JP2001097929A - Compound containing unsaturated group and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new compound containing an unsaturated group, exhibiting excellent patterning characteristics even at a low light exposure and giving a color filter having high hardness. SOLUTION: The objective compound (III) containing an unsaturated group is produced by the etherification reaction of a compound (I) having one epoxy group and one or more (meth)acryloyl groups with the phenolic hydroxy group of a compound (II) (e.g. 9,9-bis(hydrozyphenylene)fluorene). A compound (IV) containing unsaturated group and having carboxy group is produced by the esterification reaction of the hydroxy group of the compound (III) having unsaturated group with the carboxy group and/or acid snhydride group of a polybasic acid and/or its acid anhydride.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel unsaturated group-containing compound and its use such as a color filter.

[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 capable of obtaining a color filter having excellent patterning characteristics and high hardness even with a small amount of light exposure, and its use. Is to do. The use thereof is particularly to provide a color filter using the resin composition for a color filter containing the novel unsaturated group-containing compound.

[0004]

Means for Solving the Problems In order to solve the above problems, the present invention provides the following inventions. (1) The epoxy group of the compound (I) having one epoxy group and one or more (meth) acryloyl groups, and at least one compound selected from the compounds represented by the following general formulas (1) to (4) An unsaturated group-containing compound (III) obtained by subjecting a compound (II) to an etherification reaction with a phenolic hydroxyl group.

[0005]

Embedded image

(However, R ¹ and R ² represent a hydrocarbon group having 1 to 20 carbon atoms. P and q are integers of 0 to 4.) (2) The unsaturated group-containing compound (III) An unsaturated group-containing compound (IV) having a carboxyl group, obtained by subjecting a hydroxyl group to a carboxyl group and / or an acid anhydride group of a polybasic acid and / or an acid anhydride thereof. (3) A resin composition containing the unsaturated group-containing compound (IV) as an essential component and, if necessary, a colorant.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in order according to the order of the reaction. The unsaturated group-containing compound (III) is selected from compounds (I) having one epoxy group and one or more (meth) acryloyl groups, and compounds represented by the following general formulas (1) to (4). At least one compound (II)
Obtained by the reaction with The unsaturated group-containing compound (II
Since I) is also a novel substance, the present invention also provides this unsaturated group-containing compound (III).

[0008]

Embedded image

(However, R ¹ and R ² represent a hydrocarbon group having 1 to 20 carbon atoms. P and q are integers of 0 to 4.) As shown in the following chemical reaction formula, the above reaction is carried out. Compound (I)
And the phenolic hydroxyl group of compound (II) is etherified by this reaction, and the epoxy group is opened to form a hydroxyl group. Since compound (II) has two phenolic hydroxyl groups, stoichiometrically compound (II) 1
The reaction is carried out at a ratio of 2 mol of the compound (I) to 1 mol of the compound (I), thereby producing 1 mol of the unsaturated group-containing compound (III). The unsaturated group-containing compound (III) is derived from the compound (I) (meth)
It has at least two acryloyl groups and two hydroxyl groups generated by ring opening of the epoxy group.

[0010]

Embedded image

(Where R represents a hydrogen atom or a methyl group)
Represent. Y₁Represents a single bond or a divalent organic group, and n is 2
In the above cases, they may be the same or different
No. Y _TwoIs a single bond or a divalent or higher organic group;_Two
And Cα and Cβ form a cyclic structure.
You may. Here, a single bond means that there is no organic group,
Y means₁And Y_TwoAnd are both single bonds
Never be. Here, Cα and Cβ are substituents
Is a carbon atom which may have Z is the following general formula
At least one selected from (1 ′) to (4 ′)
You. n is an integer of 1 or more. Hereinafter, R, Y₁, Y_Two,
Z and n represent the same thing.

[0012]

Embedded image

(However, R ¹ and R ² each represent a hydrocarbon group having 1 to 20 carbon atoms. P and q are integers of 0 to 4.) As the compound (I), one epoxy group and The compound is not particularly limited as long as it has one or more (meth) acryloyl groups, and examples thereof include glycidyl acrylate, glycidyl methacrylate, acrylate having an alicyclic epoxy group, and methacrylate having an alicyclic epoxy group.
Among these, acrylates having an alicyclic epoxy group and / or acrylates having a glycidyl group are preferred from the viewpoint of curability, and acrylates and / or glycidyl groups having an epoxycyclohexyl group are preferred from the viewpoint of epoxy group reactivity. Acrylates having the following are preferred.

Compound (I) may be used alone,
Two or more kinds may be used in combination. Compound (II) is at least one compound selected from compounds represented by general formulas (1) to (4), and includes 9,9-bis (4-hydroxyphenylene) fluorene, binaphthol, phenanthrene hydroquinone, and anthra Among them, bisphenols having a fluorene structure, which is one of the compounds represented by the general formula (1), are preferred from the viewpoint of the reactivity of the phenolic hydroxyl group. , 9-Bis (4-hydroxyphenylene) fluorene is preferred.

Compound (II) may be used alone,
Two or more kinds may be used in combination. Compound (I) and compound (I
As an example of the reaction of I), (epoxycyclohexyl) methyl acrylate is used as the compound (I), and 9,9-bis (hydroxy) which is one of the compounds represented by the general formula (1) is used as the compound (II). The chemical reaction formula when using (phenylene) fluorene is shown below.

[0016]

Embedded image

The compound (I) and the compound (II) are used in a stoichiometric ratio of 2 moles of the compound (I) to 1 mole of the compound (II). : Compound (II) is preferably charged in the range of 1: 1 to 5: 1, more preferably 1.5: 1 to 4: 1. When the amount of the compound (I) used is larger than the above range, a large amount of the compound (I) remains, and the compound (IV) having a wide molecular weight distribution by the subsequent reaction with a polybasic acid and / or an acid anhydride thereof ) Will be generated. When the amount of the compound (I) used is less than the above range, the (meth) acryloyl equivalent of the unsaturated group-containing compound (III) and the unsaturated group-containing compound (IV) becomes too large, and the curability decreases. It will be.

Since the unreacted phenolic hydroxyl group of the compound (II) acts as a polymerization inhibitor, an epoxy compound having excellent reactivity such as ethylene oxide, propylene oxide and glycidol is used in order to minimize the unreacted phenolic hydroxyl group. With compound (I) and compound (II)
May be added simultaneously with or after the reaction with. The use amount thereof is preferably about 1 to 100 mol per 1 mol of unreacted phenolic hydroxyl groups. The unsaturated group-containing compound (III) is obtained as a reaction product containing the unsaturated group-containing compound (III) by reacting the compound (I) with the compound (II). The unsaturated group-containing compound (III) may be isolated from the reaction product and used, or the reaction product may be used as it is.

The unsaturated group-containing compound (III) is used not only as a raw material of the unsaturated group-containing compound (IV) but also in the same manner as generally used unsaturated group-containing reactive oligomers and polymers. It can be used industrially as a paint, an adhesive, a photocurable resin, a binder for ink, a sealing material, and the like. The unsaturated group-containing compound (IV) is obtained by reacting the unsaturated group-containing compound (III) with a polybasic acid and / or an acid anhydride thereof. This unsaturated group-containing compound (IV) 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 acid and / or its acid anhydride include maleic acid, succinic acid, itaconic acid, phthalic acid,
Tetrahydrophthalic acid, hexahydrophthalic acid, methylendmethylenetetrahydrophthalic acid, chlorendic acid,
Methyltetrahydrophthalic acid, trimellitic acid and their anhydrides; aromatic polyvalent carboxylic acids such as pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid and biphenylethertetracarboxylic acid, and their acid dianhydrides Examples thereof include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, phthalic anhydride, and trimellitic anhydride in view of the high reactivity of the acid anhydride and the ease of adjusting the acid value. And at least one compound selected from the group consisting of pyrimellitic dianhydride and pyromellitic dianhydride.

The compound (III), the polybasic 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 a hydroxyl group of compound (III) and a carboxyl group and / or an acid anhydride group of a polybasic acid and / or an acid anhydride thereof. Because multiple esterification reactions occur simultaneously,
Although the structure of the resulting unsaturated group-containing compound (IV) cannot be completely specified, at least the following structure (6):
It is an aggregate of an unsaturated group-containing compound having a carboxyl group.

[0022]

Embedded image

Typical structures of the unsaturated group-containing compound (IV) are shown in (IV-1) to (IV-5) below. The following (IV-
1) is a polybasic acid and / or an acid anhydride thereof,
It is an example of an unsaturated group-containing compound (IV) obtained when using trimellitic acid and / or an acid anhydride thereof, which is a tricarboxylic acid and / or an acid anhydride thereof. The esterification reaction occurs between the hydroxyl group of the unsaturated group-containing compound (III) and the carboxyl group of the polybasic acid or the acid anhydride group of the polybasic acid anhydride.

[0024]

Embedded image

The following (IV-2) is used as a polybasic acid and / or an acid anhydride thereof, together with a tricarboxylic acid and / or an acid anhydride thereof, trimellitic acid and / or an acid anhydride thereof, and a tetracarboxylic acid and / or an acid anhydride thereof. It is an example of an unsaturated group-containing compound (IV) obtained when using pyromellitic acid and / or its acid anhydride, which is an acid and / or its acid anhydride. The esterification reaction occurs between the hydroxyl group of the unsaturated group-containing compound (III) and the carboxyl group of the polybasic acid or the acid anhydride group of the polybasic acid anhydride.

[0026]

Embedded image

The ratio of the unsaturated group-containing compound (III) to the polybasic acid and / or its anhydride must be such that a carboxyl group is present in the resulting unsaturated group-containing compound (IV). is there. Specifically, the total number of moles of the carboxyl groups contained in the polybasic acid and / or the acid anhydride thereof (the acid anhydride group is a carboxyl group) with respect to the total number of moles of the hydroxyl groups contained in the unsaturated group-containing compound (III) (Counted as 2 groups) is preferably charged in the range of 0.1 to 4 times,
More preferably, it is 0.8 to 2 times. Polybasic acids and / or
Alternatively, when the amount of the acid anhydride is more than the above range, the pigment dispersibility is reduced, and the molecular weight distribution of the unsaturated group-containing compound (IV) becomes large. The solubility in a solution is reduced, which causes a reduction in developability.

In the reaction of the unsaturated group-containing compound (III) with the polybasic acid and / or its acid anhydride, the (meth) acryloyl equivalent, the acid value and the molecular weight of the unsaturated group-containing compound (IV) are adjusted. An epoxy compound may coexist for the purpose of performing. The reaction procedure at this time is not particularly limited, and after reacting the unsaturated group-containing compound (III) with the polybasic acid and / or the acid anhydride, the epoxy compound is reacted, and the polybasic acid and / or the acid is further 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, a carboxyl group of a polybasic acid or an acid anhydride group of a polybasic anhydride,
The epoxy compound reacts with the epoxy group. 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 compounds having one epoxy group such as ethylene oxide and propylene oxide in addition to the above-mentioned compound (I); bisphenol A epoxy resin, bisphenol F epoxy resin, biphenyl epoxy resin Examples thereof include compounds having two or more epoxy groups such as polyphenol type epoxy resins such as resins, polyglycidylamine type epoxy resins, alcohol type epoxy resins, ester type epoxy resins, and alicyclic epoxy resins. 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.

In the following (IV-3), as in the above (IV-1), as a polybasic acid and / or an acid anhydride thereof, tricarboxylic acid and / or its anhydride, trimellitic acid and / or its anhydride, Or an example of an unsaturated group-containing compound (IV) obtained when an anhydride thereof is used and an epoxy compound having one epoxy group coexists. It is obtained by reacting a carboxyl group of a polybasic acid or an acid anhydride group of a polybasic acid anhydride with an epoxy group of the epoxy compound.

[0030]

Embedded image

In the following (IV-4), as in the above (IV-2), as a polybasic acid and / or an acid anhydride thereof, trimellitic acid and / or an acid anhydride thereof, such as trimellitic acid and 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 further allowed to coexist. This is an example of the unsaturated group-containing compound (IV) obtained.
It is obtained by reacting a carboxyl group of a polybasic acid or an acid anhydride group of a polybasic acid anhydride with an epoxy group of the epoxy compound.

[0032]

Embedded image

In the following (IV-5), as in (IV-1) above, trimellitic acid and / or its anhydride, which is a tricarboxylic acid and / or its anhydride, are used as the polybasic acid and / or its anhydride. This is an example of an unsaturated group-containing compound (IV) obtained when an acid anhydride thereof is used and an epoxy compound having two or more epoxy groups is allowed to coexist. It is obtained by reacting a carboxyl group of a polybasic acid or an acid anhydride group of a polybasic acid anhydride with an epoxy group of the epoxy compound. Further, a cross-linking bond is formed via an epoxy compound.

[0034]

Embedded image

The (meth) acryloyl equivalent of the unsaturated group-containing compound (IV) is preferably from 190 to 5,000, more preferably from 250 to 1,000. If the (meth) acryloyl equivalent of the unsaturated group-containing compound (IV) 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 compound (IV) is preferably from 20 to 200,
More preferably, it is 0 to 150. When the acid value of the unsaturated group-containing compound (IV) is more than the above range, the dispersibility of the pigment may be reduced, and the cured portion may be whitened during development,
If the amount is less than the above range, the solubility in an alkaline solution is reduced, which causes a reduction in developability.

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

When the resin composition is used as a resin for a color filter of a liquid crystal display device, the R of the color filter
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.

In the embodiment of the present invention, the color filter obtained by using the resin composition has one of preferred modes.
One.

[0039]

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] In a four-necked flask equipped with a thermometer, a stirrer, an air blowing tube and a reflux condenser, 78.0 parts of 9,9-bis (4-hydroxyphenylene) fluorene and (epoxycyclohexyl) methyl acrylate were placed. (Average epoxy equivalent: 191) 93.6 parts, propylene glycol monomethyl ether acetate 19.1 parts, methoquinone 0.1
7 parts and 0.52 parts of tetraphenylphosphonium bromide as a catalyst were charged and reacted at 115 ° C. for 10 hours in a mixed gas (set to an oxygen concentration of 7%) gas stream.
Thereafter, 0.52 parts of triethylamine was added as a catalyst, and 11.4 parts of propylene oxide was added dropwise at 105 ° C. over 30 minutes, followed by a reaction at 115 ° C. for 6 hours to obtain a reaction containing the unsaturated group-containing compound (III). The product was obtained.

The obtained reaction product was treated with phthalic anhydride 1
8.7 parts, 12.8 parts of trimellitic anhydride and 92.5 parts of propylene glycol monomethyl ether acetate were added, and the mixture was reacted at 115 ° C. for 5 hours to give a carboxyl group-containing unsaturated group-containing compound having an acid value of 70 ( A resin composition (A-1) containing IV) was obtained. [Examples 2 to 6] Table 1 shows the starting compounds in Example 1.
The same reaction as in Example 1 was carried out except for the changes as shown in (1) to (4) to obtain the desired resin compositions (A-2) to (A-6).

[0041]

[Table 1]

Example 7 In a four-necked flask equipped with a thermometer, a stirrer, an air blowing tube and a reflux condenser, 9,9-
Bis (4-hydroxyphenylene) fluorene100.
0 parts, 163.7 parts of (epoxycyclohexyl) methyl acrylate (average epoxy equivalent: 191), 65.9 parts of propylene glycol monomethyl ether acetate,
To a mixture of 0.26 part of methoquinone and 0.79 part of tetraphenylphosphonium bromide as a catalyst, 115
The reaction was carried out at a temperature of 10 ° C. for 10 hours in a mixed gas (set at an oxygen concentration of 7%). Thereafter, 0.79 parts of triethylamine was added as a catalyst, and propylene oxide was added at 105 ° C.
After dropping 6 parts over 30 minutes, the mixture was reacted at 115 ° C. for 6 hours to obtain a reaction product containing the unsaturated group-containing compound (III).

To the obtained reaction product, 47.7 parts of trimellitic anhydride, 6 parts of bisphenol A diglycidyl ether and 73 parts of propylene glycol monomethyl ether acetate were added, and the mixture was reacted at 115 ° C. for 5 hours. A resin composition (A-7) containing a carboxyl group-containing unsaturated group-containing compound (IV) having a valence of 80 was obtained. [Examples 8 to 11] The same reaction as in Example 7 was carried out except that the compounds of the raw materials in Example 7 were changed as shown in Table 2, to obtain the desired resin compositions (A-8) to (A-8). -1
1) was obtained. [Example 12] In a four-necked flask equipped with a thermometer, a stirrer, an air blowing tube and a reflux condenser, 9,9-bis (4-
(Hydroxyphenylene) fluorene 100.0 parts, (epoxycyclohexyl) methyl acrylate (average epoxy equivalent 191) 163.7 parts, propylene glycol monomethyl ether acetate 29.3 parts, methoquinone 0.26 parts, and tetraphenylphosphonium bromide 0 as a catalyst .79 parts were charged and reacted at 115 ° C. for 10 hours in a mixed gas (set at an oxygen concentration of 7%) gas stream. Thereafter, 0.79 part of tetraethylammonium bromide and 37.7 parts of propylene glycol monomethyl ether acetate were added as a catalyst, and 4.3 parts of propylene oxide was added dropwise at 105 ° C over 30 minutes.
Reaction at 5 ° C. for 6 hours to give unsaturated group-containing compound (III)
A reaction product containing was obtained.

To the obtained reaction product were added 54.9 parts of trimellitic anhydride, 54.6 parts of (epoxycyclohexyl) methyl acrylate (average epoxy equivalent: 191), and propylene glycol monomethyl ether acetate 18
After adding 4.7 parts and reacting at 115 ° C. for 7 hours, 38.4 parts of trimellitic anhydride, 6.2 parts of pyromellitic dianhydride and 93.7 parts of propylene glycol monomethyl ether acetate were added. The reaction was continued for 5 hours while maintaining the temperature at 115 ° C. to obtain a resin composition (A-12) containing a carboxyl group-containing unsaturated group-containing compound (IV) having an acid value of 60. Unsaturated group-containing compound (III) in Example 12
And a N of the resin composition (A-12)
The MR spectra are shown in FIGS. 1 and 2, respectively. FIG.
From the spectrum, it can be seen that the reaction product contains the unsaturated group-containing compound (III) represented by the general formula (5). From the spectrum of FIG. 2, the resin composition (A-
12) includes the structure represented by the formula (6) and the unsaturated group-containing compound (IV) having a carboxyl group.

Example 13 A four-necked flask equipped with a thermometer, a stirrer, an air blowing tube and a reflux condenser was charged with 9,9
-Bis (4-hydroxyphenylene) fluorene 10
0.0 part, 218.3 parts of (epoxycyclohexyl) methyl acrylate (average epoxy equivalent: 191), 0.22 part of methoquinone, and 0.66 part of tetraphenylphosphonium bromide as a catalyst were charged, and a mixed gas (115 ° C.) was added. (The oxygen concentration was set to 7%). Thereafter, 0.66 parts of tetraethylammonium bromide was added as a catalyst, 4.3 parts of propylene oxide was added dropwise at 105 ° C. over 30 minutes, and the mixture was reacted at 115 ° C. for 6 hours, followed by propylene glycol monomethyl ether acetate 80.7 parts. The reaction product containing the unsaturated group-containing compound (III) was obtained.

91.1 parts of trimellitic anhydride and 257.8 parts of propylene glycol monomethyl ether acetate were added to the obtained reaction product, and the mixture was reacted at 115 ° C. for 4 hours. 3.7 parts of anhydride and 3.0 parts of propylene glycol monomethyl ether acetate were added, and the mixture was reacted for 2 hours while maintaining the temperature at 115 ° C. to obtain a resin composition containing a carboxyl group-containing unsaturated group-containing compound (IV) having an acid value of 60 ( A-13) was obtained. [Example 14] In Example 13, the starting compounds were listed in Table 2.
The same reaction as in Example 13 was carried out, except that the composition was changed as shown in the above, to obtain a desired resin composition (A-14).

[0047]

[Table 2]

Example 15 Using the resin compositions (A-1) to (A-14) obtained in Examples 1 to 14, black, red, green and blue colored photosensitive materials were prepared according to the following composition. Resin compositions (1) to (14) were prepared. -Black photosensitive resin compositions (1) to (14) Resin compositions (A-1) to (A) obtained in Examples 1 to 14
-14): each 40 parts 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 composition (1) to (14) Resin composition obtained in Examples 1 to 14 ( A-1) to (A
-14): 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 (14) Resin compositions obtained in Examples 1 to 14 ( A-1) to (A
-14): 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 (14) Obtained in Examples 1 to 14 Resin compositions (A-1) to (A
-14): 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 (14) of 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. Color filters (1) to (1) in which an image is formed and R, G, B image patterns are formed
4) was obtained. It was visually confirmed that there was no color transfer or color bleeding in the R, G, B colored images of these color filters.

During the production of the color filter, a color filter intermediate product having the first color pattern formed on the substrate is sandwiched between two deflection plates, and the deflection axes of these two deflection plates are parallel. The ratio (contrast) of the amount of transmission between a certain time and the time of going straight was measured. Each of the color filter intermediate products had a contrast ratio exceeding 3000 times, and it was confirmed that the so-called deflection characteristics were good.
In addition, 230 ° C.
The degree of discoloration after one hour of hot-air heating was visually evaluated. As a result, no discoloration was observed in any of the color filter intermediate products, and it was found that the intermediate products had good heat resistance.

No defects or defects were observed in any of the obtained patterns, and no undissolved matter remained in a 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. The characteristics of the color filter as a color filter were also good. Further, various physical properties of the color filter were also good. [Comparative Example 1] In Example 15, the resin composition (A-
Same as Example 15 except that methacrylic acid / methyl methacrylate / 2-hydroxyethyl methacrylate / benzyl methacrylate (copolymerization ratio 15/50/15/20, weight average molecular weight 22,000) copolymer was used instead of 1). Thus, a colored photosensitive resin composition was prepared.

Using these colored photosensitive resin compositions, a pattern was formed on a substrate in the same manner as in Example 15 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.

[0052]

According to the present invention, it is possible to provide a novel unsaturated group-containing compound which is excellent in patterning characteristics even with a small amount of exposure and can obtain a cured product having high hardness. The resin composition of the present invention containing the unsaturated group-containing compound (IV) as an essential component provides a coating film having high hardness.
The resin composition of the present invention containing the unsaturated group-containing compound (IV) and a coloring agent as essential components is useful as a resin composition for a color filter. The color filter obtained from this resin composition has good pattern formation and physical properties of the substrate, and also has excellent characteristics as a color filter.

[Brief description of the drawings]

FIG. 1 is an NMR spectrum of a reaction product containing an unsaturated group-containing compound (III) obtained in Example 12.

FIG. 2 shows a resin composition (A-1) obtained in Example 12.
It is an NMR spectrum of 2).

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 299/02 C08F 299/02 G02B 1/04 G02B 1/04

Claims (8)

[Claims] 1. One epoxy group and one or more (meth)
Etherifying the epoxy group of the compound (I) having an acryloyl group with a phenolic hydroxyl group of at least one compound (II) selected from compounds represented by the following general formulas (1) to (4): The unsaturated group-containing compound (III) obtained by Embedded image (However, R ¹ and R ² represent a hydrocarbon group having 1 to 20 carbon atoms. P and q are integers of 0 to 4.) 2. The unsaturated group-containing compound (III) according to claim 1, wherein the compound (I) is an acrylate having an epoxycyclohexyl group and / or an acrylate having a glycidyl group. 3. An unsaturated group represented by the following general formula (5):
Containing compound (III). Embedded image(However, R represents a hydrogen atom or a methyl group.₁Is
Represents a single bond or a divalent organic group, and when n is 2 or more,
Each may be the same or different. Y _TwoIs simply
A bond or a divalent or higher organic group,_TwoPart of and C
α and Cβ may form a cyclic structure.
Here, a single bond means that there is no organic group,
Y means₁And Y_TwoAnd are both single bonds
There is no. Here, Cα and Cβ have a substituent.
May be a carbon atom. Z is the following general formula (1 ′)-
At least one selected from (4 ′). n is 1 or more
Is the integer above. Embedded image(However, R¹, R^TwoRepresents a hydrocarbon group having 1 to 20 carbon atoms.
You. p and q are integers of 0-4. )) 4. A hydroxyl group of the unsaturated group-containing compound (III) according to any one of claims 1 to 3, and a carboxyl group and / or an acid anhydride group of a polybasic acid and / or an acid anhydride thereof. To obtain an unsaturated group-containing compound having a carboxyl group (I
V). 5. The polybasic acid and / or acid anhydride thereof is a group consisting of tetrahydrophthalic anhydride, hexahydrophthalic anhydride, phthalic anhydride, trimellitic anhydride and pyromellitic dianhydride. The unsaturated group-containing compound (IV) according to claim 4, which is at least one selected from the group consisting of: 6. A resin composition comprising the unsaturated group-containing compound (IV) according to claim 4 as an essential component. 7. A resin composition for a color filter comprising the unsaturated group-containing compound (IV) according to claim 4 and a coloring agent as essential components. 8. A color filter obtained by using the resin composition for a color filter according to claim 7.