WO2007010919A1 - Fluorine-containing copolymer, alkali-developable resin composition, and alkali-developable photosensitive resin composition - Google Patents

Abstract

Disclosed is an alkali-developable resin composition containing a fluorine-containing copolymer (E) which is obtained by modifying a part or all of hydroxyl groups in a block copolymer (C) with a polybasic acid anhydride (D). The block copolymer (C) is composed of a segment A which is a fluorine-containing segment obtained from one or more fluorine monomers (A) and a segment B which is a fluorine-free segment obtained from one or more fluorine-free monomers (B), and the hydroxyl groups are contained in the segment A and/or the segment B. Also disclosed is an alkali-developable photosensitive resin composition containing such an alkali-developable resin composition containing a fluorine-containing copolymer. This alkali-developable photosensitive resin composition is excellent in ink repellency, alkali developability, sensitivity, resolution, transparency, adhesion and alkali resistance, and enables to form a fine pattern precisely.

Description

 Specification

 Fluorine-containing copolymer, alkali-developable resin composition, and alkali-developable photosensitive resin composition

 Technical field

 [0001] The present invention relates to a fluorine-containing copolymer, an alkali-developable resin composition containing the fluorine-containing copolymer and a specific compound having an ethylenically unsaturated bond, and the alkali-developable resin composition. The present invention relates to an alkali-developable photosensitive resin composition containing a photopolymerization initiator.

 Background art

 An alkali-developable photosensitive resin composition contains an alkali-developable resin composition containing a compound having an ethylenically unsaturated bond and a photopolymerization initiator. Since this alkali-developable photosensitive resin composition can be polymerized and cured by irradiation with ultraviolet rays or electron beams, photocurable ink, photosensitive printing plate, printed wiring plate, various photoresists, Used in color filters used in color liquid crystal display devices and image sensors. Recently, along with the progress of miniaturization and high functionality of electronic devices, an alkali-developable photosensitive resin composition capable of forming a fine pattern with high accuracy is desired.

 The alkali-developable photosensitive composition has been used for color filter substrates used in color display devices such as color liquid crystal displays. In recent years, an inkjet method has been proposed as a simple method for producing the color filter substrates. Being sung.

 [0004] As a method for producing a color filter substrate using an inkjet method, Patent Document 1 discloses a color filter using a black matrix containing a fluorine-containing compound, and Patent Document 2 discloses a fluorine-containing substrate. A resin composition for a color filter containing a copolymer and a fluorine-containing organic compound is disclosed.

 [0005] Patent Document 1: Patent No. 3470352

 Patent Document 2: Specification of Patent No. 3644243

[0006] However, containing the above-mentioned fluorine-containing compound, fluorine-containing copolymer and fluorine-containing organic compound The alkali-developable photosensitive resin composition using the alkali-developable resin composition has a poor ink repellency when the pixel pattern is formed using the inkjet method, and the colorant is colored and diffuses outside the intended area. There is a problem that coating properties are poor, such as display unevenness. There was also a problem of poor alkali developability.

 Disclosure of the invention

 Problems to be solved by the invention

 [0007] As described above, the problems to be solved are excellent in ink repellency and alkali developability, and have an appropriate pattern while maintaining characteristics such as sensitivity, resolution, transparency, adhesion, and alkali resistance. In other words, the alkali-developable resin composition and alkaline-developable photosensitive resin composition that can efficiently obtain the shape and fine pattern of the ink are the key to date.

 Accordingly, an object of the present invention is to provide an alkali-developable resin composition and an alkali-developable photosensitive resin composition that have solved the above problems.

 Means for solving the problem

 [0009] The present invention is a block copolymer (C) having both an A segment and a B segment, wherein the A segment is a fluorine-containing segment obtained from one or more types of fluorine-based monomers (A). The segment is a non-fluorine segment that can also obtain one or more types of non-fluorine monomers (B), and the A segment and the Z or B segment have a hydroxyl group in part or all of the hydroxyl groups of the block copolymer (C). The above object is achieved by providing a fluorine-containing copolymer) obtained by modifying with a basic acid anhydride (D).

 [0010] Further, the present invention provides an epoxy adduct having a structure in which an unsaturated monobasic acid (G) is added to a polyfunctional epoxy resin (F), and a polybasic acid anhydride (D '). The object is achieved by providing an alkali-developable resin composition containing the reaction product (H) obtained by the esterification reaction, and the fluorine-containing copolymer (E). .

 [ooii] Furthermore, the present invention achieves the above-mentioned object by providing an alkali-developable photosensitive resin composition comprising a photopolymerization initiator ω in the alkali-developable resin composition. is there.

Brief Description of Drawings [0012] FIG. 1 is an IR chart of fluorinated copolymer No. 1.

 [Fig. 2] IR chart of fluorinated copolymer No. 2.

 BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, the fluorine-containing copolymer, alkali-developable resin composition and alkali-developable photosensitive resin composition of the present invention will be described in detail based on preferred embodiments.

[0014] The fluorine-containing copolymer (E) of the present invention contains one or two or more kinds of fluorine-based monomers (A) A segment that is a powerful fluorine-containing segment, one kind or two or more kinds of fluorine atoms. In addition, the hydroxyl group of the block copolymer (C) having a B segment which is a non-fluorine segment that also has a non-fluorinated monomer (B) force, and further having a hydroxyl group in the A segment and Z or B segment is converted to a polybasic acid anhydride ( Denatured in D).

 [0015] The fluorine-based monomer (A) is preferably a fluorine-based monomer represented by the following general formula (I) or general formula (II).

[0016] [Chemical 1]

(Wherein R ¹ and R ² are perfluoroalkyls optionally having a hydroxyl group of 1 to 30 carbon atoms.

 f f

 Represents a ru group. )

[0017] [Chemical 2]

(Wherein R ′ represents a hydrogen atom or a methyl group, Z ¹ represents a direct bond, —R ′, —NR—SO —

2

, 1 R, ⁵ 1 NR—CO—, —CH 2 —CH (OH) 1 CH— or 1 CH—CH (OH) — C

 2 2 2

 H—O—force represents a selected group, R ′, represents an alkylene group having 1 to 4 carbon atoms, R

2 ί

³ is the same as R ^{2 in the} general formula (I). R is a hydrogen atom or a hydroxy acid having 1 to 30 carbon atoms

 f

 The alkyl group which may have a group is represented. )

[0018] In the above general formulas (I) and (II), a hydroxyl group having 1 to 30 carbon atoms represented by

Examples of the fluoroalkyl group that may have F (CF) (CH), F (CF) (CH), F ( CF) (CH), H (CF) CH, (CF) CF (CF) (CH), (CF) CF (CF) (CH)

2 10 2 2 2 8 2 3 2 2 6 2 2 3 2 2 8 2

, F (CF) (CF), F (CF) (CF), F (CF) (CF), H (CF) CF, (CF) CF (

2 2 6 2 2 2 8 2 2 2 10 2 2 2 8 2 3 2

CF) (CF), F (CF) (CH), F (CF), F (CF) CH (OH) CH, F (CF) CH

2 6 2 2 2 8 2 2 2 8 2 6 2 2 8 2

CH (OH) CH, (CF) CF (CF) CH CH (OH) CH, etc.

 2 3 2 2 2 2 2

 Also, F (CF) (CH) and F (CF) are preferable. In the general formula (II), the carbon atom represented by R

 2 8 2 2 2 8

 Examples of the alkyl group which may have 1 to 30 hydroxyl groups include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tertiary amyl, hexyl, cyclohexane Hexyl, cyclohexylmethyl, cyclohexylethyl, heptinole, isoheptinole, tertiary heptinole, n-octinole, isooctinole, tertiary octinole, 2-ethylhexyl, decyl, isodecyl, undecyl, lauryl, dodecyl, hexyl Xadecyl, stearyl, behexyl, glycidyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, and the like. Examples of the alkylene group having 1 to 4 carbon atoms represented by R ′ ′ include methylene, ethylene, propylene, butylene, methylethylene and the like.

 [0019] The fluorine-based monomer (A) includes, in addition to the fluorine-based monomer represented by the general formula (I) or the general formula (II), polyvinylidene fluoride, fluororefinbul ether. Examples of such a copolymer include trifluorinated styrene, vinylidene fluoride copolymer, polytetrafluoroethylene, perfluoroethylenepropylene, and perfluoroalkoxy.

 [0020] The non-fluorine monomer (B) is preferably a (meth) acrylic acid monomer, more preferably a (meth) acrylic acid monomer represented by the following general formula (V) or (VI).

[Chemical 3]

(In the formula, R represents a hydrogen atom or a methyl group, and R ⁹ may have a hydroxyl group having 1 to 30 carbon atoms and a hydroxyl group having 1 to 30 carbon atoms which may have a hydroxyl group!ヽ represents a cycloalkyl group or an aryl group that may have a hydroxyl group having 1 to 30 carbon atoms, and Z ² is the same as Z ¹ in the general formula (II). [0021] [Chemical 4]

(In the formula, R ^1Q and R ¹¹ are the same as R ⁸ in the general formula (V), and Z ³ represents an alkylene group having 2 to 8 carbon atoms.)

[0022] In the general formula (V), the alkyl group optionally having a hydroxyl group of 1 to 30 carbon atoms represented by R ⁹ is the substituent exemplified by R in the general formula (II). And may have a hydroxyl group of 1 to 30 carbon atoms represented by R ^9. Examples of the cycloalkyl group include cyclopropylene, cyclobutynole, cyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, Cyclooctyl, cyclohexyl, cyclodecyl, 1-hydroxycyclohexyl, 2 hydroxycyclohexyl, 3 hydroxycyclohexyl, 4 hydroxycyclohexyl, etc., and those having 1 to 30 carbon atoms represented by R ⁹ Examples of aryl groups that may have a hydroxyl group include phenol, naphthyl, 2-methylphenol, 3-methylphenol, 4-methylphenol, 4-phenol, 3-isopropyl. Lopyl, 4-Isopropyl, 4-Butyl, 4 Isobutyl, 4 Tertiary, 4 Primary Hexanol, 4-Cyclohexyl, 4-Octyl 4- (2-Ethinolehexyl), 4-stearyl, 2, 3 dimethyl, 2, 4 dimethyl, 2, 5 dimethyl, 2, 6 dimethyl, 3, 4 dimethyl 3,5 dimethylphenyl, 2,4 ditertiarybutylphenyl, 2,5 ditertiarybutylphenyl, 2,6 ditertiarybutylphenyl, 2,4 ditertiarypentylphenyl, 2,5 di Tertiary amyl, 2, 5 di-tert-octyl, 2, 4 Dicumyl, hexyl, biphenyl, 2, 4, 5 Trimethyl, benzyl, phenethyl, 2- Phenylpropane 2-yl, diphenylmethyl, Examples include triphenylmethyl, styryl, cinnamyl, 2-phenylpropane-2-yl, diphenylmethyl, 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl.

In the above general formula (VI), the alkylene group having 2 to 8 carbon atoms represented by Z ³ includes ethylene, methylene, ethylene, propylene, butylene, methylethylene, pentylene, hexylene, Examples include heptalene and octylene. As the non-fluorine monomer (B), in addition to the (meth) acrylic acid monomer represented by the general formula (V) or (VI), diisopropyl fumarate, dicyclohexyl fumarate, fumarate Hydroxyl-containing vinyl monomers such as di-tert-butyl acid, diisoptyl fumarate, dibenzyl fumarate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and aryl alcohol , Vinyl monomers containing carboxylic acid groups such as (meth) acrylic acid, itaconic acid, fumaric acid, maleic acid, citraconic acid, benzoic acid butyl, crotonic acid, maleic acid, fumaric acid, (meth) acrylamide, N —Minol (meth) acrylamide, N, N—dimethyl (meth) acrylamide, N- (meth) atalyloylmorpholine and other amide group-containing vinyl Monomer, (meth) acrylic acid triethylene glycol - polyethylene glycol (meth) acrylic acid such as glycol ester - le, (meth) acrylic acid dipropylene glyco - esters of polypropylene glycol such as Rue ester, styrene, Bulle toluene, Aromatic butyl monomers such as _a- methyl styrene, vinyl formate, vinyl acetate, butyl propionate, carboxylic acid butyl esters such as stearic butyl, (meth) acrylic acid N, N-dimethylaminoethyl, (meth) acrylic acid N (Meth) acrylic acid esters of alcohols having tertiary amino groups such as N, N-dimethylaminopropyl ester, (meth) acrylic acid N, N-dimethylamino ester, 2-hydroxy-1,3-methacryloxy Propyltrimethylammonium chloride, (meth) acrylic acid N, N -Quaternary ammonium salts derived from (meth) acrylic acid, such as hydrochloride of dimethylaminoethyl, hydrochloride of (meth) atalylic acid N, N-dimethylaminopropyl ester, and the like.

[0025] The block copolymer (C) according to the present invention has a hydroxyl group in the A segment and the Z or B segment. In order to introduce a hydroxyl group into the A segment, it is sufficient to use at least one monomer having a hydroxyl group in the fluorine monomer (A). To introduce a hydroxyl group into the B segment, the non-fluorine monomer (B) has a hydroxyl group. One or more monomers may be used. When a hydroxyl group is present in the A segment having fluorine, the fluorine effect such as ink repellency of the fluorine-containing copolymer (E) may be inhibited. Therefore, the one introduced only in the B segment is preferable. The easiest method for introducing a hydroxyl group into the B segment is to use a (meth) acrylic acid ester having a hydroxyl group as an ester component in the non-fluorinated monomer (B). For example, diethylene glycol and (meth) acrylic acid ester, (meth) acrylic acid glycidyl It can be introduced from the alcohol adduct of the ester.

 [0026] The block copolymer (C) can be produced, for example, by a polymer polymerization method and a polymerization method using polymer peroxide as a polymerization initiator.

 [0027] In the case of the char-on polymerization method, the molecular weight distribution adjusting agent and, if necessary, diphenylethylene are charged into a sufficiently dried container, and the solvent and the char-on polymerization are started in a nitrogen atmosphere. The agent is introduced and the temperature is raised to 120-50 ° C. Subsequently, one or more of the fluorine-based monomers (A) are dropped over 1 second to 10 minutes and held for 5 minutes to 10 hours. Subsequently, one or more of the non-fluorinated monomers (B) are added dropwise over 1 second to 10 minutes and held for 5 minutes to 24 hours. After completion of the reaction, a compound having an active proton such as methanol is added to inactivate the cation species.

 [0028] Examples of the solvent include benzene, toluene, ethylbenzene, propylbenzene, butylbenzene, xylene, cyclopentane, cyclohexane, hexane, heptane, octane, nonane, decane, undecane, dodecane, jetyl ether, dipropyl ether, and the like. Examples thereof include solvents having no active proton, such as tenole, dibutinoleethenore, dipentinoleethenore, dihexinoleethenore, tetrahydrofuran and dioxane. These solvents can be used alone or in combination.

 [0029] Examples of the above-mentioned polymerization initiator include alkyl metals such as ethyllithium, propyllithium, n-butyllithium, sbutyllithium, tbutyllithium, methyl magnesium chloride, ethylmagnesium chloride, propylmagnesium chloride. , Butyl magnesium chloride, phenol magnesium chloride, 4-methylphenol

Grignard reagents such as humubromide, 4-methylphenol magnesium bromide, alkali metals such as lithium, sodium, potassium, lithium methoxide, lithium ethoxide, lithium propoxide, lithium butoxide, sodium methoxide, sodium ethoxide, sodium propoxy And metal alcoholates such as sodium butoxide, potassium methoxide, potassium ethoxide, strong rhodium propoxide and potassium butoxide.

[0030] Further, as the ion polymerization initiator, the ion polymerization initiator exemplified above may be used as a diphenol. It is also possible to react the ruthenium in advance and use the reaction product. In this case, the amount of diphenylethylene used is 0.5 to 3 mol, preferably 1 to 2 mol, based on 1 mol of the cation polymerization initiator! /.

[0031] Examples of the molecular weight distribution regulator include lithium chloride, lithium bromide, lithium methoxide, lithium (2-methoxyethoxide), lithium (2-ethoxyethoxide), lithium (2-proboxetoxide), Lithium (2-butoxetoxide), lithium (2- (2-methoxyethoxy) ethoxide), sodium chloride, sodium bromide, sodium ethoxide, sodium (2-methoxyethoxide), sodium (2-ethoxyethoxide), Sodium (2-Proboxetoxide), Sodium (2-Butoxyshoxide), Sodium (2- (2-Methoxyethoxy) ethoxide), Potassium chloride, Potassium bromide, Potassium ethoxide, Potassium (2-Methoxyethoxide) ), Potassium (2-e Kishetokishido), potassium (2-pro Boki shell butoxide), potassium (2-butoxide shell butoxide), potassium (2- (2-Metokishe butoxy) ethoxide) can be mentioned. These molecular weight distribution regulators can be used singly or in combination. Further, the amount used is 0.5 to 50 mol, preferably 1 to 20 mol, per 1 mol of the anion polymerization initiator.

[0032] In the polymerization method using polymeric peroxide as a polymerization initiator, it can be produced by using ordinary polymer polymerization method, suspension polymerization method, solution polymerization method, emulsion polymerization method using polymeric baroxide. . In the case of the solution polymerization method, for example, a method of forming the non-fluorine monomer (B) in the first step and the fluorine monomer (A) in the second step can be used. That is, a peroxide-containing non-fluorinated polymer in which a peroxide bond is introduced into a chain by polymerizing a non-fluorinated monomer (B) in a solvent using a polymer peroxide as a polymerization initiator. Is obtained. Next, in the second step, when the polymerization is carried out with the fluoromonomer (A) in the solution obtained in the first step, the peroxide bond in the non-fluorinated polymer containing a peroxide bond is cleaved. Thus, a block copolymer (C) is obtained. In the two-stage polymerization as described above, the fluorine monomer (A) in the second step may be used in the first step, and the non-fluorine monomer (B) in the first step may be used in the second step. The amount of polymeric peroxide used in the first step is usually 0.5 to 20 parts by mass with respect to 100 parts by mass of the monomer, the polymerization temperature is 60 to 130 ° C, and the polymerization time is 2 to 10 parts. It's time. The polymerization temperature in the second step is usually 60 to 140 ° C., and the polymerization time is 3 to 15 hours.

 [0033] The polymeric peroxide is a compound having two or more peroxide bonds in one molecule. As the polymer peroxide, one or more of various polymer peroxides described in JP-B-5-59942 can be used.

[0034] The solvent is not particularly limited as long as it can dissolve or disperse the obtained block copolymer (C). For example, water, methyl alcohol, ethyl alcohol, propyl alcohol, 2-propino oleanol Reconole, 1-Butino Renoreconole, 2-Butino Renoreconole, 2-Methinore 1 Propanore, 2-Methinore 2-Propanenore, 1 Pentanolenore, 2-Pentanol, 3 Pentanol, Cyclopentanol, 2 Hexanol, 3 Hexanol, Cyclohexanol, Methylcetosolve, Ethylcetosolve, Acetone, 2-Butanone, 3-Methyl-2-butanone, 2 Pentanone, 3-Pentanone, 2-Methyl-3-pentanone, 3-Methyl-2 Pentanone, 4-Methyl-2 Pentanone, 2, 4 Dimethyl-3 —Pentanone, 4, 4 Dimethyl-2 To pentanone, 2-hexanone, 3-hexanone, cyclopentanone, cyclohexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-hexanone, 5-methyl-2-hexanone, 5-methyl-3 Xanone, Methyl acetate, Ethyl acetate, Propyl acetate, Isopropyl acetate, Butyl acetate, Trimethyl Acetic acid methylol, Isobutinol acetate, Butinole acetate, Pentinole acetate, Isoaminole acetate, Methyl propionate, Ethyl propionate, Propyl propionate, Butyl propionate , Isobutyl propionate, t-butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, methyl isobutyrate, ethyl isobutyrate, methyl 2-methylbutyrate, methyl methyl proproate, benzene, toluene, Ye Benzene, xylene, phenol, cyclohexane, hexane, heptane, octane, nonane, decane, undecane, dodecane, formamide, acetoamide, dimethylformamide, dimethylacetamide, acetonitrile, tetrahydrofuran, 1, 1, 2, —trifluoro-1, 2,2-Trichloroethane, tetrachlorodifluoroethane, methylchloroform, hexafluoroisopropanol, (meth) paraxylene hexafluoride, perfluorinated hexane, and perfluorinated heptane. These solvents can be used alone or in combination. [0035] Examples of the polybasic acid anhydride (D) include succinic acid anhydride, maleic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, 2, 2, 1 3, 3, and 1benzov. Enone tetracarboxylic acid anhydrous, 3, 3, 1, 4, 4, monobenzophenone tetracarboxylic anhydride, ethylene glycol bisanhydro trimellitate, glycerol tris anhydro trimellitate, phthalic anhydride Oxahydrophthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5- (2,5 dixotetrahydro Furyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride maleic anhydride Examples include acid-added products, dodecyl succinic anhydride, and methyl hymic anhydride. Among these, succinic anhydride, trimellitic anhydride, and tetrahydrophthalic anhydride are preferable.

 [0036] A known method can be used as a method for producing the fluorine-containing copolymer (E), and is not particularly limited. For example, the block copolymer (C) is dissolved in a solvent to obtain a polybasic compound. It can be obtained by reacting the acid anhydride (D) at a ratio of 0.1 to 1 mol, preferably 0.8 to 1 mol, with respect to 1 mol of the hydroxyl group in the block copolymer (C). it can. The polymerization temperature is 80 to 140 ° C., and the polymerization time is 2 to 10 hours.

[0037] The solvent is not particularly limited, but ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; methyl acetate , Ester solvents such as ethyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate; ethylene glycol monomethinoatenole, ethylene glycol monoethylenoatenore, propylene glycol nolemonomethyl ether acetate Cellsolve solvents such as methanol; ethanol, iso- or n-propanol, iso- or n-butanol, and amyl alcohol; BTX solvents such as benzene, toluene, and xylene; hexane, heptane, Fats such as octane and cyclohexane Hydrocarbon solvents: Halogenated aliphatic hydrocarbon solvents such as tetrasalt carbon, carbon form, trichloroethylene, and methylene chloride; Halogenated aromatic hydrocarbon solvents such as black benzene should be used. Cellsolv solvent is preferred Yes.

 [0038] In the fluorine-containing copolymer (E), the ratio of the fluorine-based monomer (A) and the non-fluorine-based monomer (B) is 10Z90 to 80Z20, preferably 15 to 85 to 40 to 40 by mass ratio. is there. If the amount of the fluorine-based monomer (未 満) is less than 10% by mass, ink repellency may be lowered. If the amount is more than 60% by mass, the resulting fluorine-containing copolymer (Ε) is dissolved in a solvent. May decrease.

 [0039] In the fluorine-containing copolymer (Ε), the mass average molecular weight is 10,000 to 100,000, preferably 20000 to 50,000. If it is less than 10000, the production efficiency of the fluorinated copolymer (Ε) may be reduced. If it exceeds 100000, it is difficult to produce the fluorinated copolymer (Ε) because of poor solubility in the solvent. . Here, the mass average molecular weight is a value in terms of polystyrene.

 [0040] In the fluorine-containing copolymer (i), the acid value is 20 mgKOHZg or more, preferably 30 mgKOHZg or more. If it is less than 20 mg KOHZg, the developability of the alkali-developable photosensitive resin composition containing the same may be deteriorated.

 [0041] The alkali-developable resin composition of the present invention comprises an unsaturated monobasic acid (G) added to the multifunctional epoxy resin (F) in addition to the fluorine-containing copolymer (E). A reaction product (H) obtained by esterifying a polybasic acid anhydride (D ′) with an epoxy adduct having the above structure.

 [0042] One preferred example of the polyfunctional epoxy resin (F) is an alkylidene bisphenol polyglycidyl ether type epoxy resin represented by the following general formula (III).

[0043] [Chemical 5]

(In the formula, Z ⁴ is a direct bond, a methylene group, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group, 0, S, SO, SS, SO, CO, OCO or the following [6]. Or the substitution represented by [匕 7]

 2

及びThe alkylidene group may be substituted with a halogen atom.

as well as

R ⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or 1 to 8 carbon atoms. Represents an alkoxy group having 2 to 5 carbon atoms or a halogen atom, and the alkyl group, alkoxy group, and alkyl group may be substituted with a halogen atom, n is an integer of 0 to 10 Represents. )

[0044] [Chemical 6]

(In the formula, Y ¹ represents a hydrogen atom, a phenyl group which can be substituted by an alkyl group having 1 to 10 carbon atoms or an alkoxy group, or a cycloalkyl group having 3 to 10 carbon atoms; Y 2 Represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a alkenyl group having 2 to 10 carbon atoms or a halogen atom, and the alkyl group, alkoxy group and alkenyl group are halogen atoms. (It may be substituted with an atom. P represents a number from 0 to 4.)

[0045] [Chemical 7]

During [0046] the above general formula (III), the alkylidene group having 1 to 4 carbon atoms as represented by Z ^4, methylcarbamoyl Ren, ethylene, propylidene, isopropylidene, butylidene, isobutylidene, and the like, with Z ⁴ Examples of the alicyclic hydrocarbon group include cyclopropylidene, cyclopentylidene, cyclohexylidene, and 4-chlorocyclohexylidene.

R²、 R³又は R⁴で表される炭素原子数 1 〜8のアルコキシ基としては、メチルォキシ、ェチルォキシ、プロピルォキシ、イソプロ ピルォキシ、ブチルォキシ、第二ブチルォキシ、第三ブチルォキシ、イソブチルォキ シ、アミルォキシ、イソアミルォキシ、第三アミルォキシ、へキシルォキシ、シクロへキ シルォキシ、ヘプチルォキシ、イソへプチルォキシ、第三へプチルォキシ、 n—ォクチ ルォキシ、イソォクチルォキシ、第三ォクチルォキシ、 2—ェチルへキシルォキシ等が 挙げられ、

R³又は R⁴で表される炭素原子数 2〜5のァルケ-ル基としては、ビ 二ノレ、 1ーメチノレエテニノレ、 2—メチノレエテニノレ、 2 プロぺニノレ、 1ーメチノレー 3 プ 口べ-ル、 3 ブテュル、 1ーメチルー 3 ブテュル、イソブテュル、 3 ペンテ-ル等 が挙げられる。 R¹ R²、 R³又は R⁴で表されるハロゲン原子としては、フッ素、塩素、臭 素、ヨウ素等が挙げられる。また、上記アルキリデン基を置換してもよいハロゲン原子 、上記アルキル基、アルコキシ基及びアルケ-ル基を置換してもよいハロゲン原子は 、 R³又は R⁴で表されるハロゲン原子として例示したものが挙げられる。 Examples of the alkyl group having 1 to 5 carbon atoms represented by R ³ or R ⁴ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isoamyl, and tert-amyl. Such as amyl,

The R ^2, R ³ or an alkoxy group having a carbon number of 1-8 represented by R ^4, Mechiruokishi, Echiruokishi, Puropiruokishi, isoproterenol Piruokishi, Buchiruokishi, second Buchiruokishi, third Buchiruokishi, Isobuchiruoki shea, Amiruokishi, Isoamiruo Xy, tertiary amyloxy, hexyloxy, cyclohexyloxy, heptyloxy, isoheptyloxy, tertiary heptyloxy, n-octyloxy, isooctyloxy, tertiary octyloxy, 2-ethylhexyloxy, etc. Named,

The alkenyl group having 2 to 5 carbon atoms represented by R ³ or R ⁴ includes bininore, 1-methinoreethinenole, 2-methinoleethenore, 2propenenole, 1-methinole Examples include oral base, 3 buthl, 1-methyl-3 butur, isobutur, and 3 pentale. Examples of the halogen atom represented by R ¹ R ² , R ³ or R ⁴ include fluorine, chlorine, fluorine and iodine. In addition, the halogen atom that may be substituted with the alkylidene group, the halogen atom that may be substituted with the alkyl group, alkoxy group, and alkyl group are those exemplified as the halogen atom represented by R ³ or R ⁴ Is mentioned.

In the above [Chemical Formula 6], the phenyl group represented by Y ¹ can also be substituted: ¹ to C: an alkyl group of LO and an alkyl group of 1 to 10 carbon atoms represented by Y ² Is methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isamyl, tert-amyl, cyclopentyl, hexyl, 2 hexyl, 3-hexyl, cyclohexyl , Bicyclohexylenoyl, 1-methylcyclohexyl, heptinole, 2heptyl, 3heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, Noel, isonoel , decyl, and the like,丫¹ represented by Hue - number of carbon atoms may be replaced by Le group 1: Arco 1 to 10 carbon atoms represented by an alkoxy group and Y ² of L0 Si groups include methyloxy, ethyloxy, propyloxy, isopropyloxy, butyloxy, sec-butyloxy, tert-butoxy, isobutyloxy, amyloxy, isoamyloxy, tert-amyloxy, hexyloxy, cyclohexyloxy, heptyloxy, Puchiruokishi isohexane, third to Puchiruokishi, n- Okuchiruokishi iso O Chi Ruo carboxymethyl, tert Okuchiruokishi, Kishiruokishi to 2- Echiru Roh - Ruokishi, Deshiruokishi and the like, the number of carbon atoms 3 to that represented by Y ¹ Examples of the cycloalkyl group 10 include cyclopropyl, cyclobutyl, cyclopentinole, 2-methinorecyclopentinole, cyclohexenole, 4 chlorocyclohexyl, etc., and the number of carbon atoms represented by Y ² is 2 to 2. As the alkenyl group of 10, vinyl, 1-methinoleethenore, 2-methinoleethenore, 2 propenore, 1-methinole 3 propenyl, 3 butenyl, 1-methyl-3-butenyl, isobutenyl, 3 pentenyl, 4 hexyl, heptul, octenyl A halogen atom that may be substituted for the halogen atom represented by Y ² , the alkyl group, the alkoxy group, and the alkenyl group. Examples of the child include those exemplified above.

 [0048] One of the preferred polyfunctional epoxy resins (F) is a phenol novolac epoxy resin represented by the following general formula (IV).

[0049] [Chemical 8]

(In the formula, R ⁵ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 2 to 5 carbon atoms, a halogen atom, or (4- Glycidyloxyphenyl) -2,2-dimethylmethylidene group, alkyl, alkoxy and alkenyl groups may be substituted with halogen atoms R ⁶ and R ⁷ are each independently a hydrogen atom Or a glycidyloxyphenyl group, and m represents an integer of 0 to 10.)

[0050] The alkyl group having 1 to 5 carbon atoms, the alkoxy group having 1 to 8 carbon atoms, the alkyl group having 2 to 5 carbon atoms, and the halogen atom represented by R ⁵ in the above [Chemical Formula 8] In addition, examples of the halogen atom that may substitute the alkyl group, the alkoxy group, and the alkyl group include those exemplified above.

 [0051] As the polyfunctional epoxy resin (F), a polyolefin-type epoxy resin having a polyfunctional epoxy group can also be used.

 [0052] Examples of epoxy compounds such as epoxy compounds represented by the above general formulas (III) and (IV) and polymethane type epoxy resins having polyfunctional epoxy groups include the following compounds No. 1 to No. 20 is mentioned.

 [0053] [Chemical 9]

Compound No. 1

[0054] [Chemical 10]

一一多2C HI

11C 2C HI

 § Mongolia.

? J / 丫 JV †. IC ^ ¾? 02. [0061] [Chemical 17]

[0062] [Chemical 18]

[0063] [Chemical 19]

 [0064] [Chemical 20]

 [0065] [Chemical 21]

 Compound No. 13

[0066] [Chemical 22]

[0067] [Chemical 23]

[0068] [Chemical 24]

 Compound No. 16

[0069] [Chemical 25]

 Compound No. 17

[0070] [Chemical 26]

 Compound No. 18

[0071] [Chemical 27] Compound No.

[0072] [Chemical 28]

Compound No. 20

 [0073] Examples of the unsaturated monobasic acid (G) used to obtain the reaction product (H) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, and hydroxyethyl methacrylate. Examples thereof include chlorate 'maleate, hydroxyethinoreatalylate' malate, hydroxypropinoremethacrylate 'maleate, hydroxypropinorea talelate' malate, dicyclopentagenate 'maleate. Among these, acrylic acid and methacrylic acid are preferable. Examples of the polybasic acid anhydride (D ′) include the compounds exemplified for the polybasic acid anhydride (D).

In the present invention, the reaction product (H) may be further reacted with a polyfunctional epoxy compound (K). The polyfunctional epoxy compound can be used for adjusting the acid value to further improve the developability of the alkali-imageable resin composition of the present invention. Examples of the polyfunctional epoxy compound include glycidyl metatalylate, methyl daricidyl ether, ethyl daricidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl daricidyl ether, isobutyl daricidyl ether, t-butyl glycidyl ether. , Pentyl glycidyl ether, hexyl glycidyl ether, heptyl daricidyl ether, octyl daricidyl ether, nonyl daricidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl Ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether Ether, propargyl daricidyl ether, p-methoxy Shetyldaricidyl ether, phenol glycidyl ether, p-methoxyglycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methylcresyl glycidyl ether, 4-norphenol glycidyl ether, benzyl Glycidyl ether, p Tamylphenyl daricidyl ether, Trityl daricidyl ether, 2, 3 Epoxy propyl metatalylate, Epoxidized soybean oil, Epoxidized linseed oil, Glycidyl butyrate, Bulcyclohexane monooxide, 1 , 2 Epoxy 4 Bulcyclohexane, Styrene oxide, Pinene oxide, Methyl styrene oxide, Cyclohexene oxide, Propylene oxide, Monoepoxy compounds such as the following compounds No. 21 and No. 22; ), Hydrogenated Bisphenol type epoxy resin such as bisphenol type epoxy resin; ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4 butanediol diglycidyl ether, 1,6 hexanediol diglycidyl ether, 1, 8 Octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3 propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether Noreite Nore, Hexaethyleneglyconoresiglicidinoreatenore, 1,4-cyclohexanedimethanol diglycidyl ether, 1, 1, 1-tri (glycidyloxymethyl) propan, 1, 1, 1 —Glycidyl ethers such as tri (glycidyloxymethyl) ethane, 1, 1,1-tri (glycidyloxymethyl) methane, 1,1,1,1-tetra (glycidyloxymethyl) methane; 3, 4-Epoxy 6-Methylcyclohexylmethyl- 3, 4-Epoxy 6-methylcyclohexanecarboxylate, 3, 4 Epoxycyclohexylmethyl- 3, 4 Epoxy cyclohexylene noroxylate, 1 Epoxy ethynole 3, 4 Epoxy cycloto Cycloaliphatic epoxy resin such as xanthine; glycidyl esters such as diglycidyl phthalate, tetrahydro phthalic acid diglycidyl ester, dimer acid glycidyl ester; tetraglycidyl diaminodiphenylmethane, triglycidyl P-aminophenol, N, N Glycidylamines such as diglycidyl dilin; 1, 3 Heterocyclic epoxy resins such as diglycidyl-1,5-dimethylhydantoin and triglycidyl isocyanurate; Dioxide compounds such as dicyclopentadienoxide; Naphthalene type epoxy resin and trif Examples include phenylmethane type epoxy resin and dicyclopentagen type epoxy resin. The acid value of the solid content of the reaction product (H) is preferably in the range of 20 to 120 mgKOH / g. The amount of the polyfunctional epoxy compound (K) used preferably satisfies the acid value. Is preferably selected.

 [Chemical 29]

 Compound No. 21

[0076] [Chemical 30]

 [0077] The alkali-developable resin composition of the present invention can be made into an alkali-developable photosensitive resin composition by further adding a photopolymerization initiator ω.

[0078] The alkali-developable resin composition and the alkali-developable photosensitive resin composition of the present invention usually have a solution-like composition to which a solvent capable of dissolving or dispersing each component is added, if necessary. Used as a thing. The solvent is not particularly limited. For example, ketones such as methyl ethyl ketone, methyl amyl ketone, jetyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl ether, dioxane, tetrahydrofuran, 1, 2 — Ether solvents such as dimethoxyethane, 1,2-diethoxyethane, and dipropylene glycol dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, and η-butyl acetate; ethylene glycol monomethylenoate, ethylene glycol Norre monomethyl E Chino les ether Honoré, cellosolve solvents such as propylene glycol Honoré mono-methylol ether acetate; methanol, ethanol, iso one or _η-propanol, iso one or η- butanol, § Alcohol solvents such as mil alcohol; Soot solvents such as benzene, toluene and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; Terpenes such as turpentine oil, D-limonene and pinene Hydrocarbon oils; mineral spirits, Suzole # 310 (Cosmo Matsuyama Oil Co., Ltd.) Paraffinic solvents such as Rubesso # 100 (Eksony Chemical Co., Ltd.); carbon tetrachloride, black mouth form

Halogenated aliphatic hydrocarbon solvents such as trichloroethylene and methylene chloride; Halogenated aromatic hydrocarbon solvents such as black mouth benzene; Carbitol solvents, Aline, Triethylamine, Pyridine, Acetic acid, Acetonitrile, Examples thereof include carbon sulfide, tetrahydrofuran, N, N-dimethylformamide, N-methylpyrrolidone and the like. Among them, ketones or a solvate solvent are preferred. These solvents can be used as one or a mixture of two or more.

 [0079] An epoxy adduct having a structure in which the component (G) is added to the component (F) is esterified with the component (D ') and further reacted with the component (K) as necessary. The content of the reaction product (H) in the solution composition is preferably 30 to 90% by mass, particularly preferably 40 to 70% by mass in the solvent.

[0080] As the photopolymerization initiator ω used in the alkali-developable photosensitive resin composition of the present invention, conventionally known compounds can be used. For example, benzophenone, phenyl biphenyl ketone, 1-hydroxy 1-Benzylcyclohexane, benzyl, benzyl dimethyl ketal, 1 benzil 1-dimethylamino 1 1 (4, 1 morpholino benzoyl) propane, 2 morpholyl 2- (4-methyl mercapto) benzo Propane, thixanthone, 1 chloro4 propoxythioxanthone, isopropylthioxanthone, jetylthioxanthone, ethylanthraquinone, 4-benzoyl 4'-methyldiphenylsulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2 hydroxy — 2— (4, —Isopropyl Benzylpropane, 4 butyl benzoyl trichloromethane, 4 phenoxybenzoyl dichloromethane, methyl benzoylformate, 1,7-bis (9,1-ataridyl) heptane, 9-η-butyl 3,6 bis (2, 1-morpholino sobutyroyl) carbazole, 2-methyl-1 [4 (methylthio) phenol] 2 morpholinopropane 1-one, 2-methyl-4,6 bis (trichloromethyl) s triazine, 2 phenol-1,6 bis (Trichloromethyl) s triazine, 2-naphthyl-1,4,6-bis (trichloromethyl) -s triazine, the following compounds No. 23, No. 24 and the like. Among these, benzophenone and 2-methyl 1- [4- (methylthio) phenol] -2- morpholinopropane 1-one are preferable. [0081] [Chemical 31]

 Compound No. 2 3

(Wherein Y ³ represents a halogen atom or an alkyl group, R ¹² represents R ^a , OR ^a , COR ^a , SR ^a , CONR ^b or CN, and R ¹³ represents R OR COR SR ^a or NR represents ^b, R "is R ^a, oR COR ^a, represents SR ^a or NR ^a R ^b, R ^a and R ^b represents an alkyl group, Ariru group, § La alkyl group or a heterocyclic group, these May be substituted with a halogen atom and Z or a heterocyclic group, and the alkylene part of the alkyl group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond, or an ester bond. Also, and R ^b may be joined together to form a ring. Q is 0-4.)

[0082] [Chemical 32]

(In the formula, R ¹² , R ¹³ , R ¹⁴ , R ^a and R ^b are the same as the above compound No. 23, Y ³ ′ is the same as Y ³ , and Z ⁹ and Z ⁹ ′ are oxygen atoms. Or a sulfur atom, r and s are each independently 1

R ¹² ′ is the same as R ¹² ; R ¹³ ′ is the same as R ¹³ ; R ¹⁴ ′ is the same as R ″; z ^1Q is the diol residue or dithiol residue Represents a group.)

[0083] In the alkali-developable photosensitive resin composition of the present invention, the content of the photopolymerization initiator ω is in the solution composition obtained by adding a solvent to the alkali-developable resin composition of the present invention. On the other hand, 0.1 to 30% by mass, particularly 0.5 to 5% by mass is preferable.

[0084] In the alkali-developable resin composition and alkali-developable photosensitive resin composition of the present invention, a monomer having an unsaturated bond, a chain transfer agent, a surfactant and the like can be used in combination. [0085] Monomers having an unsaturated bond include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, N-octyl acrylate, isooctyl acrylate, isononyl acrylate, and acrylic acid. Stearyl, methetetyl acrylate, dimethylaminoethyl acrylate, zinc acrylate, 1,6 hexanediol diatalylate, trimethylolpropane tritalylate, 1-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, methacrylic acid Butyl, tertiary butyl methacrylate, cyclohexyl methacrylate, trimethylolpropane trimetatalylate, dipentaerythritol pentaatalylate, dipentaerythritol hexaatalylate, pentaerythris Tall tetra Atari rate, pentaerythritol Atari rate include Torishikurode Kanji methylol di Atari rates.

 [0086] Examples of the chain transfer agent include thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropiool) glycine, 2 Mercaptonicotinic acid, 3- [N- (2 mercaptoethyl) power ruberamoyl] propionic acid, 3- [N- (2 mercaptoethyl) amino] propionic acid, N- (3 mercaptopropiool) alanine, 2 Mercaptoethanesulfonic acid, 3-Mercaptopropanesulfonic acid, 4 Mercaptobutanesulfonic acid, Dodecyl (4-methylthio) phenyl ether, 2 Mercaptoethanol, 3 Mercapto 1,2 Propandiol, 1 Mercapto 2 Propanol, 3 Mercapto 2 Butanol, mercaptophenol, 2-mercaptoethylamine, 2-me Mercapto compounds such as lucaptoimidazole, 2-mercapto-3-pyridinol, 2 mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate) And a disulfide compound obtained by oxidizing the mercapto compound, and a sodo alkyl compound such as sodoacetic acid, sodopropionic acid, 2-sodoethanol, 2-sodoethane sulphonic acid and 3-sodopropane sulphonic acid. .

[0087] Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkylcarboxylates, and key-on systems such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates. Surfactant, higher amine halide, No. Cationic surfactants such as quaternary ammonium salts, polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, fatty acid monoglycerides and other nonionic surfactants, amphoteric surfactants, silicone surfactants Surfactants such as agents can be used, and these may be used in combination.

 [0088] In the alkali-developable resin composition and the alkali-developable photosensitive resin composition of the present invention, the properties of the cured product can be improved by using a thermoplastic organic polymer. Examples of the thermoplastic organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene (meth) acrylic acid copolymer, (meth) Examples include methyl methacrylate methacrylate, polyvinyl butyral, cellulose ester, polyacrylamide, and saturated polyester.

 [0089] In addition, the alkali-developable resin composition and the alkali-developable photosensitive resin composition of the present invention include, if necessary, carsol, hydroquinone, pyrocatechol, tert-butylcatechol, phenothiazine and the like. Conventional additives such as a thermal polymerization inhibitor, a plasticizer, an adhesion promoter, a filler, an antifoaming agent, and a leveling agent can be provided.

 [0090] The alkali-developable photosensitive resin composition of the present invention is applied on a support substrate such as metal, paper, plastic, etc. by a known means such as a roll coater, a curtain coater, various printing and dipping. In addition, after being applied on a supporting substrate such as a film, it can be transferred onto another supporting substrate, and the application method is not limited.

 [0091] The alkali-developable photosensitive resin composition of the present invention is mainly mixed with the solvent and the photopolymerization initiator and used as an alkali-developable photosensitive resin composition. The photosensitive photosensitive resin composition can be used for various applications such as a photo-curable paint, a photo-curable adhesive, a printing plate, and a photoresist for a printed wiring board, and the application is not particularly limited.

[0092] Further, as the light source of the active light used for curing the alkali-developable photosensitive resin composition of the present invention, one that emits light having a wavelength of 300 to 450 nm can be used, for example. Ultra high pressure mercury, mercury vapor arc, carbon arc, xenon arc, etc. can be used. Example

 Hereinafter, the present invention will be described in more detail with reference to examples and the like, but the present invention is not limited to these examples.

 [0094] [Example 1] Production of fluorine-containing copolymer No. 1

 Modiper F 600 block copolymer (C) (fluorinated copolymer; manufactured by NOF Corporation), 1, 2, 3, 6-tetrahydrophthalic anhydride 16 which is polybasic acid anhydride (D) 16 Charge 4 g and 400 g of propylene glycol 1 monomethyl ether 2 acetate, stir at 120 ° C until the peak of acid anhydride disappears, and use fluorine-containing copolymer (E) as propylene glycol 1 monomethyl ether 2-acetate solution. A certain fluorine-containing copolymer No. 1 was obtained. Various analyzes were conducted on this. Mass average molecular weight 33000, Acid value 57.9mgKOHZg, Fluorine content 12.0% by mass (EDX analysis), Carbon content 64.1% by mass (EDX analysis), Oxygen 24.0% by mass (EDX analysis), IR spectrum :Figure 1.

 [0095] [Example 2] Production of fluorine-containing copolymer No. 2

 This is a fluorinated copolymer (E) as a propylene glycol 1 monomethyl ether 2-acetate solution in the same manner as in Example 1 except that the polybasic acid anhydride (D) is changed to 20.7 g of trimellitic acid anhydride. Fluorine-containing copolymer No. 2 was obtained. Various analyzes were conducted on this. Weight average molecular weight 33000, acid value 116mgKOH / g, fluorine content 11.5 mass%, carbon content 62.8 mass%, oxygen 25.3 mass% (EDX analysis), IR spectrum: Fig. 2

[0096] [Example 3] Production of fluorine-containing copolymer No. 3

 This is a fluorinated copolymer (E) as a propylene glycol 1 monomethyl ether 2-acetate solution in the same manner as in Example 1 except that the polybasic acid anhydride (D) is changed to 9.9 g of maleic anhydride. A fluorinated copolymer No. 3 was obtained (mass average molecular weight 35000, acid value 52. lmgKOH / g).

[0097] [Example 4] Production of fluorine-containing copolymer No. 4

This is a fluorinated copolymer (E) as a propylene glycol 1 monomethyl ether 2-acetate solution in the same manner as in Example 1 except that the polybasic acid anhydride (D) is changed to 15.6 g of phthalic anhydride. Fluorine-containing copolymer No. 4 was obtained (mass average molecular weight 29,000 Acid value 56.3 mg KOH / g).

 [0098] [Example 5] Production of fluorine-containing copolymer No. 5

 The block copolymer (C) was changed to Modiper F-220 (fluorinated copolymer; manufactured by NOF Corporation) 10 Og, and the polybasic acid anhydride (D) was changed to 9.9 g succinic anhydride. In the same manner as in Example 1, a fluorinated copolymer No. 5 as a fluorinated copolymer (E) was obtained as a propylene glycol 1-monomethyl ether 2-acetate solution (mass average molecular weight 36000, Acid value 31.3 mg KOHZg;).

 [0099] [Example 6] Production of fluorine-containing copolymer No. 6

 Fluorinated copolymer (E) as propylene glycol 1 monomethyl ether 2-acetate solution in the same manner as in Example 5 except that polybasic acid anhydride (D) was changed to 19.7 g of trimellitic acid anhydride Fluorine-containing copolymer No. 6 was obtained (mass average molecular weight 3,600, acid value 64.5 mgKOH / g).

 [0100] [Example 7] Production of fluorine-containing copolymer No. 7

 This is a fluorinated copolymer (E) as a propylene glycol 1 monomethyl ether 2-acetate solution in the same manner as in Example 5 except that the polybasic acid anhydride (D) was changed to 11.4 g of itaconic acid anhydride. Fluorine-containing copolymer No. 7 was obtained (mass average molecular weight 35000, acid value 30.4 mgKOH / g).

 [0101] [Example 8] Production of fluorine-containing copolymer No. 8

 Fluorine-containing copolymer (E) as propylene glycol 1 monomethyl ether 2 acetate solution in the same manner as in Example 5 except that polybasic acid anhydride (D) was changed to 15.6 g of hexahydrophthalic anhydride. ) Was obtained (mass average molecular weight 37000, acid value 32.6 mg KOHZg;).

 [0102] [Example 9] Production of fluorine-containing copolymer No. 9

Propylene glycol 1-monomethyl ether in the same manner as in Example 5 except that the block copolymer (C) was changed to 100 g of a defender MCF-350SF (fluorinated copolymer; manufactured by Dainippon Ink & Chemicals, Inc.) Fluorinated copolymer No. 9 which is a fluorinated copolymer (E) as a 2-acetate solution was obtained (mass average molecular weight 38000, acid value 56.4 mgKOH / g) [Example 10] Production of fluorine-containing copolymer No. 10

 This is a fluorinated copolymer (E) as a propylene glycol 1 monomethyl ether 2-acetate solution in the same manner as in Example 9, except that the polybasic acid anhydride (D) is changed to 9.9 g of maleic anhydride. Fluorine-containing copolymer No. 10 was obtained (mass average molecular weight 4200

0, acid value 58.3 mg KOH / g).

[Example 11] Production of fluorine-containing copolymer No. 11

 This is a fluorinated copolymer (E) as a propylene glycol 1 monomethyl ether 2-acetate solution in the same manner as in Example 9, except that the polybasic acid anhydride (D) is changed to 15.6 g of phthalic anhydride. Fluorine-containing copolymer No. 11 was obtained (mass average molecular weight 4000

0, acid value 52.4 mg KOH / g).

[Example 12] Production of alkali-developable resin composition No. 1

 <Step 1> 1, 1 Bis (4, 1-hydroxyphenol) 1 (, 1-biphenyl) 1-Production of cyclohexylmethane

 Charge 70.5 g of bicyclohexylcyclohexyl ketone, 200.7 g of phenol, and 10.15 g of thioacetic acid, and add 180.0 g of trifluoromethanesulfonic acid to 18. C was dropped for 20 minutes. After reacting at 17 to 19 ° C. for 18 hours, 500 g of water was added to stop the reaction, 500 g of toluene was removed, and the organic layer was washed with water until the pH became 3 to 4, and the organic layer was separated. Toluene, water and excess phenol were distilled off. Toluene was added to the residue and the precipitated solid was filtered off and dispersed and washed with toluene to obtain 59.2 g of light yellow crystals (yield 51%). The melting point of the pale yellow crystals was 239.5 ° C, and it was confirmed that the pale yellow crystals were the target product.

<Step 2> Production of 1, 1 bis (4,1 epoxypropyloxyphenyl) 1 1 (, 1 biphenyl)-1-cyclohexylmethane

1, 1-bis (4, 1-hydroxyphenol) 1- (1, 1-biphenyl)-1 cyclohexylmethane 57.5g and epichlorohydrin 195.8 g obtained in step 1 were charged. In addition, 602 g of benzyltriethyl ammonium chloride was added and stirred at 64 ° C for 18 hours. Subsequently, the temperature was lowered to 54 ° C, and 43.0 g of a 24 mass% sodium hydroxide aqueous solution was added dropwise, followed by stirring for 30 minutes. Epichlorohydrin and water were distilled off, 216 g of methyl isobutyl ketone was added and washed with water, and 2.2 g of 24% by weight sodium hydroxide sodium hydroxide was added dropwise. After stirring at 80 ° C for 2 hours, cool to room temperature, 3 The mixture was neutralized with a mass% sodium monophosphate aqueous solution and washed with water. The solvent was distilled off to obtain 57 g (yield 79%) of a yellow solid. (Melting point 64.2 ° C, epoxy equivalent 282, n = 0.04). The yellow crystals were confirmed to be the target product.

 [0107] Step 3> Production of Alkali Developable Resin Composition No. 1

 1, 1 Bis (4 'epoxypropyloxyphenyl) 1- (1 "-biphenyl) 1) Polyfunctional epoxy resin (F) obtained in Step 2 16.9 g of cyclohexylmethane, unsaturated one Basic acid (G), acrylic acid 44.3 g, 2, 6 di-tert-butyl-p-cresol 0.6 g, tetrabutylammonium acetate 1. lg and propylene glycol 1-monomethyl ether-2-acetate 142.5 g And stirred for 16 hours at 120 ° C. After cooling to room temperature, 71.8 g of propylene glycol 1 monomethyl ether 2-acetate, 48.2 g of succinic anhydride, which is a polybasic acid anhydride (D ′), and tetraptyl Ammonium acetate 2.5 g was added and stirred for 5 hours at 100 ° C. Furthermore, 1, 1 bis (4, monoepoxypropyloxyphenol-polyfunctional epoxy compound (K) obtained in Step 2 was used. 1) 1— (1, 1, Bif Nyl) -1 cyclohexylmethane 50.8 g and propylene glycol 1-monomethyl ether 2-acetate 21.8 g added to 120. 12 hours at C, 2 hours at 80 ° C, 2 hours at 40 ° C After stirring for a while, 146.3 g of propylene glycol 1 monomethyl ether-2 acetate and propylene glycol-1-monomethyl of fluorine-containing copolymer No. 1 which is the fluorine-containing copolymer (E) obtained in Example 1 4. 24 g of ether-2-acetate solution was added to obtain an alkali-developable resin composition No. 1 as a target product as a propylene glycol 1 monomethyl ether 2-acetate solution.

 [Example 13] Production of alkali-developable resin composition No. 2

Polyfunctional epoxy resin (F) 1, 1 bis (4 'epoxypropyloxyphenyl) — 1 (, -biphenyl)-1 cyclohexylmethane 43g, unsaturated monobasic acid (G) Acrylic acid 33.6 g, 2,6 di-tert-butyl-p-taresole 0.04 g, tetrabutylammonium acetate 0.21 g and propylene glycol 1 monomethyl ether-2 acetate 18 g were charged and stirred at 120 ° C. for 13 hours. After cooling to room temperature, 24 g of propylene glycol-1 monomethyl ether 2 acetate and 10 g of succinic anhydride as polybasic acid anhydride (D ′) were added and stirred at 100 ° C. for 3 hours. Multifunctional epoxy Compound (K) bisphenol glycidyl ether 8g was added and stirred at 120 ° C for 4 hours, 90 ° C for 3 hours, 60 ° C for 2 hours, 40 ° C for 5 hours, and then propylene glycol 1 Add 29 g of monomethyl ether 2 acetate and propylene glycol 1 monomethyl ether 2-acetate solution 1.28 g of fluorine-containing copolymer No. 1 which is the fluorine-containing copolymer (E) obtained in Example 1 to add propylene. As a glycol 1-monomethyl ether-2-acetate solution, an alkali-developable resin composition No. 2 as a target product was obtained.

[Example 14] Production of alkali-developable resin composition No. 3

 Polyfunctional epoxy resin (F) 1, 1 bis (4 'epoxypropyloxyphenyl) — 1— (, — biphenyl) — 1-cyclohexylmethane 169.5 g, unsaturated monobasic acid (G) 44.3 g of acrylic acid, 2,6 di-tert-butyl-p-taresole 0.6 g, tetrabutylammonium acetate 1. lg and propylene glycol 1 monomethyl ether-2-acetate 142.5 g, 120 ° Stir at C for 16 h. Cool to room temperature, and add 93. lg of propylene glycol 1 monomethyl ether 2 acetate, 74. lg of polybasic acid anhydrous (D,) hexahydrophthalic anhydride and 2.5 g of tetra n butylammonium acetate. The mixture was stirred at 70 ° C for 4 hours. Further, 31.3 g of ethylene glycol diglycidyl ether and 146.3 g of propylene glycol 1 monomethyl ether 2 acetate which are polyfunctional epoxy compounds (K) and the fluorine-containing copolymer (E) obtained in Example 1 are contained. Fluorocopolymer No. 1 in propylene glycol 1 monomethyl ether 1 2 acetate solution 4. Add 31 g, and develop the alkali developable resin composition No. 1 as propylene glycol 1-monomethyl ethereol 2 acetate solution. I got 3.

 [0110] [Example 15] Production of alkali-developable resin composition No. 4

 <Step 1> Production of bisphenol Z glycidyl ether

137 g of bisphenol Z (4, 4, monocyclohexylidene bisphenol) and 406.67 g of epichlorohydrin were charged. The temperature was raised to C. 48% NaOHaq. 25.52g was added dropwise and stirred for 3 hours. Further 50-60. C, 620 to 630 mmHg-e48% NaOHaq. 59. 56 g was added dropwise and stirred for 30 minutes. The temperature was raised to 73 ° C. as it was, and epichlorohydrin was distilled off. Next, 583 g of methyl isobutyl ketone was added, 48% NaOHaq. 3. 04 g, ion-exchanged water 13. 66g and 0.116g of tetraptyl ammonium bromide were added and the temperature was raised to 80 ° C and held for 2 hours. Add 233 g of ion-exchanged water and stir at 80 ° C for 30 minutes, neutralize the organic layer with 3% aqueous sodium monophosphate solution lOOg, wash with water, and then distill off the organic layer at 140 ° C. As a result, a polyfunctional epoxy resin (F) having a cyclohexylenedine group was obtained.

 [0111] Step 2> Production of Alkali Developable Resin Composition No. 4

 Polyfunctional epoxy resin (F) bisphenol Z glycidyl ether obtained in step 1 94. 78 g, 2, 6 di-tert-butyl-p talesol 0.13 g, benzyltriethylammo-um chloride 1.28 g and methoxy Propyl acetate 128. l lg was charged and the temperature was raised to 90 ° C. Subsequently, 33.33 g of acrylic acid, which is an unsaturated monobasic acid (G), was added, and the temperature was raised to 120 ° C. and held for 15 hours. Furthermore, 39.41 g of biphthalic acid dianhydride, which is a polybasic acid anhydride (D ′), and 0.13 g of tetrabutyl ammonium bromide were added, and the mixture was kept at 120 ° C. for 3 hours. Thereafter, it was cooled to 80 ° C. and held for 10 hours. Subsequently, the temperature was raised to 90 ° C., 26.33 g of glycidyl metatalylate, a multi-functional epoxy compound (K), was added, the temperature was raised to 120 ° C. and held for 10 hours. Thereafter, the mixture was cooled to 50 ° C., and 156 g of methoxypropyl acetate and the fluorinated copolymer No. 1 of propylene glycol— 1-monomethyl ether—2 as the fluorinated copolymer (E) obtained in Example 1 were used. Acetate solution 2.62 g was added to obtain a 35% methoxypropyl acetate solution of the target alkali-developable resin composition No. 4 (photopolymerizable unsaturated compound).

 [0112] [Example 16] Production of alkali-developable resin composition No. 5

Polyfunctional epoxy resin (F), bisphenol fluorene type epoxy resin (epoxy equivalent 231) 184g, unsaturated monobasic acid (G), acrylic acid 58g, 2, 6 di-tert-butyl-p-taresol 0 26 g, tetraptyl ammonium acetate 0.1 l lg and propylene glycol 1 monomethyl ether 2 acetate 23 g were charged and stirred at 120 ° C. for 16 hours. Cool to room temperature, add 35 g of propylene glycol-1-monomethyl ether-2 acetate, 59 g of polyphthalic anhydride (D '), biphthalic dianhydride, and 0.24 g of tetra-n-butylammonium bromide. The mixture was stirred at ° C for 4 hours. In addition, 20 g of tetrahydrophthalic anhydride, which is a polybasic acid anhydride (D), was added, and it was 4 hours at 120 ° C, 3 hours at 100 ° C, 4 hours at 80 ° C, 6 hours at 60 ° C, After stirring for 11 hours at 40 ° C, propylene glycol Recall-1-monomethyl ether-2 acetate 90g and fluorinated copolymer No. 1 propylene glycol 1 monomethyl ether-2 acetate solution obtained in Example 1 as a fluorine-containing copolymer (E) 4. 33 g was obtained, and the target alkali-developable resin composition No. 5 was obtained as a propylene glycol 1 monomethyl ether 2 acetate solution.

 [0113] [Example 17] Production of alkali developable resin composition No. 6

 Bisphenol A type epoxy resin (epoxy equivalent 190) 154g, acrylic acid 59g of unsaturated monobasic acid (G), 2, 6 di-tert-butyl-p-talesol 0.26 g, tetraptyl ammonium acetate 0.1 g and propylene glycol 1 monomethyl ether-2 acetate 23 g, 1

 Stir at 20 ° C for 16 hours. Cool to room temperature, add 365 g of propylene glycol-1-monomethyl ether-2-acetate, 67 g of polybasic acid anhydride (D ′), biphthalic dianhydride, and 0.24 g of tetra-n-butylammonium bromide. After stirring at 120 ° C for 4 hours, at 100 ° C for 3 hours, at 80 ° C for 4 hours, at 60 ° C for 6 hours and at 40 ° C for 11 hours, 90 g of propyleneglycol 1 monomethyl ether 2 acetate and examples Fluorine-containing copolymer No. 1 propylene glycol 1 monomethyl ether-2 acetate solution obtained in 1 above 3. Include 78 g of the alkali-developing resin that is the target product Composition No. 6 was obtained as a propylene glycol 1 monomethyl ether 2 acetate solution.

 [0114] [Example 18] Production of alkali-developable resin composition No. 7

 Step 1> 1, 1 Manufacture of bis (4, 1-hydroxyphenol) 1 (, 1-biphenyl) ethane

75 g of phenol and 50 g of 4-acetyl biphenyl were heated and melted at 60 ° C., 5 g of 3 mercaptopropionic acid was added and stirred, and hydrogen chloride gas was blown in for 24 hours, followed by reaction for 72 hours. After washing with warm water at 70 ° C, the vapor was distilled off by heating to 180 ° C under reduced pressure. Xylene was added to the residue and cooled, and the precipitated crystals were collected by filtration and dried under reduced pressure to obtain 65 g of light yellow crystals (yield 68%). The melting point of the pale yellow crystals was 184 ° C, and it was confirmed that the pale yellow crystals were the target product. [0115] <Step 2> 1, 1 Production of bis (4, 1-epoxypropyloxyphenyl) 1 (, 1-biphenyl) ethane

 Charge 37 g of 1,1-bis (4,1 hydroxyphenol) 1- (1,1, biphenol) ethane and 19.5 g of epichlorohydrin obtained in step 1 and add benzyltriethylamine. A mixture of 0.45 g of umchloride was stirred at 64 ° C for 18 hours. Subsequently, the temperature was lowered to 54 ° C., 32.6 g of a 24 mass% aqueous sodium hydroxide solution was added dropwise, and the mixture was stirred for 30 minutes. Epichlorohydrin and water were distilled off, and after adding 140 g of methyl isobutyl ketone and washing with water, 1.7 g of 24 mass% sodium hydroxide sodium salt was added dropwise. After stirring at 80 ° C for 2 hours, the mixture was cooled to room temperature, neutralized with a 3 mass% aqueous sodium monophosphate solution, and washed with water. The solvent was distilled off to obtain 38.7 g (yield 80%) of a yellow viscous liquid. (Epoxy equivalent 248, n = 0.04). The yellow viscous liquid was confirmed to be the target product.

 [0116] Step 3> Production of Alkali Developable Resin Composition No. 7

 The polyfunctional epoxy resin (F) obtained in Step 2 is 1, 1 bis (4 'epoxypropyloxyphenyl) 1 1 (1, -biphenyl) ethane 49.6 g, unsaturated monobasic acid ( G) Acrylic acid 14.4 g, 2,6 di tert-butyl-p-taresol 0.05 g, tetrabutylammonium acetate 0.14 g and propylene glycol 1 monomethyl ether-2-acetate 27.4 g at 120 ° C Stir for 16 hours. After cooling to room temperature, 41.5 g of propylene glycol 1 monomethyl ether 2 acetate and 12.4 g of biphenyltetracarboxylic dianhydride which is a polybasic acid anhydride (D) were added and stirred at 120 ° C. for 8 hours. In addition, add 7.9 g of tetrahydrophthalic anhydride, a polybasic acid anhydride (D ′), to 120. 4 hours at C, 100. 3 hours at C, 80. 4 hours at C, 60. 6 hours at C, 40. After stirring for 11 hours at C, 34 g of propylene glycol-1-monomethyl ether-2-acetate and the propylene glycol of fluorocopolymer No. 1 which is the fluorocopolymer (E) obtained in Example 1— 1-Monomethyl ether-2 acetate solution 1.14 g was added to obtain the target ally reproducible resin composition No. 7 as propylene glycol-1 monomethyl ether 2-acetate solution.

[0117] [Example 19] Production of alkaline developable resin composition No. 8

Fluorine-containing copolymer (E) Propylene of fluorine-containing copolymer No. 2 obtained in Example 2 Glycol-1-monomethyl ether-2-acetate solution 4. Alkali-developable resin composition No. 8 was obtained in the same manner as in Example 12 except that the solution was changed to 10 g.

[0118] [Example 20] Production of alkali-developable resin composition No. 9

 Fluorine-containing copolymer (E) Propylene glycol-1 -monomethyl ether-2-acetate solution of fluorine-containing copolymer No. 3 obtained in Example 3 1. Except for changing to 28 g Example 13 Similarly, alkali-developable resin composition No. 9 was obtained.

[Example 21] Production of alkali-developable resin composition No. 10

 Example 14 except that the fluorine-containing copolymer (E) was changed to a propylene glycol-1-monomethyl ether-2-acetate solution of the fluorine-containing copolymer No. 4 obtained in Example 4 and 91 g. Similarly, alkali-developable resin composition No. 10 was obtained.

[0120] [Example 22] Production of alkali-developable resin composition No. 11

Propylene glycol of the fluorocopolymer (E) Example 5 fluorocopolymer No. 5 obtained in - 1-monomethyl ether -. Except for changing the 2-acetate solution ₃ 84 g, Example 12 Similarly, alkali-developable resin composition No. 11 was obtained.

[0121] [Example 23] Production of alkali-developable resin composition No. 12

 Example 16 with the exception that the fluorocopolymer (E) was changed to a propylene glycol-1-monomethyl ether-2-acetate solution 3.93 g of the fluorocopolymer No. 6 obtained in Example 6. Similarly, alkali-developable resin composition No. 12 was obtained.

[Example 22] Production of alkali-developable resin composition No. 13

 Example 15 and Example 15 except that the fluorine-containing copolymer (E) was changed to the propylene glycol-1-monomethyl ether-2-acetate solution of the fluorine-containing copolymer No. 7 obtained in Example 7 2.22 g Similarly, alkali-developable resin composition No. 13 was obtained.

[Example 25] Manufacture of alkali-developable resin composition No. 14

 Example 18 with the exception that the fluorine-containing copolymer (E) was changed to a propylene glycol-1-monomethyl ether-2-acetate solution 3.38 g of the fluorine-containing copolymer No. 8 obtained in Example 8. Similarly, alkali-developable resin composition No. 14 was obtained.

[0124] [Example 26] Production of alkali-developable resin composition No. 15

Fluorine-containing copolymer (E) Propylene of fluorine-containing copolymer No. 9 obtained in Example 9 Glycol - 1-monomethyl ether -. Except for changing the 2-acetate solution ₃ 84 g, in the same manner as in Example 12 to obtain alkali-developable榭脂composition No. 15.

[Example 27] Production of alkali-developable resin composition No. 16

 Example 13 except that the fluorine-containing copolymer (E) was changed to a propylene glycol-1—monomethyl ether-2-acetate solution of the fluorine-containing copolymer No. 10 obtained in Example 10 1. 28 g. In the same manner as above, an alkali-developable resin composition No. 16 was obtained.

[Example 28] Production of alkaline developable resin composition No. 17

Propylene glycol of the fluorine-containing copolymer No. 11 in which the fluorine-containing copolymer (E) obtained in Example 11 - 1- monomethyl ether -. 2- acetate solution ₃ except for changing the 9 ₃ g

In the same manner as in Example 16, an alkali-developable resin composition No. 17 was obtained.

[Example 29] Production of alkali-developable photosensitive resin composition No. 1

 To 14 g of the alkali-developable resin composition No. 1 obtained in Example 12, add 5.9 g of trimethylolpropane tritalylate, 2. lg of benzophenone, and 78 g of ethyl acetate sorb, and stir well. Photosensitive photosensitive resin composition No. 1 was obtained.

[Example 30] Production of alkali-developable photosensitive resin composition No. 2

 To 14 g of the alkali-developable resin composition No. 2 obtained in Example 13, add 5.9 g of trimethylolpropane tritalylate, 2. lg of benzophenone, and 78 g of ethoxylate sorb, and stir well to develop the alkali. Photosensitive resin composition No. 2 was obtained.

[Example 31] Production of alkali-developable photosensitive resin composition No. 3

 To 14 g of the alkali-developable resin composition No. 3 obtained in Example 14, add 5.9 g of trimethylolpropane tritalylate, 2. lg of benzophenone, and 78 g of solvate solvate, and stir well. Photosensitive resin composition No. 3 was obtained.

[0130] [Example 32] Production of alkali-developable photosensitive resin composition No. 4

 To 14 g of the alkali-developable resin composition No. 4 obtained in Example 15, add 5.9 g of trimethylolpropane tritalylate, 2. lg of benzophenone, and 78 g of solvate solvate, and stir well. Photosensitive resin composition No. 4 was obtained.

[0131] [Example 33] Production of alkali-developable photosensitive resin composition No. 5

Trimethylo with respect to 14 g of the alkali-developable resin composition No. 5 obtained in Example 16 Lepropane tritalylate (5.9 g), benzophenone (2.lg) and ethyl acetate sorb (78 g) were added and stirred well to obtain an alkali-developable photosensitive resin composition No. 5.

[0132] [Example 34] Production of alkali-developable photosensitive resin composition No. 6

 To 14 g of the alkali-developable resin composition No. 6 obtained in Example 17, add 5.9 g of trimethylolpropane tritalylate, 2. lg of benzophenone, and 78 g of ethyl acetate sorb, and stir well. Photosensitive resin composition No. 6 was obtained.

[Example 35] Production of alkali-developable photosensitive resin composition No. 7

 To 14 g of the alkali-developable resin composition No. 7 obtained in Example 18, add 5.9 g of trimethylolpropane tritalylate, 2. lg of benzophenone, and 78 g of ethyl acetate sorb, and stir well. Photosensitive resin composition No. 7 was obtained.

[Example 36] Production of alkali-developable photosensitive resin composition No. 8

 To 14 g of the alkali-developable resin composition No. 8 obtained in Example 19, add 5.9 g of trimethylolpropane tritalylate, 2. lg of benzophenone, and 78 g of ethyl acetate sorb, and stir well. Photosensitive resin composition No. 8 was obtained.

[Example 37] Production of alkali-developable photosensitive resin composition No. 9

 To 14 g of the alkali-developable resin composition No. 9 obtained in Example 20, add 5.9 g of trimethylolpropane tritalylate, 2. lg of benzophenone, and 78 g of ethyl acetate sorb, and stir well. Photosensitive resin composition No. 9 was obtained.

[Example 38] Production of alkali-developable photosensitive resin composition No. 10

 To 14 g of the alkali-developable resin composition No. 10 obtained in Example 21, add 5.9 g of trimethylolpropane tritalylate, 2. lg of benzophenone, and 78 g of solvate solvate, and stir well. Photosensitive resin composition No. 10 was obtained.

[Example 39] Production of alkali-developable photosensitive resin composition No. 11

 To 14 g of the alkali-developable resin composition No. 11 obtained in Example 22, add 5.9 g of trimethylolpropane tritalylate, 2. lg of benzophenone, and 78 g of solvate solvate, and stir well. Photosensitive resin composition No. 11 was obtained.

[Example 40] Production of alkali-developable photosensitive resin composition No. 12

Trimethylo with respect to 14 g of the alkali-developable resin composition No. 12 obtained in Example 23 Lepropane tritalylate 5.9 g, benzophenone 2. lg, and ethyl acetate sorb 78 g were added and stirred well to obtain an alkali-developable photosensitive resin composition No. 12.

[Example 41] Production of alkali-developable photosensitive resin composition No. 13

 To 14 g of the alkali-developable resin composition No. 13 obtained in Example 24, add 5.9 g of trimethylolpropane tritalylate, 2. lg of benzophenone, and 78 g of ethyl acetate sorb, and stir well. Photosensitive resin composition No. 13 was obtained.

[Example 42] Production of alkali-developable photosensitive resin composition No. 14

 To 14 g of the alkali-developable resin composition No. 14 obtained in Example 25, add 5.9 g of trimethylolpropane tritalylate, 2. lg of benzophenone, and 78 g of solvate solvate, and stir well. Photosensitive resin composition No. 14 was obtained.

[0141] [Example 43] Production of alkali-developable photosensitive resin composition No. 15

 To 14 g of the alkali-developable resin composition No. 15 obtained in Example 26, add 5.9 g of trimethylolpropane tritalylate, 2. lg of benzophenone, and 78 g of ethyl acetate sorb, and stir well. Photosensitive resin composition No. 15 was obtained.

[0142] [Example 44] Production of alkali-developable photosensitive resin composition No. 16

 To 14 g of the alkali-developable resin composition No. 16 obtained in Example 27, add 5.9 g of trimethylolpropane tritalylate, 2. lg of benzophenone, and 78 g of solvate solvate, and stir well. Photosensitive resin composition No. 16 was obtained.

[Example 45] Production of alkali-developable photosensitive resin composition No. 17

 To 14 g of the alkali-developable resin composition No. 17 obtained in Example 28, add 5.9 g of trimethylolpropane tritalylate, 2. lg of benzophenone, and 78 g of ethyl acetate sorb, and stir well. Photosensitive resin composition No. 17 was obtained

[Example 46] Production of alkali-developable photosensitive resin composition No. 18

 To 12 g of the alkali-developable resin composition No. 1 obtained in Example 12, 8. lg of dipentaerythritol hexatalylate, 1.9 g of benzophenone, 47 g of ethyl acetate sorb, and 3 lg of cyclohexanone were added. Stir well and obtain alkali-developable photosensitive resin composition No. 18.

[Example 47] Production of alkali-developable photosensitive resin composition No. 19 To 7.2 g of the alkali-developable resin composition No. 1 obtained in Example 12, 4.3 g of trimethylolpropane tritalylate, 2-methyl-1- (4- (methylthio) phenol ] -2 1.5 g of morpholinopropane 1-on and 87 g of ethyl acetate sorb were added and stirred well to obtain an alkali-developable photosensitive coloring composition No. 19.

 [Example 48] Production of alkali-developable photosensitive resin composition No. 20

 For 20 g of the alkali-developable resin composition No. 1 obtained in Example 12, 8.7 g of trimethylolpropane tritalylate, 4.6 g of acrylic copolymer, 2-methyl-1- [4- (Methylthio) phenyl] 2 morpholinopropane 1-on (1.7 g) and ethyl acetate mouthsolve (65 g) were added and stirred well to obtain an alkali-developable photosensitive coloring composition No. 20.

 The acrylic copolymer is composed of 20 parts by mass of methacrylic acid, 15 parts by mass of hydroxyethyl methacrylate, 10 parts by mass of methyl methacrylate and 55 parts by mass of butyl methacrylate. It was obtained by adding 0.75 parts by mass of azobisisobutylnitrile under a nitrogen atmosphere and reacting at 70 ° C. for 5 hours.

 [0147] [Comparative Example 1] Production of alkali-developable resin composition No. 18

 Alkali-developable resin composition No. 18 was obtained in the same manner as in Example 12 except that the fluorine-containing copolymer was changed to 0.95 g of the compound represented by the following [Chemical Formula 33].

[0148] [Chemical 33]

[0149] [Comparative Example 2] Production of alkali-developable resin composition No. 19

 Alkaline-developable resin composition No. 19 was obtained in the same manner as Example 12 except that the fluorinated copolymer was not added.

 [0150] [Comparative Example 3] Production of alkali-developable photosensitive resin composition No. 21

 To 14 g of the alkali-developable resin composition No. 18 obtained in Comparative Example 1, add 5.9 g of trimethylolpropane tritalylate, 2. lg of benzophenone, and 78 g of ethoxylate sorb, and stir well. Photosensitive resin composition No. 21 was obtained.

 [0151] [Comparative Example 4] Production of alkali-developable photosensitive resin composition No. 22

Trimethylo to 14 g of alkali-developable resin composition No. 19 obtained in Comparative Example 2 Lepropane tritalylate (5.9 g), benzophenone (2.lg) and ethyl acetate sorb (78 g) were added and stirred well to obtain an alkali-developable photosensitive resin composition No. 22.

[0152] The obtained alkali-developable photosensitive resin compositions Nos. 1 to 22 were evaluated as follows.

 Specifically, r-glycidoxypropylmethylethoxysilane was spin-coated on a glass substrate and spin-dried well, and then the alkali-developable photosensitive resin composition was spin-coated (1300 r.p.m, 50 Seconds) and dried. After 20 minutes of pre-beta treatment at 70 ° C, a 5% by mass solution of polyvinyl alcohol was coated to form an oxygen barrier film. After drying at 70 ° C for 20 minutes, the film was exposed using an ultrahigh pressure mercury lamp as a light source, developed by immersion in 2.5% by weight sodium carbonate solution at 25 ° C for 30 seconds, and washed thoroughly with water. After washing with water and drying, the test substrate was obtained by baking at 230 ° C for 1 hour. The contact angle of the obtained test substrate was measured. The results are shown in Table 1.

[0153] [Table 1]

Alkali-developable photosensitive resin composition Contact angle

 No. 1 (Example 29) 41

No. 2 (Example 30) 42 ⁰

 No. 3 (Example 3 1) 41

 No, 4 (Example 32) 43 °

 No. 5 (Example 33) 39 °

 No. 6 (Example 34) 36 °

 No. 7 (Example 35) 38 °

 No. 8 (Example 36) 39 °

 No. 9 (Example 37) 41 °

 No. 1 0 (Example 38) 43 °

 No. 1 1 (Example 39) 39 °

 No. 1 2 (Example 40) 37 °

 No. 1 3 (Example 41) 38 °

 No. 14 (Example 42) 34 °

 No. 1 5 (Example 43) 37 °

No. 1 6 (Example 44) 35 ⁰

No. 1 7 (Example 45) 36 ⁰

No. 1 8 (Example 46) 44 ^σ

 No. 1 9 (Example 47) 42 "

No. 20 (Example 48) 43 ⁰

 No. 2 1 (Comparative Example 3) 10 ° or less

 No. 22 (Comparative example 4) 10 ° or less

[0154] The alkali-developable photosensitive resin compositions of Examples 29 to 48 had a high contact angle of 30 ° or more and excellent ink repellency. Further, the obtained coating film was excellent in adhesion to the substrate and alkali resistance.

 In contrast, the alkali-developable photosensitive resin compositions of Comparative Examples 3 to 4 were inferior in ink repellency with a contact angle as low as 10 ° or less.

[0155] [Comparative Example 5] Production of alkali-developable photosensitive resin composition No. 23

An alkali-developable resin composition was prepared in the same manner as in Example 12, except that the fluorine-containing copolymer (E) was changed to the same mass of Modiper F-600 (fluorine-containing copolymer; manufactured by Nippon Oil & Fats Co., Ltd.). Alkaline-developable photosensitive resin composition No. 23 was obtained in the same manner as in Example 29 except that the obtained alkali-developable resin composition No. 1 was changed to the obtained alkali-developable resin composition. It was. [0156] Evaluation of alkali-developable photosensitive resin compositions No. 1 and No. 23 was carried out as follows: o

 Γ-Glycidoxypropylmethylethoxysilane may be spin-coated on a glass substrate, spin-dried, and then spin-coated (1300 rpm, 50 seconds) with the alkali-developable photosensitive resin composition and dried. I let you. After pre-beta treatment at 70 ° C for 20 minutes, the film was developed by being immersed in a 2.5 mass% sodium carbonate solution at 25 ° C for 30 seconds, and washed thoroughly with water. After washing with water and drying, beta was tested at 230 ° C for 1 hour to obtain a test substrate. About the obtained test board | substrate, the residual film was checked visually. The substrate using the alkali-developable photosensitive resin composition No. 1 showed no residual film, but the substrate using the alkali-developable photosensitive resin composition No. 23 was observed to have a residual film. It was done. This indicates that the alkali-developable photosensitive resin composition No. 1 has good alkali developability, and the alkali-developable photosensitive resin composition No. 23 has been difficult to be alkali-developed.

 Industrial applicability

[0157] Al force reproducible photosensitive resin composition using the alkali-developable resin composition containing the fluorine-containing copolymer of the present invention is ink repellency, alkali developability, sensitivity, resolution, and transparency. , Excellent adhesion, and alkali resistance, and a fine pattern can be formed with high accuracy.

Claims

Claims [1] A block copolymer (C) that has both the A segment and the B segment, where the A segment is a fluorine-containing segment that can also provide one or more types of fluorine-based monomer (A), and the B segment A non-fluorine segment obtained from two or more types of non-fluorine monomers (B), and a part or all of the hydroxyl groups of the block copolymer (C) in which the A segment and the Z or B segment have a hydroxyl group are polybasic acid The fluorine-containing copolymer (E) obtained by modification with an anhydride (D) [2] The fluorine-containing monomer (A) is represented by the following general formula (I), Fluorine copolymer (E). [Chemical 1]

(In the formula, R ¹ and R ² may have a hydroxyl group having 1 to 30 carbon atoms.  Represents a ru group. )  The fluorine-containing copolymer (E) according to claim 1, represented by the following general formula (II): [Chemical 2]

(Wherein R ′ represents a hydrogen atom or a methyl group, Z ¹ represents a direct bond, —R ′, —NR—SO — 2 , 1 R, ⁵ 1 NR—CO—, —CH 2 —CH (OH) 1 CH— or 1 CH—CH (OH) — C  2 2 2  H—O—force represents a selected group, R ′, represents an alkylene group having 1 to 4 carbon atoms, R 2 ί ³ is the same as R ^{2 in the} general formula (I). R is a hydrogen atom or a hydroxy acid having 1 to 30 carbon atoms f  The alkyl group which may have a group is represented. ) [4] The non-fluorine monomer (B) is a (meth) acrylic acid monomer. The fluorine-containing copolymer (E) according to any one of Items 3 to 3. [5] The mass ratio of the fluorine monomer (A) to the non-fluorine monomer (B) is 10Z90-80 The fluorine-containing polymer (E) according to any one of claims 1 to 4, which is Z20. [6] The fluorine-containing copolymer (E) according to any one of claims 1 to 5, having a mass average molecular weight of 1,000 to 10,000. [7] The fluorine-containing copolymer (E) according to any one of claims 1 to 6, wherein the acid value is 20 mgKOH / g or more.  [8] The fluorine-containing copolymer according to any one of claims 1 to 7, wherein the hydroxyl group of the block copolymer (C) is modified with a polybasic acid anhydride (D). (E) Manufacturing method.  [9] Obtained by esterification of an epoxy adduct having a structure in which an unsaturated monobasic acid (G) is added to a polyfunctional epoxy resin (F) and a polybasic acid anhydride (D ′). An alkaline developable resin composition comprising the reaction product (H) obtained and the fluorine-containing copolymer (E) according to any one of claims 1 to 7.  [10] The alkali-developable resin composition according to claim 9, which is an alkylidene bisphenol polyglycidyl ether type epoxy resin represented by the following general formula (III): object.  [Chemical 3]

(In the formula, Z ⁴ is a direct bond, a methylene group, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group, 0, S, SO, SS, SO, CO, OCO or the following [6]. Or the substitution represented by [y 匕 7]  2 The alkylidene group may be substituted with a halogen atom.

as well as Each R ⁴ independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 2 to 5 carbon atoms or a halogen atom; The alkoxy group and the alkenyl group may be substituted with a halogen atom. N represents an integer of 0 to 10. ) [Chemical 4]

(Wherein, Y ¹ represents a hydrogen atom, Hue may be substitution by alkyl or alkoxy group having 1 to 10 carbon atoms - a cycloalkyl group group or a carbon atom number. 3 to 10, Upsilon ² Represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a alkenyl group having 2 to 10 carbon atoms or a halogen atom, and the alkyl group, alkoxy group and alkenyl group are halogen atoms. It may be substituted with an atom. Ρ represents a number from 0 to 4.) [Chemical 5]

 10. The alkali-developable resin composition according to claim 9, which is a phenol novolac epoxy resin represented by the following general formula (IV).  [Chemical 6]

(In the formula, R ⁵ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 2 to 5 carbon atoms, a halogen atom, or (4- Glycidyloxyphenyl) -2,2-dimethylmethylidene group, alkyl, alkoxy and alkenyl groups may be substituted with halogen atoms R ⁶ and R ⁷ are each independently a hydrogen atom Or a glycidyloxyphenyl group, and m represents an integer of 0 to 10.) The alkali-developable resin composition according to any one of claims 9 to 11, wherein the photopolymerization initiator ω An alkali-developable photosensitive resin composition comprising