JP2011236362A - Photosensitive resin, and photosensitive resin composition and colored photosensitive resin composition for color filter containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin which has high exposure sensitivity, ensures good pigment dispersibility, and achieves good developability with an aqueous alkali solution when used in a colored photosensitive resin composition.SOLUTION: The photosensitive resin is obtained by copolymerizing 2-95 mol% of (a) glycidyl (meth)acrylate, 3-50 mol% of (b) at least one selected from the group composed of dicyclopentanyl methacrylate, dicyclopentenyl oxyethyl acrylate, norbornene, etc., and 2-85 mol% of (c) another radically polymerizable compound capable of copolymerizing with the components (a) and (b) in such a way that the total amount becomes 100 mol%; adding (d) an unsaturated monobasic acid to 90-100% of glycidyl groups contained in the resulting copolymer; adding (e) a polybasic acid anhydride to 5-100% of hydroxyl groups formed in the addition of the component (d); and adding (f) a radically polymerizable compound having one glycidyl group and no photosensitive group, such as a phenyl glycidyl ether to 5-70% of carboxyl groups formed in the addition of the component (e).

Description

  The present invention produces a color filter used for an organic EL display capable of color display using a black matrix, a color filter, a photo spacer, a transparent protective film and an organic EL element for manufacturing a liquid crystal display panel, and further, a color filter by inkjet. The present invention relates to a photosensitive resin that can be used as a photosensitive resin material that can be applied.

In recent years, radiation curable resins that can be cured with ultraviolet rays or electron beams have been widely used in the fields of printing, paints, and adhesives from the viewpoint of resource saving and energy saving.
Also in the field of electronic equipment such as printed wiring boards, solder resist is used to protect circuit boards after mounting components for a long period of time. Acid pendant type novolak epoxy acrylate is generally used as a material for printed wiring boards by the photoresist method, but the adhesion to copper plating is not sufficient, and when used for multilayer printed wiring boards, it is a conductor. In addition to the problem that sufficient adhesion strength between the circuits cannot be obtained, there is also a problem that it is easy to break due to poor flexibility.
In order to solve these problems, a method of mixing an inorganic filler into a photosensitive resin composition using a (meth) acrylic copolymer has been proposed (for example, Patent Document 1), but an acid pendant type novolak epoxy is proposed. The subject that heat resistance was inferior to acrylate remained.

  Color filters are used in color liquid crystal display devices and solid-state image sensors, and these are colored colors in which three colors of red (R), green (G), and blue (B) are formed in a predetermined pattern on a substrate. It consists of a coating film and a black black matrix between these three color filters of RGB. Usually, a black matrix is formed on a transparent substrate such as glass, and then R, G, and B patterns are sequentially formed.

In general, color filters include production methods such as dyeing, printing, pigment dispersion, and electrodeposition. Among these, in particular, a photocurable resin composition mainly composed of an alkali-soluble resin, a reactive diluent, a photopolymerization initiator, a pigment and a solvent is used, applied onto a transparent substrate, and exposed, developed, and postcured. The pigment dispersion method produced by the repeated photolithographic method is currently mainstream because it has excellent durability such as light resistance and heat resistance and has few defects such as pinholes.
While the pigment dispersion method has the above-mentioned advantages, the pattern of black matrix, R, G, and B is repeatedly formed, so that high heat resistance is required for the alkali-soluble resin that becomes the binder of the coating film.

Conventionally, as a method for improving heat resistance, a resin composition (for example, Patent Document 2) containing a (meth) acrylic acid ester having a cyclic structure in the side chain as a copolymerization component, or a monomer containing maleimide is used. A resin composition (for example, Patent Document 3), which is a copolymerization component, has been proposed.
However, in the former resin composition with (meth) acrylic acid ester having a cyclic structure in the side chain as a copolymerization component, the side chain is thermally decomposed during post-curing and becomes a volatile component, which contaminates the production line. There was a problem to do. In addition, the resin composition having the latter maleimide-containing monomer as a copolymerization component has a yellow to yellow-brown color caused by nitrogen atoms contained in the molecule, and the transparency of the coating film is improved. make worse. Furthermore, there has been a problem that coloring proceeds during post-curing after heat treatment.

In order to solve the above technical problems, the present applicant has developed a photosensitive resin composition using a resin prepared from a specific monomer having a cyclic structure and a crosslinked structure and a compound such as an unsaturated monobasic acid. (Patent Documents 4 and 5).
However, even such a resin may have insufficient performance as a photosensitive resin.

JP 2006-190848 A JP 2004-240396 A JP 2003-029018 A JP 2008-076860 A JP 2001-089533 A

  The inventors of the present invention have a photosensitive resin that can be used for a color filter and the like and that has further superior performance than the conventional ones, and in particular, has a high exposure sensitivity, good pigment dispersibility, and a colored photosensitive resin composition. It is an object of the present invention to provide a photosensitive resin having good developability with an alkaline aqueous solution.

The present invention provides (a) glycidyl (meth) acrylate, (meth) acrylate having an alicyclic epoxy group and a lactone adduct thereof, and mono- of 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate. (Meth) acrylic acid ester, dicyclopentenyl (meth) acrylate epoxidized product and dicyclopentenyloxyethyl (meth) acrylate epoxidized product, at least one selected from 2 to 95 mol%,
(B) The following group

を有するモノ（メタ）アクリレート、下記基

Mono (meth) acrylate having the following groups

を有するモノ（メタ）アクリレート及び下記一般式（１）

Mono (meth) acrylate having the following general formula (1)

（式中、ｘ及びｙは、それぞれ独立して、水素原子又は直鎖もしくは分岐していてもよい炭素数１〜４の炭化水素基を示し、Ｒ^１及びＲ^２は、それぞれ独立して、水素原子、置換基を有していてもよい炭素数１〜２０の炭化水素基又はカルボキシル基を示し、Ｒ^１及びＲ^２を結ぶ環状構造をとっていてもよい）
で表される化合物からなる群から選択される少なくとも１種３〜５０モル％と、
（ｃ）前記（ａ）及び（ｂ）と共重合し得る他のラジカル重合性化合物２〜８５モル％と
をその合計が１００モル％となる量で共重合させ、得られた共重合物に含まれるグリシジル基の９０〜１００％に（ｄ）不飽和一塩基酸を付加させ、前記（ｄ）を付加させた時に生成した水酸基の５〜１００％に（ｅ）多塩基酸無水物を付加させ、前記（ｅ）を付加させた時に生成したカルボキシル基の５〜７０％に（ｆ）下記一般式（２）

(Wherein x and y each independently represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R ¹ and R ² are each independently A hydrogen atom, a C1-C20 hydrocarbon group which may have a substituent or a carboxyl group, which may have a cyclic structure connecting R ¹ and R ² )
3 to 50 mol% of at least one selected from the group consisting of compounds represented by:
(C) The other radical polymerizable compound that can be copolymerized with (a) and (b) is copolymerized in an amount such that the total is 100 mol%, and the resulting copolymer is obtained. (D) Unsaturated monobasic acid is added to 90 to 100% of the glycidyl group contained, and (e) polybasic acid anhydride is added to 5 to 100% of the hydroxyl group produced when (d) is added. And (f) the following general formula (2): 5 to 70% of the carboxyl group formed when (e) is added

（式中、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７は、それぞれ独立して、水素原子又は置換基を有していてもよい炭素数１〜２０の炭化水素基を示す）
で表される化合物を付加させて得られることを特徴とする感光性樹脂。
本発明において、感光性樹脂の分子量分布（Ｍｗ／Ｍｎ）は６．０以下であることが好ましい。

(Wherein R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent)
A photosensitive resin obtained by adding a compound represented by the formula:
In the present invention, the molecular weight distribution (Mw / Mn) of the photosensitive resin is preferably 6.0 or less.

The present invention is a photosensitive resin composition comprising the photosensitive resin, a photopolymerizable monomer, a photopolymerization initiator, and a solvent.
The present invention also provides a color comprising the photosensitive resin, a photopolymerizable monomer, a photopolymerization initiator, a solvent, and at least one selected from the group consisting of a pigment and a dye. It is the coloring photosensitive resin composition for filters.

  According to the present invention, a photosensitive resin that can be used for a color filter or the like and has further superior performance than conventional ones, in particular, high exposure sensitivity, good pigment dispersibility, and a colored photosensitive resin composition. It is possible to provide a photosensitive resin having good developability with an alkaline aqueous solution.

Hereinafter, the photosensitive resin of the present invention will be described in detail.
The photosensitive resin (A) of the present invention includes (a) glycidyl (meth) acrylate, (meth) acrylate having an alicyclic epoxy group and a lactone adduct thereof, 3,4-epoxycyclohexylmethyl-3 ′, 4 ′. -Epoxycyclohexanecarboxylate mono (meth) acrylic acid ester, dicyclopentenyl (meth) acrylate epoxidation product and dicyclopentenyloxyethyl (meth) acrylate epoxidation product Mol%, and (b) the following group (hereinafter referred to as tricyclodecane skeleton):

を有するモノ（メタ）アクリレート、下記基（以下、ジシクロペンタジエン骨格という）

Mono (meth) acrylate having the following group (hereinafter referred to as dicyclopentadiene skeleton)

を有するモノ（メタ）アクリレート及び下記一般式（１）

Mono (meth) acrylate having the following general formula (1)

（式中、ｘ及びｙは、それぞれ独立して、水素原子又は直鎖もしくは分岐していてもよい炭素数１〜４の炭化水素基を示し、Ｒ^１及びＲ^２は、それぞれ独立して、水素原子、置換基を有していてもよい炭素数１〜２０の炭化水素基又はカルボキシル基を示し、Ｒ^１及びＲ^２を結ぶ環状構造をとっていてもよい）
で表される化合物からなる群から選択される少なくとも１種３〜５０モル％と、（ｃ）前記（ａ）及び（ｂ）と共重合し得る他のラジカル重合性化合物２〜８５モル％とをその合計が１００モル％となる量で共重合させ、得られた共重合物に含まれるグリシジル基の９０〜１００％に（ｄ）不飽和一塩基酸を付加させ、前記（ｄ）を付加させた時に生成した水酸基の５〜１００％に（ｅ）多塩基酸無水物を付加させ、前記（ｅ）を付加させた時に生成したカルボキシル基の５〜７０％に（ｆ）下記一般式（２）

(Wherein x and y each independently represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R ¹ and R ² are each independently A hydrogen atom, a C1-C20 hydrocarbon group which may have a substituent or a carboxyl group, which may have a cyclic structure connecting R ¹ and R ² )
3 to 50 mol% of at least one selected from the group consisting of compounds represented by: (c) 2 to 85 mol% of another radical polymerizable compound that can be copolymerized with the above (a) and (b) Are added in an amount such that the total amount is 100 mol%, (d) an unsaturated monobasic acid is added to 90 to 100% of the glycidyl groups contained in the obtained copolymer, and (d) is added. (E) a polybasic acid anhydride is added to 5 to 100% of the hydroxyl groups formed when the (e) is added, and (f) the following general formula (5) is added to 5 to 70% of the carboxyl groups formed when the (e) is added. 2)

（式中、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７は、それぞれ独立して、水素原子又は置換基を有していてもよい炭素数１〜２０の炭化水素基を示す）
で表される化合物を付加させて得られるものである。

(Wherein R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent)
It is obtained by adding a compound represented by the formula:

  The component (a) used in the present invention is glycidyl (meth) acrylate, (meth) acrylate having an alicyclic epoxy group and its lactone adduct, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxy Radical polymerization having at least one glycidyl group selected from the group consisting of epoxides of mono (meth) acrylic acid esters, dicyclopentenyl (meth) acrylates and epoxidized dicyclopentenyloxyethyl (meth) acrylates It is a sex compound. Specific examples of the (meth) acrylate having an alicyclic epoxy group include, for example, 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer (registered trademark) A200, M100 manufactured by Daicel Chemical Industries, Ltd.), etc. Is mentioned. Said (a) may be used independently and may be used in combination of 2 or more type. Among these, glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate are preferable from the viewpoint of easy availability of raw materials.

The component (b) used in the present invention is selected from the group consisting of a mono (meth) acrylate having a tricyclodecane skeleton, a mono (meth) acrylate having a dicyclopentadiene skeleton, and a compound represented by the general formula (1). At least one kind. Specific examples of mono (meth) acrylates having a tricyclodecane skeleton include trade names FA-513A (dicyclopentanyl acrylate) and trade names FA-513M (dicyclopentanyl methacrylate) manufactured by Hitachi Chemical Co., Ltd. Is mentioned. Specific examples of mono (meth) acrylate having a dicyclopentadiene skeleton include trade name FA-511A (dicyclopentenyl acrylate), trade name FA-512A (dicyclopentenyloxyethyl acrylate) manufactured by Hitachi Chemical Co., Ltd. FA-512M (dicyclopentenyloxyethyl methacrylate) and the like. Specific examples of the compound represented by the general formula (1) include norbornene (bicyclo [2.2.1] hept-2-ene), 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, dicyclopentadiene, tricyclo [5.2.1.0 ^2,6 ] dec-8-ene, tricyclo [5.2.1.0 ^2,6 ] dec-3 -Ene, tricyclo [4.4.0.1 ^2,5 ] undec-3-ene, tricyclo [6.2.1.0 ^1,8 ] undec-9-ene, tricyclo [6.2.1.0 ^1,8 ] undec-4-ene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 . 0 ^1,6 ] dodec-3-ene, 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 . 0 ^1,6 ] dodec-3-ene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,12 ] dodec-3-ene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 . 0 ^1,6 ] dodec-3-ene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadeca-4-ene, pentacyclo [7.4.0.1 ^2,5. 1 ^9,12 . 0 ^8,13] pentadeca-3-ene, 5-norbornene-2-carboxylic acid, 5-norbornene-2,3-dicarboxylic acid and 5-norbornene-2,3-dicarboxylic acid anhydride. The above-mentioned compounds may be used alone or in combination of two or more. Among these, norbornene, dicyclopentadiene, and 5-norbornene-2,3-dicarboxylic acid anhydride are preferable from the viewpoint of heat resistance, adhesion, and development characteristics.

  The component (c) used in the present invention is not particularly limited as long as it is a radically polymerizable compound having an ethylenically unsaturated group that can be copolymerized with (a) and (b). Specific examples thereof include dienes such as butadiene, 2,3-dimethylbutadiene, isoprene, and chloroprene; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and iso-propyl (meth) acrylate. , N-butyl (meth) acrylate, sec-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) relate, lauryl (meth) acrylate, dodecyl (meth) ) Acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (acrylate, neopentyl (meth) acrylate, benzyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (Meth) acrylate, 2-ethylhexyl (meth) acrylate, ethylcyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, Rosin (meth) acrylate, norbornyl (meth) acrylate, 5-methylnorbornyl (meth) acrylate, 5-ethylnorbornyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, piperonyl (meth) Acrylate, salicyl (meth) acrylate, furyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofuryl (meth) acrylate, pyranyl (meth) acrylate Phenethyl (meth) acrylate, cresyl (meth) acrylate, 1,1,1-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro -Iso-propyl (meth) acrylate, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- Such as hydroxypropyl (meth) acrylate, glyceryl mono (meth) acrylate, butanetriol mono (meth) acrylate, pentanetriol mono (meth) acrylate, naphthalene (meth) acrylate, anthracene (meth) acrylate ( (Meth) acrylic acid esters; (meth) acrylic acid amide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N-dipropylamide, (Meth) acrylic acid amides such as (meth) acrylic acid N, N-di-iso-propylamide, (meth) acrylic acid anthracenyl amide; (meth) acrylic acid anilide, (meth) acryloylnitrile, acrolein, chloride Vinyl compounds such as vinyl, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine, vinyl acetate; styrene, α-, o-, m-, p-alkyl, nitro, cyano, amide of styrene Derivatives: such as diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itaconate The sum dicarboxylic acid diester; N- phenylmaleimide, N- cyclohexyl maleimide, N- lauryl maleimide, N- (4-hydroxyphenyl) monomaleimide such as maleimide; N- (meth) acryloyl phthalimide, and the like. The above-mentioned compounds may be used alone or in combination of two or more. Among these, benzyl (meth) acrylate, vinyl toluene and monomaleimides are preferable from the viewpoint of adhesion and heat resistance of the cured coating film, and vinyl toluene is most preferable.

  Specific examples of the component (d) used in the present invention include (meth) acrylic acid, crotonic acid, cinnamic acid, a polyfunctional (meth) acrylate having one hydroxyl group and one or more (meth) acryloyl groups (for example, , Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, etc.) and a polybasic acid anhydride. The above-mentioned compounds may be used alone or in combination of two or more. Among these, (meth) acrylic acid is preferable.

  Specific examples of the component (e) used in the present invention include succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride. Examples include acid, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. The above-mentioned compounds may be used alone or in combination of two or more. Among these, tetrahydrophthalic anhydride and succinic anhydride are preferable.

  The component (f) used in the present invention is a compound represented by the above general formula (2). Specific examples thereof include o, m, p-sec-butylphenyl glycidyl ether, o, m, p-tert-butylphenyl glycidyl ether, o, m, p-methylphenyl glycidyl ether, phenyl glycidyl ether, o, m. , P-nonylphenyl glycidyl ether, o, m, p-octylphenyl glycidyl ether, and the like. The above-mentioned compounds may be used alone or in combination of two or more.

  In order to obtain the photosensitive resin (A) of the present invention, first, a copolymer comprising the component (a), the component (b), and the component (c) is prepared. The copolymerization ratio is (a) component 2 to 95 mol%, preferably 20 to 80 mol%, (b) component 3 to 50 mol%, preferably 10 to 45 mol%, and (c) component 2 to 85 mol%. , Preferably 3 to 50 mol%. The addition amount of the (d) component mentioned later is determined by the copolymerization ratio of the (a) component. When the component (a) is 2 mol% or more, a decrease in the amount of double bonds is suppressed, and when it is 95 mol% or less, an increase in molecular weight when the component (d) is added can be suppressed.

  Next, the amount of the component (d) added to the copolymer comprising the component (a), the component (b) and the component (c) is 90 to 100 with respect to the glycidyl group contained in the obtained copolymer. %, Preferably 95 to 100%. If the addition amount of the component (d) is less than 90%, due to the influence of the remaining glycidyl group, it tends to cause high molecular weight or gelation when the component (d) is added, and if it exceeds 100%, the unreacted component (d) This is undesirable because it increases the amount of outgassing during post-baking.

  The amount of component (e) added is 5 to 100%, preferably 10 to 90%, and most preferably 15 to 80%, based on the hydroxyl group formed when component (d) is added. Moreover, the addition amount of (f) component is 5-70% with respect to the carboxyl group produced | generated when (e) component was added, Preferably it is 10-50%, Most preferably, it is 15-40%. By setting the addition amount of the component (e) and the component (f) within the above range, the acid value (JIS K6901) of the photosensitive resin (A) can be controlled to a preferable range of 20 to 180 KOHmg / g. In addition, the acid value of the photosensitive resin (A) in the present invention is the number of mg of potassium hydroxide necessary for neutralizing 1 g of the photosensitive resin, and is described in the acid value of JIS K6901: 1999, 5.3. It is measured according to the method.

  The weight average molecular weight of the photosensitive resin (A) of the present invention is 3,000 to 50,000, preferably 5,000 to 30,000 in terms of polystyrene. When the weight average molecular weight is 3,000 or more, a decrease in heat resistance can be prevented, and when the weight average molecular weight is 50,000 or less, a decrease in developability can be prevented. Furthermore, the development speed is adjusted by setting the molecular weight distribution (Mw / Mn) of the photosensitive resin (A) of the present invention to a range of preferably 1.0 to 6.0, most preferably 1.0 to 5.5. In addition, the linearity of the pattern can be improved, and the development residue is hardly left.

In addition, the value of the molecular weight of the photosensitive resin (A) in this invention is measured on the following conditions using gel permeation chromatography (GPC), and is calculated in polystyrene conversion. The weight average molecular weight and molecular weight distribution are calculated with the calculation range from the rise time of GPC to 21 minutes.
Column: Shodex LF-804 + LF-804
Column temperature: 40 ° C
Developing solvent: Tetrahydrofuran Detector: Differential refractometer (Shodex RI-101)
Flow rate: 1 mL / min

The radical copolymerization reaction for obtaining the photosensitive resin (A) is not particularly limited, and a conventional radical polymerization method conventionally performed can be applied.
For example, it has a glycol ether solvent such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate (sometimes abbreviated as PGMAc), a hydrocarbon group such as toluene and xylene, and a functional group such as ethyl acetate. In a non-organic solvent, the components (a), (b) and (c) are dissolved in a desired ratio to obtain azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, t-butyl per A polymerization initiator such as oxy-2-ethylhexanoate is mixed and polymerized in a reflux state at about 50 to 130 ° C. for about 1 to 20 hours, whereby (a) component, (b) component and (c An organic solvent solution of a copolymer consisting of the above component) is obtained. The amount of the polymerization initiator used is usually about 0.5 to 20 parts by mass, preferably 1.0 to 15 parts per 100 parts by mass of the total amount of the components (a), (b) and (c). Part by mass.
Bulk polymerization may be performed using only the component (a), the component (b), the component (c) and the polymerization initiator without using an organic solvent.

The amount of the organic solvent used is usually about 30 to 1,000 parts by mass, preferably 50 to 800 parts by mass with respect to 100 parts by mass of the total amount of the components (a), (b) and (c). is there. By making the usage-amount of an organic solvent into 30 mass parts or more, abnormal polymerization reaction can be prevented, stable polymerization reaction can be advanced, and resin can be prevented from being colored or gelled. On the other hand, when the amount of the organic solvent used is 1000 parts by mass or less, the molecular weight of the copolymer is prevented from being lowered by the chain transfer action, and the solid content concentration of the finally obtained photosensitive resin is in an appropriate range. Can be controlled.
The photosensitive resin of the present invention is a photosensitive resin composition in which a photopolymerizable monomer, a photopolymerization initiator and a solvent described later are mixed, and is mainly used as an electronic material such as a resist. Therefore, when manufacturing the photosensitive resin (A) by radical copolymerization as described above, a glycol ester solvent such as propylene glycol monomethyl ether acetate is preferably used.

  A photosensitive resin composition is obtained by adding the photopolymerizable monomer (B), the photopolymerization initiator (C), and the solvent (D) to the photosensitive resin (A) obtained as described above. . Moreover, it can also be set as the colored photosensitive resin composition for color filters by adding at least 1 sort (s) selected from the group which consists of a pigment and dye to this photosensitive resin composition.

The photopolymerizable monomer (B) that can be used in the present invention is not particularly limited as long as it can react with the photosensitive resin. Specific examples thereof include aromatic vinyl monomers such as styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, divinylbenzene, diallylphthalate, and diallylbenzenephosphonate; polycarboxylic acids such as vinyl acetate and vinyl adipate Monomers: methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, β-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, ethylene glycol di (meth) acrylate , Diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylo (Meth) acrylic monomers such as tripropane (tri) methacrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris (hydroxyethyl) isocyanurate tri (meth) acrylate, triallyl cyanurate, etc. Is mentioned. The above-mentioned compounds may be used alone or in combination of two or more.
The addition amount of a photopolymerizable monomer (B) is 10-200 mass parts normally with respect to 100 mass parts of photosensitive resins, Preferably it is 20-150 mass parts. By setting it as the said range, photocurability can be maintained in an appropriate range, and a viscosity can also be adjusted.

When the photosensitive resin composition of the present invention is photocured using an active energy ray such as ultraviolet rays, a photopolymerization initiator (C) is added to the photosensitive resin composition. Specific examples of the photopolymerization initiator (C) include benzoin such as benzoin, benzoin methyl ether and benzoin ethyl ether and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone Acetophenones such as 4- (1-t-butyldioxy-1-methylethyl) acetophenone; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone; 2,4 -Thioxanthones such as dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; Ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; Benzophenone, 4- (1-t-butyl) Benzophenones such as rudioxy-1-methylethyl) benzophenone and 3,3 ′, 4,4′-tetrakis (t-butyldioxycarbonyl) benzophenone; 2-methyl-1- [4- (methylthio) phenyl] -2 -Morpholino-propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1; acylphosphine oxides and xanthones. The above-mentioned compounds may be used alone or in combination of two or more.
The addition amount of the photopolymerization initiator (C) is usually 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass, and most preferably with respect to 100 parts by mass of the solid content in the photosensitive resin composition. Is 1 to 10 parts by mass. By setting it in the above range, the photocurability can be maintained in an appropriate range.

The solvent (D) that can be used in the present invention can be used without limitation as long as it is an inert solvent that does not react with the photosensitive resin (A) and the photopolymerizable monomer (B). Specific examples thereof include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, isopropyl acetate, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, Examples include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monoethyl ether acetate, and diethylene glycol ethyl ether acetate. The above-mentioned compounds may be used alone or in combination of two or more. Among these, propylene glycol monomethyl ether acetate preferably used in the radical polymerization reaction is preferable.
The addition amount of the solvent (D) is usually 30 to 1000 parts by mass, preferably 50 to 800 parts by mass with respect to 100 parts by mass of the photosensitive resin (A). By setting it as the said range, a viscosity can be kept moderate.

Specific examples of the pigment (E) include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214; I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; I. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265; C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; I. Violet pigments such as C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38; I. Green pigments such as CI Pigment Green 7 and 36; I. C.I. Brown pigments such as CI Pigment Brown 23 and 25; I. And black pigments such as CI pigment blacks 1 and 7, carbon black, titanium black, and iron oxide. These pigments are used singly or in combination of two or more depending on the color of the target pixel.
In order to improve the dispersibility of the pigment, a known dispersant may be added to the colored photosensitive resin composition. As the dispersant, a polymer dispersant is preferable from the viewpoint of excellent dispersion stability over time. Examples of the polymer dispersant include a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene glycol diester dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified ester. And the like, and the like. Specific examples of such a dispersant are trade names of EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbyk (manufactured by BYK Chemie), Disparon (manufactured by Enomoto Kasei Co., Ltd.), and SOLPERSE (manufactured by GENECA). Etc.

  As the dye (F), an acid dye having an acid group such as a carboxylic acid, an acid dye having solubility in an organic solvent or an alkali developer, interaction with other components in the photosensitive resin composition, heat resistance, etc. A salt with a nitrogen compound, a sulfonamide of an acidic dye, or the like is used. Specific examples of dyes that can be used include acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; acid chroma violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56,63,74,95; acid red1,4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,69,73 , 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 13 , 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; acid violet 6B, 7, 9, 17 , 19; acid yellow 1,3,9,11,17,23,25,29,34,36,42,54,72,73,76,79,98,99,111,112,114,116; food yellow3 And derivatives thereof. Among these, azo, xanthene, anthraquinone or phthalocyanine acid dyes are preferable. These dyes are used alone or in combination of two or more according to the color of the target pixel.

  Furthermore, a known antifoaming agent, coupling agent, leveling agent and the like can be added to the photosensitive resin composition of the present invention or the colored photosensitive resin composition for a color filter, if necessary.

  The photosensitive resin composition of the present invention or the colored photosensitive resin composition for a color filter is applied, for example, on a printed wiring board by a screen printing method, a roll coater method, a curtain coater method, a spray coater method, a spin coat method, or the like. After the necessary portion is photocured, development is performed by washing away the uncured (unexposed) portion with an alkaline aqueous solution.

  As an aqueous alkali solution used for development, an aqueous solution of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide or the like, or an amine type, an aminophenol type compound is also useful, but a p-phenylenediamine type compound is preferably used. Representative examples thereof include 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N- Examples include ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, and aqueous solutions of these sulfates, hydrochlorides or p-toluenesulfonates. It is done.

  As a light source used for curing the coated surface by light irradiation, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metahalide lamp, or the like is used.

  The photosensitive resin composition of the present invention and the colored photosensitive resin composition for a color filter have high exposure sensitivity and good developability with an alkaline aqueous solution, and the cured coating film after development has electrical characteristics and mechanical characteristics. Excellent in heat resistance, chemical resistance, etc., solder resist for printed wiring board manufacture, electroless plating resist, build-up method printed wiring board insulation layer or wide range printing plate, for liquid crystal display materials, for plasma display, organic It is extremely useful as a photosensitive material for EL displays.

  Furthermore, since thermosetting is also possible by blending a known epoxy resin and a curing accelerator in the photosensitive resin composition of the present invention or the colored photosensitive resin composition for a color filter, a thermosetting inkjet method. It is also applicable to.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to these.

(Synthesis Example 1)
In a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 323.5 parts by mass of propylene glycol monomethyl ether acetate was added, stirred while replacing with nitrogen, and heated to 120 ° C. Next, a monomer mixture composed of 6.6 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.), 77.3 parts by mass of 2-ethylhexyl acrylate, and 78.1 parts by mass of glycidyl methacrylate. 19.4 parts by mass of t-butyl peroxy-2-ethylhexanoate (Nippon Co., Ltd., Perbutyl (registered trademark) O) was added. This was added to the flask from the dropping funnel over 2 hours and further stirred at 120 ° C. for 2 hours to obtain a copolymer solution.
Next, the inside of the flask was replaced with air, and 38.4 parts by mass of acrylic acid, 0.8 part by mass of triphenylphosphine, and 0.2 part by mass of methylhydroquinone were charged into the solution of the above copolymer, at 120 ° C. The reaction was continued, and the reaction was terminated when the acid value of the solid content reached 0.8 KOH mg / g. Next, 24.0 parts by mass of succinic anhydride was added and reacted at 115 ° C. for 2 hours, and further 15.0 parts by mass of phenylglycidyl ether was added and reacted at 120 ° C. for 1 hour to obtain a solid content acid value of 45 A photosensitive resin solution having a resin solid content of 38.0% by mass was obtained. Table 1 shows the blending ratio of the monomers used, and the weight average molecular weight, number average molecular weight, and molecular weight distribution of the obtained photosensitive resin.

(Synthesis Example 2)
Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas introduction tube, 349.3 parts by mass of propylene glycol monomethyl ether acetate was added, stirred while replacing with nitrogen, and heated to 120 ° C. Next, t- was added to a monomer mixture comprising 66.0 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.), 11.8 parts by mass of vinyltoluene and 85.2 parts by mass of glycidyl methacrylate. 19.6 parts by mass of butyl peroxy-2-ethylhexanoate (Nippon Co., Ltd., Perbutyl (registered trademark) O) was added. This was added to the flask from the dropping funnel over 2 hours and further stirred at 120 ° C. for 2 hours to obtain a copolymer solution.
Next, the inside of the flask was replaced with air, and 41.9 parts by mass of acrylic acid, 0.8 part by mass of triphenylphosphine, and 0.2 part by mass of methylhydroquinone were charged into the solution of the above copolymer, at 120 ° C. The reaction was continued, and the reaction was terminated when the acid value of the solid content reached 0.8 KOH mg / g. Next, 40.0 parts by mass of succinic anhydride was added and reacted at 115 ° C. for 2 hours. Further, 15.0 parts by mass of phenylglycidyl ether was added and reacted at 120 ° C. for 1 hour to obtain an acid value of 65 A photosensitive resin solution having a resin solid content of 38.1% by mass was obtained. Table 1 shows the blending ratio of the monomers used, and the weight average molecular weight, number average molecular weight, and molecular weight distribution of the obtained photosensitive resin.

(Synthesis Example 3)
Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 359.1 parts by mass of propylene glycol monomethyl ether acetate was added and stirred while replacing with nitrogen, and the temperature was raised to 120 ° C. Next, to a monomer mixture composed of 6.6 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.), 25.6 parts by mass of n-butyl acrylate, and 109.3 parts by mass of glycidyl methacrylate. 17.0 parts by mass of t-butyl peroxy-2-ethylhexanoate (Nippon Co., Ltd., Perbutyl (registered trademark) O) was added. This was added to the flask from the dropping funnel over 2 hours and further stirred at 120 ° C. for 2 hours to obtain a copolymer solution.
Next, the inside of the flask was replaced with air, and 53.8 parts by mass of acrylic acid, 0.8 parts by mass of triphenylphosphine, and 0.2 parts by mass of methylhydroquinone were charged into the solution of the above copolymer, and at 120 ° C. The reaction was continued, and the reaction was terminated when the acid value of the solid content reached 0.8 KOH mg / g. Next, 60.0 parts by mass of succinic anhydride was added and reacted at 115 ° C. for 2 hours, and further 15.0 parts by mass of phenyl glycidyl ether was added and reacted at 120 ° C. for 1 hour to obtain an acid value of 101 A photosensitive resin solution having a resin solid content of 38.5% by mass was obtained. Table 1 shows the blending ratio of the monomers used, and the weight average molecular weight, number average molecular weight, and molecular weight distribution of the obtained photosensitive resin.

(Synthesis Example 4)
Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 359.1 parts by mass of propylene glycol monomethyl ether acetate was added, stirred while replacing with nitrogen, and heated to 90 ° C. Next, 19.0 parts by mass of azobisisobutyronitrile was added to a monomer mixture composed of 2.8 parts by mass of norbornene, 77.3 parts by mass of 2-ethylhexyl acrylate, and 78.1 parts by mass of glycidyl methacrylate. This was added to the flask from the dropping funnel over 2 hours and further stirred at 120 ° C. for 2 hours to obtain a copolymer solution.
Next, the inside of the flask was replaced with air, and 38.4 parts by mass of acrylic acid, 0.8 part by mass of triphenylphosphine, and 0.2 part by mass of methylhydroquinone were charged into the solution of the above copolymer, at 120 ° C. The reaction was continued, and the reaction was terminated when the acid value of the solid content reached 0.8 KOH mg / g. Next, 45.6 parts by mass of tetrahydrophthalic anhydride was added and reacted at 115 ° C. for 2 hours. Further, 15.0 parts by mass of phenylglycidyl ether was added and reacted at 120 ° C. for 1 hour to obtain a solid content acid value. A photosensitive resin solution having 40.5 KOH mg / g and a resin solid content of 38.5% by mass was obtained. Table 1 shows the blending ratio of the monomers used, and the weight average molecular weight, number average molecular weight, and molecular weight distribution of the obtained photosensitive resin.

(Synthesis Example 5)
Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 324.3 parts by mass of propylene glycol monomethyl ether acetate was added, stirred while being purged with nitrogen, and heated to 90 ° C. Next, 32.5 parts by mass of azobisisobutyronitrile was added to a monomer mixture consisting of 9.4 parts by mass of norbornene, 35.4 parts by mass of vinyltoluene and 85.2 parts by mass of glycidyl methacrylate. This was added to the flask from the dropping funnel over 2 hours and further stirred at 120 ° C. for 2 hours to obtain a copolymer solution.
Next, the inside of the flask was replaced with air, and 41.9 parts by mass of acrylic acid, 0.8 part by mass of triphenylphosphine, and 0.2 part by mass of methylhydroquinone were charged into the solution of the above copolymer, at 120 ° C. The reaction was continued, and the reaction was terminated when the acid value of the solid content reached 0.8 KOH mg / g. Next, 40.0 parts by mass of succinic anhydride was added and reacted at 115 ° C. for 2 hours. Further, 15.0 parts by mass of phenylglycidyl ether was added and reacted at 120 ° C. for 1 hour, whereby the solid content acid value was 70. A photosensitive resin solution having a resin solid content of 38.4% by mass was obtained. Table 1 shows the blending ratio of the monomers used, and the weight average molecular weight, number average molecular weight, and molecular weight distribution of the obtained photosensitive resin.

(Synthesis Example 6)
To a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 382.1 parts by mass of propylene glycol monomethyl ether acetate was added, stirred while being purged with nitrogen, and heated to 90 ° C. Next, 32.4 parts by mass of azobisisobutyronitrile was added to a monomer mixture consisting of 6.6 parts by mass of norbornene, 25.6 parts by mass of n-butyl acrylate and 109.3 parts by mass of glycidyl methacrylate. This was added to the flask from the dropping funnel over 2 hours and further stirred at 120 ° C. for 2 hours to obtain a copolymer solution.
Next, the inside of the flask was replaced with air, and 53.4 parts by mass of acrylic acid, 0.8 parts by mass of triphenylphosphine, and 0.2 parts by mass of methylhydroquinone were charged into the solution of the above copolymer, and at 120 ° C. The reaction was continued, and the reaction was terminated when the acid value of the solid content reached 0.8 KOH mg / g. Next, 60.0 parts by mass of succinic anhydride was added and reacted at 115 ° C. for 2 hours. Further, 15.0 parts by mass of phenyl glycidyl ether was added and reacted at 120 ° C. for 1 hour, whereby a solid content acid value of 95 A photosensitive resin solution having a resin solid content of 38.6% by mass was obtained at 0.0 KOH mg / g. Table 1 shows the blending ratio of the monomers used, and the weight average molecular weight, number average molecular weight, and molecular weight distribution of the obtained photosensitive resin.

(Synthesis Example 7)
In a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 370.9 parts by mass of propylene glycol monomethyl ether acetate was added, stirred while replacing with nitrogen, and heated to 90 ° C. Next, 32.4 parts by mass of azobisisobutyronitrile was added to a monomer mixture consisting of 6.6 parts by mass of norbornene, 25.6 parts by mass of n-butyl acrylate and 109.3 parts by mass of glycidyl methacrylate. This was added to the flask from the dropping funnel over 2 hours and further stirred at 120 ° C. for 2 hours to obtain a copolymer solution.
Next, the inside of the flask was replaced with air, and 53.4 parts by mass of acrylic acid, 0.8 parts by mass of triphenylphosphine, and 0.2 parts by mass of methylhydroquinone were charged into the solution of the above copolymer, and at 120 ° C. The reaction was continued, and the reaction was terminated when the acid value of the solid content reached 0.8 KOH mg / g. Next, 60.0 parts by mass of succinic anhydride was added and reacted at 115 ° C. for 2 hours. Further, 6.0 parts by mass of phenyl glycidyl ether was added and reacted at 120 ° C. for 1 hour to obtain a solid content acid value of 110. A photosensitive resin solution having a resin solid content of 38.0% by mass was obtained. Table 1 shows the blending ratio of the monomers used, and the weight average molecular weight, number average molecular weight, and molecular weight distribution of the obtained photosensitive resin.

(Comparative Synthesis Example 1)
Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 296.7 parts by mass of propylene glycol monomethyl ether acetate was added, stirred while replacing with nitrogen, and heated to 120 ° C. Next, a monomer mixture composed of 6.6 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.), 77.3 parts by mass of 2-ethylhexyl acrylate, and 78.1 parts by mass of glycidyl methacrylate. 13.0 parts by mass of t-butylperoxy-2-ethylhexanoate (Nippon Co., Ltd., Perbutyl (registered trademark) O) was added. This was added to the flask from the dropping funnel over 2 hours and further stirred at 120 ° C. for 2 hours to obtain a copolymer solution.
Next, the inside of the flask was replaced with air, and 38.4 parts by mass of acrylic acid, 0.8 part by mass of triphenylphosphine, and 0.2 part by mass of methylhydroquinone were charged into the solution of the above copolymer, at 120 ° C. The reaction was continued, and the reaction was terminated when the acid value of the solid content reached 0.8 KOH mg / g. Next, 24.0 parts by mass of succinic anhydride was added and reacted at 115 ° C. for 2 hours to obtain a photosensitive resin solution having a solid content acid value of 61.1 KOH mg / g and a resin solid content of 37.9% by mass. . Table 1 shows the blending ratio of the monomers used, and the weight average molecular weight, number average molecular weight, and molecular weight distribution of the obtained photosensitive resin.

(Comparative Synthesis Example 2)
Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 386.8 parts by mass of propylene glycol monomethyl ether acetate was added, stirred while replacing with nitrogen, and heated to 120 ° C. Next, t- was added to a monomer mixture comprising 66.0 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.), 11.8 parts by mass of vinyltoluene and 85.2 parts by mass of glycidyl methacrylate. 19.6 parts by mass of butyl peroxy-2-ethylhexanoate (Nippon Co., Ltd., Perbutyl (registered trademark) O) was added. This was added to the flask from the dropping funnel over 2 hours and further stirred at 120 ° C. for 2 hours to obtain a copolymer solution.
Next, the inside of the flask was replaced with air, and 41.9 parts by mass of acrylic acid, 0.8 part by mass of triphenylphosphine, and 0.2 part by mass of methylhydroquinone were charged into the solution of the above copolymer, at 120 ° C. The reaction was continued, and the reaction was terminated when the acid value of the solid content reached 0.8 KOH mg / g. Next, 40.0 parts by mass of succinic anhydride was added and reacted at 115 ° C. for 2 hours. Further, 45.0 parts by mass of phenyl glycidyl ether was added and reacted at 120 ° C. for 1 hour to obtain a solid content acid value of 21 A photosensitive resin solution having a resin solid content of 39.1% by mass of 0.6 KOH mg / g was obtained. Table 1 shows the blending ratio of the monomers used, and the weight average molecular weight, number average molecular weight, and molecular weight distribution of the obtained photosensitive resin.

(Comparative Synthesis Example 3)
To a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 363.9 parts by mass of propylene glycol monomethyl ether acetate was added, stirred while replacing with nitrogen, and heated to 90 ° C. Next, 30.3 parts by mass of azobisisobutyronitrile was added to a monomer mixture consisting of 77.3 parts by mass of 2-ethylhexyl acrylate and 82.4 parts by mass of glycidyl methacrylate. This was added to the flask from the dropping funnel over 2 hours and further stirred at 120 ° C. for 2 hours to obtain a copolymer solution.
Next, the inside of the flask was replaced with air, and 40.5 parts by mass of acrylic acid, 0.8 parts by mass of triphenylphosphine, and 0.2 parts by mass of methylhydroquinone were put into the solution of the above copolymer, and at 120 ° C. The reaction was continued, and the reaction was terminated when the acid value of the solid content reached 0.8 KOH mg / g. Next, 45.6 parts by mass of tetrahydrophthalic anhydride was added and reacted at 115 ° C. for 2 hours. Further, 15.0 parts by mass of phenylglycidyl ether was added and reacted at 120 ° C. for 1 hour to obtain a solid content acid value. A photosensitive resin solution having 55.8 KOH mg / g and a resin solid content of 38.5% by mass was obtained. Table 1 shows the blending ratio of the monomers used, and the weight average molecular weight, number average molecular weight, and molecular weight distribution of the obtained photosensitive resin.

(Comparative Synthesis Example 4)
To a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 340.3 parts by mass of propylene glycol monomethyl ether acetate was added, stirred while replacing with nitrogen, and heated to 90 ° C. Next, 30.0 parts by mass of azobisisobutyronitrile was added to a monomer mixture consisting of 2.8 parts by mass of norbornene, 77.3 parts by mass of 2-ethylhexyl acrylate, and 78.1 parts by mass of glycidyl methacrylate. This was added to the flask from the dropping funnel over 2 hours and further stirred at 120 ° C. for 2 hours to obtain a copolymer solution.
Next, the inside of the flask was replaced with air, and 38.4 parts by mass of acrylic acid, 0.8 part by mass of triphenylphosphine, and 0.2 part by mass of methylhydroquinone were charged into the solution of the above copolymer, at 120 ° C. The reaction was continued, and the reaction was terminated when the acid value of the solid content reached 0.8 KOH mg / g. Next, 45.6 parts by mass of tetrahydrophthalic anhydride was added and reacted at 115 ° C. for 2 hours to obtain a photosensitive resin solution having a solid content acid value of 66.6 KOHmg / g and a resin solid content of 37.8% by mass. It was. Table 1 shows the blending ratio of the monomers used, and the weight average molecular weight, number average molecular weight, and molecular weight distribution of the obtained photosensitive resin.

[Examples 1-14 and Comparative Examples 1-8]
Each component shown below was mix | blended using resin obtained from the synthesis examples 1-7 and the comparative synthesis examples 1-4, and various photocurable resin compositions (transparent resist and color resist) were obtained.

<Production of transparent resist cured coating film>
Resin composition prepared by adding 30 parts by weight of pentaerythritol tetraacrylate and 4 parts by weight of 2,2-dimethoxy-2-phenylacetophenone as a photopolymerization initiator to 100 parts by weight of the solid content of each photosensitive resin solution Is applied to a glass substrate with an applicator at a thickness of 10 μm when wet, and low boiling point substances are volatilized in a hot air dryer at 100 ° C., and then an ultra high pressure mercury lamp manufactured by Oak Manufacturing Co., Ltd. is used as necessary. After exposure at 50 mJ / cm ² through a mask to obtain a cured coating film having a thickness of 2 μm, alkali development was performed.

(1) Evaluation of adhesion The cross-cut test was performed on the cured coating film according to JIS K5400, and the peeling state of 100 cross-cuts was visually observed and evaluated according to the following criteria. The results are shown in Table 2.
○: No separation was observed.
Δ: Peeling is observed in less than 10% of the whole.
X: Exfoliation is recognized in 10% or more of the whole.

<Preparation of color resist (pigment type)>
(Preparation of green pigment dispersion)
In a SUS container filled with 180 parts by mass of zirconia beads having a diameter of 0.5 mm, C.I. 10.00 parts by mass of I Pigment Green 36, 33.75 parts by mass of solvent (PGMAc), and 6.25 parts by mass of a dispersant (Bicchemy Japan Co., Ltd. Disperbyk-161) are added and dispersed for 3 hours with a paint shaker. Thus, a green pigment dispersion was obtained.

  Using the green pigment dispersion obtained above, a color resist (pigment type) was prepared at a blending ratio shown in Table 3 below.

<Preparation of color resist (dye type)>
A color resist (dye type) was prepared using the dye “Acid Green 3” at a blending ratio shown in Table 4 below.

<Preparation of color resist cured coating>
A color resist was spin-coated on a 5 cm square glass substrate (non-alkali glass) so as to have a film thickness of 2.2 μm when dried, prebaked at 80 ° C. for 3 minutes, and a photomask was placed at a distance of 100 μm from the coating film. The exposure was performed at 150 mJ / cm ² . Next, spray development was performed with a 0.1% by mass aqueous sodium carbonate solution at a water pressure of 0.3 MPa, and then post-baking was performed at 230 ° C. for 30 minutes to obtain a cured color resist coating film.

(2) Evaluation of alkali developability The cured coating film exposed through a mask was spray-developed at 23 ° C. using a 0.1% by mass aqueous sodium carbonate solution, and the time when the pattern was completely visible and the presence or absence of a residue after development. Was visually evaluated. The results are shown in Tables 5 and 6.

(3) Development mode In the development process of the negative resist, the unexposed portion of the resist layer that has not been cured is dissolved by the alkali developer and is released from the substrate. There are a peeling type in which the part is peeled off mainly as a large lump, and a dissolving type in which the dye is gradually dissolved and diffused so as to dissolve in water. The former peeling type is a development mode that is not preferred because the solid-liquid mass remains in the system as a foreign substance and easily contaminates the pixels of other colors, and the latter dissolution type is a development type that the latter is desired. . The results are shown in Tables 5 and 6.
×: Peeling type ○: Dissolving type

(4) Evaluation of sensitivity The cured coating film exposed through the mask was subjected to spray development for 30 seconds at 23 ° C. using a 0.1 mass% aqueous sodium carbonate solution, and the amount of film loss before and after alkali development was measured. The smaller the film loss, the better the sensitivity. The results are shown in Tables 5 and 6.
○: Less than 0.20 μm ×: 0.20 μm or more

(5) Evaluation of solvent resistance In preparation of a cured color resist coating film, a cured coating film was prepared in the same manner as (7) sensitivity evaluation except that the entire surface was exposed without using a photomask. Next, 200 ml of n-methyl 2-pyrrolidone was placed in a 500 ml glass bottle capable of being covered, and the cured coating film was immersed therein, and the color change after 60 minutes at 23 ° C. was compared with a color difference meter. The results are shown in Tables 5 and 6.
○: ΔE * ab is less than 0.3 ×: ΔE * ab is 0.3 or more

(6) Viscosity change rate As a measure of pigment dispersion stability, the viscosity change of a color resist (pigment type) was measured. When the pigment dispersion stability is poor, the viscosity increases, which is not preferable. This will be specifically described below.
Immediately after preparing a color resist (pigment type) excluding Photopolymerization Initiator 1 and Photopolymerization Initiator 2 and after standing in a thermostatic bath at 23 ° C. for 7 days (Toki Sangyo Co., Ltd. E) Mold viscometer, rotor 1 ° 34 ′ × R24, 23 ° C., 20 rpm). As a measure of good pigment dispersion stability, the viscosity change after 7 days is 10% or less, preferably 5% or less with respect to the initial viscosity. The results are shown in Table 5.
○: 5% or less △: Greater than 5% and 10% or less ×: Greater than 10%

  The transparent resist was evaluated for item (1), the color resist using pigment was evaluated for items (2) to (6), and the color resist using dye was evaluated for items (2) to (5).

Claims (4)

(A) Glycidyl (meth) acrylate, (meth) acrylate having an alicyclic epoxy group and its lactone adduct, mono (meth) acrylic of 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate 2 to 95 mol% of at least one selected from the group consisting of an acid ester, an epoxidized product of dicyclopentenyl (meth) acrylate and an epoxidized product of dicyclopentenyloxyethyl (meth) acrylate;
(B) The following group

Mono (meth) acrylate having the following groups

Mono (meth) acrylate having the following general formula (1)

(Wherein x and y each independently represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R ¹ and R ² are each independently A hydrogen atom, a C1-C20 hydrocarbon group which may have a substituent or a carboxyl group, which may have a cyclic structure connecting R ¹ and R ² )
3 to 50 mol% of at least one selected from the group consisting of compounds represented by:
(C) The other radical polymerizable compound that can be copolymerized with (a) and (b) is copolymerized in an amount such that the total is 100 mol%, and the resulting copolymer is obtained. (D) Unsaturated monobasic acid is added to 90 to 100% of the glycidyl group contained, and (e) polybasic acid anhydride is added to 5 to 100% of the hydroxyl group produced when (d) is added. And (f) the following general formula (2): 5 to 70% of the carboxyl group formed when (e) is added

(Wherein R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent)
A photosensitive resin obtained by adding a compound represented by the formula:   The photosensitive resin according to claim 1, wherein the photosensitive resin has a molecular weight distribution (Mw / Mn) of 6.0 or less.   A photosensitive resin composition comprising the photosensitive resin according to claim 1, a photopolymerizable monomer, a photopolymerization initiator, and a solvent.   The photosensitive resin according to claim 1, comprising a photopolymerizable monomer, a photopolymerization initiator, a solvent, and at least one selected from the group consisting of a pigment and a dye. Colored photosensitive resin composition for color filters.