JP2007045925A - Method for producing compound containing unsaturated group and resin solution containing unsaturated group compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a compound containing an unsaturated group and capable of suppressing the formation of precipitate. <P>SOLUTION: A compound containing an unsaturated group is produced by reacting epoxy acrylate with an acid anhydride in a solvent containing a dialkylene glycol monoalkyl ether. The dialkylene glycol monoalkyl ether is preferably expressed by formula (1): R<SP>1</SP>-O-C<SB>n</SB>H<SB>2n</SB>-O-C<SB>n</SB>H<SB>2n</SB>-OH (R<SP>1</SP>is a 1-8C straight chain, branched or cyclic alkyl group or an aryl group; and n is an integer of 2-5). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing an unsaturated group-containing compound and an unsaturated group-containing compound solution. In particular, the present invention relates to a method for producing an unsaturated group-containing compound suitable for a photosensitive composition for forming a black matrix or a color filter, and a resin solution containing the unsaturated group-containing compound.

Conventionally, a liquid crystal panel, particularly a liquid crystal panel such as a TN system or an STN system, has a black matrix for emphasizing the contrast of an image or an RGB color generally composed of red (R), green (G), and blue (B). A color filter having a colored layer is provided. This black matrix or colored layer is obtained by applying a photosensitive composition containing black or each colorant and an unsaturated group-containing compound to a substrate and drying, then exposing and developing the resulting coating film to obtain a desired pattern. It is formed by repeating. Preferred examples of the unsaturated group-containing compound include those described in Patent Documents 1 and 2.
By the way, when the photosensitive composition is applied to a substrate, there is a problem that foreign matters are generated on the substrate. This foreign matter becomes a defect of the black matrix and / or the color filter, causing a problem that it cannot be used as a product.
The foreign matter is generated due to precipitates generated during the production of the unsaturated group-containing compound. This precipitate is considered to be a reaction residue resulting from the poor solubility of the unsaturated group-containing compound in the solvent.
JP-A-5-339356 JP 2001-354735 A

  This invention is made | formed in view of the said problem, and it is providing the resin solution containing the manufacturing method of the unsaturated group containing compound which can suppress generation | occurrence | production of a precipitate, and an unsaturated group containing compound.

The method for producing an unsaturated group-containing compound of the present invention is a method for producing an unsaturated group-containing compound obtained by reacting an epoxy acrylate and an acid anhydride in a solvent, wherein the solvent is dialkylene glycol monoalkyl. It is characterized by containing ether.
The dialkylene glycol monoalkyl ether is represented by the following formula (1):
^{_{R 1 -O-C n H 2n}} -O-C n H 2n -OH (1)
(Here, R ¹ represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms or an aryl group, and n represents an integer of 2 to 5)
The solvent represented by these is preferable.
Further, the resin solution of the present invention is a resin solution containing an unsaturated group-containing compound obtained by reacting an epoxy acrylate and an acid anhydride, and includes a dialkylene glycol monoalkyl ether as a solvent. Yes.

According to the manufacturing method of said unsaturated machine containing compound, generation | occurrence | production of the precipitate in an unsaturated group containing compound can be suppressed. Therefore, by using this unsaturated group-containing compound, it is possible to suppress the generation of foreign matters during coating, particularly during coating by a coating method using a slit nozzle. Thereby, a high-quality black matrix and a color filter can be provided, and thus a high-quality liquid crystal panel can be provided.
Further, according to the resin solution, the unsaturated group-containing compound obtained by reacting the epoxy acrylate with the acid anhydride has high solubility in dialkylene glycol monoalkyl ether, and suppresses the generation of precipitates and the like. it can. Therefore, by using this resin solution, the generation of foreign matters can be suppressed at the time of application, particularly at the time of application by an application method using a slit nozzle. Thereby, a high-quality black matrix and a color filter can be provided, and thus a high-quality liquid crystal panel can be provided.

  The method for producing an unsaturated group-containing compound of the present invention is a method for producing an unsaturated group-containing compound obtained by reacting an epoxy acrylate and an acid anhydride in a solvent, wherein the solvent is a dialkylene glycol monoalkyl ether. It is characterized by including.

The solvent contains dialkylene glycol monoalkyl ether as an essential component.
Examples of the dialkylene glycol monoalkyl ether include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol mono-n-hexyl ether, and diethylene glycol. Monophenyl ether, diethylene glycol mono 2-ethylhexyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol monoisobutyl ether, dipropylene glycol mono-n-butyl ether, etc. Is mentioned. In addition, isomers of dialkylene glycol monoalkyl ether are also included.

As this dialkylene glycol monoalkyl ether, the following formula (1)
^{_{R 1 -O-C n H 2n}} -O-C n H 2n -OH (1)
(Here, R ¹ represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, or an aryl group, and n represents an integer of 2 to 5)
The solvent represented by these is preferable.
R ¹ is particularly preferably a linear alkyl group having 1 to 8 carbon atoms, and more preferably a linear alkyl group having 1 to 4 carbon atoms. Further, n is preferably 2 or 3.
Among the above solvents, dipropylene glycol monomethyl ether is particularly preferable.

Moreover, you may mix with solvents other than the said dialkylene glycol monoalkyl ether.
Examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol monomethyl ether, propylene Glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol Monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monophenyl Ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate (PGMEA), propylene glycol monopropyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate (MBA) 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4 -Propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxy Pentyl acetate, 4-methyl-4-methoxypentyl acetate, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, tetrahydrofuran, cyclohexanone, propionic acid Methyl, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3- Ethoxypropionate (EEP), ethyl-3-propoxypropionate, propyl-3-methoxypropionate, isopropyl-3-methoxypropionate, ethyl ethoxyacetate, ethyl oxyacetate, 2-hydroxy-3-methylbutane Methyl acid, propyl acetate, butyl acetate, isoamyl acetate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl lactate, lactic acid Til, butyl lactate, ethyl hexyl lactate, benzyl methyl ether, benzyl ethyl ether, dihexyl ether, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, benzene, toluene, xylene, cyclohexanone, butanol, 3- Mention may be made of methyl-3-methoxybutanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerin and the like. These solvents may be used alone or in combination of two or more.
Among these, the unsaturated group-containing compound produced is preferably used for a photosensitive composition for forming a color filter or a black matrix later (improved coating properties of the photosensitive composition, storage). (Stability), 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl-3-ethoxypropionate. In particular, it is preferable to contain 3-methoxybutyl acetate from the viewpoint of stability over time.
Moreover, it is preferable that 1-95 mass% of dialkylene glycol monoalkyl ether is contained in the reaction solvent, and it is more preferable that it is 5-30 mass%.
Furthermore, it is preferable that 15-85 mass% of 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, cyclohexanone, and ethyl-3-ethoxypropionate are respectively contained in the reaction solvent.

  The epoxy acrylate is a reaction product of an epoxy compound having two or more epoxy groups and an unsaturated monocarboxylic acid such as acrylic acid or methacrylic acid.

（式中、Ｒ^２はそれぞれ独立して水素原子、炭素数１〜６の炭化水素基、ハロゲン原子を示し、Ｗは単結合、−ＣＯ−、−ＳＯ_２−、−Ｃ（ＣＦ_３）_２−、−Ｓｉ（ＣＨ_３）_２−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、または

を表す。
このエポキシ化合物は、下記ビスフェノール成分の誘導体が挙げられる。
Ｗとして単結合のものとしては４，４’−ビフェノール、３，３’−ビフェノール等、
Ｗとして−ＣＯ−を含むビスフェノール成分としてはビス（４−ヒドロキシフェニル）ケトン、ビス（４−ヒドロキシ−３，５−ジメチルフェニル）ケトン、ビス（４−ヒドロキシ−３，５−ジクロロフェニル）ケトン等、Ｗとして−ＳＯ_２−を含むビスフェノール成分としてはビス（４−ヒドロキシフェニル）スルホン、ビス（４−ヒドロキシ−３，５−ジメチルフェニル）スルホン、ビス（４−ヒドロキシ−３，５−ジクロロフェニル）スルホン等、
Ｗとして−Ｃ（ＣＦ_３）_２−を含むものとしてはビス（４−ヒドロキシフェニル）ヘキサフルオロプロパン、ビス（４−ヒドロキシ−３，５−ジメチルフェニル）ヘキサフルオロプロパン、ビス（４−ヒドロキシ−３，５−ジクロロフェニル）ヘキサフルオロプロパン等から、また、Ｗとして−Ｓｉ（ＣＨ_３）_２−を含むものとしてはビス（４−ヒドロキシフェニル）ジメチルシラン、ビス（４−ヒドロキシ−３，５−ジメチルフェニル）ジメチルシラン、ビス（４−ヒドロキシ−３，５−ジクロロフェニル）ジメチルシラン等、
Ｗとして−ＣＨ_２−を含むものとしてはビス（４−ヒドロキシフェニル）メタン、ビス（４−ヒドロキシ−３，５−ジクロロフェニル）メタン、ビス（４−ヒドロキシ−３，５−ジブロモフェニル）メタン等、
Ｗとして−Ｃ（ＣＨ_３）_２−を含むものとしては２，２−ビス（４−ヒドロキシフェニル）プロパン、２，２−ビス（４−ヒドロキシ−３，５−ジメチルフェニル）プロパン、２，２−ビス（４−ヒドロキシ−３，５−ジクロロフェニル）プロパン、２，２−ビス（４−ヒドロキシ−３−メチルフェニル）プロパン、２，２−ビス（４−ヒドロキシ−３−クロロフェニル）プロパン等、
Ｗとして−Ｏ−を含むものとしてはビス（４−ヒドロキシフェニル）エーテル、ビス（４−ヒドロキシ−３，５−ジメチルフェニル）エーテル、ビス（４−ヒドロキシ−３，５−ジクロロフェニル）エーテル等、
また、Ｗとして

を含むものとしては９，９−ビス（４−ヒドロキシフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−３−クロロフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−３−ブロモフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−３−フルオロフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−３−メトキシフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−３，５−ジメチルフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−３，５−ジクロロフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−３，５−ジブロモフェニル）フルオレン等、から誘導されるものを挙げることができる。 Examples of the epoxy acrylate include those obtained by reacting the above epoxy compound with acrylic acid or methacrylic acid which is preferable as an unsaturated monocarboxylic acid.

(In the formula, each R ² independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and W represents a single bond, —CO—, —SO ₂ —, —C (CF ₃ ) _{2. -, - Si (CH 3)} 2 -, - CH 2 -, - C (CH 3) 2 -, - O-, or

Represents.
Examples of the epoxy compound include derivatives of the following bisphenol components.
As a single bond as W, 4,4′-biphenol, 3,3′-biphenol, etc.
Examples of bisphenol components containing -CO- as W include bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, bis (4-hydroxy-3,5-dichlorophenyl) ketone, and the like. Examples of the bisphenol component containing —SO ₂ — as W include bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, and bis (4-hydroxy-3,5-dichlorophenyl) sulfone. ,
Examples of those containing -C (CF ₃ ) _2- as W include bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, and bis (4-hydroxy-3). , 5-dichlorophenyl) hexafluoropropane and the like, and those containing -Si (CH ₃ ) _2- as W include bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3,5-dimethylphenyl). ) Dimethylsilane, bis (4-hydroxy-3,5-dichlorophenyl) dimethylsilane, etc.
Examples of those containing —CH ₂ — as W include bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dichlorophenyl) methane, and bis (4-hydroxy-3,5-dibromophenyl) methane.
Examples of those containing -C (CH ₃ ) _2- as W include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2 -Bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, etc.
Examples of those containing -O- as W include bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3,5-dichlorophenyl) ether, and the like.
Also as W

9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) Fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3) , 5-dibromophenyl) fluorene and the like.

で表されるエポキシ基を有するエポキシ化合物に常法に従い、アクリル酸またはメタクリル酸を反応させて合成することができる。この式（ｉｉ）で表されるエポキシ化合物は、例えば、ビスフェノール化合物（上記ビスフェノール成分に相当する）にエピクロルヒドリンなどのエピハロヒドリンを反応させることにより容易に得ることができる。 Here, the epoxy acrylate represented by the formula (i) is represented by the following formula (ii)

According to a conventional method, an epoxy compound having an epoxy group represented by can be synthesized by reacting acrylic acid or methacrylic acid. The epoxy compound represented by the formula (ii) can be easily obtained by, for example, reacting a bisphenol compound (corresponding to the bisphenol component) with an epihalohydrin such as epichlorohydrin.

の化合物（９，９−ビス［４−｛（２−ヒドロキシ−３−アクリロキシ）プロポキシエトキシ｝フェニル］フルオレン）が挙げられる。 Particularly preferable examples of these epoxy acrylates include, for example, the following formula (ia)

(9,9-bis [4-{(2-hydroxy-3-acryloxy) propoxyethoxy} phenyl] fluorene).

（式中、Ｘは下記式

で表される基、Ｒ^２はそれぞれ独立して水素原子、炭素数１〜６の炭化水素基、ハロゲン原子を表し、Ｒ^３はそれぞれ独立して水素原子またはメチル基を表し、Ｗは単結合、−ＣＯ−、−ＳＯ_２−、−Ｃ（ＣＦ_３）_２−、−Ｓｉ（ＣＨ_３）_２−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、または

を表し、Ｙはジカルボン酸無水物の酸無水物基を除いた残基、Ｚはテトラカルボン酸二無水物の酸無水物基を除いた残基であり、ｍは０〜２０の整数である）
で表される不飽和基含有化合物を例にして説明する。
まず、上記式（ｉ）で表されるエポキシアクリレートに、ジアルキレングリコールモノアルキルエーテルを含む溶剤中において、下記式

（ここで、Ｚはテトラカルボン酸二無水物の酸無水物基を除いた残基である）
で表されるテトラカルボン酸二無水物を反応させ、次いで下記式

（ここで、Ｙはジカルボン酸無水物の酸無水物基を除いた残基である）
で表されるジカルボン酸無水物を反応させる。
上記反応における反応温度としては、テトラカルボン酸二無水物及びジカルボン酸無水物とエポキシアクリレートにおける水酸基とが定量的に反応する温度であればよい。例えばテトラカルボン酸二無水物との反応においては、通常１００〜１３０℃の範囲で選定され、ジカルボン酸無水物との反応においては、通常８０〜１２０℃の範囲で選定される。
上記反応においてエポキシアクリレートにおける水酸基１００モル部に対して、テトラカルボン酸二無水物とジカルボン酸無水物における酸無水物基の合計が、６０〜１００モル部の割合になるように反応させることが好ましい。
酸無水物基の合計量を６０モル部以上にすることにより、製造される不飽和基含有化合物の分子量を十分に増加させて高感度を得るのに必要な重合性二重結合を十分に導入することができる。
また、酸無水物基の合計量を１００モル部以下にすることにより、分子量を十分に増加させて高感度に必要な重合性二重結合を十分導入することができる。さらに、未反応のテトラカルボン酸二無水物やジカルボン酸無水物を低減することができ、感光性組成物に用いた場合の現像性を向上させることができる。
上記テトラカルボン酸二無水物とジカルボン酸無水物との割合は、モル比で、通常１：９９〜９９：１、好ましくは５：９５〜８０：２０の範囲で選定される。ジカルボン酸無水物の割合が全酸無水物の１モル％以上にすることにより、樹脂粘度を適度にして作業性を高めることができる。また、分子量を大きくなりすぎるのを防止することができるため、感光性組成物に用いたときの未露光部の現像液に対する溶解性を向上させることができ、目的のパターンを形成することができる。また、ジカルボン酸無水物の割合が全酸無水物の９９モル％未満にすることにより、分子量が小さくなるのを防止することができる。 Here, about the manufacturing method of the unsaturated group containing compound of this application, following formula (I)

(Where X is the following formula

And R ² each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, R ³ each independently represents a hydrogen atom or a methyl group, and W is a single bond. _{, -CO -, - SO 2 -} , - C (CF 3) 2 -, - Si (CH 3) 2 -, - CH 2 -, - C (CH 3) 2 -, - O-, or

Y is a residue excluding the acid anhydride group of dicarboxylic anhydride, Z is a residue excluding the acid anhydride group of tetracarboxylic dianhydride, and m is an integer of 0-20. )
An example of the unsaturated group-containing compound represented by
First, in the epoxy acrylate represented by the above formula (i), in a solvent containing dialkylene glycol monoalkyl ether, the following formula:

(Here, Z is a residue obtained by removing the acid anhydride group of tetracarboxylic dianhydride)
Is reacted with a tetracarboxylic dianhydride represented by the following formula:

(Where Y is a residue obtained by removing the acid anhydride group of the dicarboxylic acid anhydride)
The dicarboxylic acid anhydride represented by this is reacted.
The reaction temperature in the above reaction may be a temperature at which tetracarboxylic dianhydride and dicarboxylic anhydride and the hydroxyl group in epoxy acrylate react quantitatively. For example, the reaction with tetracarboxylic dianhydride is usually selected in the range of 100 to 130 ° C., and the reaction with dicarboxylic acid anhydride is usually selected in the range of 80 to 120 ° C.
In the above reaction, it is preferable to cause the reaction so that the total of the acid anhydride groups in the tetracarboxylic dianhydride and the dicarboxylic anhydride is 60 to 100 parts by mole with respect to 100 parts by mole of the hydroxyl group in the epoxy acrylate. .
By making the total amount of acid anhydride groups 60 mol parts or more, sufficiently introduce the polymerizable double bond necessary to obtain a high sensitivity by sufficiently increasing the molecular weight of the unsaturated group-containing compound to be produced. can do.
Moreover, by making the total amount of acid anhydride groups 100 mol parts or less, the molecular weight can be sufficiently increased to sufficiently introduce polymerizable double bonds necessary for high sensitivity. Furthermore, unreacted tetracarboxylic dianhydride and dicarboxylic anhydride can be reduced, and developability when used in the photosensitive composition can be improved.
The ratio of the tetracarboxylic dianhydride and the dicarboxylic anhydride is selected in a molar ratio of usually 1:99 to 99: 1, preferably 5:95 to 80:20. When the ratio of the dicarboxylic acid anhydride is 1 mol% or more of the total acid anhydride, the resin viscosity can be moderated and workability can be improved. In addition, since the molecular weight can be prevented from becoming too large, the solubility of the unexposed area in the developer when used in the photosensitive composition can be improved, and a desired pattern can be formed. . Moreover, it can prevent that molecular weight becomes small by making the ratio of dicarboxylic acid anhydride less than 99 mol% of all the acid anhydrides.

  Examples of the dicarboxylic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl endomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyl Examples include tetrahydrophthalic anhydride and glutaric anhydride. Examples of the tetracarboxylic dianhydride include pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, and the like. In the above, these dicarboxylic acid anhydrides and tetracarboxylic dianhydrides are reacted separately, but they may be mixed and used.

By using dialkylene glycol monoalkyl ether as the solvent as described above, the solubility of each component used in the reaction and the reaction product in the solvent can be improved. Thereby, it is considered that the reaction can be caused uniformly, the reaction residue, the reaction product between the epoxy acrylates, the high molecular weight component, and the like can be reduced, and the precipitate in the solvent can be reduced.
Furthermore, the photosensitive composition using the unsaturated group-containing compound produced by this production method (the reaction solution can be used as it is) has high adhesion to the substrate when a fine line of about 8 μm is formed.
1-100 mass% is preferable, as for the ratio with respect to all the solvents in the reaction solution of this dialkylene glycol monoalkyl ether, 2-50 mass% is more preferable, and 5-20 mass% is further more preferable.
Further, by reacting in a solvent containing dialkylene glycol monoalkyl ether, the reaction solution can be used as it is as a material for a photosensitive composition for forming a color filter and a black matrix. Furthermore, since the dialkylene glycol monoalkyl ether can improve the solubility of each component used in the reaction and the reaction product in the solvent as described above, the unsaturated group-containing compound and solvent according to the present application A resin solution containing an alkylene glycol ether is particularly suitable for using a photosensitive composition used for a color filter or a black matrix. The ratio of dialkylene glycol monoalkyl ether to the total solvent in this resin solution is preferably 1 to 100% by mass, more preferably 2 to 50% by mass, and further preferably 5 to 20% by mass.

  When producing a photosensitive composition as described above, a photopolymerization initiator may be mixed in the reaction solution. Moreover, the unsaturated group containing compound which concerns on this application is used suitably for the photosensitive composition used for a color filter and a black matrix, and what is necessary is just to mix | blend a coloring agent in this case.

  Examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) phenyl] -2- Hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2 -Methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, eta 1,1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4 -Benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoate Acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, o-benzoylbenzoic acid Acid methyl, 2,4-diethylthioxanthone, 2-chlorothioxyl N, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone , Octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidar, 2-mercaptobenzoxazole, 2-mercapto Benzothiazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p, p′-bisdimethylaminobenzophenone, 4,4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, Benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p -Tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α, α-dichloro-4-fe Xyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis- (9-acridinyl) heptane, 1,5-bis -(9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6- Bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan- 2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-die Tylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl)- s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromide 4-methoxy) styrylphenyl -s- triazine, 2,4-bis - such as trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl -s- triazine and the like. This photopolymerization initiator may be used alone or in combination of two or more.

Moreover, you may combine a photoinitiator adjuvant with the said photoinitiator.
Examples of this photoinitiator include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoate. 2-ethylhexyl acid, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 9, Examples include 10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. These photoinitiators may be used alone or in combination of two or more.

  The photosensitive composition may be blended with a photopolymerizable compound that polymerizes and cures upon irradiation with light such as ultraviolet rays. As the photopolymerizable compound, a compound having an ethylenic double bond is preferable. Specifically, acrylic acid, methacrylic acid, fumaric acid, maleic acid, monomethyl fumarate, monoethyl fumarate, 2-hydroxyethyl acrylate, 2 -Hydroxyethyl methacrylate, ethylene glycol monomethyl ether acrylate, ethylene glycol monomethyl ether methacrylate, ethylene glycol monoethyl ether acrylate, ethylene glycol monoethyl ether methacrylate, glycerol acrylate, glycerol methacrylate, acrylic acid amide, methacrylic acid amide, acrylonitrile, methacrylonitrile , Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isobutyl Acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, benzyl acrylate, benzyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol Diacrylate, tetraethylene glycol dimethacrylate, butylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate, tetramethylo Rupropanetetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate (DPHA), dipentaerythritol hexaacrylate Monomers and oligomers such as methacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, cardo epoxy diacrylate; polyester obtained by condensing polyhydric alcohols with monobasic acid or polybasic acid Polyester (meth) acrylate obtained by reacting (meth) acrylic acid with prepolymer Polyurethane (meth) acrylate obtained by reacting a compound having a polyol group and two isocyanate groups and then reacting with (meth) acrylic acid; bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type Epoxy resin, phenol or cresol novolac type epoxy resin, resol type epoxy resin, triphenolmethane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ester, aliphatic or cycloaliphatic epoxy resin, amine epoxy resin, dihydroxybenzene An epoxy (meth) acrylate resin obtained by reacting an epoxy resin such as a type epoxy resin with (meth) acrylic acid can be used. Further, a resin obtained by reacting the epoxy (meth) acrylate resin with a polybasic acid anhydride can also be suitably used.

Moreover, you may mix | blend a polymer binder with the said photosensitive composition.
As the polymer binder, a binder capable of alkali development is preferable because of easy development.
Specifically, monomers having a carboxyl group such as acrylic acid and methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxy Propyl methacrylate, N-butyl acrylate, N-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, benzyl acrylate, benzyl methacrylate, phenoxy acrylate, phenoxy methacrylate, isobornyl acrylate, isobornyl methacrylate, glycidyl methacrylate, styrene, acrylamide, acrylonitrile, etc. Copolymer, and phenol novolac epoxy acrylate polymer, phenol novola Click epoxy methacrylate polymer, cresol novolak epoxy acrylate polymer, cresol novolak epoxy methacrylate polymer, a bisphenol A type epoxy acrylate polymer, a bisphenol S type epoxy acrylate polymers include resins such as. Since the acryloyl group or the methacryloyl group is introduced into the resin, the crosslinking efficiency is improved, and the light resistance and chemical resistance of the coating film are excellent. Content of the monomer component which has carboxyl groups, such as acrylic acid and methacrylic acid which comprises the said resin, has the good range of 5-40 mass%. The preferred range of the weight average molecular weight of the polymer binder is 1,000 to 100,000. By making the weight average molecular weight 1,000 or more, the coating film can be made uniform. Moreover, developability can be made favorable by making it 100,000 or less.

The unsaturated group-containing compound and the photopolymerizable compound according to the present application may be blended in a range of 10 to 60 parts by mass in a total of 100 parts by mass of the unsaturated group-containing compound, the photopolymerizable compound and the photopolymerization initiator. . When the blending amount is 10 parts by weight or more, a film can be easily formed during coating and drying, and the coating strength after curing can be sufficiently increased. Moreover, developability can be made favorable by a compounding quantity being 60 weight part or less.
Furthermore, the ratio of the unsaturated group-containing composition to the photopolymerizable compound is preferably in the range of 20:80 to 100: 0, more preferably in the range of 60:40 to 95: 5, by mass ratio. By setting it in the above range, poor photocuring can be prevented, and sufficient heat resistance and chemical resistance can be obtained.

  Examples of the colorant include, for example, compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), specifically, the following color index (C .. I.) Numbers can be mentioned.

  C. I. Pigment Yellow 1 (hereinafter, “CI Pigment Yellow” is the same and only the number is described) 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180, 185;

C. I. Pigment Orange 1 (hereinafter, “CI Pigment Orange” is the same, and only the number is described) 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, 73;
C. I. Pigment Violet 1 (hereinafter, “CI Pigment Violet” is the same and only the numbers are described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50;

  C. I. Pigment Red 1 (hereinafter, “CI Pigment Red” is the same and only the number is described) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 79, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265;

C. I. Pigment Blue 1 (hereinafter, “CI Pigment Blue” is the same and only the numbers are described), 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 37;
C. I. Pigment brown 23, C.I. I. Pigment brown 25, C.I. I. Pigment brown 26, C.I. I. Pigment brown 28;
C. I. Pigment Black 1 and Pigment Black 7.
Moreover, when forming a black matrix, a light-shielding agent is used as a colorant. The light-shielding agent is not particularly limited as long as it has a sufficient light-shielding rate when used as a light-shielding layer, and examples thereof include black pigments. Examples of the black pigment include carbon black, titanium black, and perylene black.
These colorants may be used alone or in combination of two or more in order to adjust the color tone.

Furthermore, you may mix | blend a solvent with the said photosensitive composition for a coating property improvement and a viscosity adjustment.
Examples of the solvent include the above-mentioned dipropylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether. , Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol Nomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol Monobutyl ether acetate, diethylene glycol monophenyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-methoxybutyl acetate, 3- Toxibutyl acetate (MBA), 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4 -Ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3 -Methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, tetrahydrofuran , Cyclohexanone, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate , Ethyl-3-ethoxypropionate, ethyl-3-propoxypropionate, propyl-3-methoxypropionate, isopropyl-3-methoxypropionate, ethyl ethoxyacetate, ethyl oxyacetate, 2-hydroxy-3 -Methyl methyl butanoate, propyl acetate, butyl acetate, isoamyl acetate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate , Methyl lactate, ethyl lactate, butyl lactate, ethyl hexyl lactate, benzyl methyl ether, benzyl ethyl ether, dihexyl ether, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, benzene, toluene, xylene, Examples include cyclohexanone, butanol, 3-methyl-3-methoxybutanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, and glycerin. Among these, it is preferable to contain 3-methoxybutyl acetate particularly in terms of stability over time.
Although the usage-amount of a solvent is not specifically limited, The density | concentration which can apply | coat a photosensitive composition to a board | substrate etc. is set suitably according to a coating film thickness. The viscosity of the photosensitive composition in the present invention is 1 to 100 cp, preferably 2 to 50 cp, more preferably 2 to 10 cp. Moreover, it is preferable that solid content concentration is 5-100 mass%, and it is more preferable that it is 10-40 mass%.

Moreover, you may add a thermal-polymerization inhibitor, an antifoamer, surfactant, etc. to the photosensitive composition of this invention. These can be used alone or in combination of several kinds.
The thermal polymerization inhibitor may be a conventionally known one, and examples thereof include hydroquinone and hydroquinone monoethyl ether.
As said antifoamer, a conventionally well-known thing may be used and a silicone type and a fluorine-type compound are mentioned.
The surfactant may be a conventionally known surfactant, and examples thereof include anionic, cationic and nonionic compounds.

<Method for preparing photosensitive composition>
The photosensitive composition of the present invention can be prepared by the following method.
A reaction solution of the unsaturated group-containing compound, a photopolymerization initiator, and, if necessary, a colorant, a photopolymerizable compound, a solvent, other organic additives, etc. are added to a three-roll mill, a ball mill, a sand mill, etc. A photosensitive composition is prepared by mixing (dispersing and kneading) with a stirrer and filtering through, for example, a 5 μm membrane filter.

<Method for forming light shielding layer (black matrix)>
Here, an example of a method for forming a black matrix will be described as an embodiment of a method for forming a light shielding layer using a photosensitive composition.
First, a photosensitive composition using a light-shielding agent as a colorant is applied onto a substrate with a contact transfer type coating device such as a roll coater, reverse coater, bar coater, spinner (rotary coating device), curtain flow coater, or slit nozzle. Coating is performed using a non-contact type coating apparatus such as a non-spin coater. As the substrate, a light-transmitting substrate is used, for example, a glass substrate.
After application of the photosensitive composition, the solvent is removed by drying.
Next, exposure is performed partially by irradiating active energy rays such as ultraviolet rays and excimer laser light through a negative mask. For the exposure, a light source that emits ultraviolet rays, such as a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, or a carbon arc lamp can be used. The energy dose to be irradiated varies depending on the composition of the photosensitive composition, but is preferably about 30 to 2000 mJ / cm ² , for example.
The black matrix is formed by developing the exposed film using a developer. The development method is not particularly limited, and for example, an immersion method, a spray method, or the like can be used. A pre-wet may be adopted. Post-baking, post-photocuring, etc. may be employed for the purpose of enhancing the drying of the developer after the image formation and the curing of the resist film. Specific examples of the developer include organic ones such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.

<Method for forming color filter>
The photosensitive composition is applied, dried, exposed and developed in the same manner as described above to the substrate on which the black matrix is formed, and a colored layer of a predetermined color is patterned at a predetermined position (opening) of the black matrix. (Stripes or dots) are formed. For example, in the case of producing red (R), green (G), and blue (B) RGB color filters, the photosensitive composition containing the colorant of each color of R, G, and B is used. The process is repeated to form three colored layers.
As described above, a color filter can be formed.

  Even when no colorant is used, a pattern can be formed in the same manner as the black matrix and the color filter.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these Examples.

Example 1
After dissolving 100 g of 9,9-bis [4-{(2-hydroxy-3-acryloxy) propoxyethoxy} phenyl] fluorene as an epoxy acrylate in 90 g of 3-methoxybutyl acetate and 10 g of dipropylene glycol monomethyl ether as a solvent, As an acid anhydride, 40 g of 1,2,3,6-tetrahydrophthalic anhydride, 20 g of benzophenone tetracarboxylic dianhydride, and 0.5 g of tetraethylammonium bromide were added and mixed, and the temperature was raised to 115 ° C. for 2 hours. Reaction was performed to obtain an unsaturated group-containing compound (reaction solution).

(Example 2)
An unsaturated group-containing compound (reaction solution) was obtained in the same manner as in Example 1, except that 90 g of propylene glycol monomethyl ether acetate and 10 g of dipropylene glycol monomethyl ether were used as solvents.

(Example 3)
An unsaturated group-containing compound (reaction solution) was obtained in the same manner as in Example 1, except that 95 g of propylene glycol monomethyl ether acetate and 5 g of dipropylene glycol monomethyl ether were used as solvents.

Example 4
An unsaturated group-containing compound (reaction solution) was obtained in the same manner as in Example 1, except that 70 g of propylene glycol monomethyl ether acetate and 30 g of dipropylene glycol monomethyl ether were used as solvents.

(Example 5)
An unsaturated group-containing compound (reaction solution) was obtained in the same manner as in Example 1 except that 100 g of dipropylene glycol monomethyl ether was used as a solvent.

(Example 6)
An unsaturated group-containing compound (reaction solution) was obtained in the same manner as in Example 1, except that 90 g of ethyl-3-ethoxypropionate and 10 g of dipropylene glycol monomethyl ether were used as solvents.

(Comparative Example 1)
An unsaturated group-containing compound (reaction solution) was obtained in the same manner as in Example 1 except that 100 g of 3-methoxybutyl acetate was used as a solvent.

(Comparative Example 2)
An unsaturated group-containing compound (reaction solution) was obtained in the same manner as in Example 1, except that 100 g of propylene glycol monomethyl ether acetate was used as a solvent.

(Comparative Example 3)
An unsaturated group-containing compound (reaction solution) was obtained in the same manner as in Example 1 except that 100 g of ethyl-3-ethoxypropionate was used as a solvent.

After the reaction solutions obtained in Examples 1 to 6 and Comparative Examples 1 to 3 were diluted 10 times with a reaction solvent, the presence or absence of precipitates was visually confirmed. The results are shown in Table 1.
When this precipitate was measured by gel permeation chromatography, a large amount of a high molecular weight component having a molecular weight of 3000- (average molecular weight in terms of polystyrene) or more was contained.

(Examples 7-12 and Comparative Examples 4-6)
20 g of the reaction solution obtained in each of Examples 1 to 6 and Comparative Examples 1 to 3, 5 g of pentaerythritol tetraacrylate as a photopolymerizable compound, and Irgacure 369 (2-benzyl-2-dimethylamino-1-) as a photopolymerization initiator 0.5 g (4-morpholinophenyl) butan-1-one: Ciba Specialty Chemicals) and CGI242 (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) ]-, 1- (O-acetyloxime): 0.5 g, carbon dispersion CF black (carbon concentration 20%, solvent: 3-methoxybutyl acetate, made by Gokoku Dye) as a colorant, and 3-Methoxybutyl acetate was mixed as a solvent to prepare a photosensitive composition.

  The prepared photosensitive composition was applied on a glass substrate having a clean surface of 1 mm in thickness using a reverse coater (Round Coater: manufactured by Dainippon Screen) so that the dry film thickness was 1.5 μm. A photosensitive layer was formed by drying at 80 ° C. for 1 minute. Next, the photosensitive layer was selectively irradiated with ultraviolet rays through a negative mask (exposure amounts: 100 mJ, 120 mJ), followed by spray development with a 0.5 wt% sodium carbonate aqueous solution at 25 ° C. for 60 seconds to form a fine line pattern of 8 μm. The adhesion of the fine line pattern to the glass substrate was confirmed. The one having high adhesion (no peeling) was marked with ◯, and the one having low adhesion (with peeling) x. The results are shown in Table 2.

As described above, in Examples 7 to 12, the adhesiveness is high even at an exposure amount of 100 mJ.

Claims (13)

In the manufacturing method of the unsaturated group containing compound obtained by making an epoxy acrylate and an acid anhydride react in a solvent, The said solvent contains dialkylene glycol monoalkyl ether, Manufacturing of an unsaturated group containing compound characterized by the above-mentioned. Method. The dialkylene glycol monoalkyl ether is represented by the following formula (1):
^{_{R 1 -O-C n H 2n}} -O-C n H 2n -OH (1)
(Here, R ¹ represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms or an aryl group, and n represents an integer of 2 to 5)
The method for producing an unsaturated group-containing compound according to claim 1, wherein the solvent is represented by the formula: R ¹ above method for manufacturing a unsaturated group-containing compound according to claim 2, wherein the straight-chain alkyl having 1 to 4 carbon atoms.   4. The method for producing an unsaturated group-containing compound according to claim 2, wherein n is 2 or 3.   The method for producing an unsaturated group-containing compound according to claim 1, wherein the dialkylene glycol monoalkyl ether is dipropylene glycol monomethyl ether. Formula (I)

(Where X is the following formula

And R ² each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, R ³ each independently represents a hydrogen atom or a methyl group, and W is a single bond. _{, -CO -, - SO 2 -} , - C (CF 3) 2 -, - Si (CH 3) 2 -, - CH 2 -, - C (CH 3) 2 -, - O-, or

Y is a residue excluding the acid anhydride group of dicarboxylic anhydride, Z is a residue excluding the acid anhydride group of tetracarboxylic dianhydride, and m is an integer of 0-20. )
A method for producing the unsaturated group-containing compound represented by:
Formula (i) below

In the epoxy acrylate represented by

(Here, Z is a residue obtained by removing the acid anhydride group of tetracarboxylic dianhydride)
Is reacted with a tetracarboxylic dianhydride represented by the following formula:

(Where Y is a residue obtained by removing the acid anhydride group of the dicarboxylic acid anhydride)
The method for producing an unsaturated group-containing compound according to any one of claims 1 to 5, wherein a dicarboxylic acid anhydride represented by the formula is reacted. A resin solution containing an unsaturated group-containing compound obtained by reacting an epoxy acrylate with an acid anhydride,
A resin solution comprising a dialkylene glycol monoalkyl ether as a solvent. The dialkylene glycol monoalkyl ether is represented by the following formula (1):
^{_{R 1 -O-C n H 2n}} -O-C n H 2n -OH (1)
(Here, R ¹ represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms or an aryl group, and n represents an integer of 2 to 5)
The resin solution according to claim 6, wherein the resin solution is represented by the formula: The resin solution according to claim 7, wherein R ¹ is a linear alkyl having 1 to 4 carbon atoms.   n is 2 or 3, The resin solution of Claim 7 or 8 characterized by the above-mentioned.   The resin solution according to claim 6, wherein the dialkylene glycol monoalkyl ether is dipropylene glycol monomethyl ether.   The said dialkylene glycol monoalkyl ether is 1-50 mass% in 5 in all the solvents, The resin solution of any one of Claims 6-10 characterized by the above-mentioned. The unsaturated group-containing compound has the following formula:

(Where X is the following formula

Y is a residue excluding the acid anhydride group of dicarboxylic anhydride, Z is a residue excluding the acid anhydride group of tetracarboxylic dianhydride, and m is 0-20. Is an integer)
It is represented by these. The resin solution of any one of Claims 7-12 characterized by the above-mentioned.