JPH06102669A - Photosensitive resin composition and color filter using the same - Google Patents

Abstract

PURPOSE:To attain suitable application for color filter excellent in heat resistance, resolving property, durability, light resistance, resistance to chemicals by constituting the photosensitive resin composition capable of being developed by dil. alkallin aq. soln. with the UV-setting resin which is obtained by reacting the reacted product between specified compd. and unsatd. mono carboxylic acid with satd. or unsatd. multibasic acid anhydride, a photo-polymerization initiator, a diluent and a colorant. CONSTITUTION:The composition is composed of the UV-setting resin which is obtained by treating the reacted product between the compd. expressed by the formula and unsatd. mono carboxylic acid with satd. or unsatd. multibasic acid anhydride, or by treating the reacted product between the compd. expressed by the formula and unsatd. mono carboxylic acid with isocyanate compd. having at least two isocyanate group in a molecule such as isophorone isocyanate and satd. or unsatd. multibasic acid anhydride, a photo-polymerization initiator, a diluent and a colorant. In the formula, R is the org. compd. residual group having (k) active hydrogens, n1, n2...nk is 0 or integer 1-5 and its sum is 1-50.

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 which can be developed with a dilute aqueous alkali solution and is useful for manufacturing color filters for color liquid crystal display devices and the like, and a color filter using the same.

[0002]

2. Description of the Related Art Conventionally, color filters formed on a glass substrate or the like have been widely used in color liquid crystal display devices, color facsimiles, color video cameras and the like. In the manufacture of this color filter, the use of color liquid crystal display devices for OA devices and the like and the market have expanded, and the technology has diversified, and dyeing methods, printing methods, electrodeposition methods, dispersion methods, etc. have been proposed. Among them, the dyeing method was the mainstream.

In the dyeing method, a predetermined pattern is formed on a glass substrate using a water-soluble resist agent such as acrylic resin and gelatin to which photosensitivity is imparted, and then a colored pattern is obtained through a dyeing, fixing and dye-proofing process. . This process is repeated three times to form red (R), green (G) and blue (B) colored layers, and a protective film is further applied onto the colored layers. Although the dyeing method is excellent in terms of fineness and spectral characteristics,
As described above, the process is complicated and the durability is slightly inferior.

Therefore, in recent years, the dispersion method has attracted attention. In the dispersion method, a resist agent in which a color pigment is dispersed in advance is applied to a glass substrate and exposed and developed to obtain a predetermined pattern. This process is repeated three times to form red (R), green (G) and blue (B) colored layers, and a protective film is further applied on the colored layers as needed. in this way,
The dispersion method is advantageous in that productivity can be improved because dyeing and fixing steps are unnecessary, and it is not always necessary to provide a protective film on the colored layer. Specifically, as a resist agent used in the dispersion method, an SBQ-PVA type photosensitive resin is used (Japanese Patent Laid-Open No. 60-129738).
No.), using a photosensitive resin of vinylpyrrolidone-methylmethacrylate copolymer system (JP-A-63-3145).
No. 01) and the like.

However, the dispersion method also has a problem in heat resistance. In particular, although the resist agent used for the color filter of the liquid crystal color display device is exposed to the heat treatment process of forming the transparent conductive film and the alignment film, it is required not to be colored by heat of 200 ° C. or higher, but the above-mentioned known photosensitive materials The functional resin turns yellow by heating at 180 ° C. for about 1 hour, and the blue peak transmittance particularly near 450 nm is lowered, and if an attempt is made to improve this transmittance, the color purity is deteriorated.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above heat resistance problem and develop with a dilute alkali which is excellent in high resolution, durability, light resistance and chemical resistance. An object of the present invention is to provide a possible photosensitive resin composition and a color filter using the same.

[0007]

The liquid photosensitive resin composition according to the present invention, which can be developed with a dilute aqueous alkaline solution, comprises: A reaction product of a compound represented by the following general formula (I) and an unsaturated monocarboxylic acid is reacted with a saturated or unsaturated polybasic acid anhydride, or a compound represented by the general formula (I) and an unsaturated monocarboxylic acid are reacted. At least 2 isocyanate groups in the molecule, such as isophorone diisocyanate, are added to the reaction product with carboxylic acid.
An ultraviolet-curable resin obtained by reacting an isocyanate compound having one and a saturated or unsaturated polybasic acid anhydride,

[0008]

[Chemical 3]

[Wherein R is an organic compound residue having k active hydrogens, n ₁ , n ₂ ... N _k are 0 or 1 to 5]
It is an integer of 0 and the sum is 1 to 50. In addition, the following functional groups in the formula

[0010]

[Chemical 4]

[0011]

(However, R'represents a hydrogen atom, an alkyl group, an alkylcarbonyl group or an arylcarbonyl group)
May be replaced with ]

B. A photopolymerization initiator, C.I. Diluent and D.I. It comprises a colorant.

In the above composition, the E. A thermosetting compound may be contained, and in the synthesis of the component A, a compound represented by the general formula (I) instead of a reaction product of the compound represented by the general formula (I) and an unsaturated monocarboxylic acid, and A reaction product of another epoxy compound and an unsaturated monocarboxylic acid may be used.

The present invention will be described in detail below. <A. About UV-Curable Resin> As described above, the UV-curable resin is obtained by reacting a reaction product of the compound represented by the general formula (I) with an unsaturated monocarboxylic acid with a saturated or unsaturated polybasic acid anhydride. Or a reaction product of a compound represented by the general formula (I) with an unsaturated monocarboxylic acid, an isocyanate compound having at least two isocyanate groups in the molecule, such as isophorone diisocyanate, and a saturated or unsaturated polybasic anhydride It can be obtained by reacting things.

The alicyclic epoxy resin represented by the general formula (I) used in the present invention can be synthesized by a known method. For example, an organic compound having activated hydrogen in the molecule, that is, a mono compound. It can be obtained by ring-opening polymerization of 4-vinylcyclohexene-1-oxide using an alcohol, a polyalcohol such as diol or triol, a phenol, a thiol, a carboxylic acid or the like as an initiator. Among these organic compounds, methanol, allyl alcohol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, acrylic acid and the like are particularly preferable in the present invention.

As the unsaturated monocarboxylic acid, for example,
Acrylic acid, methacrylic acid, crotonic acid, cinnamic acid and the like can be mentioned, but acrylic acid is particularly preferable.

Examples of the isocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate and toluidine. Examples thereof include diisocyanate, lysine diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, triphenylmethane triisocyanate and polymethylene polyphenyl polyisocyanate. These can be used alone or in combination of two or more, but isophorone diisocyanate, hydrogenated xylylene diisocyanate, tolylene diisocyanate and xylylene diisocyanate are particularly preferable, and among them, there is little problem of coloring at high temperature. Therefore, those having no aromatic ring such as isophorone diisocyanate and hydrogenated xylylene diisocyanate are most suitable.

Further, as the saturated or unsaturated polybasic acid anhydride, for example, maleic anhydride, succinic anhydride,
Dibasic acid anhydrides such as itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride, and trimellitic anhydride, anhydrous An acid anhydride having three or more basic acids such as pyromellitic acid, benzophenone tetracarboxylic acid anhydride, and methylcyclohexene tetracarboxylic acid anhydride can be mentioned.

The method for producing the UV-curable resin will be described in detail. For example, the compound represented by the general formula (I) is dissolved in an organic solvent such as carbitol acetate, cellosolve acetate and methyl ethyl ketone to prepare hydroquinone and hydroquinone monomethyl ether. Such as a thermal polymerization inhibitor, tertiary amines such as benzyldimethylamine and triethylamine, quaternary ammonium salts such as trimethylbenzylammonium chloride and methyltriethylammonium chloride, or a catalyst such as triphenylstibine. Then, the unsaturated monocarboxylic acid such as acrylic acid is preferably about 0.7 to 1.3 chemical equivalents, and particularly preferably about 0.9 to 1.1 chemical equivalents per one chemical equivalent of the epoxy group. By a conventional method, the ratio is preferably 60 to 50 ° C., particularly preferably 80 to
The reaction is carried out at a reaction temperature of 120 ° C. to obtain a first reaction product composed of epoxy acrylate. Subsequently, the first reaction product is reacted with an acid anhydride in a ratio of 0.99 to 0.10 chemical equivalent of acid anhydride to 1 chemical equivalent of hydroxyl group in the first reaction product. At this time, as the acid anhydride, at least one kind is selected from the saturated or unsaturated polybasic acid anhydrides, and they are reacted by heating and stirring at a reaction temperature of 70 to 120 ° C. by a conventional method to obtain the required UV curability. Get the resin.

When an isocyanate compound such as isophorone diisocyanate is used for synthesizing an ultraviolet-curable resin, first, the above-mentioned first reaction product is obtained, and then the isocyanate compound is added to the former secondary hydroxyl group 1 chemical equivalent. With respect to the isocyanate group is preferably 0.01 to 0.90 chemical equivalent, particularly preferably the isocyanate group 0.05 to
With a ratio of 0.40 chemical equivalent, by a conventional method, an organotin compound such as dibutyltin dilaurate or a tertiary amine such as benzyldimethylamine was added as a catalyst or a catalyst compounded in the above reaction with or without a tertiary amine, 20-100 ° C
The second reaction product is obtained by reacting at a reaction temperature of 1 by heating and stirring. The reaction amount of the isocyanate group with respect to 1 chemical equivalent of the hydroxyl group in the first reaction product was 0.90.
If it is more than the chemical equivalent, the solubility of the ultraviolet curable resin in the diluent tends to be poor, and in particular 0.05 to 0.40.
The best use properties are obtained in the stoichiometric range.

Subsequently, an acid anhydride is added to the second reaction product, and the acid anhydride is 0.99 to 0.10 chemical equivalent to 1 chemical equivalent of the hydroxyl group in the first reaction product. React in a ratio. At this time, as the acid anhydride, at least one kind is selected from the above-mentioned saturated or unsaturated polybasic acid anhydrides and reacted by a conventional method, preferably by heating and stirring at 70 to 120 ° C. to obtain an ultraviolet curable resin.

The UV-curable resin has not only excellent heat resistance but also excellent film strength after pre-cure, by appropriately selecting the molecular weight of the compound represented by the general formula (I). Therefore, not only the so-called off-contact method but also the contact exposure of the pattern can be easily performed,
Further, it is possible to obtain an excellent resist agent capable of forming a good pattern even in the exposure with a low light amount. The same adjustment of the coating properties can be achieved by partially crosslinking the isocyanate as described above.

The UV-curable resin is not limited to the above-mentioned synthetic examples, and can be synthesized by various conventional synthetic methods. For example, the compound represented by the general formula (I) may be a compound such as acrylic acid or the like. It can also be synthesized by reacting a saturated monocarboxylic acid to form an epoxy acrylate, first reacting with an acid anhydride, and then reacting with an isocyanate compound or the like.

By the way, as the raw material epoxy compound for the ultraviolet curable resin, not only the compound represented by the general formula (I) but also the compound represented by the general formula (I) and other epoxy compounds such as bisphenol A type epoxy are used. Resin, bisphenol F type epoxy resin, novolac type epoxy resin (phenol novolac type, cresol novolac type), cycloaliphatic epoxy resin, tris (hydroxyphenyl) methane-based multifunctional epoxy resin, Yuka Shell Epoxy Epicoat 157 It is also possible to use a mixture with an epoxy resin corresponding to the series, triglycidyl isocyanurate, or the like. However, since many of the other epoxy compounds listed here tend to be colored by heating when blended in a large amount, the compounding ratio of the compound represented by the general formula (I) to the total amount of the raw material epoxy compound is 25% by weight. Above all, it is desirable to keep the content at 50% by weight or more.

The acid value of the obtained ultraviolet curable resin is 30.
It is preferably about 160 mgKOH / g. If the acid value is less than 30, the solubility in an alkali developing solution will be poor, and if it is more than 160, it will be a factor that deteriorates the properties such as chemical resistance of the cured resist film.

The UV-curable resin is, for example, an epoxy acrylate to which a known polybasic acid anhydride is added, or an UV-curable resin derived from other epoxy compounds by the same method as the UV-curable resin according to the present invention. Can also be used in combination as appropriate.

<B. Photopolymerization Initiator> Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and other benzoins and their alkyl ethers, and acetophenone and 2,2-dimethoxy-2.
-Phenylacetophenone, 2,2-diethoxy-2-
Phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone and 2-methyl-1- [4- (methylthio) phenyl]-
Acetophenones such as 2-morpholino-propan-1-one, and anthraquinones such as 2-methylanthraquinone and 2-amylanthraquinone, and 2,4
-Dimethylthioxanthone, 2,4-diethylthioxanthone, thioxanthones such as 2-chlorothioxanthone and 2,4-diisopropylthioxanthone, and ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal, and benzophenones such as benzophenone or xanthones, And Lucillin TP
O (2,4,6-trimethylbenzoyldiphenylphosphine oxide manufactured by BASF) and the like can be mentioned, and these may be used in combination with a known photopolymerization accelerator such as a benzoic acid type or a tertiary amine type. These photopolymerization initiators are preferably added in an amount of 0.1 to 30 parts by weight, particularly preferably 1 to 25 parts by weight, based on 100 parts by weight of the ultraviolet curable resin.

<C. About diluent> As a diluent,
A photopolymerizable monomer and / or an organic solvent can be used. Examples of the photopolymerizable monomer include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, N-vinylpyrrolidone, acryloylmorpholine, methoxytetraethylene glycol acrylate, methoxy polyethylene glycol acrylate, polyethylene glycol diacrylate, N, N-.
Dimethylacrylamide, N-methylolacrylamide, N, N-dimethylaminopropylacrylamide,
N, N-dimethylaminoethyl acrylate, N, N-
Water-soluble monomers such as dimethylaminopropyl acrylate and melamine acrylate, or methacrylates corresponding to the acrylates, and diethylene glycol diacrylate, triethylene glycol diacrylate, propylene glycol diacrylate, tripropylene glycol diacrylate, phenoxyethyl acrylate tetrahydrofurfuryl Acrylate, cyclohexyl acrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, isobonyl acrylate, cyclopentanyl (mono or di Water-insoluble, such as acrylate, cyclopentenyl (mono or di) acrylate, or each methacrylate corresponding to said acrylate and mono-, di-, tri- or higher polyester of hydroxyalkyl (meth) acrylate and polybasic acid Monomer,
And epoxy acrylates such as polyester acrylate, urethane acrylate, bisphenol A type epoxy acrylate, phenol novolac type epoxy acrylate and cresol novolac type epoxy acrylate, triglycidyl isocyanurate, or epoxy acrylate derived from the compound represented by the general formula (I). (These epoxy acrylates may be partially crosslinked with a compound having at least two isocyanate groups in the molecule or a polybasic acid anhydride), polyester acrylate, urethane acrylate and other high molecular weight acrylate monomers You can The water-soluble monomer, water-insoluble monomer, high molecular weight acrylate monomer and the like can be used alone or in combination with each other as appropriate.

Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone,
And aromatic hydrocarbons such as toluene and xylene; cellosolves such as cellosolve and butyl cellosolve; carbitols such as carbitol and butyl carbitol; and ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate and butyl carbitol. Acetates such as acetate and propylene glycol monomethyl ether acetate may be mentioned.

The photopolymerizable monomer such as the water-soluble monomer, the water-insoluble monomer and the high molecular weight acrylate monomer dilutes the ultraviolet curable resin to make it easy to apply and adjusts the acid value and the photopolymerizability. When a water-soluble monomer is used alone or in combination with a water-insoluble monomer or a high molecular weight acrylate monomer, the solubility in an alkaline aqueous solution is improved when the mixing ratio of the water-soluble monomer is increased. Since the water resistance of the completely cured resist film is lowered, it may be added in an amount of 100% by weight or less with respect to the ultraviolet curable resin, to the extent that the resist film is hardly soluble in an alkaline aqueous solution. In addition, the organic solvent dissolves and dilutes the ultraviolet curable resin so that it can be applied as a liquid and dried to form a film.

Although depending on the coating method, the diluent is preferably added alone or as a mixture of two or more kinds in the range of 10 to 95% by weight based on the total amount of the photosensitive resin composition.

<D. Colorant> The colorant used in the photosensitive thermosetting resin composition of the present invention is for coloring the coating film for a color filter, for example, azo lake type, insoluble azo type, phthalocyanine type, quinacridone type, Organic pigments such as dioxazine-based, isoindolinone-based, perinone-based, anthraquinone-based, perylene-based, slene-based, and azo-based organic pigments, and milori blue, iron oxide, cobalt-based, manganese-based, ultramarine blue, navy blue, cobalt blue, cerulean Inorganic pigments such as blue, pyriazine, emerald green and cobalt green, and dyes such as oil-soluble dyes, dispersible dyes, basic dyes and disperse dyes can be used alone or in combination.

<E. Thermosetting compound> Each component A to above
The photosensitive resin composition containing D further contains a thermosetting compound, for example, a thermosetting epoxy compound, and the photocuring reaction and the thermosetting reaction are simultaneously or sequentially advanced to thereby improve the adhesiveness. , Light resistance, chemical resistance, and film strength may be further improved.

Examples of the thermosetting epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, N-glycidyl type epoxy resin or alicyclic epoxy resin. , "YX
-4000 "(Epoxy resin made by Yuka Shell Epoxy Co., Ltd.)
Examples thereof include those having two or more epoxy groups in one molecule. From the viewpoint of heat resistance, hydrogenated bisphenol A type epoxy resin, triglycidyl isocyanurate, and the general formula used in the present invention are particularly preferable. The compound represented by (I) and the like are desirable.

The photosensitive resin composition according to the present invention may further contain an imidazole derivative, polyamines, guanamines, tertiary amines, quaternary ammonium salts, polyphenols and polybasic acid anhydrides, if necessary. Epoxy resin curing agents and curing accelerators, etc., and fillers such as barium sulfate, silicon oxide, talc, clay and calcium carbonate, and adhesion promoters such as defoamers and silane coupling agents, leveling agents, halation. Various additives such as an inhibitor and a dispersant, or a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butyl catechol and phenothiazine may be added.

The photosensitive resin composition according to the present invention is prepared, for example, by kneading the above-mentioned respective components A to D or A to E and additives with a three-roll, ball mill, sand mill or the like. It

The photosensitive resin composition according to the present invention may be used, for example, by dipping on a glass substrate, spraying,
After coating with a spin coater, roll coater, screen printing, etc., in order to evaporate the solvent, for example, 60
After heating and drying at ~ 120 ° C, a patterned mask is applied to the dried coating surface with or without contact, and a chemical lamp, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, The desired resist film can be formed by irradiating with ultraviolet rays using a xenon lamp, a metal halide lamp or the like, and developing to form a pattern. When a thermosetting compound is added, a heat curing step may be further added after the development.

[0039]

The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. The "parts" and "%" used below are all on a weight basis, and the "coloring agent" is a lionogen red GD (manufactured by Toyo Ink Mfg. Co., Ltd.) for red, and a rio for blue. Nord Blue ES (manufactured by Toyo Ink Mfg. Co., Ltd.) and, in the case of green, Rionol Green 2YS (manufactured by Toyo Ink Mfg. Co., Ltd.) were used.

Example 1 A compound represented by the following general formula (II) [EHPE-3150 manufactured by Daicel Chemical Industries, Ltd., epoxy equivalent 185]

[0041]

[Chemical 5]

(In the formula, n ₁ , n ₂ , and n ₃ are integers of 1 to 18, and the sum thereof is 10 to 20.) 185 parts by heating and dissolving in 60 parts of carbitol acetate are stirred. To 74 parts of acrylic acid, 0.1 parts of hydroquinone and 0.7 parts of benzyldimethylamine were added, and 90-
The reaction was carried out at 100 ° C for 24 hours. After cooling the reaction solution,
Carbitol acetate 65 parts, Swazol 1500
(Aromatic solvent manufactured by Maruzen Petrochemical Co., Ltd.) 125 parts and tetrahydrophthalic anhydride 76 parts were added, and the temperature was raised to 100 ° C. and reacted for about 3 hours under stirring to obtain an ultraviolet curable resin (A-1). It was

[Ingredients] UV curable resin (A-1) 55 parts "Irgacure 907" (Ciba-Geigy photoinitiator) 4 parts "Modaflow" (Monsanto leveling agent) 0.5 part Colorant 12 parts "Swasol 1500" (aromatic solvent manufactured by Maruzen Petrochemical Co., Ltd.) 6 parts Cellosolve acetate 7.5 parts ────────────────────────── ───────── Total 85 copies

In the above composition, first, a compounding component using a red colorant as a colorant is kneaded with a three-stage roll to prepare a dilute alkali developing red photosensitive resin composition, and in the same manner, blue and green are prepared. Blue and green photosensitive resin compositions were prepared using colorants.

Next, the red photosensitive resin composition was diluted 3 times (weight ratio) with propylene glycol monomethyl ether acetate and spin-coated on the entire surface of a glass substrate, and then 90 ° C. to volatilize the solvent. Drying was carried out for 20 minutes to obtain a dry coating film having a film thickness of 2 μm. Then, apply a mask with a pattern to the surface of the coating film,
A patterned red colored layer was formed by irradiating with 0 mj of ultraviolet rays and then developing with a 1% sodium carbonate aqueous solution as a developing solution. Then, on the glass substrate on which the red colored layer is formed, the blue colored layer and the green colored layer are sequentially formed using the blue and green photosensitive resin compositions in the same manner as described above, and the color filter is formed. I made a test piece.

[Example 2] [Blending component] UV curable resin (A-1) 43 parts Trimethylolpropane triacrylate 8 parts "Lucirin TPO" (BASF photoinitiator) 4 parts "Polyflow S" (Kyoeisha) Oil and fat company leveling agent) 0.5 part Colorant 12 parts "Swasol 1500" (Aromatic solvent manufactured by Maruzen Petrochemical Co., Ltd.) 6 parts Propylene glycol monomethyl ether acetate 11.5 parts ─────────── ──────────────────────── Total 85 copies

The components of the above composition were kneaded in the same manner as in Example 1 to prepare red, blue and green photosensitive resin compositions, respectively.

Next, using the above-mentioned photosensitive resin composition, a red colored layer, a blue colored layer and a green colored layer were formed on a glass substrate in the same manner as in Example 1 to prepare a color filter test piece.

[Embodiment 3] The general formula (I
I) a compound [EHPE-3150 manufactured by Daicel Chemical Industries, Ltd., epoxy equivalent 185] 185 parts was heated and dissolved in 60 parts carbitol acetate, 74 parts acrylic acid and 0.1 parts hydroquinone under stirring.
And benzyldimethylamine (0.7 part) were added, and the mixture was reacted at 90 to 100 ° C. for 24 hours by a conventional method. After cooling the reaction solution, 65 parts of carbitol acetate, 133 parts of Swazol 1500 (aromatic solvent manufactured by Maruzen Petrochemical Co., Ltd.),
7 parts of isophorone diisocyanate and 0.1 part of dibutyltin dilaurate were added, and the mixture was reacted at 50 ° C. for 4 hours while stirring. In addition, tetrahydrophthalic anhydride 76
Parts were added, the temperature was raised to 100 ° C., and the mixture was reacted for about 3 hours under stirring to obtain an ultraviolet curable resin (A-2).

[Ingredients] UV curable resin (A-2) 55 parts Benzyl dimethyl ketal 4 parts "DC-3PA" (manufactured by Toray Silicone) 0.5 parts Colorant 12 parts "Swazol 1500" (Maruzen Petrochemical Aromatic solvent manufactured by the company) 6 parts propylene glycol monomethyl ether acetate 7.5 parts ──────────────────────────────── ── Total 85 copies

The components of the above composition were kneaded in the same manner as in Example 1 to prepare red, blue and green photosensitive resin compositions, respectively.

Next, using the above-mentioned photosensitive resin composition, a red colored layer, a blue colored layer and a green colored layer were formed on a glass substrate in the same manner as in Example 1 to prepare a color filter test piece.

Example 4 An ultraviolet curable resin (A-3) was obtained by the same procedure as in Example 3 except that tolylene diisocyanate was used instead of isophorone diisocyanate in Example 3. .

[Blending components] UV curable resin (A-3) 43 parts Dipentaerythritol hexaacrylate 8 parts Benzyl dimethyl ketal 4 parts "Modaflow" (Monsanto leveling agent) 0.5 parts Colorant 12 parts "Swazol 1500 "(Aromatic solvent manufactured by Maruzen Petrochemical Co., Ltd.) 6 parts Cellosolve acetate 11.5 parts ────────────────────────────── ───── Total 85 copies

The components of the above composition were kneaded in the same manner as in Example 1 to prepare red, blue and green photosensitive resin compositions, respectively.

Next, using the above-mentioned photosensitive resin composition, a red colored layer, a blue colored layer and a green colored layer were formed on a glass substrate in the same manner as in Example 1 to prepare a color filter test piece.

Example 5 The general formula (I
I) compound [EHPE-3150 manufactured by Daicel Chemical Industries, Ltd., epoxy equivalent 185] 130 parts and Epotote ST-3000 (hydrogenated bisphenol A epoxy resin manufactured by Toto Kasei Co., epoxy equivalent 235) 7
To 0.5 parts of which 0.5 parts of carbitol acetate was heated and dissolved, 74 parts of acrylic acid, 0.1 part of hydroquinone and 0.7 part of benzyldimethylamine were added with stirring.
The reaction was carried out at 90 to 100 ° C for 24 hours by a conventional method. After cooling the reaction solution, 70 parts of carbitol acetate and Swazol 1500 (Aromatic solvent manufactured by Maruzen Petrochemical Co., Ltd.) 13
Add 8 parts, 11 parts isophorone diisocyanate and 0.1 parts dibutyltin dilaurate and stir at 50 ° C. for 4 hours.
Reacted for hours. Furthermore, 76 parts of tetrahydrophthalic anhydride was added thereto, and the temperature was raised to 100 ° C. and the reaction was performed for about 3 hours under stirring to obtain an ultraviolet curable resin (A-4).

[Ingredients] UV curable resin (A-4) 55 parts "Irgacure 907" 4 parts "Modaflow" (Monsanto leveling agent) 0.5 parts Colorant 12 parts "Swazol 1500" (Maruzen Petrochemical) Aromatic solvent manufactured by the company) 6 parts Cellosolve acetate 7.5 parts ────────────────────────────────── Total 85 copies

The components of the above composition were kneaded in the same manner as in Example 1 to prepare red, blue and green photosensitive resin compositions, respectively.

Next, using the above-mentioned photosensitive resin composition, a red colored layer, a blue colored layer and a green colored layer were formed on a glass substrate in the same manner as in Example 1 to prepare a color filter test piece.

[Example 6] [Blending components] UV curable resin (A-2) 43 parts Hydroxyethyl acrylate 6 parts "Irgacure 907" (Ciba-Geigy photopolymerization initiator) 4 parts "TEPIC" (Nissan Chemical Co., Ltd.) Epoxy resin, epoxy equivalent 100) 4 parts "Modaflow" (Monsanto leveling agent) 1 part Colorant 12 parts 2-Methylimidazole 0.1 part "Swazol 1500" (Maruzen Petrochemical aromatic solvent) 6 parts Butyl glycol 8.9 parts ────────────────────────────────── Total 85 parts

The components of the above composition were kneaded in the same manner as in Example 1 to prepare red, blue and green photosensitive resin compositions, respectively.

Next, using the above-mentioned photosensitive resin composition, a red colored layer, a blue colored layer and a green colored layer were formed on a glass substrate by the same method as in Example 1 and then heated at 150 ° C. for 30 minutes. Curing was performed to prepare a color filter test piece.

Example 7 Compound (III) represented by the following general formula [EHPE-1150 manufactured by Daicel Chemical Industries, Ltd., epoxy equivalent 172]

[0065]

[Chemical 6]

(In the formula, n is an integer of 10 to 20.)
To 172 parts of which was heated and dissolved in 60 parts of carbitol acetate, 74 parts of acrylic acid, 0.1 part of hydroquinone and 0.7 part of benzyldimethylamine were added with stirring.
The reaction was carried out at 90 to 100 ° C for 24 hours by a conventional method. After cooling the reaction solution, 65 parts of carbitol acetate and Swazol 1500 (aromatic solvent manufactured by Maruzen Petrochemical Co., Ltd.) 11
Add 8 parts and 76 parts tetrahydrophthalic anhydride and add 10
The temperature was raised to 0 ° C. and the reaction was performed for about 3 hours with stirring to obtain an ultraviolet curable resin (A-5).

[Blending components] UV curable resin (A-5) 55 parts "Irgacure 907" (Ciba Geigy photoinitiator) 4 parts "Modaflow" (Monsanto leveling agent) 0.5 part Colorant 12 parts "Swasol 1500" (aromatic solvent manufactured by Maruzen Petrochemical Co., Ltd.) 6 parts Cellosolve acetate 7.5 parts ────────────────────────── ───────── Total 85 copies

The components of the above composition were kneaded in the same manner as in Example 1 to prepare red, blue and green photosensitive resin compositions, respectively.

Next, using the above-mentioned photosensitive resin composition, a red colored layer, a blue colored layer and a green colored layer were formed on a glass substrate in the same manner as in Example 1 to prepare a color filter test piece.

Example 8 The general formula (II
172 parts of a compound represented by I) [EHPE-1150, manufactured by Daicel Chemical Industries, Ltd., epoxy equivalent 172], dissolved in 60 parts of carbitol acetate by heating,
While stirring, 74 parts of acrylic acid, 0.1 part of hydroquinone and 0.7 part of benzyldimethylamine were added and reacted at 90 to 100 ° C. for 24 hours by a conventional method. After cooling the reaction solution, 65 parts of carbitol acetate and 15 parts of Swazol
123 parts of 00 (Aromatic solvent manufactured by Maruzen Petrochemical Co., Ltd.), 7 parts of isophorone diisocyanate and 0.1 part of dibutyltin dilaurate were added and reacted at 50 ° C. for 4 hours under stirring. Furthermore, 76 parts of tetrahydrophthalic anhydride was added thereto, and the temperature was raised to 100 ° C. and the reaction was performed for about 3 hours under stirring to obtain an ultraviolet curable resin (A-6).

[Ingredient] UV curable resin (A-3) 55 parts Benzyl dimethyl ketal 4 parts "DC-3PA" (manufactured by Toray Silicone) 0.5 parts Colorant 12 parts "Swazol 1500" (Maruzen Petrochemical) Aromatic solvent manufactured by the company) 6 parts propylene glycol monomethyl ether acetate 7.5 parts ──────────────────────────────── ── Total 85 copies

The components of the above composition were kneaded in the same manner as in Example 1 to prepare red, blue and green photosensitive resin compositions, respectively.

Next, using the above-mentioned photosensitive resin composition, a red colored layer, a blue colored layer and a green colored layer were formed on a glass substrate in the same manner as in Example 1 to prepare a color filter test piece.

[Comparative Example 1] N-methyl-4- (p-formylstyryl) pyridinium methosulfate was added to polyvinyl alcohol (average degree of polymerization 1700, degree of saponification 88 mol%) by an acetalization reaction to carry out the reaction. The solution was poured into a large amount of acetone to precipitate the resin, which was thoroughly washed with methanol and dried to give styrylpyridinium-added polyvinyl alcohol (1.2 mol% addition).
(Hereinafter, referred to as “SBQ-PVA”).

900 parts of water was added to 100 parts of this SBQ-PVA and stirred at room temperature for 1 hour to obtain 10% of SBQ-PVA.
An aqueous solution was prepared.

[Blending components] 10% aqueous solution of SBQ-PVA 70 parts water 27 parts coloring agent 3 parts ────────────────────────────── ───── Total 100 copies

In the above composition, the compounding ingredients using a red colorant as a colorant were kneaded with a three-stage roll to obtain SBQ-P.
A VA-based red photosensitive resin composition was prepared, and in the same manner,
Blue and green photosensitive resin compositions were prepared using blue and green colorants, respectively.

The red photosensitive resin composition was applied on the entire surface of a glass substrate by spin coating, and dried at 70 ° C. for 20 minutes to volatilize water to obtain a dry coating film having a thickness of 2 μm. After that, a patterned mask was applied to the surface of the coating film, irradiated with ultraviolet rays of 300 mj, and then developed by using water / isopropanol = 10/3 (weight ratio) as a developing solution to form a patterned red coloring layer. Was formed. Then, on the glass substrate on which the red colored layer was formed, in the same manner as described above, a blue colored layer and a green colored layer were sequentially formed using each of the blue and green photosensitive resin compositions, and a color filter test was performed. I made a piece.

[Comparative Example 2] 178 parts of Epicoat 154 (Novolak epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent: 178) dissolved in 68 parts of carbitol acetate by heating were mixed with 74 parts of acrylic acid and 0.1 parts of hydroquinone under stirring. 1 part and benzyl dimethylamine 0.7 part were added, and it was made to react at 90-100 degreeC for 24 hours by a conventional method. After cooling the reaction solution, carbitol acetate 20
Parts, 88 parts of Swasol 1500 (aromatic solvent manufactured by Maruzen Petrochemical Co., Ltd.) and 76 parts of tetrahydrophthalic anhydride are added, and the mixture is heated to 100 ° C. and reacted for about 3 hours under stirring to obtain an ultraviolet curable resin (B- 2) was obtained.

[Blending components] UV curable resin (B-2) 43 parts Dipentaerythritol hexaacrylate 8 parts Benzyl dimethyl ketal 4 parts "Modaflow" (Monsanto leveling agent) 0.5 parts Colorant 12 parts "Swazol 1500 "(Aromatic solvent manufactured by Maruzen Petrochemical Co., Ltd.) 6 parts Cellosolve acetate 11.5 parts ────────────────────────────── ───── Total 85 copies

The components of the above composition were kneaded in the same manner as in Example 1 to prepare red, blue and green photosensitive resin compositions, respectively.

Next, using the above-mentioned photosensitive resin composition, a red colored layer, a blue colored layer and a green colored layer were formed on a glass substrate in the same manner as in Example 1 to prepare a color filter test piece.

<Test Results> Tables 1 and 2 show the results of various physical property tests on the test pieces obtained in the above-mentioned Examples and Comparative Examples.
And shown in Table 3.

[0084]

[Table 1]

[0085]

[Table 2]

[0086]

[Table 3]

The evaluation method of the test results is as follows. ◎ ---- It is extremely excellent. ○ ---- Excellent. △ ---- Slightly inferior. × −−− Inferior.

[0088]

As described above, the photosensitive resin composition according to the present invention is excellent in heat resistance, high resolution, durability, light resistance and chemical resistance, and is suitable for color filters of color liquid crystal display devices and the like. It can be suitably used for production.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location G03F 7/027 502 513 7/028 7/032 501

Claims (5)

[Claims] 1. A. An ultraviolet curable resin obtained by reacting a reaction product of a compound represented by the following general formula (I) with an unsaturated monocarboxylic acid with a saturated or unsaturated polybasic acid anhydride: [Wherein, R is an organic compound residue having k active hydrogens, n ₁ , n ₂ ... N _k are 0 or an integer of 1 to 50,
The sum is 1 to 50. In addition, the following functional groups in the formula: (However, R'represents a hydrogen atom, an alkyl group, an alkylcarbonyl group, or an arylcarbonyl group). ] B. A photopolymerization initiator, C.I. Diluent and D.I. A photosensitive resin composition comprising a colorant, which is developable with a dilute aqueous alkali solution. 2. A. Ultraviolet rays obtained by reacting a reaction product of a compound represented by the general formula (I) and an unsaturated monocarboxylic acid with a compound having at least two isocyanate groups in the molecule and a saturated or unsaturated polybasic acid anhydride Curable resin, B. A photopolymerization initiator, C.I. Diluent and D.I. A photosensitive resin composition comprising a colorant, which is developable with a dilute aqueous alkali solution. 3. In the synthesis of the component A, a compound represented by the general formula (I) and another epoxy compound are used in place of the reaction product of the compound represented by the general formula (I) with an unsaturated monocarboxylic acid. The photosensitive resin composition according to claim 1, wherein a reaction product with an unsaturated monocarboxylic acid is used. 4. E. The photosensitive resin composition according to claim 1, 2 or 3, which contains a thermosetting compound. 5. A color filter manufactured using the photosensitive resin composition according to claim 1, claim 2, claim 3, or claim 4.