JPH06194514A - Photosensitive resin composition for forming color filter - Google Patents

Abstract

PURPOSE:To obtain a high-quality color filter which is not cracked or crazed at low cost in good yield by mixing a colorant dispersed with a polymer having a pyrrolidonyl group into a specified photosensitive resin soln. of polyvinyl acetal. CONSTITUTION:This composition consists of (A) a colorant composition in which a colorant is dispersed with a polymer having a pyrrolidonyl group, (B) a polyvinyl acetal resin having a group having an ethylenic unsaturated bond and a carboxyl group and a polyacetal resin consisting of a structural unit shown by formulas I, II, III and IV or V, (C) a photopolymerization initiator and (D) a photosensitizer, as required, a photopolymerizable monomer having at least one ethylenic unsaturate double bond and/or a photo-cross-linking agent. In the formulas, R<1> and R<4> are hydrogen and alkyls, R<2> is alkyls, aralkyls, etc., R<3> and R<6> are hydrogen atom and a group having an ethylenic unsaturated double bond, and R<5> is alkylene and arylene groups.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored photosensitive resin composition for pattern formation which can be used in liquid crystal displays such as televisions, computers or video monitors, and image scanners.

[0002]

2. Description of the Related Art Conventionally, as a typical example of a method for forming a color filter, a dyeing method (for example, Japanese Examined Patent Publication No.
No. 7375, Japanese Patent Publication No. 52-17376),
Vapor deposition method (JP-A-55-146406, etc.), electrodeposition method (JP-A-59-90818, etc.), printing method (JP-A-59-29225, etc.), pigment dispersion method (JP-A-SHO). No. 60-237403, etc.) and the like.

On the other hand, as a polyvinyl alcohol type photosensitive resin, a polyvinyl alcohol type resin has been proposed as a polymer which can be developed by eluting the unpolymerized portion with water. This known example can be roughly classified into two. (I)
Fully or partially saponified polyvinyl acetate (so-called,
Photopolymerizable monomer having an ethylenically unsaturated double bond in (polyvinyl alcohol) or an azide compound soluble in an organic solvent to impart photosensitivity (JP-A-57-124730). Showa 57-21221
7 and Japanese Patent Publication No. 3-61938). (Ii) Photopolymerization is imparted by reacting a compound having an unsaturated group with a hydroxyl group contained in fully or partially saponified polyvinyl acetate (Japanese Patent Publication No. 48-696).
2 and JP-A-2-77403).

As the alkali-soluble photosensitive resin, a vinyl compound-based copolymer having a carboxyl group,
For example, a photopolymerizable composition comprising a photopolymerizable monomer and a photopolymerization initiator in styrene and maleic anhydride or a half-esterified copolymer thereof (Japanese Patent Laid-Open No. 153909/1990) can be mentioned.

[0005]

However, the color filter obtained by the dyeing method is a light-sensitized product obtained by adding a photosensitizer such as potassium dichromate to a water-soluble resin such as gelatin, polyvinyl alcohol, polyvinylpyrrolidone and casein. Is a method of forming a patterned photo-cured film with a functional resin and then dyeing with an acid dye, a reactive dye, etc., but a further dyeing step is required after the pattern formation,
Since the manufacturing process is long, the yield is poor, the cost is high, and the resin to be dyed and the dye are inferior in heat resistance and light resistance, and lack in reliability. The evaporation method has a problem that the process is long. Printing can be expected as a cost-reducing method, but there are problems in forming a highly accurate pattern and flatness of the film surface. JP-A-60
In the pigment dispersion method according to Japanese Patent Laid-Open No. 237403, since the photosensitive polyimide precursor is used, the light transmittance of the color filter is reduced due to the material configuration that absorbs light, and the color reproduction equivalent to that of CRT is achieved. However, there is a problem in that the cost is high, the dispersion stability of the pigment decreases with time (secondary aggregation occurs), and the cost is high.

On the other hand, as a polyvinyl alcohol resin having photosensitivity, in order to obtain good water developability,
In the case of (i), the relief film is fragile due to the limitation of the average degree of polymerization (low average degree of polymerization) of completely saponified or partially saponified polyvinyl acetate (so-called polyvinyl alcohol), or due to the high degree of average polymerization. And the time required for development becomes long, and the sensitivity is good when an azide-based photosensitizer is used, but the color reproducibility is deteriorated because a compound having an azo bond is produced from the azide-based photosensitizer by photoreaction. (Ii) In the case of (1), there is a problem that the water developability is lowered because the hydroxyl group imparting water solubility is consumed in large amount by the introduction of the unsaturated group.

In the alkali-soluble type photosensitive resin,
Since the carboxyl group is introduced, it is possible to obtain good developability with an aqueous alkaline solution. However,
It is difficult to increase the average molecular weight of styrene and maleic anhydride or its half-esterified copolymer, or it is difficult to increase sensitivity due to restrictions such as difficulty in introducing a group having an ethylenically unsaturated bond into the carboxyl group,
Further, since the styrene monomer is used, the relief film formed is fragile, and there is a problem that cracks are formed later during the film formation.

Accordingly, as a photosensitive resin composition which has improved the above-mentioned disadvantages, a photosensitive resin composition having high sensitivity, strong base polymer, excellent heat resistance and developable with an alkaline aqueous solution is
It is also desired due to pollution problems. Therefore, the present inventors have solved the problems in the conventional polyvinyl acetal as described above, and as a result of diligent studies to effectively utilize the excellent properties of the polyvinyl acetal resin, a novel photosensitive resin composition for forming a color filter is obtained. That is, the above colorant composition, a polyvinyl acetal resin having an ethylenically unsaturated bond, a photopolymerization initiator and optionally a photosensitizer, and a light having at least one ethylenically unsaturated double bond. The present invention has been found to be one that is composed of a polymerizable monomer and / or a photocrosslinking agent and is extremely useful for the above purpose, and has arrived at the present invention.

[0009]

The photosensitive resin composition for forming a color filter according to the present invention is a colorant composition in which (A) a colorant is dispersed in a polymer having a pyrrolidonyl group,
(B) A polyvinyl acetal-based resin having an ethylenically unsaturated double bond obtained by introducing an ethylenically unsaturated double bond into a carboxyl group contained in the polyvinyl acetal resin having a carboxyl group, (C)
A color comprising a photopolymerization initiator, (D) an optional photosensitizer, a photopolymerizable monomer having at least one ethylenically unsaturated double bond, and / or a photocrosslinking agent. It is a photosensitive resin composition for forming a filter, and by using a polyvinyl acetal-based resin having an ethylenically unsaturated bond, while having the same coating film physical properties as the polyvinyl acetal resin, it has been given thermosetting and photocuring properties. It was also found that the compatibility with a colorant composition in which a colorant (pigment) is dispersed in a polymer having a pyrrolidonyl group is excellent. That is, (A) a colorant composition in which a colorant is dispersed in a polymer having a pyrrolidonyl group, (B) a polyvinyl acetal resin having a group having an ethylenically unsaturated bond and a carboxyl group, a general formula (Chemical Formula 11)

[0010]

[Chemical 11]

The structural unit represented by 0 to 30 mol%,
General formula (Formula 12)

[0012]

[Chemical 12]

The constitutional unit represented by is 0 to 30 mol%,
General formula (formula 13)

[0014]

[Chemical 13]

(In the formula, R ¹ is a hydrogen atom, an alkyl group, and R ² is an alkyl group, a cyclic alkyl group, an aryl group or an aryl group having a substituent.) Of 30 to 70 mol% and the general formula (Chemical formula 14)

[0016]

[Chemical 14]

(In the formula, R ³ is a hydrogen atom or an alkyl group, R ⁴ is a divalent alkylene group or a phenylene group, and R ⁵ is a hydrogen atom or an alkyl group.)
~ 20 mol% or the general formula (Formula 15)

[0018]

[Chemical 15]

(However, in the formula, R ⁶ is a group having an ethylenically unsaturated bond.)
Resin consisting of 0 mol% and 100 mol% in total,
Color filter formation comprising (C) photopolymerization initiator, (D) optionally and photosensitizer, photopolymerizable monomer having at least one ethylenically unsaturated double bond and / or photocrosslinking agent The present invention provides a photosensitive resin composition for use. The above-mentioned polyacetal resin is manufactured as follows.

That is, an aqueous polyvinyl alcohol solution having a saponification degree of 70 mol% or more and an average degree of polymerization of 500 to 4000 and the general formula R ⁷ COR ⁸ COOR ⁹ (wherein R ⁷ is a hydrogen atom, a methyl or ethyl group, R ⁸ is a divalent alkyl group, a cyclic alkyl group, an aryl group, R ⁹ is a hydrogen atom or an alkyl group, or a compound represented by the general formula R ¹⁰ C
A compound represented by OR ¹¹ OH (wherein R ¹⁰ is a hydrogen atom, a methyl or ethyl group, and R ¹¹ is a divalent aryl group) and a compound represented by the general formula R ¹² COR ¹³ (wherein R ¹² is A hydrogen atom, a methyl or ethyl group, and R ¹³ is a divalent alkyl group, a cyclic alkyl group, an aryl group or a group having a substituent, an aryl group.) At a temperature in the presence of an acid catalyst. After reacting at 13 to 35 ° C. and then at 35 to 80 ° C., the reaction product is neutralized, the obtained polyvinyl acetal is dissolved in an organic solvent, and an isocyanate group and ethylenically unsaturated The polyvinyl acetal resin is obtained from the step of reacting the compound having a bond.

The present invention will be described in detail below.

First, the coloring material (pigment) used in the present invention
Examples of the polymer having a pyrrolidonyl group to disperse are poly (N-vinyl-2-pyrrolidone), N-vinyl-2-pyrrolidone-vinyl acetate copolymer, N-vinyl-2-pyrrolidone-α-olefin. Copolymer, general formula,
(Chemical formula 16)

[0023]

[Chemical 16]

(In the formula, R ¹⁴ is a hydrogen atom or a methyl group, and n is 1 to 4) and a copolymer with a vinyl compound is exemplified. These polymers can be used as long as they have a molecular weight in the range of 5,000 to 1,200,000, but the molecular weight is not particularly limited. Particularly preferred is poly (N-vinyl-2-pyrrolidone) and N-vinyl-2-pyrrolidone-from the viewpoint of cost.
Vinyl acetate copolymer is good. A colorant composition in which a colorant is dispersed in a polymer having a pyrrolidonyl group is a composition comprising a polymer having a pyrrolidonyl group and a pigment, or a composition in which a dispersion aid and a solvent are added as necessary. Become. In the method for producing this composition, a polymer having a pyrrolidonyl group, a pigment and, if necessary, a dispersion aid are kneaded with a disperser. Further, a polymer having a pyrrolidonyl group, a pigment, and if necessary, a dispersion aid and an organic solvent are kneaded in a disperser. The polymer having a pyrrolidonyl group has an excellent dispersing effect as a pigment-dispersing resin, and at the same time, the development promoting effect of the alkali development in the present invention is remarkably remarkable, and has both effects. More specifically, in the alkali development used in the present invention, addition of this dispersion resin not only shortens the alkali development time, but also provides a sharp pattern with no development residue.

Examples of the disperser for dispersing the pigment with the polymer dispersion resin having a pyrrolidonyl group include an ultrasonic disperser, a two-roll, a three-roll, a ball mill, a sand mill, a homomixer and a kneader. The dispersion state depends on the particle size distribution and particle size of the pigment, but can be adjusted by changing the kneading frequency and time of the disperser. The dispersed state is measured with a particle size measuring device. The colorant composition can be used in the form of a color paste containing a solvent, or can be used in a natural or forcedly dried state. Generally, the state of the color paste containing the solvent can be uniformly dispersed in the photosensitive resin.

The blending ratio of the polymer having a pyrrolidonyl group and the pigment is 10: 100 to 60: 100, preferably 20: 100 to 50: 100% by weight.

In the polyvinyl acetal resin according to the present invention, the hydrogen atom of the hydroxyl group contained in the polyvinyl acetal is replaced with a cyanoethyl group, the cyanoethyl group is converted into a carboxylethyl group, and further the ethylenic unsaturated double bond is added to the carboxyl group. Is introduced, and polyvinyl alcohol having a saponification degree of 70 mol% or more and an average degree of polymerization of 500 to 4000 is acetalized with an aldehyde compound or a ketone compound having a carboxyl group such as glyoxylic acid, that is, the present invention is generally Formula (Formula 17), (Formula 18), (Formula 19)

[0028]

[Chemical 17]

[0029]

[Chemical 18]

[0030]

[Chemical 19]

And (Chem. 20)

[0032]

[Chemical 20]

Alternatively, the general formulas (Formula 21), (Formula 22), (Formula 23) and

[0034]

[Chemical 21]

[0035]

[Chemical formula 22]

[0036]

[Chemical formula 23]

And (24)

[0038]

[Chemical formula 24]

(Wherein R ¹ and R ⁴ are a hydrogen atom, an alkyl group, R ² is an alkyl group, a cyclic alkyl group, an aryl group or a group each having a substituent, and R ³ and R ⁶ are hydrogen atoms. And a group having an ethylenically unsaturated double bond, R ⁵ is an alkylene group, a cyclic alkylene group, or an arylene group.), Which is a polyvinyl acetal-based resin. Is manufactured as follows.

That is, (A) with a saponification degree of 70 mol% or more,
An aqueous solution of polyvinyl alcohol having an average degree of polymerization of 500 to 4000 and the general formula R ¹ COR ² (wherein R ¹ is a hydrogen atom, a methyl or ethyl group, R ² is a hydrogen atom, an alkyl group, a cyclic alkyl group, an aryl group or An aqueous solution of a compound represented by the formula (1), each of which has a substituent.
After reacting at a temperature of 13 to 40 ° C. in the presence of an acid catalyst, and then at a temperature of 35 to 80 ° C., the reaction product is neutralized, and (B) the obtained polyvinyl acetal is added to water and water. A step of dissolving in a solvent that dissolves and reacting acrylonitrile at a temperature of 45 ° C. or lower in the presence of an alkaline aqueous solution, and (C) the obtained cyanoethylated polyvinyl acetal at a temperature of 50 ° C. or higher in the presence of an alkaline aqueous solution. After the reaction, the step of neutralizing, and (D) the obtained carboxylethylated polyvinyl acetal resin is represented by the general formula (Formula 25)

[0041]

[Chemical 25]

[Wherein R ⁷ is a hydrogen atom or a methyl group, R ⁸
Is a hydrogen atom or an aryl group, and Y is an oxycarbonyl bond (-OCO-) or an ether bond. ] Reacting the compound represented by the following in the presence of a base catalyst, or (E)
A step of heating the obtained carboxyethylated polyvinyl acetal resin at 100 ° C. or higher, and (F) the obtained polyvinyl acetal resin having an acid anhydride group,
General formula, (26)

[0043]

[Chemical formula 26]

[Wherein R ⁹ is an alkylene group, R ¹⁰ is a hydrogen atom or a methyl group, R ¹¹ is a hydrogen atom or an aryl group, X is
Is hydroxy (-OH), an amino group (-NH _2), Y
Is an oxycarbonyl bond (-OCO-) and an amide bond (-NHCO-). ] The polyvinyl acetal resin is obtained from the step of reacting the compound represented by the following in the presence of a base catalyst.

(A) An aqueous solution of polyvinyl alcohol having a saponification degree of 70 mol% or more and an average polymerization degree of 500 to 4000 and the general formula R ¹ COR ² (wherein R ¹ is a hydrogen atom, a methyl or ethyl group, R ² is a hydrogen atom, an alkyl group, a cyclic alkyl group, an aryl group or a group each having a substituent), and R ⁴ COR ⁵ COOH (R ⁴
Is a hydrogen atom or an alkyl group, and R ⁵ is an alkylene, cyclic alkylene or arylene group. ) With an aqueous solution of a compound represented by the formula (1) at a temperature of 13 to 40 ° C. in the presence of an acid catalyst, and then at a temperature of 35 to 80 ° C., and then neutralizing the reaction product. ) The obtained carboxylated polyvinyl acetal-based resin has the general formula

[0046]

[Chemical 27]

[Wherein R ⁷ is a hydrogen atom or a methyl group, R ⁸
Is a hydrogen atom or an aryl group, and Y is an oxycarbonyl bond (-OCO-) or an ether bond. ] Reacting the compound represented by the following in the presence of a base catalyst, or (C)
1 of the obtained carboxylated polyvinyl acetal resin
The step of heating at 00 ° C. or higher, and (D) the obtained polyvinyl acetal-based resin having an acid anhydride group have the general formula:

[0048]

[Chemical 28]

[Wherein R ⁹ is an alkylene group, R ¹⁰ is a hydrogen atom or a methyl group, R ¹¹ is a hydrogen atom or an aryl group, X is
Is hydroxy (-OH), an amino group (-NH _2), Y
Is an oxycarbonyl bond (-OCO-) and an amide bond (-NHCO-). ] The polyvinyl acetal resin which consists of the process of reacting the compound represented by these in the presence of a base catalyst is obtained.

The blending ratio of the polymer having a pyrrolidonyl group and the pigment is 10: 100 to 60: 100, preferably 20: 100 to 50: 100% by weight.

As the base polymer for the photosensitive resin used in the present invention, the degree of polymerization of polyvinyl alcohol is 500.
To 4000, preferably 550 to 300
0, more preferably 550 to 1700, and the saponification degree is preferably 70 mol% or more, and most preferably 88 to 95 mol%. A polyvinyl alcohol aqueous solution is prepared by dissolving polyvinyl alcohol in water. The solid content concentration of polyvinyl alcohol dissolved in water is 5 to 15
It is desirable to set it as the weight%. The acid catalyst for the acetalization reaction of polyvinyl alcohol with an aldehyde or acetone compound is an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid, or an organic acid such as paratoluenesulfonic acid, and hydrochloric acid or sulfuric acid is particularly preferable. The amount of the acid catalyst added is 3 to 12% by weight, preferably 4 to 10% by weight, based on the aqueous solution. If the amount of the acid catalyst added is less than 3% by weight with respect to the aqueous solution, the acetalization reaction does not proceed sufficiently and the production time becomes long, and if it exceeds 12% by weight, excess acid may be generated. Since the aldehyde derivative and the ketone derivative cause aldol condensation, the obtained polyvinyl acetal is colored and the post-treatment of the neutralization step becomes complicated.

The concentration of the acid catalyst is weakly acidic in the first reaction,
The second reaction is strongly acidic (pH 2 or less).

Further, the general formula R ⁷ COR ⁸ used in the present invention is used.
COOR ⁹ (wherein R ⁷ is a hydrogen atom, a methyl or ethyl group, R ⁸ is a divalent alkyl group, a cyclic alkyl group or an aryl group, and R ⁹ is a hydrogen atom or an alkyl group). Examples of the compound include glyoxylic acid, levulinic acid (also known as γ-ketovaleric acid), alkyl acetoacetate,
Pyruvate (also called 2-ketopropionic acid), 4-carboxybenzaldehyde, 4-formylphenoxyacetic acid and the like can be mentioned.

Examples of the compound represented by the general formula R ¹⁰ COR ¹¹ OH (wherein R ¹⁰ is a hydrogen atom, a methyl or ethyl group, and R ¹¹ is a divalent aryl group) include, for example,
4-hydroxybenzdehyde, 3-hydroxybenzdehyde, 2-hydroxybenzdehyde and the like can be mentioned. General formula R ¹² COR ¹³ (wherein R ¹² is a hydrogen atom, a methyl or ethyl group, and R ¹³ is a divalent alkyl group, a cyclic alkyl group, an aryl group or a group having a substituent, an aryl group). The compound represented is formaldehyde,
At least one selected from known compounds such as acetaldehyde, propionaldehyde, butyraldehyde, heptylaldehyde, acrolein, crotonaldehyde, cyclohexanaldehyde, benzaldehyde, furfural, acetone, methylethylketone, methylpropylketone, and methylbutylketone.

General Formula Used in the Present Invention General Formula R ⁷ C
OR ⁸ COOR ⁹ (wherein R ⁷ is a hydrogen atom, a methyl or ethyl group, R ⁸ is a divalent alkyl group, a cyclic alkyl group or an aryl group, and R ⁹ is a hydrogen atom or an alkyl group). Compound or the general formula R ^{1 0} COR ¹¹ OH
(However, in the formula, R ¹⁰ is a hydrogen atom, a methyl or ethyl group, or R
^The compound represented by the formula ( ¹¹ is a divalent aryl group) is added in a polyvinyl alcohol unit, i.e., -CH (O).
H) It is advisable to add 3 to 25 mol% to CH ₂ -2 mol. It is preferably 5 to 15 mol%. Further, in the general formula R ¹² COR ¹³ (wherein, R ¹² is a hydrogen atom, a methyl or ethyl group, R ¹³ is a divalent alkyl group, a cyclic alkyl group,
An aryl group or a group having a substituent, an aryl group. )
The addition amount of the compound represented by 20 is 20 with respect to the polyvinyl alcohol unit, that is, -CH (OH) CH ₂ -2 mol.
It is better to add ~ 80 mol%. Preferably 30-60
Mol% is good.

The surfactant used in the synthesis of the polyvinyl acetal resin of the present invention is known and is not particularly limited. For example, nonionic surfactants such as polyoxyethylene aryl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene-based surfactant, and polyoxyethylene alkyls (HLB). 6 to 15), polyhydric alcohol surfactants such as sorbitan fatty acid ester, and anionic surfactants such as sodium lauryl sulfate, sodium dodecylbenzene sulfonate, sodium hexadecane sulfonate, and sodium alkylaryl polyether sulfonate. Etc. The amount of the polyvinyl acetal added in the dispersion system is 0.01 to
An amount of 3.0% by weight is preferable, but preferably 0.03 to
Although it is 1.0% by weight, it is not particularly limited.

The reaction conditions used in the present invention include polyvinyl alcohol and the general formula R ⁷ COR ⁸ COOR ⁹ (wherein R ⁷ is a hydrogen atom, a methyl or ethyl group, and R ⁸ is 2
A divalent alkyl group, a cyclic alkyl group, an aryl group, R ⁹ is a hydrogen atom or an alkyl group. ) Or a compound represented by the general formula R ¹⁰ COR ¹¹ OH (wherein R ¹⁰ is a hydrogen atom, a methyl or ethyl group, and R ¹¹ is a divalent aryl group) and the general formula R ¹² COR ¹³ (However,
In the formula, R ¹² is a hydrogen atom, a methyl or ethyl group, and R ¹³ is a divalent alkyl group, a cyclic alkyl group, an aryl group or a group having a substituent, an aryl group. The first reaction temperature with the compound represented by the formula (1) is in the range of 13 to 40 ° C. 13-35 degreeC is preferable. If the temperature is 13 ° C or lower, the reaction product may be difficult to dissolve in the solvent, and if the temperature is 40 ° C or higher, the generated polymer precipitate particles may adhere to each other and block. Next, the second reaction temperature is 35 to 80 ° C., and aging is carried out to further advance the reaction. The reaction time at the first reaction temperature is 1
It is preferable to continue stirring for ˜2 hours (including the dropping period of the above compound) and for the reaction time at the second reaction temperature for 1 to 5 hours.
In the case of precipitating and precipitating the polymer, bulky (small density) particles can be obtained by precipitating and precipitating the polymer by lowering the temperature after finishing the first reaction.

Next, an alkaline substance for neutralizing the inorganic or organic acid added to the reaction system as a catalyst to pH 6 to 8, that is, an alkali hydroxide such as sodium hydroxide or potassium hydroxide, or a carbonate such as sodium carbonate. The reaction system is neutralized by adding alkali, hydrogencarbonate such as sodium hydrogencarbonate, etc., and aqueous ammonia. In this case, the temperature is 30 to 6
It may be 0 ° C.

The present invention will be described in detail below.

First, the degree of polymerization of the polyvinyl alcohol used in the present invention is 500 to 4000, preferably 550 to 3000, more preferably 550 to 1700, and the saponification degree is preferably 70 mol% or more, 88. To 95 mol% is most suitable. Although polyvinyl alcohol is dissolved in water to prepare a polyvinyl alcohol aqueous solution, it is desirable that the solid concentration of polyvinyl alcohol dissolved in water is 5 to 15% by weight. The acid catalyst is an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid, or an organic acid such as paratoluenesulfonic acid, and hydrochloric acid is particularly preferable.
The amount of the acid catalyst added is 3 to 12% by weight, preferably 4 to 10% by weight, based on the aqueous solution. When the addition amount of the acid catalyst is less than 3% by weight with respect to the aqueous solution, the acetalization reaction does not proceed sufficiently, the production time becomes long, and
When it exceeds 12% by weight, the aldehyde derivative and the ketone derivative cause aldol condensation due to the excess acid, so that the obtained polyvinyl acetal is colored and the post-treatment of the neutralization step becomes complicated.

The concentration of the acid catalyst is weakly acidic in the first reaction,
The second reaction is strongly acidic (pH 2 or less).

Further, the general formula R ¹ CO used in the present invention is
R ² (wherein R ¹ is a hydrogen atom or an alkyl group, R ² is a hydrogen atom, an alkyl group, a cyclic alkyl group, an aryl group or an acetal group having a reactive substituent on each). Formaldehyde,
Acetaldehyde, propionaldehyde, butyraldehyde, heptylaldehyde, acrolein, crotonaldehyde, cyclohexanaldehyde, benzaldehyde, p-carboxybenzaldehyde, furfural,
At least one compound can be selected from known compounds such as 4-hydroxybenzaldehyde, acetone, methyl ethyl ketone, methyl propyl ketone, and methyl butyl ketone.

R ⁴ COR ⁵ COOR ⁶ (R ⁴ is a hydrogen atom,
An alkyl group, R ⁵ is an alkylene, a cyclic alkylene, an arylene group, and R ⁶ is a hydrogen atom or an alkyl group. Examples of the compound represented by) include known compounds such as glyoxylic acid, 3-formylpropionic acid, 5-formylpentanoic acid, methyl acetoacetate, ethyl acetoacetate, levulinic acid, methyl levulinate, and ethyl levulinate. At least one can be selected.

General formula used in the present invention R ¹ COR
² (wherein R ¹ is a hydrogen atom or an alkyl group, R ² is a hydrogen atom, an alkyl group, a cyclic alkyl group, an aryl group or an acetal group having a reactive substituent on each of them). The addition amount of is preferably 0 to 70 mol% with respect to 2 mol of the polyvinyl alcohol unit. It is preferably 10 to 50 mol%.

A compound represented by the general formula R ⁴ COR ⁵ COOR ⁶ (R ⁴ is hydrogen atom, alkyl group, R ⁵ is alkylene, cyclic alkylene, arylene group, R ⁶ is hydrogen atom, alkyl group) It is preferable to add 300 to 100 mol% to 2 mol of the polyvinyl alcohol unit. It is preferably 50 to 90 mol%.

The surfactant used in the present invention is a known one and is not particularly limited. For example, nonionic surfactants such as polyoxyethylene aryl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene-based surfactant, and polyoxyethylene alkyls (HLB). ; 6 to 1
5), polyhydric alcohol surfactants such as sorbitan fatty acid ester, and anionic surfactants such as sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium hexadecanesulfonate, and sodium alkylaryl polyethersulfonate. To be
The addition amount is preferably such that the concentration of the polyvinyl acetal in the dispersion liquid system is 0.01 to 3.0% by weight, but preferably 0.03 to 1.0% by weight, but is not particularly limited. Absent.

The reaction conditions used in the present invention include polyvinyl alcohol and the general formula R ¹ COR ² (wherein R ¹ is a hydrogen atom or an alkyl group, R ² is a hydrogen atom, an alkyl group, a cyclic alkyl group, an aryl group). The first reaction temperature with the compound represented by the group or an acetal group having a reactive substituent on each of them reacts in the range of 13 to 40 ° C. 13-35 degreeC is preferable. If the temperature is lower than 13 ° C, the reaction product may be difficult to dissolve in the solvent.
If the temperature is 40 ° C. or higher, the polymer precipitate particles produced may adhere to each other to form a block. Next, the second reaction temperature is 35 to 80 ° C., and aging is carried out to further advance the reaction. The reaction time at the first reaction temperature is preferably 1 to 2 hours (including the dropping period of the general formula R ¹ COR ² compound), and the reaction time at the second reaction temperature is preferably 1 to 5 hours. In the case of precipitating and precipitating the polymer, bulky (small density) particles can be obtained by precipitating and precipitating the polymer by lowering the temperature after finishing the first reaction.

Next, an alkaline substance for neutralizing the inorganic or organic acid added to the reaction system as a catalyst to pH 6 to 8, that is, alkali hydroxide such as sodium hydroxide or potassium hydroxide, or carbonic acid such as sodium carbonate. The reaction system is neutralized by adding alkali, hydrogencarbonate such as sodium hydrogencarbonate, etc., and aqueous ammonia. In this case, the temperature is 30 to 6
It may be 0 ° C.

The method for producing the carboxylethylated polyvinyl acetal used in the present invention is as follows: a polyvinyl acetal is dissolved in a water-soluble inert organic solvent and reacted with acrylonitrile in the presence of an alkali hydroxide catalyst dissolved in water to produce cyanoethyl polyvinyl acetal. It is produced by producing an acetal and further hydrolyzing it at a temperature of 45 ° C or higher to neutralize it (pH 6 to 7). At the time of this production, it is adjusted by dissolving it in a water-soluble organic solvent such as dioxane of polyvinyl acetal. The solid content concentration of polyvinyl acetal dissolved in the water-soluble organic solvent is 5 to 15% by weight, preferably 5% by weight. -10
It is desirable to set it as the weight%. Examples of the alkali hydroxide catalyst include sodium hydroxide and potassium hydroxide. The alkali hydroxide catalyst may be added in an amount of 3 mol based on 2 to 4 mol of the polyvinyl alcohol structural unit of polyvinyl acetal, and the acrylonitrile reaction rate may be 90 to 30 mol%. Preferably 8
It is desirable to set it to 0 to 50 mol%. However, the addition amount of the organic solvent is 1 to 2 times, preferably 1 to 1.5 times the total volume 1 of water, polyvinyl acetal and alkali hydroxide.
Double is desirable. The reaction temperature of acrylonitrile is 20 to
40 ℃ is desirable, the reaction is slow below 20 ℃, 40 ℃
In the above case, the CN group may be hydrolyzed. If the reaction rate of acrylonitrile is controlled to 90 to 30 mol%, the CN group may be hydrolyzed at 40 ° C. or higher to change to a carboxyl group. In particular, the reaction temperature of acrylonitrile is not limited.

The carboxylethylated or carboxylated polyvinyl acetal resin having an ethylenically unsaturated double bond used in the present invention has a general formula (Formula 29) in which 1) the carboxyl group in the polymer is treated with a base catalyst such as triethylamine.

[0071]

[Chemical 29]

[Wherein R ⁷ is a hydrogen atom or a methyl group, R ⁸
Is a hydrogen atom or an aryl group, and Y is an oxycarbonyl bond (-OCO-) or an ether bond. ] Compounds represented by glycidyl (meth) acrylate, allyl glycidyl ether, vinyl cyclohexene monoepoxide compound, α-ethyl glycidyl acrylate, crotonyl glucidyl ether, itaconic acid monoalkyl monoglycidyl ester, and the like to react with Or carboxylethylated or carboxylated polyvinyl acetal resin is heated to make it an acid anhydride, and then an unsaturated alcohol is added to the acid anhydride as a triethylamine amine compound or an alkali metal alcoholate such as lithium alcoholate, sodium alcoholate or potassium alcoholate. It can be obtained by reacting under a base catalyst. The unsaturated alcohol has the general formula:

[0073]

[Chemical 30]

[Wherein R ⁹ is an alkylene group, R ¹⁰ is a hydrogen atom or a methyl group, R ¹¹ is a hydrogen atom or an aryl group, X is
Is hydroxy (-OH), an amino group (-NH _2), Y
Is an oxycarbonyl bond (-OCO-) and an amide bond (-NHCO-). ] The compound represented by these is mentioned. For example, 2-hydroxyethyl acrylate, 2
-Hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate and the like can be mentioned. Other, N- methylolacrylamide, N-methylene (meth) acrylamide group such as N- methylol methacrylamide (-CH ₂ -NHCOC
H (or CH ₃ ) = CH ₂ , allyl cellosolve and the like can be mentioned.

N-methylene (meth) acrylamide groups (-CH ₂ -NHCOCH (or CH ₃ ) = C such as N-methylolacrylamide and N-methylolmethacrylamide.
H ₂ and allyl cellosolve are reacted with the hydroxyl group in polyvinyl acetal in the presence of an acid catalyst such as phosphoric acid, hydrochloric acid, paratoluene sulfonic acid, and citric acid, or when the hydroxyl group of polyvinyl alcohol is reacted with an aldehyde compound, an aldehyde compound The reaction may be carried out in the coexistence with or after the acetalization.

As the polyvinyl acetal resin used in the present invention, a polymer having a group having an ethylenically unsaturated double bond and a carboxyl group in the polymer can be used. The above-mentioned ethylenic unsaturated bond is reacted with the carboxyl group contained in the polyvinyl acetal resin,
It suffices that the carboxyl groups necessary for carrying out the alkali development remain in the reacted polyvinyl acetal resin. In that case, the acid value is preferably 30 to 150, and more preferably 50 to 100.

The polymerization inhibitor used in the above reaction includes, for example, known polymerization inhibitors such as hydroquinone, hydroquinone methyl ether and parabenzoquinone, and the solvent used for them includes dioxane and polymer. Is not particularly limited as long as it dissolves and is inactive.

Further, as the photopolymerizable monomer having at least one vinyl group used in the present invention, conventionally known ones can be used, but from the viewpoint of high sensitivity, an acrylate-based monomer can be used. Preference is given to using monomers or methacrylate monomers. For example, trimethylol propane triacrylate, trimethylol propane diacrylate, triethylene glycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, hexamethylene glycol diacrylate, neopentyl glycol diacrylate, tetramethylol methane tetraacrylate, resorcinol diacrylate Acrylate, ethylene glycol pentaerythritol triacrylate, 1,6-hexanediol diacrylate, 2,2-bis (4-acryloxyethoxyphenyl) propane, 2,2-bis (4-methacryloxyethoxyphenyl) propane, dipenta Erythritol pentaacrylate, or methacrylate and methylenebisacryle having the same structure as the above compounds. Amide, polyacrylate or polymethacrylate of polyhydric alcohol such as urethane diacrylate, adduct of trimethylpropane triglycidyl ether with acrylic acid or methacrylic acid, bisphenol A, epichlorohydrin epoxy resin, phthalic anhydride-neopentyl glycol- Examples thereof include low molecular weight unsaturated polyesters such as a 1: 1: 2 condensation product of acrylic acid.

Further, known monofunctional monomers such as (meth) acrylic acid ester monomers are also included. These components can use at least 1 type or more.

Examples of the photopolymerization initiator used in the present invention include benzophenone, 4-methyl-4'-diethylaminobenzophenone, 4-methoxy-4'-diethylaminobenzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (dipropylamino) benzophenone, 4,4'-bis (diisopropylamino) benzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromo Benzophenone, 4,4 '
-Dimethoxybenzophenone, 4,4'-diethoxybenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 4-benzoyl-4'-ethyldiphenylsulfide, 4-benzoyl-4'-propyldiphenylsulfide, 4-benzoyl- 4'-isopropyldiphenyl sulfide and the like can be mentioned. The above-mentioned photopolymerization initiators benzophenone, 4-benzoyl-4′-alkyldiphenyl sulfide compound, 4,4′-dialkylaminobenzophenone compound, 4,4′-dihalogenoaminobenzophenone compound, 4,4 ′ In order to enhance the photopolymerizability of the -dialkoxybenzophenone compound, it is preferable to contain a p- (dialkylamino) benzoic acid alkyl ester. Specifically, for example, p
-(Dimethylamino) benzoic acid methyl ester, p-
(Dimethylamino) benzoic acid ethyl ester, p- (dimethylamino) benzoic acid propyl ester, p- (dimethylamino) benzoic acid isopropyl ester, p- (diethylamino) benzoic acid methyl ester, p- (diethylamino) benzoic acid ethyl ester , P- (diethylamino) benzoic acid propyl ester, p- (diethylamino) benzoic acid isopropyl ester and the like.

Further, substituted or unsubstituted benzoins, benzoin ethers, thioxanthones, polynuclear quinones,
Benzyl and other known photopolymerization initiators may be used. Examples of the polynuclear quinones include 2-methylanthraquinone, 2-ethylanthraquinone, and the like.
-Alkylanthraquinone, 1,4-dimethylanthraquinone, 2,3-dimethylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 3-chloro-2-methylanthraquinone, 1,4-naphthoquinone, 2-methyl-1,4 -Naphthoquinone, 2,3-dichloronaphthoquinone, octamethyl anlaquinone, 9,1
Examples thereof include 0-phenanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone and 7,8,9,10-tetrahydronaphthacenequinone. Examples of the above-mentioned benzoins include benzoin, methylbenzoin, ethylbenzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether. Examples of the above thioxanthones include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-propylthioxanthone, 2-isopropylthioxanthone,
2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and the like can be mentioned. Examples of the above-mentioned benzyls include benzyl, 4-chlorobenzyl, 4-methoxybenzyl, 4-ethylbenzyl, 4- (dimethylamino) benzyl, 4-methylmercaptobenzyl, 4-methoxycarbonylbenzyl, 4-benzylaminobenzyl. , 2-chloro-4'-methoxybenzyl, 4,4'-
Dichlorobenzyl, 4,4'-dibromobenzyl, 4,
4'-dimethylbenzyl, 4,4'-diethylbenzyl, 4,4'-dimethoxybenzyl, 3,3'-dimethoxybenzyl, 4,4'-diethoxybenzyl, 4,
4'-bis (methylmercapto) benzyl, 4,4'-
Bis (methoxycarbonyl) benzyl, 4,4'-diacetoxybenzyl, 4,4'-bis (dimethylamino)
Benzyl, 4,4'-chlorobromobenzyl, 4-methoxy-4'-methylbenzyl, 4-methoxy-4'-chlorobenzyl, 2,4-dimethoxy-2 ', 4'-dimethoxybenzyl, 3,4. 5-trimethoxy-3 ',
4 ', 5'-trimethoxybenzyl, 4,4'-diacetylbenzyl, 4-chloro-3', 4'-dimethoxybenzyl, 4-methoxy-4'-acetoxybenzyl, 2
-Chloro-4-methoxybenzyl, 4- (phenylmercapto) benzyl, 4- (p-methoxyphenylmercapto) benzyl, 4- (p-chlorophenylmercapto) -4'-methoxybenzyl, 4- (phenylmercapto) -4 '-Methoxybenzyl, 4- (phenylmercapto) -4'-methoxy-2'-chlorobenzyl, 4
-(P-Methoxyphenylmercapto) -4'-methoxybenzyl, 4- (p-methoxyphenylmercapto)
-4'-ethoxybenzyl, 4-chloro-4'-phenylmercaptobenzyl, 2-chloro-4 '-(p-methoxyphenylmercapto) benzyl, 4-dimethylamino-4'-(phenylmercapto) benzyl, 4- Benzoyl-4 ′-(phenylmercapto) benzyl, 4-
Methylmercapto-4 ′-(phenylmercapto) benzyl, 4-acetoxy-4 ′-(o-tolylmercapto) benzyl, 4-acetoxy-4 ′-(p-tolylmercapto) benzyl, 2-chloro-4-methoxy- 4 '
Examples include-(phenylmercapto) benzyl, 2,4-dimethoxy-4 '-(phenylmercapto) benzyl, 2-chloro-4-methoxy-4'-(p-methoxyphenylmercapto) benzyl.

Further, as the organic solvent used for the photosensitive resin composition solution (hereinafter abbreviated as photosensitive solution) by dissolving the polymer, the photopolymerization initiator, the photopolymerizable monomer, etc. in a solvent, a ketone solvent is used. , Cellosolve-based solvents, alcohol-based solvents, ether-based solvents and the like. As these solvents,
For example, methyl ethyl ketone, cyclohexanone, methyl cellosolve, ethyl cellosolve, butyl cellosolve,
Methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, ethylene glycol mono-n-hexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tri Ethylene glycol dimethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol mono-n Butyl ether, propylene glycol methyl ether acetate, propylene glycol diacetate, propylene glycol phenyl ether, 3-methyl-3-methoxy - butyl acetate, N
-Methyl-2-pyrrolidone, N-hydroxymethyl-2
-Pyrrolidone, N-hydroxyethyl-2-pyrrolidone, ethyl alcohol, isopropyl alcohol, tetrahydrofuran, dioxane, toluene, xylene, ethyl acetate and the like can be mentioned. At least 1 of these ingredients
More than one species can be used.

Examples of the method of applying the photosensitive liquid used in the present invention include roll coater, spin coater, spray dip, gravure coater, whaler, curtain flow coater, wire bar, air knife coater, and the like, and known methods are used. can do. The support coated with the photosensitive liquid is not particularly limited, but a metal plate such as aluminum, copper, nickel, iron, and chromium, or an alloy sheet containing them as a main component, acrylic resin, polyester, polycarbonate And synthetic resin plates, sheets, glass plates, glass plates with a conductive material, and the like.

Examples of the alkaline developer of the photosensitive solution used in the present invention include aqueous solutions of weakly alkaline compounds such as sodium carbonate, and aqueous solutions of organic amines such as mono-, di-, triethanolamine and the like. If necessary, a mixture of a small amount of water-soluble organic solvent can be used.

[0085]

As a component used in the present invention, (A) a colorant composition in which a colorant is dispersed in a polymer having a pyrrolidonyl group, (B) (1) a saponification degree of 70 mol% or more and an average polymerization degree. The hydrogen atom of the hydroxyl group contained in 500 to 4000 polyvinyl alcohol is replaced with a cyanoethyl group,
A polyvinyl acetal resin obtained by converting a cyanoethyl group into a carboxylethyl group and further introducing an ethylenically unsaturated double bond into the carboxyl group, or 2) a saponification degree of 70 mol% or more and an average degree of polymerization 500
To 4000 polyvinyl acetate acetalized with an aldehyde compound or a ketone compound having a carboxyl group such as glyoxylic acid, and then introducing an ethylenically unsaturated double bond into the carboxyl group, (C ) A photopolymerization initiator, (D) a photosensitizer, if necessary, a photosensitizer for forming a color filter, which comprises a photopolymerizable monomer having at least one ethylenically unsaturated bond and / or a photocrosslinking agent. The resin is a polyvinyl acetal resin with a new ethylenically unsaturated bond that has thermosetting and photocuring properties while having the same heat resistance and coating properties as the polyvinyl acetal resin. As a photosensitive resin, heat resistance,
Mechanical properties of coating film (especially elongation and stiffness), carbon,
Those having excellent dispersibility such as pigments and adhesiveness to the support are extremely useful.

The present invention will be specifically described below with reference to Examples in more detail and comparison with Comparative Examples.

[0087]

【Example】

Example 1 (Synthesis of carboxyethylated polyvinyl acetal resin) Ion-exchanged water 27 in a 500 ml three-necked flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel.
Charge 3g, saponification degree 88%, polymerization degree 1700
50 g of polyvinyl alcohol (1.115 mol of polyvinyl alcohol unit) was dispersed and heated with stirring to obtain a 15% aqueous solution of polyvinyl alcohol. To this aqueous solution, 3.4 g of 35% concentrated hydrochloric acid was added, and 2 g of nonionic surfactant C ₁₀ H ₂₁ C ₆ H ₄ O (CH ₂ CH ₂ O) ₆ H 4.8 g was added.
What was dissolved in 0 g of water was added, and 12.24 g of n-butyraldehyde (0.1700
mol Polyvinyl alcohol unit 20.5 mol 30.5
(mol%) was added dropwise, and precipitation of polyvinyl butyral in the form of white fine particles was deposited. 35% concentrated hydrochloric acid 25.
After adding 4 g and adjusting the pH of the reaction system to 0.5 or less, 25 ° C
The temperature was raised to 45 ° C./hour and the temperature was kept at this temperature for 4 hours for aging. The reaction system was neutralized by adding sodium hydroxide, and the pH was adjusted to 8.5. The aging time was 3 hours in the strongly acidic region at a temperature of 30 ° C. or higher. The obtained resin was washed with water and dried according to a conventional method to obtain a white fine powder. The degree of butyralization at this time was 30%.

50 g of the obtained polyvinyl acetal having a degree of acetalization of 30% (polyvinyl alcohol unit 0.
682 mol) was dispersed in 450 g of 1,4-dioxane and heated with stirring to obtain a 10% solution of polyvinyl acetal. To this, 500 g of a 5% aqueous sodium hydroxide solution was mixed, and to this was added a solution of 5 g (0.094 mol) of acrylonitrile mixed with 350 g of 1,4-dioxane, and the mixture was stirred at 30 ° C. for 6 hours.
After stirring for a period of time, a part of the reaction liquid was extracted and 100
It was dried at ℃ for 1 hour, and a colorless transparent film was obtained. The remaining reaction solution was subsequently stirred at 60 ° C. for 2 hours and at 80 ° C. for 2 hours, and then allowed to cool to room temperature. The reaction solution was added dropwise to a large amount of water and stirred to generate a white precipitate. This is filtered, washed with water,
A carboxyethylated polyvinyl acetal resin was obtained by drying. A part of this precipitate was dissolved in 1,4-dioxane and dried at 100 ° C. for 1 hour to obtain a colorless transparent film.

(Synthesis of Carboxyethylated Polyvinyl Acetal Resin Having Ethylenically Unsaturated Bond) 50 g of carboxyethylated polyvinyl acetal resin was dissolved in methyl ethyl ketone, and glycidyl methacrylate and triethylamine were added and reacted to obtain polyvinyl having a methacroyl group. Acetal resin P-1 was obtained.
The acid value was 60.

(Pigment Dispersion Type Photosensitive Solution PR-I) A photosensitive solution was prepared from the following composition.

1) Polyvinylpyrrolidone (manufactured by GAF,
Product name PVP, K-90) 50% by weight, blue pigment phthalocyanine blue (C.I. pigment) as a colorant
The mixing ratio of blue 15-6, average particle size 0.5 μm) and purple pigment dioxazine violet (CI pigment violet 23, average particle size 0.5 μm) was 9
45% by weight mixed colorant 1: 9, dispersant A-600
(Daiichi Kogyo Seiyaku Co., Ltd.) 5% by weight and a colorant composition comprising a solvent propylene glycol monomethyl ether
26 parts 2) Polyvinyl acetal resin having methacryloyl group P-1 75 parts 3) 4,4'-bis (diethylamino) benzophenone 3 parts Ethyl p-dimethylaminobenzoate 2 parts 4) Trimethylolpropane triacrylate 20 parts N, A photosensitive solution PR-I containing 530 parts of N-dimethylacetamide and 0.1 part of p-methoxyphenol was prepared. The obtained photosensitive solution was applied onto a glass substrate with a spin coater and dried at 30 ° C. to form a film. The film thickness was 2 μm. A UGRA plate control wedge and a Kodak step tablet No. No. 2 was placed, and contact exposure was performed with an ultra high pressure mercury lamp 2KW manufactured by Oak Co., Ltd. with a light amount of 30 mJ / cm ² . After exposure, dip this glass substrate in the developer,
It was developed. The development conditions are a development temperature of 25 ° C. and 20 seconds. The developing solution at this time consists of a solution of triethanolamine 2%, isopropyl alcohol 1%, and water 97%.
The resulting pattern was well cut. The long-term stability of the pigment dispersion in the photosensitive liquid was good. The heat resistance and light resistance were also good.

Examples 2 to 6 (Synthesis of carboxyethylated polyvinyl acetal resin) 8.28 g of n-butyraldehyde (20.6% based on 2 mol of 0.115 mol polyvinyl alcohol unit), 3.3 g of acrylonitrile (0.063 mol) A solution of carboxyethylated polyvinyl acetal resin was obtained in the same manner as in Example 1 except for the above.

The polyvinyl butyral resin obtained had a butyralization degree of 20%.

(Synthesis of Carboxyethylated Polyvinyl Acetal Resin Having Ethylenically Unsaturated Bond) 12 g of 50 g of carboxyethylated polyvinyl acetal resin was used.
By heating at 0 ° C., acid anhydride was performed. This resin was dissolved in methyl ethyl ketone, and glycidyl acrylate and triethylamine were added and reacted to obtain a polyvinyl acetal resin P-2 having a methacroyl group. The acid value was 80.

(Pigment dispersion type photosensitive liquid PR-II) A photosensitive liquid was prepared from the following composition.

1) Polyvinylpyrrolidone (manufactured by GAF,
45% by weight of product name PVP, K-90), a green pigment as a colorant is brominated phthalocyanine green (CI Pigment Green 36, average particle size 0.05 μm) and a yellow pigment is isoindolinone yellow (C Pigment Yellow 139, average particle size 0.5 μm) in a mixing ratio of 91: 9, 50% by weight, and a dispersant A-600.
(Manufactured by Dai-ichi Kogyo Co., Ltd.) Colorant composition consisting of 5% and solvent propylene glycol monomethyl ether 26 parts 2) Methacryloyl group-containing polyvinyl acetal resin PR-2 75 parts 3) Trimethylolpropane triacrylate 20 parts 4) 4 , 4'-Bis (diethylamino) benzophenone 3 parts Ethyl p-dimethylaminobenzoate 2 parts 5) Propylene glycol monomethyl ether acetate 530 parts p-Methoxyphenol 0.1 part A photosensitive solution PR-II was prepared. The obtained photosensitive solution was applied onto a glass substrate with a spin coater and dried at 30 ° C. to form a film. The film thickness was 5 μm. A UGRA plate control wedge and a Kodak step tablet No. No. 2 was placed, and contact exposure was performed with an ultra high pressure mercury lamp 2KW manufactured by Oak Co., Ltd. with a light amount of 30 mJ / cm ² . After exposure, dip this glass substrate in the developer,
It was developed. The development conditions are a development temperature of 25 ° C. and 20 seconds. The developing solution at this time consists of a solution of 2% triethanolamine and 98% water. The resulting pattern was good.

(Pigment Dispersion Type Photosensitive Solution PR-III) A photosensitive solution was prepared from the following composition.

1) Polyvinylpyrrolidone (manufactured by GAF,
Product name PVP, K-90) 45% by weight, red pigment as a colorant is dianthraquinonyl red (CI Pigment Red 177, average particle diameter 0.02 μm) and yellow pigment isoindolinone yellow (C.I. I. Pigment Yellow 139, mixture 50 of average particle size 0.5 μm)
Colorant composition consisting of wt% and dispersant A-600 (manufactured by Dai-ichi Kogyo Co., Ltd.) 5% and solvent propylene glycol monomethyl ether 26 parts 2) Methacryloyl group-containing polyvinyl acetal resin PR-2 75 parts 3) Trimethylol Propane triacrylate 20 parts 4) 4,4'-bis (diethylamino) benzophenone 3 parts Ethyl p-dimethylaminobenzoate 2 parts 5) Propylene glycol monomethyl ether acetate 530 parts p-Methoxyphenol 0.1 part Photosensitive solution PR- Created III. The obtained photosensitive solution was applied onto a glass substrate with a spin coater and dried at 30 ° C. to form a film. The film thickness was 5 μm. UGRA on this coating
The plate control wedge of No. 2 and a step tablet No. 2 manufactured by Kodak Co. for sensitivity measurement were placed, and contact exposure was carried out by a super high pressure mercury lamp 2KW manufactured by Oak Co. at a light amount of 30 mJ / cm ² . After the exposure, the glass substrate was immersed in a developing solution for development. Development conditions are development temperature 25 ° C, 20
Seconds. At this time, the developing solution is triethanolamine 2
%, 98% water. The resulting pattern was good.

(Pigment Dispersion Type Photosensitive Solution PR-IV) A photosensitive solution was prepared from the following composition.

1) Polyvinylpyrrolidone (manufactured by GAF,
Product name PVP, K-90) 45% by weight, carbon black as a black pigment (# 75 manufactured by Mitsubishi Kasei Co., Ltd.)
0B, average particle size 0.018 μm), a dispersant Solsperse 2000 (manufactured by 1C1 Co.) 5%, and a solvent propylene glycol monomethyl ether as a colorant composition 26 parts 2) Methacryloyl group-containing polyvinyl acetal resin PR-2 75 parts 3) trimethylolpropane triacrylate 20 parts 4) 4,4'-bis (diethylamino) benzophenone 3 parts ethyl p-dimethylaminobenzoate 2 parts 5) propylene glycol monomethyl ether acetate 530 parts p-methoxyphenol 0.1 part A photosensitive solution PR-IV was prepared. The obtained photosensitive solution was applied onto a glass substrate with a spin coater and dried at 30 ° C. to form a film. The film thickness was 5 μm. A UGRA plate control wedge and a Kodak step tablet No. No. 2 was placed, and contact exposure was performed with an ultra high pressure mercury lamp 2KW manufactured by Oak Co., Ltd. with a light amount of 30 mJ / cm ² . After exposure, dip this glass substrate in the developer,
It was developed. The development conditions are a development temperature of 25 ° C. and 20 seconds. The developing solution at this time consists of a solution of 2% triethanolamine and 98% water. The resulting pattern was good.

Comparative Example 1 1) Colorant composition dispersed with the same composition as in Example 1 except that polyvinylpyrrolidone was changed to 50 wt% of polyethylene oxide (manufactured by Sumitomo Seika, PEO, average molecular weight 150,000) 26 Parts 2) polyvinyl acetal resin P-1 having a methacryloyl group P-1 75 parts 3) 4,4'-bis (diethylamino) benzophenone 3 parts ethyl p-dimethylaminobenzoate 2 parts 4) trimethylolpropane triacrylate 20 parts 5) propylene A photosensitive solution PR-1 containing 530 parts of glycol monomethyl ether acetate and 0.1 part of p-methoxyphenol was prepared. However, the pigment-dispersed photosensitive liquid caused secondary aggregation, and the pigment separated into the photosensitive liquid.

[0102]

The effects of the present invention are as described above. Colored photosensitive resin for color filters, which is a mixture of a new (meth) acryloyl group-containing polyvinyl acetal-based photosensitive resin solution with a colorant (pigment) dispersed in a polymer having a pyrrolidonyl group, is Dispersed colorants
Dispersed colorant (pigment) only by stirring and dissolving (pigment)
Since there is no secondary aggregation and the dispersion stability is excellent for a long period of time, the manufacturing cost is low. Further, since the colored film is excellent in coating film physical properties and heat resistance, the patterned color filter does not have cracks or breaks, and a high quality color filter can be obtained with good yield. By using a polymer having a pyrrolidonyl group as the dispersion resin, the alkali developing rate is increased, the pattern breaks (resolution) is good, and the processing accuracy of the color filter is excellent. It is extremely useful as a colored photosensitive resin for color filters.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tsutomu Sato 1-1-1 Nishishinjuku, Shinjuku-ku, Tokyo Within Hitachi Chemical Co., Ltd. (72) Takashi Morinaga 1-1-1 Nishishinjuku, Shinjuku-ku, Tokyo No. within Hitachi Chemical Co., Ltd.

Claims (2)

[Claims] 1. A colorant composition in which a colorant is dispersed in a polymer having (A) a pyrrolidonyl group, (B) a polyvinyl acetal resin having a group having an ethylenically unsaturated bond and a carboxyl group, and a compound represented by the general formula: 1) (Chemical formula 2) (Chemical formula 3) [Chemical 2] [Chemical 3] And (Chemical formula 4) Or (Chemical formula 5) (However, in the formula, R ¹ and R ⁴ are a hydrogen atom, an alkyl group, R ²
Is an alkyl group, a cyclic alkyl group, an aryl group or a group having a substituent on each of them, R ³ and R ⁶ are groups having a hydrogen atom and an ethylenically unsaturated double bond, R ⁵ is an alkylene, a cyclic alkylene or an arylene group. is there. ) A polyvinyl acetal resin comprising a structural unit represented by (C) a photopolymerization initiator, (D) optionally and a photosensitizer, and a photopolymerizable monomer having at least one ethylenically unsaturated double bond and / or a photocrosslinking agent. And a photosensitive resin composition for forming a color filter. 2. General formulas (formula 6) (formula 7) (formula 8) [Chemical 7] [Chemical 8] And (Chemical Formula 9) Or (Chemical Formula 10) (However, in the formula, R ¹ and R ⁴ are a hydrogen atom, an alkyl group, R ²
Is an alkyl group, a cyclic alkyl group, an aryl group or a group having a substituent on each of them, R ³ and R ⁶ are groups having a hydrogen atom and an ethylenically unsaturated double bond, R ⁵ is an alkylene, a cyclic alkylene or an arylene group. is there. ), And the structural unit represented by (1) is 0 to 3
0 mol%, the structural unit represented by (2) is 0 to 30 mol%, the structural unit represented by (3) is 30 to 70 mol%,
0 to 20 mol% of the structural unit represented by (4), or 0 to 30 mol% of the structural unit represented by (1), (2)
The constituent unit represented by is 0 to 30 mol%, the constituent unit represented by (3) is 30 to 70 mol%, and the constituent unit represented by (6) is 30 to 70 mol%, and the total is 100 mol. %, The polyvinyl acetal resin according to claim 1.