JP3016532B2 - Photosensitive resin composition for color filter and color filter using the same - Google Patents

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 a color filter which is useful for producing a color filter for a color liquid crystal display device and the like and which can be developed with a dilute alkaline aqueous solution, and a color filter using the same.

[0002]

2. Description of the Related Art Hitherto, a color filter formed on a glass substrate or the like has been widely used for a color liquid crystal display device, a color facsimile, a color video camera and the like. In the production of this color filter, the use of color liquid crystal display devices for OA equipment and the like and the market are expanding, and the technology is diversified. Dyeing methods, printing methods, electrodeposition methods, dispersion methods and the like 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 an acrylic resin or gelatin imparted with photosensitivity, and then a colored pattern is obtained through a dyeing, fixing and anti-staining process. . This process is repeated three times to form red (R), green (G), and blue (B) colored layers, and a protective film is applied on the colored layers. Although the dyeing method is excellent in terms of fineness and spectral characteristics,
As described above, there are disadvantages that 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 coloring pigment is dispersed in advance is applied to a glass substrate, and a predetermined pattern is obtained by exposure and development. This process is repeated three times to form red (R), green (G), and blue (B) colored layers, and a protective film is formed on the colored layers as necessary. in this way,
The dispersing method has advantages in that productivity can be improved because a dyeing and fixing step is not required, and a protective film does not necessarily need to be provided on the colored layer. As a resist agent used in the dispersion method, specifically, one using an SBQ-PVA-based photosensitive resin (JP-A-60-129938)
No.) and those using a vinylpyrrolidone-methyl methacrylate copolymer-based photosensitive resin or the like (JP-A-63-3145).
No. 01).

However, the dispersion method has a problem in terms of heat resistance. Particularly, the resist agent used for the color filter of the liquid crystal color display device is exposed to a heat treatment step of forming a transparent conductive film and an alignment film, and is required not to be colored by heat of 200 ° C. or more. The conductive resin turns yellow when heated at 180 ° C. for about 1 hour, and particularly, the peak transmittance of blue at around 450 nm decreases, and the color purity deteriorates if the transmittance is to be improved.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problem of heat resistance, and furthermore, 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 photosensitive resin composition for a color filter and a color filter using the same.

[0007]

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

[0008]

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Wherein R is an organic compound residue having k active hydrogens, n ₁ , n ₂ and _nk are 0 or 1 to 50
And the sum is 1 to 50 , and k is an integer of 1 to 3.
It is . Also, the following functional groups in the formula

[0010]

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[0011]

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

B. A photopolymerization initiator, C.I. Diluent and D. It contains a coloring agent.

[0014] In the above composition, E. coli. It may contain a thermosetting compound, 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 the unsaturated monocarboxylic acid; A reaction product of another epoxy compound and an unsaturated monocarboxylic acid may be used.

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

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 monofunctional epoxy compound, It is obtained by subjecting 4-vinylcyclohexene-1-oxide to ring-opening polymerization using polyalcohols such as alcohols, diols or triols, phenols, thiols, carboxylic acids and the like as initiators. Among these organic compounds, particularly preferable ones in the present invention include methanol, allyl alcohol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol and acrylic acid.

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 preferred.

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 kinds. Particularly, isophorone diisocyanate, hydrogenated xylylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate and the like are preferable, and among them, there is little problem of coloring at high temperature. Most preferred are those having no aromatic ring, such as isophorone diisocyanate and hydrogenated xylylene diisocyanate.

Further, as the saturated or unsaturated polybasic anhydride, for example, maleic anhydride, succinic anhydride,
Dibasic anhydrides such as itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride; and trimellitic anhydride, anhydride Examples thereof include acid anhydrides of three or more basic acids such as pyromellitic acid, benzophenonetetracarboxylic anhydride and methylcyclohexenetetracarboxylic anhydride.

The method for producing the ultraviolet 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, and hydroquinone and hydroquinone monomethyl ether are dissolved. And tertiary amines such as benzyldimethylamine and triethylamine, and quaternary ammonium salts such as trimethylbenzylammonium chloride and methyltriethylammonium chloride, or a catalyst such as triphenylstibine. The unsaturated monocarboxylic acid such as acrylic acid is used in an amount of preferably about 0.7 to 1.3 chemical equivalents, more preferably about 0.9 to 1.1 chemical equivalents with respect to one chemical equivalent of the epoxy group. In a conventional manner, preferably from 60 to 50 ° C., particularly preferably 80 to
The reaction is performed 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 at a ratio of 0.99 to 0.10 chemical equivalents of the acid anhydride to 1 chemical equivalent of the hydroxyl group in the first reaction product. At this time, as the acid anhydride, at least one selected from the above-mentioned saturated or unsaturated polybasic acid anhydrides is reacted by heating and stirring at a reaction temperature of 70 to 120 ° C. according to a conventional method to obtain a desired ultraviolet curable property. Obtain resin.

When an isocyanate compound such as isophorone diisocyanate is used for synthesizing an ultraviolet-curable resin, first, the first reaction product is obtained, and then the isocyanate compound is replaced with one equivalent of the secondary hydroxyl group of 1 equivalent. Is preferably 0.01 to 0.90 chemical equivalent of isocyanate group, and particularly preferably 0.05 to 0.05 isocyanate group.
At a ratio of 0.40 chemical equivalents, a catalyst blended in the previous reaction with or without the addition of an organic tin compound such as dibutyltin dilaurate or a tertiary amine such as benzyldimethylamine as a catalyst by a conventional method, 20-100 ° C
The reaction is carried out by heating and stirring at the reaction temperature described above to obtain a second reaction product. The reaction amount of the isocyanate group with respect to 1 chemical equivalent of the hydroxyl group in the first reaction product is 0.90.
When the amount is larger than the chemical equivalent, the solubility of the ultraviolet curable resin in the diluent tends to be poor, and particularly, 0.05 to 0.40.
The best use characteristics are obtained in the range of the chemical equivalent.

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

By appropriately selecting the molecular weight of the compound represented by the general formula (I), the UV-curable resin can have not only excellent heat resistance but also excellent film properties such as excellent film strength after precure. Therefore, not only the so-called off-contact method, but also the contact exposure of the pattern is easily possible,
Further, it is possible to obtain an excellent resist agent capable of forming a good pattern even in 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 synthesis examples, and can be synthesized by various conventional synthesis methods. For example, the compound represented by the general formula (I) may be synthesized with a compound such as acrylic acid. After the reaction with a saturated monocarboxylic acid to form an epoxy acrylate, first, an acid anhydride may be reacted, and then, an isocyanate compound or the like may be reacted for synthesis.

Incidentally, as the raw material epoxy compound of 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, for example, bisphenol A type epoxy Resin, bisphenol F type epoxy resin, novolak type epoxy resin (phenol novolak type, cresol novolak type), cycloaliphatic epoxy resin, polyfunctional epoxy resin based on tris (hydroxyphenyl) methane, Epicoat 157 manufactured by Yuka Shell Epoxy It is also possible to use a mixture with an epoxy resin, triglycidyl isocyanurate or the like corresponding to the series. However, many of the other epoxy compounds listed here are liable to be colored by heating when blended in a large amount, so that the compounding ratio of the compound represented by the general formula (I) in the total amount of the raw material epoxy compound is 25% by weight. It is desirable to keep the above, especially at least 50% by weight.

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 greater than 160, it will be a factor of deteriorating properties such as chemical resistance of the cured resist film.

The UV-curable resin may be a known UV-curable resin derived from a known polybasic acid anhydride-added epoxy acrylate or other epoxy compound in the same manner as the UV-curable resin according to the present invention. Can also be used in combination as appropriate.

<B. Regarding photopolymerization initiator> Examples of photopolymerization initiators include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether and their alkyl ethers, and acetophenone, 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
-Thioxanthones such as dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone, and ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal, and benzophenones or xanthones such as benzophenone; And Lucirin TP
O (2,4,6-trimethylbenzoyldiphenylphosphine oxide manufactured by BASF) and the like may be used, and these may be used in combination with a known photopolymerization accelerator such as a benzoic acid or a tertiary amine. These photopolymerization initiators are preferably used 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 diluent,
Photopolymerizable monomers and / or organic solvents can be used. Examples of the photopolymerizable monomer include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, N-vinylpyrrolidone, acryloylmorpholine, methoxytetraethylene glycol acrylate, methoxypolyethylene glycol acrylate, polyethylene glycol diacrylate, and 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 each methacrylate corresponding to the acrylate, 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, isobornyl acrylate, cyclopentanyl (mono or di Water-insoluble such as acrylate, cyclopentenyl (mono or di) acrylate, or methacrylates corresponding to the acrylate and mono-, di-, tri- or higher polyesters of polybasic acid and hydroxyalkyl (meth) acrylate Monomer,
And epoxy acrylates such as polyester acrylate, urethane acrylate, bisphenol A epoxy acrylate, phenol novolak epoxy acrylate and cresol novolak epoxy acrylate, epoxy acrylate derived from triglycidyl isocyanurate or a 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), and high molecular weight acrylate monomers such as polyester acrylate and urethane acrylate. Can be. The water-soluble monomer, the water-insoluble monomer, the polymer acrylate monomer and the like can be used alone or in combination with one another as appropriate.

Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone;
And aromatic hydrocarbons such as toluene and xylene; and cellosolves such as cellosolve and butyl cellosolve; and 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 can be exemplified.

The photopolymerizable monomer such as the water-soluble monomer, water-insoluble monomer, and high-molecular-weight acrylate monomer dilutes the ultraviolet-curable resin to make it easy to apply, and adjusts the acid value and 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 reduced, the resist film may be blended to such an extent that the resist film does not become sparingly soluble in an aqueous alkali solution, preferably in a range of 100% by weight or less based on the ultraviolet curable resin. In addition, the organic solvent dissolves and dilutes the ultraviolet curable resin, makes it applicable as a liquid, and forms a film by drying.

The above-mentioned diluent is preferably used alone or as a mixture of two or more kinds in a range of 10 to 95% by weight based on the total amount of the photosensitive resin composition, though it depends on a coating method.

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

<E. Thermosetting compound> Each of the above components A to
The photosensitive resin composition containing D further contains a thermosetting compound, for example, a thermosetting epoxy compound, and allows the photocuring reaction and the thermosetting reaction to proceed simultaneously or sequentially, thereby improving the adhesion. Further, light resistance, chemical resistance, film strength and the like may be further improved.

Examples of the thermosetting epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, N-glycidyl type epoxy resin and alicyclic epoxy resin. , "YX
-4000 "(epoxy resin manufactured by Yuka Shell Epoxy)
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) is desirable.

The photosensitive resin composition according to the present invention may further contain an imidazole derivative, a polyamine, a guanamine, a tertiary amine, a quaternary ammonium salt, a polyphenol and a polybasic acid anhydride, if necessary. Epoxy resin curing agents and curing accelerators; fillers such as barium sulfate, silicon oxide, talc, clay and calcium carbonate; and adhesion promoters such as defoamers and silane coupling agents, leveling agents, and halation. Various additives such as an inhibitor and a dispersant, or a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol and phenothiazine may be added.

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

The method of using the photosensitive resin composition according to the present invention includes, for example, immersion on a glass substrate, spraying,
After being applied by a spin coater, a roll coater or screen printing, for example, 60
Heat drying at ~ 120 ° C, then apply the mask with the pattern drawn on or without contacting the dried coating surface, chemical lamp, low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, A target resist film can be formed by irradiating ultraviolet rays using a xenon lamp or a metal halide lamp and developing the pattern to form a pattern. In the case where a thermosetting compound is added, a heat curing step may be further added after the development.

[0039]

EXAMPLES 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. In the following, "parts" and "%" are all based on weight, and "colorant" is Lionogen Red GD (manufactured by Toyo Ink Mfg. Co., Ltd.) for red, and Rio Nord Blue ES (manufactured by Toyo Ink Mfg. Co., Ltd.) and, in the case of green, Lionol Green 2YS (manufactured by Toyo Ink Mfg. Co., Ltd.) were used.

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

[0041]

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

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

In the above composition, first, a compound using a red colorant as a colorant is kneaded with a three-stage roll to prepare a red alkali-developable red photosensitive resin composition. Blue and green photosensitive resin compositions were each prepared using a coloring agent.

Next, the above red photosensitive resin composition was diluted three times (weight ratio) with propylene glycol monomethyl ether acetate, and the whole was coated on a glass substrate by spin coating. For 20 minutes to obtain a dried coating film having a thickness of 2 μm. Then, a mask with a pattern is applied to the coating surface,
Irradiation with ultraviolet light of 0 mj was performed, and then development was performed using a 1% aqueous solution of sodium carbonate as a developer to form a patterned red colored layer. Subsequently, on the glass substrate on which the red coloring layer is formed, a blue coloring layer and a green coloring layer are sequentially formed using the blue and green photosensitive resin compositions in the same manner as described above, and a color filter is formed. A test piece was created.

Example 2 [Components] 43 parts of ultraviolet curable resin (A-1) 8 parts of trimethylolpropane triacrylate 8 parts of “lucirin TPO” (photo initiator from BASF) 4 parts of “Polyflow S” (Kyoeisha) 0.5 part Coloring agent 12 parts "Swazol 1500" (Aromatic solvent manufactured by Maruzen Petrochemical Co., Ltd.) 6 parts Propylene glycol monomethyl ether acetate 11.5 parts合計 85 copies in total

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, 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 using the photosensitive resin composition to prepare a color filter test piece.

Example 3 The general formula (I) used in Example 1 was used.
185 parts of a compound represented by the formula (I) [EHPE-3150, epoxy equivalent 185, manufactured by Daicel Chemical Industries, Ltd.] dissolved in 60 parts of carbitol acetate under heating was mixed with 74 parts of acrylic acid and hydroquinone 0.1 under stirring.
And 0.7 parts of benzyldimethylamine 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 Swazole 1500 (an 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 with stirring. In addition, tetrahydrophthalic anhydride 76
Then, the mixture was heated to 100 ° C. and reacted with stirring for about 3 hours 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 part Colorant 12 parts “Swazol 1500” (Maruzen Petrochemical) (Aromatic solvent manufactured by Co.) 6 parts Propylene glycol monomethyl ether acetate 7.5 parts ──────────────────────────────── 85 copies in total

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, a red-colored layer, a blue-colored layer and a green-colored layer were formed on a glass substrate using the photosensitive resin composition 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 in the same manner as in Example 3, except that tolylene diisocyanate was used instead of isophorone diisocyanate. .

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

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, 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 by using the photosensitive resin composition to prepare a color filter test piece.

Example 5 The general formula (I) used in Example 1 was used.
130 parts of the compound represented by I) [EHPE-3150, epoxy equivalent 185, manufactured by Daicel Chemical Industries, Ltd.] and Epototo ST-3000 (hydrogenated bisphenol A type epoxy resin, epoxy equivalent 235, manufactured by Toto Kasei) 7
To a solution obtained by heating and dissolving 0.5 part of 65 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, 70 parts of carbitol acetate, 13 swazole 1500 (an aromatic solvent manufactured by Maruzen Petrochemical Co., Ltd.) 13
8 parts, 11 parts of isophorone diisocyanate and 0.1 part of dibutyltin dilaurate were added, and stirred at 50 ° C. for 4 hours.
Allowed to react for hours. Further, 76 parts of tetrahydrophthalic anhydride was added thereto, and the mixture was heated to 100 ° C. and reacted for about 3 hours with stirring to obtain an ultraviolet curable resin (A-4).

[Ingredients] UV curable resin (A-4) 55 parts “Irgacure 907” 4 parts “Modaflow” (leveling agent manufactured by Monsanto) 0.5 part Colorant 12 parts “Swazol 1500” (Maruzen Petrochemical) Aromatic solvent manufactured by Sharp Corporation 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, a red-colored layer, a blue-colored layer and a green-colored layer were formed on a glass substrate using the photosensitive resin composition in the same manner as in Example 1 to prepare a color filter test piece.

Example 6 [Components] Ultraviolet-curable resin (A-2) 43 parts Hydroxyethyl acrylate 6 parts "Irgacure 907" (photopolymerization initiator manufactured by Ciba Geigy) 4 parts "TEPIC" (Nissan Chemical) Epoxy resin, epoxy equivalent 100) 4 parts "Modaflow" (leveling agent manufactured by Monsanto) 1 part Colorant 12 parts 2-methylimidazole 0.1 part "Swazol 1500" (Aromatic solvent manufactured by Maruzen Petrochemical Co., Ltd.) 6 parts butyl glycol 8.9 parts ８５ 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, a red coloring layer, a blue coloring layer, and a green coloring layer were formed on a glass substrate using the photosensitive resin composition in the same manner as in Example 1, and then heated at 150 ° C. for 30 minutes. After curing, a color filter test piece was prepared.

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

[0065]

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(In the formula, n is an integer of 10 to 20.)
To a solution prepared by heating and dissolving 172 parts of carbitol acetate in 60 parts, 74 parts of acrylic acid, 0.1 part of hydroquinone and 0.7 parts 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, swazole 1500 (aromatic solvent manufactured by Maruzen Petrochemical Co.) 11
8 parts and 76 parts of tetrahydrophthalic anhydride were added, and 10 parts were added.
The temperature was raised to 0 ° C., and the mixture was reacted for about 3 hours with stirring to obtain an ultraviolet curable resin (A-5).

[Ingredients] Ultraviolet-curable resin (A-5) 55 parts “Irgacure 907” (photoinitiator manufactured by Ciba-Geigy) 4 parts “Modaflow” (leveling agent manufactured by Monsanto) 0.5 part Colorant 12 parts "Swazol 1500" (aromatic solvent manufactured by Maruzen Petrochemical Co., Ltd.) 6 parts cellosolve acetate 7.5 parts ───────────────────────── 85 copies in total

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

Example 8 The general formula (II) used in Example 7
In a solution obtained by heating and dissolving 172 parts of a compound represented by I) [EHPE-1150, epoxy equivalent 172, manufactured by Daicel Chemical Industries, Ltd.] in 60 parts of carbitol acetate,
Under stirring, 74 parts of acrylic acid, 0.1 part of hydroquinone and 0.7 parts of benzyldimethylamine were added, and the mixture was reacted at 90 to 100 ° C. for 24 hours by a conventional method. After cooling the reaction mixture, 65 parts of carbitol acetate and 15 parts of swazole were used.
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 with stirring. Further, 76 parts of tetrahydrophthalic anhydride was added thereto, and the mixture was heated to 100 ° C. and reacted with stirring for about 3 hours to obtain an ultraviolet curable resin (A-6).

[Ingredients] UV curable resin (A-3) 55 parts Benzyl dimethyl ketal 4 parts “DC-3PA” (manufactured by Toray Silicone) 0.5 part Colorant 12 parts “Swazol 1500” (Maruzen Petrochemical) (Aromatic solvent manufactured by Co.) 6 parts Propylene glycol monomethyl ether acetate 7.5 parts ──────────────────────────────── 85 copies in total

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, 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 by using the photosensitive resin composition 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, saponification degree: 88 mol%) by an acetalization reaction. The solution was poured into a large amount of acetone to precipitate the resin, which was thoroughly washed with methanol, dried, and styrylpyridinium-added polyvinyl alcohol (1.2 mol% added).
(Hereinafter, referred to as “SBQ-PVA”) ”.

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

[Ingredients] SBQ-PVA 10% aqueous solution 70 parts Water 27 parts Colorant 3 parts １００ 100 copies in total

In the above composition, a compound using a red colorant as a colorant is kneaded with a three-stage roll, and the SBQ-P
A VA-based red photosensitive resin composition was prepared, and similarly,
Blue and green photosensitive resin compositions were prepared using blue and green colorants, respectively.

The red photosensitive resin composition was applied to the entire surface of a glass substrate by spin coating, and dried at 70 ° C. for 20 minutes in order to volatilize water, thereby obtaining a dried coating film having a thickness of 2 μm. Thereafter, a mask having a pattern drawn thereon is applied to the coating film surface, irradiated with 300 mj of ultraviolet light, and then developed using water / isopropanol = 10/3 (weight ratio) as a developer to form a patterned red colored layer. Was formed. Subsequently, on the glass substrate on which the red coloring layer was formed, a blue coloring layer and a green coloring layer were sequentially formed using the blue and green photosensitive resin compositions in the same manner as described above, and a color filter test was performed. Created a piece.

Comparative Example 2 A mixture of 178 parts of Epicoat 154 (epoxy equivalent of novolak epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd., 178) in 68 parts of carbitol acetate was heated to 74 parts of acrylic acid and 0.1 part of hydroquinone under stirring. 1 part and 0.7 parts of benzyldimethylamine were added, and the mixture was reacted at 90 to 100 ° C. for 24 hours by a conventional method. After cooling the reaction solution, carbitol acetate 20
, 88 parts of Swazol 1500 (aromatic solvent manufactured by Maruzen Petrochemical Co.) and 76 parts of tetrahydrophthalic anhydride, and the mixture was heated to 100 ° C. and reacted for about 3 hours with stirring. 2) was obtained.

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

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, 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 by using the photosensitive resin composition 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 Examples and Comparative Examples.
And Table 3.

[0084]

[Table 1]

[0085]

[Table 2]

[0086]

[Table 3]

The evaluation method of the test results is as follows. A --- Excellent. ○ ---- Excellent. Δ −−− Slightly inferior. X --- Inferior.

[0088]

As described above, the color filter according to the present invention is
The photosensitive resin composition for filter has excellent heat resistance and 20
No coloration by heating at 0 ° C or higher, and high resolution.
It has excellent durability, light resistance and chemical resistance, and can be suitably used for the production of color filters for color liquid crystal display devices and the like.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI G03F 7/027 502 G03F 7/027 502 513 513 7/028 7/028 7/032 501 7/032 501 (56) References Special features Japanese Unexamined Patent Publication (Kokai) No. 4-170547 (JP, A) Japanese Unexamined Patent Publication (Kokai) No. 4-194942 (JP, A) Japanese Unexamined Patent Publication (Kokai) No. 2-173749 (JP, A) JP, A) JP-A-49-2601 (JP, A) JP-A-60-170620 (JP, A) JP-A-60-161973 (JP, A) JP-A-63-251416 (JP, A) JP-A-61-272 (JP, A) JP-A-63-296037 (JP, A) JP-A-6-93221 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F 7 / 038 C08F 2/50 G02B 5/20 101 G03F 7/004 G03F 7/027 G03F 7/028 G03F 7/032

Claims (5)

(57) [Claims] 1. A. First Embodiment 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 and _nk are 0 or an integer of 1 to 50, the sum of which is 1 to 50 , and k is 1 -3 . Further, the following functional group 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. A color film that can be developed with a dilute alkaline aqueous solution and contains a colorant.
A photosensitive resin composition for filters . 2. A. Ultraviolet light obtained by reacting a reaction product of the compound represented by the general formula (I) with an unsaturated monocarboxylic acid with a compound having at least two isocyanate groups in the molecule and a saturated or unsaturated polybasic anhydride. Curable resin, B. A photopolymerization initiator, C.I. Diluent and D. A color film that can be developed with a dilute alkaline aqueous solution and contains a colorant.
A photosensitive resin composition for filters . 3. In the synthesis of the component A, a compound represented by the general formula (I) and another epoxy compound are used instead of a reaction product of the compound represented by the general formula (I) and the unsaturated monocarboxylic acid. The photosensitive resin composition for a color filter according to claim 1 or 2, wherein a reaction product with an unsaturated monocarboxylic acid is used. 4. E. The photosensitive resin composition for a color filter according to claim 1, which comprises a thermosetting compound. 5. A color filter produced using the photosensitive resin composition according to claim 1, 2, 3, or 4.