)
The photosensitive black composition was prepared by mixing and stirring a mixture having the following composition. (Pigment concentration in solid content: 30.7%)
Carbon black dispersion: TPBK-2016 (manufactured by Mikuni Dye) 28.5 parts by weight Resin: V259-ME (manufactured by Nippon Steel Chemical Co., Ltd., solid content 56.1% by weight) 10.3 parts by weight Monomer: DPHA (Nipponization) 2.58 parts by weight initiator: OXE-02 (manufactured by Ciba Specialty Chemicals) 0.86 parts by weight Solvent: propylene glycol monomethyl ether acetate 92.0 parts by weight leveling agent 1.3 parts by weight .

<Formation of light shielding layer>
The above photosensitive black composition was applied on a transparent substrate by spin coating so as to have a film thickness of 1.5 μm. After drying at 100 ° C. for 3 minutes, 200 mJ of lattice pattern exposure is performed with an exposure machine, development is performed with an alkali developer for 60 seconds, heat treatment is performed at 230 ° C. for 60 minutes, and the lattice-like black matrix layer is formed. It formed on the transparent substrate. The alkaline developer has the following composition. In the following examples and comparative examples, development is performed using this alkaline developer.
Sodium carbonate: 1.5 parts by weight Sodium hydrogen carbonate: 0.5 parts by weight Anionic surfactant: Perirex NBL (manufactured by Kao Corporation) 8.0 parts by weight Water: 90.0 parts by weight.

<Formation of colored layer> (Preparation of red, green and blue colored compositions)
A red colored composition and a mixture having the following composition were uniformly stirred and mixed, then dispersed in a sand mill for 5 hours using a glass bead having a diameter of 1 mm, and then filtered through a 5 μm filter to prepare a red pigment dispersion.
Red pigment: C.I. I. Pigment Red254 18 parts by weight Ilgar For Red B-CF (Ciba Specialty Chemicals)
Red pigment: C.I. I. Pigment ed177 2 parts by weight Chromothal Red A2B (Ciba Specialty Chemicals)
Dispersant: Azisper PB821 (manufactured by Ajinomoto Fine Techno Co., Ltd.) 2 parts by weight Acrylic varnish (solid content 20%) 50 parts by weight Thereafter, the mixture having the following composition is stirred and mixed to be uniform, and then filtered through a 5 μm filter. A red colored composition was obtained.

72 parts by weight of the above dispersion caprolactone-modified dipentaerythritol hexaacrylate: 8 parts by weight Kayarad DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.)
Dipentaerythritol hexaacrylate: 10 parts by weight Kayalad DPHA (manufactured by Nippon Kayaku Co., Ltd.)
Methylated melamine resin: MW30 (manufactured by Sanwa Chemical Co., Ltd.) 10 parts by weight Photoinitiator: Irgacure 907 (manufactured by Ciba Specialty Chemicals) 3 parts by weight sensitizer: EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) 1 Part by weight Solvent: 253 parts by weight of cyclohexanone.

Green Coloring Composition A mixture having the following composition was uniformly stirred and mixed, then dispersed in a sand mill for 5 hours using glass beads having a diameter of 1 mm, and then filtered through a 5 μm filter to prepare a green pigment dispersion.
Green pigment: C.I. I. Pigment Green 36 16 parts by weight Lionol Green 6YK (manufactured by Toyo Ink Co., Ltd.)
Yellow pigment: C.I. I. Pigment Yellow 150 8 parts by weight Funchon First Yellow Y-5688 (manufactured by Bayer)
Dispersant: Disperbyk-163 (manufactured by Big Chemie) 2 parts by weight Acrylic varnish (solid content 20%) 102 parts by weight After that, 128 parts of the above dispersion was used, and a mixture having the following composition was further stirred and mixed to be uniform. Filtration through a 5 μm filter gave a green colored composition.
Trimethylolpropane triacrylate: 14 parts by weight NK ester ATMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photoinitiator: Irgacure 907 (Ciba Specialty Chemicals) 4 parts by weight Sensitizer: EAB-F (Hodogaya Chemical Co., Ltd.) 2 parts by weight Solvent: Cyclohexanone 257 parts by weight.

Blue colored composition A mixture of the following composition was uniformly stirred and mixed, then dispersed in a sand mill for 5 hours using glass beads having a diameter of 1 mm, and then filtered through a 5 µm filter to prepare a dispersion of a blue pigment.
Blue pigment: C.I. I. Pigment Blue15 30 parts by weight Lionol Blue ES (manufactured by Toyo Ink Manufacturing Co., Ltd.)
Purple pigment: C.I. I. Pigment Violet 23 2 parts by weight Paliogen Violet 5890 (manufactured by BASF)
Dispersant: Sols Birds 20000 (manufactured by Zeneca) 6 parts by weight Acrylic varnish (solid content 20%) 200 parts by weight Then, the mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 5 μm filter to give a blue color. A composition was obtained.
Dispersion: 238 parts by weight Trimethylolpropane triacrylate: 19 parts by weight NK ester ATMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photoinitiator: Irgacure 907 (Ciba Specialty Chemicals) 4 parts by weight Sensitizer: EAB-F (Hodogaya Chemical Co., Ltd.) 2 parts by weight Solvent: 214 parts by weight of cyclohexanone.

<Formation of colored layer>
Using the obtained red colored composition, green colored composition, and blue colored composition, a colored layer serving as a pixel was formed in the following manner. On the transparent substrate on which the light shielding layer was formed, the red coloring composition was applied by spin coating so as to have a film thickness of 2 μm. After drying, a striped pattern was exposed with an exposure machine, developed with an alkaline developer for 90 seconds, heated at 230 ° C. for 20 minutes, fixed, and a striped red colored layer was formed on the transparent substrate.

  Next, the green coloring composition is similarly applied by spin coating so that the film thickness becomes 2 μm. After drying, the green colored layer adjacent to the red colored layer was formed by exposing and developing the striped colored layer in a position different from the red colored layer with an exposure machine.

  Further, in the same manner as red and green, the blue colored composition was formed with a blue colored layer adjacent to the red colored layer and the green colored layer with a film thickness of 2 μm.

<Formation of transparent film layer>
In a 1 liter 5-neck flask,
Cyclohexanone 200 g N-cyclohexylmaleimide 30 g 2-hydroxyethyl methacrylate 30 g Methacrylic acid 20 g Butyl methacrylate 20 g was charged, and 1.0 g of azobisisobutyronitrile was added in a nitrogen atmosphere and reacted at 80 to 85 ° C. for 8 hours.
Then
7 g of isocyanate ethyl methacrylate 0.03 g of tin octylate dissolved in 10 g of cyclohexane was dropped in about 10 minutes, and after dropping, the mixture was reacted at 80 to 85 ° C. for 30 minutes to give a resin solution having a polymerizable methacryloyl group in the side chain. Synthesized. Furthermore, the resin was prepared with cyclohexaneone so that the nonvolatile content of the resin was 20% by weight, and a solution of binder resin 1 was obtained.

<Preparation of photosensitive resin composition 1>
A photosensitive resin composition 1 was prepared by mixing and stirring a mixture having the following composition.
(A) Photopolymerization initiator: Chemical formula 2DFI-020 (manufactured by Daitokemix) 6 parts by weight (b) Binder polymer: Binder resin prepared in Synthesis Example 1 500 parts by weight (c) Photosensitive monomer: Dipentaerythritol tri Acrylate 136 parts by weight (d) Surfactant: F-550 (Dainippon Ink Chemical Co., Ltd.) 0.09 parts by weight (e) Solvent: Propylene glycol monomethyl ether acetate 228 parts by weight (f) Epoxy compound: Orthocresol novolak Type epoxy resin 27 parts by weight Sumiepoxy ESCN-195XL-80 (manufactured by Sumitomo Chemical)
<Formation of transparent film layer 1>
The photosensitive resin composition 1 was spin-coated on the glass substrate on which the light-shielding layer and the colored layer were formed so as to have a film thickness of 2.0 μm, and dried at 90 ° C. for 5 minutes. The light from a high-pressure mercury lamp was irradiated through a photomask for forming a transparent film layer at 50 mJ / cm ² . In addition, it exposed with the space | interval (exposure gap) of a photomask and a glass substrate being 100 micrometers. Thereafter, development is performed for 40 seconds using an alkali developer as described below, followed by washing with water, followed by baking at 230 ° C. for 30 minutes to form transparent film layer 1
Was made.

  The same operation as in Example 1 was performed except that the photosensitive resin composition in Example 1 was changed to the following composition.

<Preparation of photosensitive resin composition 2>
A photosensitive resin composition 2 was prepared by mixing and stirring a mixture having the following composition.
(A) Photopolymerization initiator: Formula 2DFI-020 (manufactured by Daitokemix) 4 parts by weight (b) Binder polymer: Binder resin prepared in Synthesis Example 1 500 parts by weight (c) Photosensitive monomer: Dipentaerythritol tri Acrylate 136 parts by weight (d) Surfactant: F-550 (Dainippon Ink Chemical Co., Ltd.) 0.09 parts by weight (e) Solvent: Propylene glycol monomethyl ether acetate 223 parts by weight (f) Epoxy compound: Orthocresol novolak Type epoxy resin 27 parts by weight Sumiepoxy ESCN-195XL-80 (manufactured by Sumitomo Chemical)
It is.

<Formation of transparent film layer 2>
The photosensitive resin composition 2 was spin-coated on the glass substrate on which the light-shielding layer and the colored layer were formed, so that the film thickness became 2.0 μm, and dried at 90 ° C. for 5 minutes. The light from a high-pressure mercury lamp was irradiated through a photomask for forming a transparent film layer at 50 mJ / cm ² . In addition, it exposed with the space | interval (exposure gap) of a photomask and a glass substrate being 100 micrometers.
Thereafter, development was performed for 40 seconds using an alkali developer as described below, followed by washing with water, followed by baking at 230 ° C. for 30 minutes to produce a transparent film layer 2.

<Formation of transparent film layer 2 (single film)>
The above-mentioned photosensitive composition 2 was spin-coated on a glass substrate so as to have a film thickness of 2.0 μm, and dried at 90 ° C. for 5 minutes. The light from a high-pressure mercury lamp was irradiated through a photomask for forming a transparent film layer at 50 mJ / cm ² . In addition, it exposed with the space | interval (exposure gap) of a photomask and a glass substrate being 100 micrometers.
Thereafter, development was performed using an alkali developer for 40 seconds, followed by washing with water, followed by baking at 230 ° C. for 30 minutes to produce a transparent film layer 2 (single film).

  The same operation as in Example 1 was performed except that the photosensitive resin composition in Example 1 was changed to the following composition.

<Preparation of photosensitive resin composition 3>
A photosensitive resin composition 3 was prepared by mixing and stirring a mixture having the following composition.
(A) Photopolymerization initiator: Formula 3DFI-091 (manufactured by Daitokemix) 6 parts by weight (b) Binder polymer: Binder resin prepared in Synthesis Example 1 500 parts by weight (c) Photosensitive monomer: Dipentaerythritol tri Acrylate 136 parts by weight (d) Surfactant: F-550 (Dainippon Ink Chemical Co., Ltd.) 0.09 parts by weight (e) Solvent: Propylene glycol monomethyl ether acetate 223 parts by weight (f) Epoxy compound: Orthocresol novolak Type epoxy resin 27 parts by weight Sumiepoxy ESCN-195XL-80 (manufactured by Sumitomo Chemical)
It is.

<Formation of transparent film layer 3>
The film thickness of the photosensitive resin composition 3 is 2.0 μm on the glass substrate on which the light shielding layer and the colored layer are formed.
The film was spin-coated to m, and dried at 90 ° C. for 5 minutes. The light from a high-pressure mercury lamp was irradiated through a photomask for forming a transparent film layer at 50 mJ / cm ² . In addition, it exposed with the space | interval (exposure gap) of a photomask and a glass substrate being 100 micrometers.
Thereafter, development was performed for 40 seconds using an alkali developer as described below, followed by washing with water, followed by baking at 230 ° C. for 30 minutes to produce a transparent film layer 3.

<Formation of transparent film layer 3 (single film)>
The above-mentioned photosensitive composition 3 was spin-coated on a glass substrate so as to have a film thickness of 2.0 μm, and dried at 90 ° C. for 5 minutes. The light from a high-pressure mercury lamp was irradiated through a photomask for forming a transparent film layer at 50 mJ / cm ² . In addition, it exposed with the space | interval (exposure gap) of a photomask and a glass substrate being 100 micrometers.
Thereafter, development was performed using an alkali developer for 40 seconds, followed by washing with water, followed by baking at 230 ° C. for 30 minutes to produce a transparent film layer 3 (single film).

<Comparative Example 1>
The same operation as in Example 1 was performed except that the photosensitive resin composition in Example 1 was changed to the following composition.

<Preparation of photosensitive resin composition 4>
A photosensitive resin composition 4 was prepared by mixing and stirring a mixture having the following composition.
(A) Photopolymerization initiator: 12 parts by weight of Irgacure 907 (manufactured by Ciba Specialty Chemicals)
(B) Binder polymer: Binder resin prepared in Synthesis Example 1 500 parts by weight (c) Photosensitive monomer: 136 parts by weight of dipentaerythritol triacrylate (d) Surfactant: F-550 (Dainippon Ink Chemical Co., Ltd.) 0.09 parts by weight (e) Solvent: Propylene glycol monomethyl ether acetate 242 parts by weight (f) Epoxy compound: Orthocresol novolac type epoxy resin 27 parts by weight Sumiepoxy ESCN-195XL-80 (manufactured by Sumitomo Chemical Co., Ltd.)
It is.

<Formation of transparent film layer 4>
The photosensitive resin composition 4 was spin-coated on the glass substrate on which the light-shielding layer and the colored layer were formed, so that the film thickness was 2.0 μm, and dried at 90 ° C. for 5 minutes. The light from a high-pressure mercury lamp was irradiated through a photomask for forming a transparent film layer at 50 mJ / cm ² . In addition, it exposed with the space | interval (exposure gap) of a photomask and a glass substrate being 100 micrometers.
Thereafter, development was performed for 40 seconds using an alkali developer as described below, followed by washing with water, followed by baking at 230 ° C. for 30 minutes to produce a transparent film layer 4.

<Formation of transparent film layer 4 (single film)>
The above-described photosensitive composition 4 was spin-coated on a glass substrate so as to have a film thickness of 2.0 μm, and dried at 90 ° C. for 5 minutes. The light from a high-pressure mercury lamp was irradiated through a photomask for forming a transparent film layer at 50 mJ / cm ² . In addition, it exposed with the space | interval (exposure gap) of a photomask and a glass substrate being 100 micrometers.
Then, after developing for 40 seconds using an alkali developer, washing with water and baking at 230 ° C. for 30 minutes, a transparent film layer 4 (single film) was produced.

<Comparative example 2>
(Preparation of photosensitive resin composition 5) A photosensitive resin composition 5 was prepared by mixing and stirring a mixture having the following composition.
(A) Photopolymerization initiator: 6 parts by weight of Irgacure 907 (manufactured by Ciba Specialty Chemicals)
(B) Binder polymer: Binder resin prepared in Synthesis Example 1 500 parts by weight (c) Photosensitive monomer: 136 parts by weight of dipentaerythritol triacrylate (d) Surfactant: F-550 (Dainippon Ink Chemical Co., Ltd.) 0.09 parts by weight (e) Solvent: Propylene glycol monomethyl ether acetate 228 parts by weight (f) Epoxy compound: Orthocresol novolac type epoxy resin 27 parts by weight (Sumiepoxy ESCN-195XL-80 manufactured by Sumitomo Chemical Co., Ltd.)
It is.

<Formation of transparent film layer 5>
The photosensitive resin composition 5 was spin-coated on the glass substrate on which the light-shielding layer and the colored layer were formed, so that the film thickness became 2.0 μm, and dried at 90 ° C. for 5 minutes. The light from a high-pressure mercury lamp was irradiated through a photomask for forming a transparent film layer at 50 mJ / cm ² . In addition, it exposed with the space | interval (exposure gap) of a photomask and a glass substrate being 100 micrometers.
Thereafter, development was carried out for 40 seconds using the following alkaline developer, followed by washing with water, followed by baking at 230 ° C. for 30 minutes to produce a transparent film layer 5.

<Formation of transparent film layer 5 (single film)>
The above-described photosensitive composition 5 was spin-coated on a glass substrate so as to have a film thickness of 2.0 μm, and dried at 90 ° C. for 5 minutes. The light from a high-pressure mercury lamp was irradiated through a photomask for forming a transparent film layer at 50 mJ / cm ² . In addition, it exposed with the space | interval (exposure gap) of a photomask and a glass substrate being 100 micrometers.
Then, after developing for 40 seconds using an alkaline developer, washing with water, and baking at 230 ° C. for 30 minutes, a transparent film layer 5 (single film) was produced.

<Comparative Example 3>
(Preparation of photosensitive resin composition 6)
A photosensitive resin composition 6 was prepared by mixing and stirring a mixture having the following composition.
(A) Photopolymerization initiator: 6 parts by weight of Irgacure 907 (manufactured by Ciba Specialty Chemicals)
(B) Binder polymer: 500 parts by weight of the binder resin prepared in Synthesis Example 1 (c) Photosensitive monomer: 150 parts by weight of dipentaerythritol triacrylate (d) Surfactant: F-550 (Dainippon Ink Chemical Co., Ltd.) 0.09 parts by weight (e) Solvent: 275 parts by weight of propylene glycol monomethyl ether acetate (f) Epoxy compound: 27 parts by weight of orthocresol novolac type epoxy resin Sumiepoxy ESCN-195XL-80 (manufactured by Sumitomo Chemical Co., Ltd.)
It is.

<Formation of transparent film layer 6>
The photosensitive resin composition 6 was spin-coated on the glass substrate on which the light-shielding layer and the colored layer were formed, so as to have a film thickness of 2.0 μm, and dried at 90 ° C. for 5 minutes. The light from a high-pressure mercury lamp was irradiated through a photomask for forming a transparent film layer at 50 mJ / cm ² . In addition, it exposed with the space | interval (exposure gap) of a photomask and a glass substrate being 100 micrometers.
Thereafter, development was carried out for 40 seconds using the following alkaline developer, followed by washing with water, followed by baking at 230 ° C. for 30 minutes to produce a transparent film layer 6.

<Formation of transparent film layer 6 (single film)>
The above-described photosensitive composition 6 was spin-coated on a glass substrate so as to have a film thickness of 2.0 μm, and dried at 90 ° C. for 5 minutes. The light from a high-pressure mercury lamp was irradiated through a photomask for forming a transparent film layer at 50 mJ / cm ² . In addition, it exposed with the space | interval (exposure gap) of a photomask and a glass substrate being 100 micrometers.
Then, after developing for 40 seconds using an alkaline developer, washing with water and baking at 230 ° C. for 30 minutes, a transparent film layer 6 (single film) was produced.

<Evaluation>
The transparent film layer produced with the photosensitive resin composition produced as mentioned above was evaluated in the following items.

<Unevenness after development>
When forming a transparent film layer (single film) with the photosensitive resin compositions obtained in the above-mentioned Examples and Comparative Examples, the appearance after development was observed under a Na lamp, and x was observed where spot unevenness was observed. What was not done was set as (circle).

<Saturated exposure>
In the photosensitive resin compositions obtained in the above examples and comparative examples, the film thickness after coating is measured when forming a transparent film layer (single film), and the exposure dose is irradiated stepwise through a photomask during exposure. (10, 20, 30, 40, 50, 60, 80, 100 mJ / cm ² ), patterning, and after the development process and baking, the film thickness at each exposure step is measured. The remaining film ratio and the saturated exposure amount at the exposure amount were calculated and judged.
Saturated exposure (mJ): Minimum exposure that saturates the remaining film rate
(Residual film ratio (%): film thickness after baking at 230 ° C. for 30 minutes ÷ film thickness at coating before development) A film having a saturated exposure amount of 50 mJ or less was marked with ◯, and a film with more than that was marked with x.
For measuring the film thickness, a two-dimensional fine shape measuring instrument ET4000T manufactured by Kosaka Laboratory Ltd. was used.

<Transmissivity>
A transparent film layer (single layer) was formed in the photosensitive resin compositions obtained in the above examples and comparative examples, and the spectral transmittance was measured using a spectral transmittance measuring device LCF-1100M manufactured by Otsuka Electronics Co., Ltd. A sample having a spectral transmittance of 99% or higher was evaluated as ◯, and a sample having a spectral transmittance of less than 99% was evaluated as ×.

<Flatness>
The transparent film layer on the color filter obtained in the above Examples and Comparative Examples was measured using a two-dimensional fine shape measuring instrument ET4000T manufactured by Kosaka Laboratory Ltd., and the flattening rate FA of the transparent film was evaluated.
FA = (FR + FG + FB) / 3 Formula (1)
FR = (HR (2) −LR (2)) / (HR (1) −LR (1)) Formula (2)
F G = (HG (2) −LG (2)) / (HG (1) −LG (1)) Formula (3)
F B = (HB (2) −LB (2)) / (HB (1) −LB (1)) Formula (4)
here,
HR (1): the maximum value of the Red pixel height before forming the transparent film layer,
LR (1): height of the center of the Red pixel before forming the transparent film layer,
HG (1): Maximum value of Green pixel height before forming the transparent film layer,
LG (1): Green pixel center height before forming the transparent film layer,
HB (1): the maximum value of the blue pixel height before forming the transparent film layer,
LB (1): the height of the blue pixel center before forming the transparent film layer,
HR (2): the maximum value of the Red pixel height after forming the transparent film layer,
LR (2): the height of the Red pixel center after forming the transparent film layer,
HG (2): Maximum value of Green pixel height after forming the transparent film layer,
LG (2): Green pixel center height after forming the transparent film layer,
HB (2): the maximum value of the blue pixel height after forming the transparent film layer,
LB (2): The height of the center of the Blue pixel after the transparent film layer is formed, and the evaluation criteria of flatness are ◯ for 85% or more and x for less than 85%.

  The results of the above evaluation are shown in Table 1.

Claims (3)

A photopolymerization initiator containing a fluorene-based oxime ester compound represented by Chemical Formula 2, an acrylic polymer having a polystyrene-equivalent weight average molecular weight of 20,000 to 40,000 and an acid value of 90 to 160 A color filter obtained by laminating a photosensitive resin composition containing a binder polymer, a photosensitive monomer, a surfactant, and a solvent as a transparent film layer on a light-shielding layer and a colored pixel layer on a glass substrate and firing at 230 ° C. And
And the flattening rate of the said transparent film layer exists in the range of 87.5-88.1%, The color filter characterized by the above-mentioned.

A photopolymerization initiator containing a fluorene-based oxime ester compound represented by Formula 3, an acrylic polymer having a polystyrene-equivalent weight average molecular weight of 20,000 to 40,000 and an acid value of 90 to 160 A color filter obtained by laminating a photosensitive resin composition containing a binder polymer, a photosensitive monomer, a surfactant, and a solvent as a transparent film layer on a light-shielding layer and a colored pixel layer on a glass substrate and firing at 230 ° C. And
And the flattening rate of the said transparent film layer exists in the range of 87.8-88.1 %, The color filter characterized by the above-mentioned.

  A liquid crystal display device using the color filter according to claim 1.