JPH10293402A - Photosensitive resin composition, color filter and liquid crystal display device using that, and production of color filter and liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive resin compsn. for formation of a color image which does not require an oxygen shielding film such as polyvinylalcohol, to obtain a color filter and its producing method using this resin compsn., and to obtain a color liquid crystal display device and its producing method. SOLUTION: This resin compsn. consists of (A) 20 to 70 wt.% compd. having 10000 to 40000 weight average mol.wt. and 50 to 150 mgKOH/g acid value, (B) 5 to 40 wt.% photopolymerizable monomers, (C) 1 to 20 wt.% photopolymn. initiator containing α-aminoalkylphenone compd. and a thioxanthone compd., and (D) 10 to 50 wt.% dye. The compd. (A) is prepared by adding 4- hydroxybutylacrylate to acid anhydrous groups of a polymer (a) produced from maleic acid anhydride and monomers which are copolymerizable with maleic acid anhydride.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition for forming a colored image useful for producing a color filter used in a color liquid crystal display, a color filter using the composition, and a liquid crystal display using the same. The present invention relates to a device, a color filter, and a method for manufacturing a liquid crystal display device.

[0002]

2. Description of the Related Art A color filter used in a color liquid crystal display device generally comprises a light-shielding black matrix (BM) made of metal, metal oxide, or colored resin;
Pixel portions that transmit light made of red (R), green (G), and blue (B) colored resins are regularly arranged on a transparent substrate such as glass. The pixels are manufactured by a dyeing method, a printing method, a pigment dispersion method, an electrodeposition method, or the like. Many color filters are manufactured by a pigment dispersion method from the viewpoint of heat resistance and pattern accuracy. Examples of the photosensitive resin used in the pigment dispersion method include JP-A-5-31300.
No. 9, a material comprising an organic pigment, an acrylic resin, a crosslinkable monomer, and a photopolymerization initiator is proposed.

[0003]

According to the invention, an acrylic resin is copolymerized with a carboxyl group-containing monomer in order to impart alkali developability to the composition, but the acrylic resin itself is subjected to a photoreaction. Since it does not have a crosslinkable functional group, the sensitivity is not sufficient, and an exposure amount of several thousand mj / cm ² or more is required, and there is a problem in productivity. Therefore, in order to prevent radical polymerization from being inhibited by oxygen in the air and increase sensitivity, it is necessary to apply a resin material on a substrate, dry the resin material, and then form an oxygen barrier film using polyvinyl alcohol or the like. However, this method requires an oxygen-blocking film forming step for each of the three RGB color patterns, which causes an increase in the manufacturing cost of the color filter. An object of the present invention is to provide a photosensitive resin composition for forming a colored image which does not require an oxygen barrier film such as polyvinyl alcohol, a color filter using the resin composition, a method for manufacturing the same, and a color liquid crystal display device and a method for manufacturing the same. It is to provide.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have obtained an acid anhydride of maleic anhydride and a polymer comprising a monomer copolymerizable with maleic anhydride. Group, a compound obtained by adding 4-hydroxybutyl acrylate is used as a main component of the photopolymerizable composition,
It has been found that a photosensitive resin composition capable of forming a fine pattern with a low exposure dose can be obtained without forming an oxygen barrier film by combining with a specific photopolymerization initiator.

That is, the photosensitive resin composition of the present invention comprises: (A) maleic anhydride and a polymer (a) obtained from a monomer copolymerizable with maleic anhydride;
-Weight average molecular weight of 10,000 to 40,000 with addition of hydroxybutyl acrylate, acid value of 50 to 150 mg
(B) 5 to 40% by weight of a photopolymerizable monomer (C) 1 to 20% by weight of a photopolymerization initiator containing an α-aminoalkylphenone compound and a thioxanthone compound ) 10-50% by weight of a dye.

At this time, it is preferable that the monomer copolymerized with the maleic anhydride contains styrene and (meth) acrylates. Further, as the photopolymerizable monomer (B), trimethylolpropane triacrylate, pentaerythritol triacrylate,
Those containing at least one selected from pentaerythritol tetraacrylate are desirable. The color filter of the present invention has a plurality of types of visible light transmitting regions patterned on a transparent substrate and formed of a cured product of the photosensitive resin composition. Further, the liquid crystal display device of the present invention is characterized by using this color filter. Further, the color filter of the present invention and the method of manufacturing a liquid crystal display device using the same include forming a coating film of the above-mentioned photosensitive resin composition on a transparent substrate, performing exposure, and adding 0.001 to 2% by weight. A step of forming a pattern by developing with an aqueous inorganic alkali solution.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION A photosensitive resin composition particularly suitable for the color filter of the present invention is a light-sensitive resin obtained by blending a compound (A) with a photopolymerizable monomer (B) and a photopolymerization initiator (C). It is obtained by blending the dye (D) with the polymerizable composition. Hereinafter, each component will be described.

[0008] The component (A) of the present invention is an essential component for forming the photosensitive resin composition for forming a colored image for a color filter which does not require an oxygen barrier film, which is the object of the present invention. The monomer polymerized with maleic anhydride as a raw material of the polymer (a) used for the synthesis of the compound (A) is preferably a monomer having a radically polymerizable unsaturated group.

Specific examples thereof include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic acid. i-butyl, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth)
Lauryl acrylate, stearyl (meth) acrylate,
Tetrahydrofurfuryl (meth) acrylate, (meth)
Benzyl acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, tricyclodecane (meth) acrylate, allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, (meth)
(Meth) acrylates such as isobornyl acrylate and phenyl (meth) acrylate, olefins such as styrene, isobutylene, methylstyrene, and vinyltoluene; methyl vinyl ether; ethyl vinyl ether;
Examples include vinyl ethers such as phenyl vinyl ether, acrylamides such as acrylamide, N-methylolacrylamide, N-butoxymethylacrylamide, and Nt-butylacrylamide, acrylonitrile, and vinyl acetate. Among them, (meth) acrylic esters are preferable because the balance between the glass transition temperature (Tg) of the polymer and the adhesion to the substrate can be easily adjusted. Further, from the viewpoint of the copolymerizability ratio of maleic anhydride, it is preferable to copolymerize an electron-donating olefin or vinyl ether, and styrene which is easy to handle and easily available industrially is most preferable.

[0010] The content of the maleic anhydride unit constituting the polymer (a) is preferably in the range of 1 to 45% by weight, more preferably in the range of 5 to 30% by weight.
If the amount of the maleic anhydride unit is less than 1% by weight, the photosensitive resin composition using the compound (A) obtained may not have sufficient photosensitivity, and if it exceeds 45% by weight, the compound (A) obtained Has an excessively high acid value and tends to cause film reduction during development. The polymerization method of the polymer (a) obtained from maleic anhydride and a monomer copolymerizable with maleic anhydride can be performed by a known method such as a bulk polymerization method or a solution polymerization method.

In the present invention, a color filter is formed by adding 4-hydroxybutyl acrylate to an acid anhydride group of a polymer (a) comprising maleic anhydride and a monomer copolymerizable with maleic anhydride. It is possible to obtain a highly sensitive resist material sufficient for manufacturing.

When a hydroxyalkyl acrylate having fewer carbon atoms than 4-hydroxybutyl acrylate is used, a highly sensitive resist material achieved by the present invention cannot be obtained. This is because, for example, when 2-hydroxyethyl acrylate is added, an acryloyl group is present near a carboxyl group derived from an acid anhydride group,
Large steric hindrance, reactivity is inhibited for both functional groups,
The radical polymerizability of the acryloyl group decreases, and the rate of the neutralization reaction of the carboxyl group also decreases. As a result, the sensitivity and the developability are reduced, and it is difficult to use the resist material for a color filter. However, when 4-hydroxybutyl acrylate is added, since the alkyl group is longer than the 2-hydroxyethyl acrylate by two carbon atoms, the above-mentioned steric hindrance is also small, radical polymerizability of acryloyl group, neutralization of carboxyl group. Low reactivity, low sensitivity, good developability, easy contrast between exposed and unexposed areas, sufficient for high-density dye-dispersed systems such as resist materials for color filters A usable colored resist is obtained.

When a hydroxyalkyl acrylate having a larger number of carbon atoms than 4-hydroxybutyl acrylate is used, the concentration of double bonds in the compound (A) obtained is relatively reduced. May decrease.

To synthesize compound (A), a polymer
The method of adding 4-hydroxybutyl acrylate to the acid anhydride group of (a) is not particularly limited, for example, dioxane, butyl acetate, isobutyl acetate, isoamyl acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl In an organic solvent such as ether acetate, propylene glycol monoethyl ether acetate, and β-methoxyisobutyric acid methyl ester that does not inhibit the half-esterification reaction, a basic catalyst such as pyridine, p-dimethylaminopyridine, triethylamine, or 2-methylimidazole is used. After the addition in the range of 0.1 to 5% by weight based on the weight of the combined product (a), 1 to 1.
4-hydroxybutyl acrylate corresponding to 5 times the number of moles is added, heated to 70 to 100 ° C., and 3 to 6 at the same temperature.
A method obtained by reacting for a time is mentioned.

The compound (A) used in the present invention has a weight average molecular weight of 1000 in terms of standard polystyrene.
It is preferably in the range of 0 to 40,000, particularly preferably in the range of 15,000 to 30,000. When the weight average molecular weight of the compound (A) is lower than 10,000, the reactivity of the obtained photopolymerizable composition is too high, so that thermal polymerization easily occurs in a solvent drying step after coating on a substrate,
The pattern may not be formed sufficiently, and the developability of the unexposed portion between the fine line patterns tends to be poor. On the other hand, when it exceeds 40,000, the thermal stability of the photopolymerizable composition using the same may be lowered or development may not be possible. Further, the acid value is preferably in the range of 50 to 150 mgKOH / g, particularly preferably 80 to 140 mgKOH / g.
g range. When the acid value of the compound (A) is lower than 50 mgKOH / g, the developability of the resulting photopolymerizable composition tends to decrease. , And the residual film ratio tends to decrease.

The compounding amount of the compound (A) is 20 to 70% by weight.
Is preferably within the range. When the amount of the compound (A) is less than 20% by weight, the developability is reduced, so that pattern formation becomes impossible. When the amount exceeds 60% by weight, the sensitivity tends to decrease. More preferably, it is in the range of 30 to 60% by weight.

The photopolymerizable monomer (B) used in the present invention
Is a component that undergoes radical polymerization with the compound (A) and the photopolymerizable monomer (B) upon exposure to ultraviolet light to reduce the solubility of the exposed portion in a developer.

Examples of the photopolymerizable monomer (B) include mono- or poly (meth) acrylates of monohydric or polyhydric alcohol. Specifically, hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, cresol ethoxy (meth) acrylate, phenoxyethyl (meth) acrylate, nonylphenoxyethyl (meth) acrylate, isobornyl Mono (meth) acrylate of monohydric alcohol such as (meth) acrylate; 1,3-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di ( Meth) acrylates,
Neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, 2,2-
Bis [4- (meth) acryloyloxyethoxyethylphenyl] propane, 2,2-bis [4- (meth) acryloyloxypropyloxypropylphenyl] propane, neopentyl glycol di (meth) acrylate hydroxypivalate, glycerin di ( (Meth) acrylate, glycerin tri (meth) acrylate, trimethylolethanedi (meth) acrylate, trimethylolethanetri (meth) acrylate, trimethylolpropanedi (meth) acrylate, trimethylolpropanetri (meth) acrylate, trimethylolpropane Tris [ethoxy (meth) acrylate], trimethylolpropane tris [diethoxy (meth) acrylate], trimethylolpropane tris [triethoxy (meth) acrylate], N, N '-[di (meth) acryloyloxyethyl] -N "-hydroxyethyl isocyanurate, N, N', N"-[tri (meth) acryloyloxyethyl] -isocyanurate, pentaerythritol di (meth) Polyhydric alcohols such as acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate Poly (meth) acrylates may be mentioned.

Specific examples of the compound other than the above (meth) acrylic acid ester include polybasic acids such as phthalic acid and adipic acid, ethylene glycol, hexanediol, and the like.
Polyester poly (meth) obtained by reaction with polyhydric alcohols such as polyethylene glycol and polytetramethylene glycol and (meth) acrylic acid or derivatives thereof
Acrylates; Epoxy poly (meth) acrylates obtained by reacting (meth) acrylic acid or a derivative thereof with a glycidyl ether compound such as bisphenol A diglycidyl ether or ethylene glycol diglycidyl ether; hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate , Xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, and other isocyanate compounds having hydroxyl groups such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate ( Urethane poly (meth) acrylates reacted with (meth) acrylate; N-methoxymethyl (meth) acrylamide N- ethoxymethyl acrylamide, N- butoxymethyl (meth) acrylamide, N-
(Meth) acrylamides such as hydroxymethyl (meth) acrylamide and methylenebis (meth) acrylamide. These photopolymerizable monomers (B)
One type or a mixture of two or more types can be used.

Among them, from the viewpoint of high sensitivity,
Compounds having three or more (meth) acryloyl groups in the molecule are preferred, and more preferred specific examples are trimethylolpropane triacrylate, pentaerythritol triacrylate, and pentaerythritol tetraacrylate. The amount of the photopolymerizable monomer (B) used in the present invention is preferably in the range of 5 to 40% by weight. 5
If the amount is less than 40% by weight, sufficient sensitivity cannot be obtained, and if the amount exceeds 40% by weight, developability tends to decrease.
More preferably, it is in the range of 10 to 30% by weight.

As the photopolymerization initiator (C) used in the present invention, it is essential to use an α-aminoalkylphenone compound and a thioxanthone compound in combination.

Specific examples of the α-aminoalkylphenone compound include 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2
-Dimethylamino-1- (4-morpholinophenyl)-
Butanone and the like. Specific examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4. -Propoxythioxanthone 2- (3-dimethylamino-2-hydroxypropoxy) -3,4-dimethyl-9H-thioxanthone-9-one mesochloride. Further, in addition to the above two photopolymerization initiators, one or more of the following photopolymerization initiators may be used in combination. Specific examples thereof include benzyl, benzophenone, methyl benzoylbenzoate, 4-benzoyl-4′-methyldiphenylsulfide, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and benzyldimethylketal. , 1-hydroxycyclohexyl-phenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,4,
6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,
4-trimethylpentylphosphine oxide, methylbenzoyl formate, 1,7-bisacridinylheptane, 9-phenylacridine and the like. The amount of the photopolymerization initiator (C) used in the present invention is 1 to 20% by weight.
Is preferable. When the amount of the component (C) is less than 1% by weight, the photosensitivity of the obtained photosensitive resin is insufficient. More preferably, 5
-15% by weight.

The photopolymerizable composition containing the components (A) to (C) used in the present invention includes, for example, p-dimethylaminoacetophenone, methyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoic acid. Known photosensitizers such as ethyl and isoamyl 4-dimethylaminobenzoate can be added.

By further adding a dye (D) to such a photopolymerizable composition, a colored photosensitive resin composition suitable for a color filter can be obtained. The following compounds can be used as the dye (D) used in the present invention. For example, azo, anthraquinone, xanthene, quinacridone, indigo, dioxazine, indanthrone, and isoindolinone pigments are useful. For example, phthalocyanine blue (CI Pigment Blue 15: 6 or CI Pigment Blue 15:
3), phthalocyanine green (CI pigment green 7, 36 or 37), perylene pigment (CI pigment red 155), anthraquinone pigment (C.I.
Pigment Red 177) and the like are useful. Also,
CI Pigment Yellow 83 as a color correction pigment,
CI Pigment Yellow 154 and CI Pigment Violet 23 are preferred. The content of the dye (D) in the photosensitive layer is preferably from 10 to 50% by weight based on the total amount of the components (A) to (D). When the content of the component (D) is less than 10% by weight, the color density of an image tends to decrease, and when it exceeds 50% by weight, the light sensitivity tends to decrease. More preferably, it is in the range of 20 to 40% by weight.

In the present invention, a dispersant is used as needed to disperse the dye in the photopolymerizable composition. Specific examples thereof include polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether. Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, oxyethylene-oxypropylene block copolymer, sorbitan fatty acid ester, glycerin fatty acid ester, phthalocyanine derivative, organosiloxane polymer, poly (meth) acrylic acid Polymers and the like can be used. These dispersants have a total amount of components (A) to (D) of 10
It is preferable to add 0.1 to 10 parts by weight to 0 part by weight.

The viscosity of the photosensitive resin composition of the present invention is appropriately adjusted with an organic solvent so as to be easily applied to a transparent substrate such as glass. Specific examples of usable organic solvents include dioxane, butyl acetate, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate,
Ethyl cellosolve acetate, carbitol, cyclohexanone, carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, β-methoxyisobutyric acid methyl ester, etc. At this time, those having an appropriate drying rate and evaporating to form a uniform and smooth coating film are desirable, and those having a boiling point in the range of 100 to 200 ° C are preferred. These may be used as a mixture of one or more of them as necessary.
(D) 100 to 2 parts by weight based on 100 parts by weight of the total amount of the components.
It is desirable to add in the range of 000 parts by weight. Also,
The photosensitive resin composition of the present invention, if necessary, a thermal polymerization inhibitor, a flame retardant, a leveling agent, a silane coupling agent,
Various additives such as a plasticizer and a filler can also be added.

To form a resist using the photosensitive resin composition of the present invention, a solvent is volatilized and dried after coating on various substrates to form a photosensitive layer. Thereafter, exposure is performed through a desired photomask to form a pattern, and the unexposed portions are developed and removed with an alkaline aqueous solution.

The method for applying the photosensitive resin composition of the present invention to a transparent substrate is not particularly limited, but may be any of various known methods such as spray coating, roll coating, blade coating, screen printing, curtain coating, and spin coating. It can be carried out. At that time, the dry film thickness was 0.5
It is preferable to apply so as to be 10 to 10 microns,
A circulating oven, an infrared heater, a hot plate or the like can be used for drying the coating film.

The conditions for volatilizing and drying the solvent in the coating film of the photosensitive resin composition of the present invention vary depending on the solvent contained in the photopolymerizable composition to be used. To prevent and efficiently volatilize the solvent efficiently,
It is preferable to heat in a range of 50 to 120 ° C. for 30 seconds to 30 minutes.

The pattern may be formed by an exposure method such as an ultraviolet exposure method using a photomask or a scanning exposure method using a laser beam.

A desired pattern can be obtained by dissolving and removing the unexposed portion. As a developer used in this case, an alkaline aqueous solution can be used. For example, sodium hydroxide, potassium hydroxide, Inorganic alkaline aqueous solutions such as sodium carbonate, potassium carbonate, sodium phosphate, sodium bicarbonate, potassium bicarbonate, sodium metasilicate, potassium metasilicate, sodium orthosilicate, potassium orthosilicate, and organic such as ammonia and tetramethylammonium hydroxide An aqueous alkaline solution may be used, but it is preferable to use an aqueous inorganic alkaline solution in the range of 0.001 to 2% by weight. 0.
If the amount is less than 001% by weight, the development time becomes too long,
Or, development becomes impossible. 2% by weight
When a developing solution exceeding the above is used, alkali metal ions remain in the cured pattern, and the life of a liquid crystal display device using the same may be shortened. Various surfactants, dispersants, defoamers, organic solvents, and the like can be added to these alkali developing solutions in order to impart dispersibility and defoaming properties of the developing object in the developing solution.

The method of developing a resist formed with the photopolymerizable composition of the present invention is most generally performed by a spray method, but a part of the method can be replaced by an immersion method in some cases.

In order to impart heat resistance to the resist pattern obtained by development, it is preferable to carry out post-curing (post-curing) by thermal polymerization. The post-curing is carried out at a temperature range of about 130 to 250 ° C. for about 10 to 60 minutes. It is desirable to carry out curing. A method for manufacturing a liquid crystal display device using a color filter manufactured using the photosensitive resin composition of the present invention is not particularly limited. In general, after the photosensitive resin liquid (RGB three colors) of the present invention is patterned in a matrix on the transparent glass substrate on which a black matrix pattern is formed by the above-described method, an ITO (indium tin oxide) sputtering film is formed. , An alignment film is formed, and is bonded to a TFT (thin film transistor) substrate via a spacer, and a liquid crystal is sealed therein.
It is also possible to form a color filter layer on a TFT substrate to manufacture a liquid crystal display device. Further, after the black matrix material using the photosensitive resin is formed with RGB,
It is also possible to form a black matrix pattern by coating and using the RGB pattern as a mask.

[0034]

The present invention will be described below in more detail with reference to examples. <Synthesis of Compound P1> In a 2000 ml four-necked flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer,
Under a nitrogen atmosphere, 300 g of propylene glycol monomethyl ether acetate was charged, and the internal temperature was raised to 100 ° C. And, in this system, methyl methacrylate 17
4 g, styrene 39 g, n-butyl methacrylate 30
g, 24 g of maleic anhydride and 300 g of a monomer mixture of 33 g of methacrylic acid and 6 g of azobisisobutyronitrile in 100 g of propylene glycol monomethyl ether acetate were added dropwise over 4 hours.
Next, 0.3 g of azobisisobutyronitrile was added in five portions every 30 minutes, and then the internal temperature was raised to 120 ° C. and maintained at that temperature for 2 hours to obtain a polymer solution. .

Next, the reaction atmosphere of the polymer solution was replaced with air from nitrogen, and the internal temperature was lowered to 80 ° C. Then, after adding 6 g of triethylamine as an addition catalyst to the polymer solution, 4-hydroxybutyl acrylate 3 was added.
A solution prepared by dissolving 0.2 g of hydroquinone monomethyl ether in 6 g was added dropwise over 1 hour. After dropping,
After the internal temperature was raised to 95 ° C. and maintained for 3 hours, 200 g of propylene glycol monomethyl ether acetate was added. When the infrared absorption of the obtained reaction product was measured with an FT-IR apparatus (BIO-RAD; trade name: FTS-7), almost no absorption by an acid anhydride group was observed, and the esterification reaction was almost completed. I knew I was doing it.

<Synthesis of Compounds P2, P3, P5, P6, and P7> 300 g of the monomer mixture shown in columns P2, P3, P5, P6, and P7 in Table 1, the amount of azobisisobutyronitrile, and the amount of 4-hydroxybutyl Synthesis was carried out in the same manner as for compound P1, using the amount of acrylate. <Synthesis of Compound P4> In a 2000 ml four-necked flask equipped with a nitrogen inlet, a stirrer, a condenser and a thermometer,
Under a nitrogen atmosphere, 300 g of propylene glycol monomethyl ether acetate was charged, and the internal temperature was raised to 130 ° C. Then, a solution prepared by dissolving 300 g of the monomer mixture and 12 g of azobisisobutyronitrile in 100 g of propylene glycol monomethyl ether acetate was dropped into the system over 4 hours.
Next, 0.3 g of azobisisobutyronitrile was added in five portions every 30 minutes, and the mixture was kept for 2 hours to obtain a polymer solution.

Next, the reaction atmosphere of this polymer solution was replaced with air from nitrogen, and the internal temperature was lowered to 80 ° C. Then, after adding 6 g of triethylamine as an addition catalyst to the polymer solution, 4-hydroxybutyl acrylate 3 was added.
A solution prepared by dissolving 0.2 g of hydroquinone monomethyl ether in 6 g was added dropwise over 1 hour. After dropping,
After the internal temperature was raised to 95 ° C. and maintained for 3 hours, 200 g of propylene glycol monomethyl ether acetate was added.

<Synthesis of Compound P8> A polymer solution was obtained in the same manner as for Compound P1, using 300 g of the monomer mixture shown in column P8 of Table 1. However, P8 has no acid anhydride group and does not require a 4-hydroxybutyl acrylate addition step.

About P1 to P8 thus obtained, gel permeation chromatography (manufactured by Tosoh Corporation;
Table 1 shows the weight-average molecular weight in terms of standard polystyrene and the acid value of the solid content obtained by trade name: HLC8020).

[0040]

[Table 1]

Example 1 <Preparation of red resist> As component (A), 30 g of P1 in terms of solid content, as component (B), 20 g of trimethylolpropane triacrylate, 5 g of pentaerythritol triacrylate, and (C) 8 g of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 as a component, 2 g of isopropylthioxanthone, and Pigment Red 177 as a component (D)
Was mixed, 900 g of propylene glycol monomethyl ether acetate was added, and the dispersion was stabilized using a ball mill. <Preparation of Green Resist> As the component (D), 26 g of Pigment Green 36 and 4 g of Pigment Yellow 83 were used.
The procedure was the same as in the preparation of the red resist except for mixing. <Preparation of Blue Resist> As the component (D), 28 g of Pigment Blue 15: 3, Pigment Violet 23
Was carried out in the same manner as in the preparation of the red resist except that 2 g was mixed.

<Evaluation of Colored Resist> The above resists of each color of RGB were spin-coated on a transparent glass substrate so as to have a dry film thickness of 1 μm.
Dried for minutes. Ultra-high pressure mercury lamp is used to irradiate ultraviolet rays through a 5 μm / 5 μm line / space photo mask,
27 ° C., using a 0.1% by weight aqueous solution of potassium carbonate,
After spray-developing for 60 seconds and washing with pure water, post-curing was performed for 15 minutes in a 220 ° C. circulation oven.
Thereafter, the resin film thickness after post-curing was measured using a surface roughness meter, and the residual film ratio, which is the ratio of the film thickness after exposure, development and post-curing to the dry film thickness after coating, was 90% or more, and The exposure amount at which a 5 μm / 5 μm pattern could be formed was measured as light sensitivity. As a result, a pattern could be formed at 50 mj / cm ² for each of the RGB colors, and the residual film ratio was 90% or more. Further, the content of the alkali metal of the color filter in which each of the RGB colors was formed on the matrix was measured and found to be 10 ppm, which was a concentration that would not contaminate the liquid crystal.

<Evaluation of Liquid Crystal Display> On the transparent glass substrate on which a black matrix was formed by patterning, using the above-mentioned resist, patterns of each color of RGB were formed in a matrix by the above-described method, and a color filter was produced.
An ITO transparent conductive film is formed on a color filter by a sputtering method, and a polyimide precursor is applied.
After imidization was performed by heat treatment at 20 ° C. for 2 hours, the film surface was rubbed to form an alignment film. On the other hand, as a counter substrate, a matrix-shaped TFT element and a pixel electrode corresponding to a color filter were formed on transparent glass, and then an alignment film was formed in the same manner as the color filter. The color filter substrate and the TFT substrate manufactured as described above were bonded together with a sealant through a spacer so that the gap was constant, and a liquid crystal material was sealed in the gap to manufacture a color liquid crystal display device. The liquid crystal display was subjected to a high-temperature energization test for two months, and the retention of the liquid crystal was measured. As a result, it was as good as 99.0%, and the display quality was also good.

[Examples 2 and 3] The components (A) to (D) were mixed in the proportions of parts by weight shown in the columns of Examples 2 and 3 in Table 2 and colored in the same manner as in Example 1 for each color of RGB. The resist was adjusted and evaluated similarly. The results are shown in Table 2.

[Comparative Examples 1 to 5] The components (A) to (D) were mixed in the proportions of parts by weight shown in the columns of Comparative Examples 1 to 5 in Table 1 and colored in the same manner as in Example 1 for each color of RGB. The resist was adjusted and evaluated similarly. The results are shown in Table 2.

[0046]

[Table 2]

As is evident from Table 2, the photosensitive resin composition of this example can be formed without forming an oxygen barrier film.
High sensitivity, and a color filter using the photosensitive resin composition and a liquid crystal display device having the color filter, there is no risk of contamination of the liquid crystal by an alkali metal, and the heat resistance is high and the display is high. It is of excellent quality.

Although the above embodiments have been described with reference to RGB, the present invention is not limited to RGB.
By adjusting the composition of the dye, cyan, magenta,
The present invention can also be applied to a case where yellow or the like is patterned into various shapes, for example, a well-known delta arrangement, stripe arrangement, mosaic arrangement, or square arrangement.

[0049]

According to the photosensitive resin composition of the present invention, the reaction proceeds with a small amount of exposure without forming an oxygen-blocking film, and can be developed with a low-concentration alkaline aqueous solution. This makes it possible to reduce the process cost and provide an inexpensive color filter and color liquid crystal display device.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/027 502 G03F 7/027 502 7/028 7/028 (72) Inventor Sayuri Fujiwara 606-99, Sanjo-cho, Nara-shi, Nara-ken (72) Inventor Takashi Sato 263-1 Ichihoncho, Tenri City, Nara Prefecture (72) Inventor Naofumi Kimura 2-125 Yurigaoka Higashi, Nabari City, Mie Prefecture

Claims (7)

[Claims] 1. A polymer (a) obtained from maleic anhydride and a monomer copolymerizable with maleic anhydride, wherein 4-hydroxybutyl acrylate is added to an acid anhydride group of the polymer (a). Compound having an average molecular weight of 10,000 to 40,000 and acid value of 50 to 150 mgKOH / g 20 to 70% by weight (B) 5 to 40% by weight of photopolymerizable monomer (C) Light containing α-aminoalkylphenone compound and thioxanthone compound A photosensitive resin composition comprising 1 to 20% by weight of a polymerization initiator (D) 10 to 50% by weight of a dye. 2. The photosensitive resin composition according to claim 1, wherein the monomer copolymerized with maleic anhydride contains styrene and (meth) acrylates. 3. The photopolymerizable monomer (B) according to claim 1, wherein the photopolymerizable monomer (B) contains at least one selected from trimethylolpropane triacrylate, pentaerythritol triacrylate, and pentaerythritol tetraacrylate. Photosensitive resin composition. 4. A color filter comprising a plurality of patterned visible light transmitting regions made of the photosensitive resin composition according to claim 1 on a transparent substrate. 5. A liquid crystal display device comprising the color filter according to claim 4. 6. A coating film of the photosensitive resin composition according to claim 1 is formed on a transparent substrate, and exposed to light.
A method for producing a color filter, comprising a step of forming a pattern by developing with an aqueous solution of a weight percent inorganic alkali. 7. A coating film of the photosensitive resin composition according to claim 1 is formed on a transparent substrate, and exposed to light to form a coating film of 0.001-2.
A method for manufacturing a liquid crystal display device, comprising a step of forming a pattern by developing with an aqueous solution of an inorganic alkali having a concentration of 1% by weight.