JP2001310927A - Carboxylic acid having unsaturated group - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel carboxylic acid having an unsaturated group and from which a color filter is obtained which is excellent in patterning characteristics in a short exposure, with an excellent hardness. SOLUTION: The carboxylic acid compound (II) having an unsaturated group is obtained by reacting a compound (I) having an unsaturated group which is obtained by reacting an epoxy group of epoxy resin which is obtained by reacting a bifunctional epoxy resin and a phenol compound such as a 9,9-bis(hydroxyphenyl)fluorene with a carboxyl group of a (meta)acrylic acid, and which is obtained by reacting a hydroxyl of the compound (I) having the unsaturated group with a polybasic carboxylic acid and/or its anhydride carboxylic acid and/or an acid anhydride.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel unsaturated group-containing carboxylic acid compound.

[0002]

2. Description of the Related Art In order to color a liquid crystal display device or a solid-state imaging device, R (red), G (green), B
A color filter is used in which pixels of three colors (blue) are formed in a fine pattern of a line shape or a mosaic shape. As a method of manufacturing a color filter, many methods such as a dyeing method, a photolithography method, an electrodeposition method, and a printing method are known, but a high-precision pattern can be manufactured and the manufacturing cost is low. Therefore, photolithography has become mainstream. In the photolithography method, in general, a coating film is selectively exposed to ultraviolet light by using a dispersion of a pigment in a photosensitive resin composition including a binder polymer, a monomer, a photopolymerization initiator, and the like. Is removed by development to perform patterning. Recently, shortening the exposure time has been studied for the purpose of reducing the manufacturing cost.However, with the conventionally known binder polymer, if the exposure time is shortened, the photocrosslinking does not proceed sufficiently, and the patterning does not go well. Another problem is that the hardness of the obtained color filter is insufficient.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a novel unsaturated group-containing compound which is excellent in patterning characteristics and can obtain a high hardness color filter even with a small exposure. .

[0004]

In order to solve the above-mentioned problems, the present invention provides the following unsaturated group-containing compound. (1) An unsaturated group-containing compound (I) obtained by reacting an epoxy group of an epoxy resin represented by the following general formula (1) with a carboxyl group of (meth) acrylic acid.

[0005]

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(Y is at least one selected from the general formulas (a ′) to (d ′). Z is the following general formulas (e ′) to (e ′))
(H '). n is an average number of 1 to 20.

[0007]

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(R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom. X is —CH ₂ —, —C (CH ₃ ) _2- , -O
—, —CO—, —SO ₂ —, —C (CF ₃ ) ₂ — or a single bond (absent). R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom. R ⁹ is an alkyl group having 2 to 6 carbon atoms. r is a number from 0 to 3. )

[0009]

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(R ¹⁰ and R ¹¹ each independently have 1 carbon atom
Represents up to 20 hydrocarbon groups. p and q are each independently an integer of 0 to 4. ))

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in order according to the order of the reaction. The epoxy resin represented by the general formula (1) includes at least one phenol compound selected from the compounds represented by the general formulas (e) to (h),
It can be obtained by an addition reaction with at least one bifunctional epoxy resin selected from the compounds represented by (d) to (d).

[0012]

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(R ¹⁰ , R ¹¹ , p and q are the same as above.)

[0014]

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(R ^{1 to} R ⁹ , X and r are the same as above.) The above addition reaction is an etherification reaction between a phenolic hydroxyl group of the phenol compound and an epoxy group of the bifunctional epoxy resin. By this reaction, the epoxy group is opened to form a hydroxyl group. Since the phenol compound has two phenolic hydroxyl groups and the bifunctional epoxy resin has two epoxy groups, stoichiometrically, 1 mole of the bifunctional epoxy resin is added to 1 mole of the phenol compound. The epoxy resin having a repeating unit represented by the general formula (1) is obtained. The number of n in the epoxy resin represented by the general formula (1) is 1 to 20 on average, preferably 1 to 10.

The above phenol compounds may be used alone or in combination of two or more. Examples of the phenol compound include 9,9-bis (hydroxyphenyl) fluorene, 9,9-biscresolfluorene, binaphthol, phenanthrenehydroquinone, anthrahydroquinone, and the like. From the viewpoint of the reactivity of the phenolic hydroxyl group, 9-bis (hydroxyphenyl) fluorene is preferably used. The bifunctional epoxy resins may be used alone or in combination of two or more.

Examples of the bifunctional epoxy resin include bisphenol A epoxy resins, tetrabromobisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, and other bisphenol epoxy resins, biphenyl epoxy resins, and hydroquinone epoxy resins. Epoxy resin, glycol diglycidyl ether type epoxy resin such as propylene glycol diglycidyl ether type epoxy resin, phthalic acid diglycidyl ester type epoxy resin and the like, among which, from the viewpoint of reactivity, curability, availability Bisphenol A
A type epoxy resin is preferably used.

In the addition reaction between the phenol compound and the bifunctional epoxy resin, it is preferable to use an excess of the bifunctional epoxy resin, so that the phenolic hydroxyl group of the phenol compound and the epoxy group of the bifunctional epoxy resin are reacted. It is more preferable to use a molar ratio of 0.2: 1 to 0.9: 1. If the amount of the phenolic compound is less than the above range, sufficient hardness cannot be obtained. The acrylic equivalent of the saturated group-containing carboxylic acid compound (II) increases, and the developability and the curability deteriorate.

The unsaturated group-containing compound (I) is obtained by reacting the epoxy resin represented by the general formula (1) with (meth) acrylic acid. Since the unsaturated group-containing compound (I) is a novel substance, the present invention also provides the unsaturated group-containing compound (I). As shown in the following chemical reaction formula, the above reaction is a reaction between the epoxy group of the epoxy resin represented by the general formula (1) and the carboxyl group of (meth) acrylic acid, and the epoxy group is opened by this reaction. Ring to form a hydroxyl group. Since the epoxy resin represented by the general formula (1) has two epoxy groups, 2 mol of (meth) acrylic acid is stoichiometrically based on 1 mol of the epoxy resin represented by the general formula (1). To produce 1 mole of the unsaturated group-containing compound (I). As represented by the general formula (2), the unsaturated group-containing compound (I) has two (meth) acryloyl groups derived from (meth) acrylic acid.
And two hydroxyl groups generated by ring opening of the epoxy group.
And 2n hydroxyl groups derived from the epoxy resin represented by the general formula (1), and the total number of hydroxyl groups is (2 + 2).
n).

[0020]

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(R is a hydrogen atom or CH _3. M is represented by the following general formula (1 ′).

[0022]

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(Y, Z, and n are the same as above.) The epoxy resin and (meth) acrylic acid represented by the general formula (1) may be used alone or in combination of two or more. May be used together. The use ratio of the epoxy resin represented by the general formula (1) to the (meth) acrylic acid is stoichiometrically based on 1 mol of the epoxy resin represented by the general formula (1) and (mol) acrylic acid. Since it is 2 mol, it is preferable to charge the epoxy resin represented by the general formula (1) :( meth) acrylic acid = 1: 1.6 to 1: 4.0, more preferably. Is from 1: 2.0 to 1: 2.4. When the amount of the (meth) acrylic acid used is larger than the above range, the amount of the remaining (meth) acrylic acid increases, and the resistance of the coating film decreases. On the other hand, if it is less than the above range, the acrylic equivalent of the unsaturated group-containing compound (I) becomes too large, and sufficient curability cannot be obtained.

The unsaturated group-containing compound (I) is reacted with the epoxy resin represented by the general formula (1) and (meth) acrylic acid to give a reaction product containing the unsaturated group-containing compound (I). can get. The unsaturated group-containing compound (I) may be isolated from the reaction product and used, or the reaction product may be used as it is. The unsaturated group-containing compound (I) is used not only as a raw material of the unsaturated group-containing carboxylic acid compound (II) but also as a generally used unsaturated group-containing reactive oligomer or polymer. It can be industrially used as a paint, an adhesive, a photocurable resin, a binder for ink, a sealing material, and the like.

The unsaturated group-containing carboxylic acid compound (II) is
It is obtained by reacting the unsaturated group-containing compound (I) with a polybasic carboxylic acid and / or an anhydride thereof. This unsaturated group-containing carboxylic acid compound (II) is excellent in alkali solubility because of having a carboxyl group, and excellent in curability because of having a (meth) acryloyl group. Examples of the polybasic carboxylic acid and / or its acid anhydride include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid , Trimellitic acid and their acid anhydrides; and aromatic polyvalent carboxylic acids such as pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid and biphenylethertetracarboxylic acid, and their acid dianhydrides. However, among these, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, phthalic anhydride, trimellitic anhydride and pyromellitic acid are preferred from the viewpoint of high reactivity of acid anhydride and easy adjustment of acid value. At least one compound selected from the group consisting of acid dianhydrides Masui.

The unsaturated group-containing compound (I), the polybasic carboxylic acid and / or the acid anhydride thereof may be used alone or in combination of two or more. The above reaction is an esterification reaction between the hydroxyl group of the unsaturated compound (I) and the carboxyl group and / or acid anhydride group of the polybasic carboxylic acid and / or its acid anhydride. Since a plurality of esterification reactions occur simultaneously, the structure of the resulting unsaturated group-containing carboxylic acid compound (II) cannot be completely specified, but the (2 + 2n) hydroxyl groups of the unsaturated group-containing compound (I) have At least one of (-OH) is an ester bond (-OOC-), and is an aggregate of an unsaturated group-containing carboxylic acid compound having a carboxyl group.

Representative structures of the unsaturated group-containing carboxylic acid compound (II) are shown in the following (II-1) to (II-5). However, the unsaturated group-containing compound (I) has (2 + 2n)
Since it is not possible to specify which of the individual hydroxyl groups undergoes the esterification reaction, the main chain is omitted. The following (II-1) is obtained when dicarboxylic acid and / or its anhydride, phthalic acid and / or its anhydride, are used as the polybasic carboxylic acid and / or its anhydride. This is an example of the unsaturated group-containing carboxylic acid compound (II) obtained. The esterification reaction of at least one of the hydroxyl groups of the unsaturated group-containing compound (I) with the carboxyl group of the polybasic carboxylic acid or the acid anhydride group of the polybasic carboxylic anhydride.

[0028]

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The following (II-2) shows that a polybasic carboxylic acid and / or an acid anhydride thereof is a tetracarboxylic acid and / or an acid anhydride thereof together with phthalic acid and / or an acid anhydride thereof. It is an example of an unsaturated group-containing carboxylic acid compound (II) obtained when pyromellitic acid and / or an acid anhydride thereof, which is a carboxylic acid and / or an acid anhydride thereof, is used. The esterification reaction of at least one of the hydroxyl groups of the unsaturated group-containing compound (I) with the carboxyl group of the polybasic carboxylic acid or the acid anhydride group of the polybasic carboxylic anhydride.

[0030]

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The ratio of the unsaturated group-containing compound (I) to the polybasic carboxylic acid and / or the acid anhydride is such that the total number of moles of the hydroxyl group contained in the unsaturated group-containing compound (I) is multiplied by the polybasic compound. It is preferable that the total number of carboxyl groups contained in the acidic carboxylic acid and / or the acid anhydride thereof (acid anhydride group is counted as two carboxyl groups) is in the range of 0.1 to 4.0 times, more preferably Preferably 0.6 to 2.0
It is twice. When the amount of the polybasic carboxylic acid and / or the acid anhydride thereof is larger than the above range, the pigment dispersibility is reduced or the molecular weight distribution of the unsaturated group-containing carboxylic acid compound (II) is increased, If the amount is less than the range, the solubility in an alkaline solution is reduced, which causes a decrease in developability.

In the reaction of the unsaturated group-containing compound (I) with the polybasic carboxylic acid and / or its acid anhydride, the (meth) acryloyl equivalent of the unsaturated group-containing carboxylic acid compound (II) and the acid value An epoxy compound may coexist for the purpose of adjusting the molecular weight. The procedure of the reaction at this time is not particularly limited, and after reacting the unsaturated group-containing compound (I) with the polybasic acid and / or the acid anhydride, the epoxy compound is reacted, and further, the polybasic acid and / or the acid is reacted. The polybasic acid and / or its acid anhydride and the epoxy compound can be reacted simultaneously and / or separately and / or repeatedly, such as by reacting an anhydride followed by an epoxy compound.
In this case, the carboxyl group of the polybasic carboxylic acid or the acid anhydride group of the polybasic carboxylic anhydride reacts with the epoxy group of the epoxy compound. When the addition amount of the epoxy compound is increased, the (meth) acryloyl equivalent decreases and the acid value decreases. Therefore, the amount of the epoxy compound to be used may be adjusted so as to obtain the (meth) acryloyl equivalent and the acid value described later. . Examples of the epoxy compound that can be used at this time include glycidyl (meth) acrylate and (meth) acrylate having an alicyclic epoxy group such as (epoxycyclohexyl) methyl (meth) acrylate, and epoxy groups such as ethylene oxide and propylene oxide. Compound having one; polyphenol type epoxy resin such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin,
Compounds having two or more epoxy groups such as polyglycidylamine type epoxy resin, alcohol type epoxy resin, ester type epoxy resin and alicyclic epoxy resin are exemplified. When a compound having two or more epoxy groups is used, a crosslinked structure is formed via the epoxy compound. These epoxy compounds may be used alone or in combination of two or more.

The following (II-3) is a polybasic carboxylic acid and / or an acid anhydride thereof, which is a dicarboxylic acid and / or an acid anhydride thereof, phthalic acid, similarly to the above (II-1). And / or an example of an unsaturated group-containing carboxylic acid compound (II) obtained when an acid anhydride thereof is used and an epoxy compound having one epoxy group is allowed to coexist. It is obtained by reacting a carboxyl group of a polybasic carboxylic acid or an acid anhydride group of a polybasic carboxylic anhydride with an epoxy group of the epoxy compound.

[0034]

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The following (II-4) is a polybasic carboxylic acid and / or an acid anhydride thereof, which is a dicarboxylic acid and / or an acid anhydride of phthalic acid, similar to the above (II-2). When tetracarboxylic acid and / or an acid anhydride thereof, pyromellitic acid and / or an acid anhydride thereof is used together with an acid anhydride thereof, and an epoxy compound having one epoxy group is allowed to coexist. It is an example of the resulting unsaturated group-containing carboxylic acid compound (II). It is obtained by reacting a carboxyl group of a polybasic carboxylic acid or an acid anhydride group of a polybasic carboxylic anhydride with an epoxy group of the epoxy compound.

[0036]

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The following (II-5) is a polybasic carboxylic acid and / or an acid anhydride thereof which is a dicarboxylic acid and / or an acid anhydride thereof such as phthalic acid, similarly to the above (II-1). And / or an unsaturated anhydride-containing carboxylic compound (II) obtained when an acid anhydride thereof is used and an epoxy compound having two or more epoxy groups is allowed to coexist.
This is an example. It is obtained by reacting a carboxyl group of a polybasic carboxylic acid or an acid anhydride group of a polybasic carboxylic anhydride with an epoxy group of the epoxy compound. Further, a cross-linking bond is formed via an epoxy compound.

[0038]

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The (meth) acryloyl equivalent of the unsaturated group-containing carboxylic acid compound (II) is preferably from 200 to 5,000, more preferably from 250 to 1,000. (Meth) of unsaturated group-containing carboxylic acid compound (II)
If the acryloyl equivalent is smaller than the above range, the cured product becomes brittle, and if it is larger than the above range, the curability becomes poor. The acid value of the unsaturated group-containing carboxylic acid compound (II) is 20
It is preferably from 200 to 200, and more preferably from 30 to 150. Unsaturated group-containing carboxylic acid compounds (I
When the acid value of (I) is larger than the above range, the pigment dispersibility may be reduced, or the cured portion may be whitened during development. When the acid value is smaller than the above range, the solubility in an alkaline solution may be reduced, This causes a reduction in developability.

The unsaturated group-containing carboxylic acid compound (II) is
By reacting the unsaturated group-containing compound (I) with a polybasic carboxylic acid and / or an acid anhydride thereof, it is obtained as a reaction product containing the unsaturated group-containing carboxylic acid compound (II). The unsaturated group-containing carboxylic acid compound (II) may be isolated from the reaction product and used, or the reaction product may be used as it is. The unsaturated group-containing carboxylic acid compound (II) is usually used as the unsaturated group-containing carboxylic acid compound (I).
It is used as a resin composition containing I) as an essential component. Since the resin composition has photosensitivity derived from the unsaturated group-containing carboxylic acid compound (II), it is used to form a resin for a color filter of a liquid crystal display element, a solder resist for manufacturing a printed wiring board, It is suitably used for applications such as an electrolytic plating resist, an insulating layer of a build-up method printed wiring board, and a plate making material for offset printing. As the resin composition, a reaction product of the unsaturated group-containing compound (I) with a polybasic carboxylic acid and / or an acid anhydride thereof can be used as it is. It can also be prepared by adding a solvent, a monomer such as a polyfunctional monomer, a photopolymerization initiator, a photosensitizer, a curing accelerator, a colorant (eg, a pigment) and the like. In the resin composition, the unsaturated group-containing compound (II) is 5 to 95% by weight.
, Preferably 10 to 70% by weight, more preferably 15 to 50% by weight.
More preferably, it is contained at a ratio of

When the resin composition is used as a resin for a color filter of a liquid crystal display element, the R of the color filter is
It can be used as a resin for (red), G (green), and B (blue) pixels, or as a resin for a black matrix. In any case, it is necessary to include a coloring agent for coloring the resin to a desired color. In the case of resin for pixels, color development, transparency, heat resistance,
A resin excellent in chemical resistance is preferably used. In the case of a resin for a black matrix, a resin excellent in light-shielding property, heat resistance and chemical resistance is preferably used. Known coloring agents can be used, for example, barium sulfate, zinc oxide, lead sulfate, titanium oxide, yellow lead, zinc yellow, red iron,
Inorganic pigments such as ultramarine blue, navy blue, chromium oxide green, amber, titanium black, synthetic iron black, carbon black, etc., benzin yellow G, benzin yellow GR, lithol first orange 3GL, vulcan first orange GC, pigment scarlet 3B, thiokun There are organic pigments such as digomaroon, phthalocyanine blue, phthalocyanine green, indanthrene blue, green gold, malachite green lake and the like. The amount of the colorant is preferably 10 to 1000 parts by weight, more preferably 20 to 500 parts by weight, based on 100 parts by weight of the unsaturated group-containing carboxylic acid compound (II). If the amount of the colorant is less than the above range, the colorant concentration is reduced, so that a coating film with a sufficient color density cannot be obtained.If the amount is larger than the above range, the alkali developability is reduced, There is a possibility that background dirt and film reduction may occur in a region other than the portion where the pixels are formed.

[0042]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In the following, “parts” and “%” represent “parts by weight” and “% by weight”, respectively, unless otherwise specified. [Example 1] Bisphenol A type epoxy resin GY-2
50 (made by Ciba-Geigy, epoxy equivalent: 185) 100
After heating 41.3 parts of 9,9-bis (4-hydroxyphenyl) fluorene and 36.8 parts of propylene glycol monomethyl ether acetate to 140 ° C.,
0.15 parts of triethylammonium bromide are added,
The reaction was performed for 3 hours. After cooling the reaction to 115 ° C.,
Further, 20.4 parts of acrylic acid, 0.45 parts of triethylammonium bromide, 0.17 of p-methoxyphenol
And 53.5 parts of propylene glycol monomethyl ether acetate were added and reacted for 9 hours to obtain a reaction product containing the unsaturated group-containing compound (I).

The reaction product was cooled to 90 ° C., and 39.9 parts of hexahydrophthalic anhydride and 21.5 parts of propylene glycol monomethyl ether acetate were added.
The reaction was carried out for 2.5 hours to obtain a resin composition (1) containing an unsaturated group-containing carboxylic acid compound (II) having an acid value of 73. Example 1
The NMR spectra of the reaction product containing the unsaturated group-containing compound (I) and the resin composition (1) are shown in FIGS. 1 and 2, respectively. [Examples 2 to 10] The same reaction as in Example 1 was carried out except that the compounds of the raw materials in Example 1 were changed as shown in Tables 1 and 2, to obtain the desired resin compositions (2) to (10). ) Got.

[0044]

[Table 1]

[0045]

[Table 2]

Example 11 Using the resin compositions (1) to (10) obtained in Examples 1 to 10, according to the following composition, black, red, green and blue colored photosensitive resin compositions (1) to (10) were prepared. -Black photosensitive resin compositions (1) to (10) Resin compositions (1) to (1) obtained in Examples 1 to 10
0): 40 parts each Dipentaerythritol hexaacrylate: 30 parts Propylene glycol monomethyl ether acetate:
70 parts Titanium black (black pigment): 70 parts Irgacure 369 (trade name, manufactured by Ciba Geigy): 5 parts Red photosensitive resin compositions (1) to (10) Resin compositions obtained in Examples 1 to 10 ( 1) to (1)
0): 40 parts each Dipentaerythritol hexaacrylate: 30 parts Propylene glycol monomethyl ether acetate:
70 parts Pyrazolone red (red pigment): 35 parts Irgacure 369 (trade name, manufactured by Ciba Geigy): 5 parts Green photosensitive resin compositions (1) to (10) Resin compositions obtained in Examples 1 to 10 ( 1) to (1)
0): 40 parts each Dipentaerythritol hexaacrylate: 30 parts Propylene glycol monomethyl ether acetate:
75 parts Lionol Green 2Y-301 (green pigment): 40 parts Irgacure 369 (trade name, manufactured by Ciba Geigy): 5 parts Blue photosensitive resin composition (1) to (10) Obtained in Examples 1 to 10 Resin compositions (1) to (1)
0): 40 parts each Dipentaerythritol hexaacrylate: 30 parts Propylene glycol monomethyl ether acetate:
85 parts Fast dogen blue (blue pigment): 32 parts Irgacure 369 (trade name, manufactured by Ciba Geigy): 5 parts Next, a grid-like pattern is formed on a transparent substrate made of soda glass having a surface coated with a SiO ₂ film. Then, a black photosensitive resin composition (1) to (10) among the above photosensitive resin compositions was applied using a spin coater.
This was prebaked at 80 ° C. for 15 minutes, and then irradiated with 200 mJ / cm ² ultraviolet light by an exposure device using a high-pressure mercury lamp as a light source. Thereafter, the uncured resin was dissolved with an aqueous alkali solution using an automatic developing apparatus, and then washed with water.
It was air-dried and post-baked at 200 ° C. for 30 minutes. A similar process is repeated to form a red relief image in a region where a red pixel is to be formed, a green relief image in a region where a green pixel is to be formed, and a blue relief image in a region where a blue pixel is to be formed. An image was formed, and color filters (1) to (10) were produced.

No defects or defects were found in any of the obtained patterns, and no undissolved matter remained in the region where no pattern was formed on the substrate. When the pencil hardness of the cured coating film was measured, it was 5H in all cases. [Comparative Example 1] In Example 11, instead of the resin composition (1), methacrylic acid / methyl methacrylate / 2-
A colored photosensitive resin composition was prepared in the same manner as in Example 11, except that a copolymer of hydroxyethyl methacrylate / benzyl methacrylate (copolymerization ratio: 15/50/15/20, weight average molecular weight: 22,000) was used.

Using these colored photosensitive resin compositions, a pattern was formed on a substrate in the same manner as in Example 11 to produce a color filter. The resulting pattern was partially missing. Further, the pencil hardness of the cured coating film was measured, and it was H.

[0049]

According to the present invention, it is possible to provide a novel unsaturated group-containing carboxylic acid compound which is excellent in patterning characteristics and can obtain a cured product having high hardness even with a small amount of exposure. This unsaturated group-containing carboxylic acid compound (I
I) and a resin composition containing a colorant as an essential component,
It is useful as a resin for color filters.

[Brief description of the drawings]

FIG. 1 is an NMR spectrum of a reaction product containing an unsaturated group-containing compound (I) obtained in Example 1.

FIG. 2 is an NMR spectrum of a resin composition (1) containing an unsaturated group-containing compound (II) obtained in Example 1.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G02B 5/20 101 G02B 5/20 101 G03F 7/027 515 G03F 7/027 515 (72) Inventor Rie Inoue 5-8 Nishiburi-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd. (72) Inventor Fumihide Tamura 992, Nishioki, Okihama-shi, Aboshi-ku, Himeji-shi, Hyogo F-term in Nippon Shokubai Co., Ltd. BC74 BC85 CC11 FA03 FA17 FA29 2H048 BA45 BA47 BA48 BB02 BB42 4J002 CD201 DA036 DE106 DE116 DE136 DG046 EU006 EZ006 FD096 4J036 AA02 AB01 AB09 AB10 AC01 AC05 AC06 AD01 AD04 AD05 AD09 AD12 AD13 AD15 CA21 CA22 HA02 JA15

Claims (5)

[Claims] 1. An unsaturated group-containing compound (I) obtained by reacting an epoxy group of an epoxy resin represented by the following general formula (1) with a carboxyl group of (meth) acrylic acid. Embedded image (Y is at least one selected from the general formulas (a ') to (d'). Z is at least one selected from the following general formulas (e ') to (h'). N is an average value of 1 ~ 20
Is the number of Embedded image (R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom. X
Is _{-CH 2 -, - C (CH} 3) 2 -, - O -, - CO-,
—SO ₂ —, —C (CF ₃ ) ₂ — or a single bond (absent)
It is. R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom. R ⁹ is an alkyl group having 2 to 6 carbon atoms. r is 0
Number 3 ) (R ¹⁰ and R ¹¹ each independently represent a hydrocarbon group having 1 to 20 carbon atoms. P and q each independently represent an integer of 0 to 4.) 2. The epoxy resin represented by the general formula (1) comprises at least one phenol compound selected from the compounds represented by the general formulas (e) to (h) and the epoxy resin represented by the general formulas (a) to (h): d) an epoxy resin obtained by an addition reaction with at least one bifunctional epoxy resin selected from the compounds represented by d), and a phenolic hydroxyl group of the phenol compound and an epoxy group of the bifunctional epoxy resin. Is from 0.2: 1 to 0.9: 1
The unsaturated group-containing compound (I) according to claim 1, wherein the compound (I) is used in an amount to be used. Embedded image (R ¹⁰ and R ¹¹ each independently represent a hydrocarbon group having 1 to 20 carbon atoms. P and q each independently represent an integer of 0 to 4.) (R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom. X
Is _{-CH 2 -, - C (CH} 3) 2 -, - O -, - CO-,
—SO ₂ —, —C (CF ₃ ) ₂ — or a single bond (absent)
It is. R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom. R ⁹ is an alkyl group having 2 to 6 carbon atoms. r is 0
Number 3 ) 3. The reaction of a hydroxyl group of the unsaturated group-containing compound (I) according to claim 1 with a carboxyl group and / or an acid anhydride group of a polybasic carboxylic acid and / or an anhydride thereof. The carboxylic acid compound (II) containing an unsaturated group obtained by the above. 4. A resin composition comprising the unsaturated group-containing carboxylic acid compound (II) according to claim 3 as an essential component. 5. A resin composition for a color filter, comprising the unsaturated group-containing carboxylic acid compound (II) according to claim 3 and a coloring agent as essential components.