KR101308955B1 - Fluorine-containing copolymer, alkali-developable resin composition, and alkali-developable photosensitive resin composition - Google Patents

Abstract

A block copolymer (C) consisting of an A segment and a B segment, wherein the A segment is a fluorine-containing segment obtained from at least one fluorine monomer (A), and the B segment is a non-fluorine segment obtained from at least one non-fluorine monomer (B). Alkali development which contains the fluorine-containing copolymer (E) obtained by modifying one or all the hydroxyl groups of the said block copolymer (C) in which A segment and / or B segment have a hydroxyl group by polybasic acid anhydride (D). A resinous resin composition and an alkali developable photosensitive resin composition. The alkali developable photosensitive resin composition using the alkali developable resin composition containing the fluorine-containing copolymer of the present invention is excellent in ink repellency, alkali developability, sensitivity, resolution, transparency, adhesion, and alkali resistance, and fine patterns are precisely formed. Can be formed.

Alkali developability, ink repellency, sensitivity, resolution, transparency, adhesiveness, alkali resistance

Description

Fluorine-containing copolymer, alkali developable resin composition and alkali developable photosensitive resin composition {FLUORINE-CONTAINING COPOLYMER, ALKALI-DEVELOPABLE RESIN COMPOSITION, AND ALKALI-DEVELOPABLE PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to an alkali developable resin composition comprising a fluorine-containing copolymer, the above-described fluorine-containing copolymer and a specific compound having an ethylenically unsaturated bond, and an alkali developable photosensitive composition obtained by containing a copolymerization initiator in the alkali developable resin composition. It relates to a resin composition.

The alkali developable photosensitive resin composition contains an alkali developable resin composition and a photopolymerization initiator containing a compound having an ethylenically unsaturated bond. Since the alkali developable photosensitive resin composition can be polymerized and cured by irradiating ultraviolet rays or electron beams, it is used for color filters used in photocurable inks, photosensitive printing plates, printed wiring boards, various photoresists, color liquid crystal display devices, image sensors, and the like. In recent years, with the progress of light and short and small functionalization of electronic devices, the alkali developable photosensitive resin composition which can form a fine pattern with high precision is desired.

The alkali developable photosensitive composition is used for color filter substrates used in color display devices such as color liquid crystal displays, and an inkjet method has recently been proposed as a simple method for manufacturing the color filter substrate.

As a method of manufacturing a color filter substrate using an inkjet method, Patent Document 1 discloses a color filter using a black mattress containing a fluorine-containing compound, and Patent Document 2 discloses a color filter containing a fluorine-containing copolymer and a fluorine-containing organic compound. The resin composition for this is disclosed.

Patent Document 1: Japanese Patent No. 3470352

Patent Document 2: Japanese Patent No. 3644243

However, the alkali developable photosensitive resin composition using the alkali developable resin composition containing the fluorine-containing compound, the fluorine-containing copolymer and the fluorine-containing organic compound has poor ink repellency when the pixel pattern is formed using the inkjet method. There was a problem of poor coatability, such as spreading out of the colored target area or uneven display. There was also a problem of poor alkali developability.

As described above, the problem to be solved is excellent in ink repellency and alkali developability, and an appropriate pattern shape or fine pattern can be efficiently obtained while maintaining characteristics such as sensitivity, resolution, transparency, adhesion, alkali resistance, and the like. It is that there exists no alkali developable resin composition and alkali developable photosensitive resin composition so far.

Therefore, the objective of this invention is providing the alkali developable resin composition which solved the said subject, and alkali developable photosensitive resin composition.

The present invention is a block copolymer (C) consisting of an A segment and a B segment, wherein the A segment is a fluorine-containing segment obtained from at least one fluorine monomer (A), and the B segment is obtained from at least one non-fluorine monomer (B). By providing a fluorine-containing copolymer (E) which is a non-fluorine segment and is obtained by modifying a part or all of the hydroxyl groups of the block copolymer (C) in which the A and / or B segments have hydroxyl groups, the polybasic acid anhydride (D). The purpose was achieved.

The present invention also provides a reaction product (H) obtained by esterifying an epoxy adduct having a structure in which unsaturated monobasic acid (G) is added to a polyfunctional epoxy resin (F), and a polybasic acid anhydride (D '), and the above-mentioned. The said objective is achieved by providing the alkali developable resin composition containing a fluorine-containing copolymer (E).

Furthermore, this invention achieves the said objective by providing the alkali developable photosensitive resin composition which contains a photoinitiator (J) in the said alkali developable resin composition.

1 is an IR chart of fluorinated copolymer No. 1.

2 is an IR chart of fluorinated copolymer No. 2;

EMBODIMENT OF THE INVENTION Hereinafter, the fluorine-containing copolymer, alkali developable resin composition, and alkali developable photosensitive resin composition of this invention are demonstrated in detail based on preferable embodiment.

The fluorine-containing copolymer (E) of the present invention is an A segment which is a fluorine-containing segment composed of one or two or more kinds of fluorine monomers (A), and a non-fluorine monomer (B) that does not contain one or two or more kinds of fluorine atoms. The hydroxyl group of the block copolymer (C) which has the B segment which is the non-fluorine segment which consists of, and which has a hydroxyl group in A segment and / or B segment is modified | denatured by polybasic acid anhydride (D).

As said fluorine-type monomer (A), the fluorine-type monomer represented by the following general formula (I) or general formula (II) is preferable.

(Wherein, R _f ¹ and R _f ² represent a perfluoroalkyl group which may have a hydroxyl group having 1 to 30 carbon atoms.)

Wherein R 'represents a hydrogen atom or a methyl group, Z ¹ represents a direct bond, -R''-NR-SO _2- , R''-NR-CO-, -CH ₂ -CH (OH) -CH Represents a group selected from ₂ -or -CH ₂ -CH (OH) -CH ₂ -O-, R '' represents an alkylene group having 1 to 4 carbon atoms, and R _f ³ represents R of the general formula (I) is the same as _f ^2. R represents an alkyl group which may have a hydrogen atom or a hydroxyl group of 1 to 30 carbon atoms.)

In the general formulas (I) and (II), as the fluoroalkyl group which may have a hydroxyl group having 1 to 30 carbon atoms represented by R _f ¹ , R _f ² , and R _f ³ , F (CF ₂ ) ₆ (CH ₂ ) ₂ , F (CF ₂ ) ₈ (CH ₂ ) ₂ , F (CF ₂ ) ₁₀ (CH ₂ ) ₂ , H (CF ₂ ) ₈ CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₆ (CH ₂ ) ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₈ (CH ₂ ) ₂ , F (CF ₂ ) ₆ (CF ₂ ) ₂ , F (CF ₂ ) ₈ (CF ₂ ) ₂ , F (CF ₂ ) ₁₀ (CF ₂ ) ₂ , H (CF ₂ ) ₈ CF ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₆ (CF ₂ ) ₂ , F (CF ₂ ) ₈ (CH ₂ ) ₂ , F (CF ₂ ) ₈ , F (CF ₂ ) ₆ CH (OH) CH ₂ , F (CF ₂ ) ₈ CH ₂ CH (0H) CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₂ CH ₂ CH (OH) CH _2, etc. Among these, F (CF ₂ ) ₈ (CH ₂ ) ₂ and F (CF ₂ ) ₈ are preferable. Examples of the alkyl group which may have a hydroxyl group having 1 to 30 carbon atoms represented by R in the general formula (II) include methyl, ethyl, propyl, isopropyl, butyl, second butyl, third butyl, isobutyl, amyl, isoamyl, Tertiary amyl, hexyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, decyl, isodecyl, undecyl, Lauryl, dodecyl, hexadecyl, stearyl, behenyl, 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, and methylethylene.

As said fluorine-type monomer (A), in addition to the fluorine-type monomer represented by said general formula (I) or general formula (II), a polyvinylidene fluoride, a fluoroolefin vinyl ether type copolymer, a trifluoride ethylene-vinylidene fluoride copolymer, Polytetrafluoroethylene, perfluoroethylene propylene, perfluoroalkoxy, etc. are mentioned.

As said non-fluorine-type monomer (B), a (meth) acrylic-acid monomer is preferable, and the (meth) acrylic-acid monomer represented by the following general formula (V) or (VI) is more preferable.

(Wherein R ⁸ represents a hydrogen atom or a methyl group, R ⁹ represents an alkyl group having 1 to 30 carbon atoms which may have a hydroxyl group, a cycloalkyl group or 1 to 30 carbon atoms which may have a hydroxyl group having 1 to 30 carbon atoms) An aryl group which may have a hydroxyl group is represented, and Z ² is the same as Z ¹ in General Formula (II).)

(In formula, R <^10> and R <^11> is the same as that of R <^8> in the said general formula (V), Z <^3> shows the C2-C8 alkylene group.)

As said alkyl group which may have a hydroxyl group of 1-30 carbon atoms represented by R <^9> in the said General formula (V), the substituent illustrated by R in the said General formula (II) is mentioned, The carbon atom number represented by R <^9> is mentioned. Examples of the cycloalkyl group which may have a hydroxyl group of 1 to 30 include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, 1-hydroxycyclohexyl, 2-hydroxy And hydroxycyclohexyl, 3-hydroxycyclohexyl, 4-hydroxycyclohexyl and the like. Examples of the aryl group which may have a hydroxyl group having 1 to 30 carbon atoms represented by R ⁹ include phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-vinylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-tertbutylphenyl, 4-hexylphenyl, 4- Cyclohexylphenyl, 4-octylphenyl, 4- (2-ethylhexyl) phenyl, 4-stearyl Neyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-dize3 Butylphenyl, 2,5-dizethibutylphenyl, 2,6-di-tertiarybutylphenyl, 2,4-dizethipentylphenyl, 2,5-dizethiyl amylphenyl, 2,5-dzethioctylphenyl, 2,4-dicumylphenyl, cyclohexylphenyl, biphenyl, 2,4,5-trimethylphenyl, benzyl, phenethyl, 2-phenylpropan-2-yl, diphenylmethyl, triphenylmethyl, styryl, cinna Mill, 2-phenylpropan-2-yl, diphenylmethyl, 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl and the like.

Examples of the alkylene group having 2 to 8 carbon atoms represented by Z ³ in the general formula (VI) include ethylene, methylene, ethylene, propylene, butylene, methylethylene, pentylene, hexylene, heptylene, octylene and the like. have.

As said non-fluorine-type monomer (B), in addition to the (meth) acrylic-acid monomer represented by the said general formula (V) or (VI), diisopropyl fumarate, dicyclohexyl fumarate, di t-butyl fumarate, diisobutyl fumarate, Fumaric acid esters, such as dibenzyl fumarate, hydroxyl-containing vinyl monomers, such as (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, and allyl alcohol, (meth) acrylic acid, itaconic acid, fumaric acid, maleic acid, Carboxylic acid group-containing vinyl monomers such as citraconic acid, vinyl benzoate, crotonic acid, maleic acid and fumaric acid, (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, Polyethylene glycol of (meth) acrylic acid, such as amide group containing vinyl monomers, such as N- (meth) acryloyl morpholine, and (meth) acrylic-acid triethylene glycol ester, and (meth) acrylic-acid dipropylene glycol ester Aromatic vinyl monomers, such as ester of polypropylene glycol, such as styrene, vinyltoluene, and (alpha) -methylstyrene, vinyl ester of carboxylic acid, such as vinyl formate, vinyl acetate, vinyl propionate, and vinyl stearate, N, N-dimethyl (meth) acrylate (Meth) acrylic acid ester of alcohol which has tertiary amino groups, such as amino ethyl and (meth) acrylic acid N, N-dimethylaminopropyl ester, (meth) acrylic acid N, N-dimethylamino ester, 2-hydroxy-3- Quaternary ammonium salts derived from (meth) acrylic acid such as methacryloxypropyltrimethylammonium chloride, hydrochloride of (meth) acrylic acid N, N-dimethylaminoethyl, and hydrochloride of (meth) acrylic acid N, N-dimethylaminopropyl ester Can be mentioned.

The block copolymer (C) according to the present invention has a hydroxyl group in the A segment and / or the B segment. In order to introduce a hydroxyl group into the A segment, one or more monomers (B) having a hydroxyl group may be used in the fluorine monomer (A), and in order to introduce the hydroxyl group into the B segment, a monomer having a hydroxyl group in the non-fluorine monomer (B) may be used. You can use more than one kind. When a hydroxyl group exists in the A segment which has fluorine, since the effect of fluorine, such as ink repellency of a fluorine-containing copolymer (E), may be impaired, it is preferable to introduce only into B segment. The easiest way to introduce a hydroxyl group into the B segment is to use a (meth) acrylic acid ester having a hydroxyl group in the ester component in the non-fluorine monomer (B). For example, it can introduce | transduce in the alcohol addition product of the ester of diethylene glycol, (meth) acrylic acid, and the (meth) acrylic acid glycidyl ester.

The block copolymer (C) can be produced, for example, by an anionic polymerization method and a polymerization method using a polymeric peroxide as a polymerization initiator.

In the anion polymerization method, a molecular weight distribution adjusting agent and diphenylethylene are added to a container sufficiently dried, a solvent and an anion polymerization initiator are introduced under a nitrogen atmosphere, and the temperature is raised to -120 to 50 ° C. Then, 1 type or multiple types of fluorine-type monomer (A) is dripped over 1 second-10 minutes, and it hold | maintains for 5 minutes-10 hours. Then, 1 type or multiple types of a non-fluorine-type monomer (B) is dripped over 1 second-10 minutes, and it hold | maintains for 5 minutes-24 hours. After completion of the reaction, a compound having an active proton such as methanol is added to deactivate the anionic species.

As the solvent, for example, benzene, toluene, ethylbenzene, propylbenzene, butylbenzene, xylene, cyclopentane, cyclohexane, hexane, heptane, octane, nonane, decane, undecane, dodecane, diethyl ether, dipropyl ether The solvent which does not have active protons, such as dibutyl ether, dipentyl ether, dihexyl ether, tetrahydrofuran, dioxane, is mentioned. These solvents can be used individually or in mixture.

Examples of the anionic polymerization initiator include alkyl metals such as ethyl lithium, propyl lithium, n-butyl lithium, s-butyl lithium, t-butyl lithium, methyl magnesium chloride, ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, and phenyl Alkali metals such as magnesium chloride, 4-methylphenylmagnesium chloride, methylmagnesium bromide, ethylmagnesium bromide, propylmagnesium bromide, butylmagnesium bromide, phenylmagnesium bromide and 4-methylphenylmagnesium bromide, and alkali metals such as lithium, sodium, and potassium Lithium methoxide, lithium ethoxide, lithium propoxide, lithium butoxide, sodium methoxide, sodium ethoxide, sodium propoxide, sodium butoxide, potassium methoxide, potassium ethoxide, potassium propoxide, And metal alcoholates such as potassium butoxide.

As the anionic polymerization initiator, diphenylethylene may be reacted with the anionic polymerization initiator exemplified above in advance, and the reactant may be used. In this case, the amount of diphenylethylene used is preferably 0.5 to 3 moles, preferably 1 to 2 moles per 1 mole of anionic polymerization initiator.

As said molecular weight distribution regulator, for example, lithium chloride, lithium bromide, lithium ethoxide, lithium (2-methoxyethoxide), lithium (2-ethoxyethoxide), lithium (2-propoxyethoxide) ), Lithium (2-butoxyethoxide), lithium (2- (2-methoxyethoxy) ethoxide), sodium chloride, sodium bromide, sodium ethoxide, sodium (2-methoxyethoxide) , Sodium (2-ethoxyethoxide), sodium (2-propoxyethoxide), sodium (2-butoxyethoxide), sodium (2- (2-methoxyethoxy) ethoxide), Potassium chloride, potassium bromide, potassium ethoxide, potassium (2-methoxyethoxide), potassium (2-ethoxyethoxide), potassium (2-propoxyethoxide), potassium (2-butoxy Ethoxide) and potassium (2- (2-methoxyethoxy) ethoxide). These molecular weight distribution regulators can be used individually or in mixture of multiple types. Moreover, as the usage-amount, it is 0.5-50 mol with respect to 1 mol of said anionic polymerization initiators, Preferably it is 1-20 mol.

In the polymerization method using a polymeric peroxide as a polymerization initiator, it can manufacture by a conventional bulk polymerization method, suspension polymerization method, solution polymerization method, and emulsion polymerization method using a polymeric peroxide. In the case of the solution polymerization method, for example, a method of forming a non-fluorine monomer (B) in the first step and a fluorine monomer (A) in the second step can be used. That is, the peroxide bond containing non-fluorine-type polymer in which peroxide bond was introduce | transduced in the chain by polymerizing a non-fluorine-type monomer (B) in a solvent using a polymeric peroxide as a polymerization initiator. Next, when the fluorine-based monomer (A) is added to the solution obtained in the first step in the second step to perform polymerization, the peroxide bond in the perfluorine-containing non-fluorine-based polymer is cleaved to obtain a block copolymer (C). . In the two-step polymerization as described above, the fluorine-based monomer (A) of the second step may be used for the first step, and the non-fluorine-based monomer (B) of the first step may be used for the second step. The amount of the polymer 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 hours. Moreover, the polymerization temperature in a 2nd process is 60-140 degreeC normally, and a polymerization time is 3 to 15 hours.

The polymer peroxide is a compound having two or more peroxy bonds in one molecule. As the polymer peroxide, one kind or two or more kinds of various polymer peroxides described in Japanese Patent Application Laid-open No. Hei 5-59942 can be used.

The solvent is not particularly limited as long as it is a solvent capable of dissolving or dispersing the obtained block copolymer (C). For example, water, methyl alcohol, ethyl alcohol, propyl alcohol, 2-propyl alcohol, 1-butyl alcohol, 2 -Butyl alcohol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, cyclopentanol, 2-hexanol, 3-hexanol, cyclo Hexanol, methylcellosolve, ethylcellosolve, 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-pentanone, 2-hexanone, 3-hexanone, cyclopenta Paddy, cyclohexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-hexanone, 5-methyl-2-hexanone, 5-methyl-3-hexanone, methyl acetate , Ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, trimethyl methyl acetate, isobutyl acetate, s-butyl acetate, pentyl acetate, isoacetic acid acetate Mill, 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, methyl isobutyrate Methyl-butyrate, methyl caproate, benzene, toluene, ethylbenzene, xylene, phenol, cyclohexane, hexane, heptane, octane, nonane, decane, undecane, dodecane, formamide, acetamide, dimethylformamide, dimethyl Acetamide, acetonitrile, tetrahydrofuran, 1,1,2-trifluoro-1,2,2-trichloroethane, tetrachlorodifluoroethane, methylchloroform, hexafluoroisopropanol, (meth) paraxylene Hexafluoride, perfluorohexane, and perfluoroheptane. These solvents can be used individually or in mixture.

Examples of the polybasic acid anhydride (D) include succinic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, 2,2, '-3,3'-benzophenonetetracarboxylic anhydride, 3,3'-4,4 '-Benzophenonetetracarboxylic acid anhydride, ethylene glycol bis anhydro trimellitate, glycerol tris hydrohydro trimellitate, phthalic anhydride, hexahydro phthalic anhydride, methyl tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, nadic acid anhydride, methyl Nadic acid anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trialkyl Tetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl anhydrous succinic acid, methyl hymic anhydride and the like. Among these, succinic anhydride, trimellitic anhydride, and tetrahydrophthalic anhydride are preferable.

A well-known method can be used as a manufacturing method of the said fluorine-containing copolymer (E), Although there is no restriction | limiting in particular, For example, the said block copolymer (C) is melt | dissolved in a solvent, and polybasic acid anhydride (D) is contained in the said block air. It can be obtained by making it react with 0.1-1 mol, Preferably it is 0.8-1 mol with respect to 1 mol of hydroxyl groups in copolymer (C). The polymerization temperature is 80 to 140 ° C and the polymerization time is 2 to 10 hours.

Although there is no restriction | limiting in particular as said solvent, For example, Ether solvent, such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2- diethethane ethane, dipropylene glycol dimethyl ether; Ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate and n-butyl acetate; Cellosolve solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and propylene glycol monomethyl ether acetate; Alcohol-based solvents such as methanol, ethanol, iso-or n-propanol, iso- or n-butanol, and amyl alcohol; BTX type solvents such as benzene, toluene and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; Halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene and methylene chloride; Halogenated aromatic hydrocarbon solvents, such as chlorobenzene, etc. can be used, A cellosolve solvent is preferable.

In the said fluorine-containing copolymer (E), the ratio of the said fluorine-type monomer (A) and a non-fluorine-type monomer (B) is 10/90-80/20 by mass ratio, Preferably it is 15/85-60/40. When the said fluorine-type monomer (A) is less than 10 mass%, ink repellency may fall, and when more than 60 mass%, the solubility to the solvent of the obtained fluorine-containing copolymer (E) may fall.

In the said fluorine-containing copolymer (E), the mass mean molecular weight is 10000-100000, Preferably it is 20000-50000. If it is less than 10000, there exists a possibility that the manufacturing efficiency of a fluorine-containing copolymer (E) may fall, and when it is larger than 100000, the solubility to a solvent of the fluorine-containing copolymer (E) is bad, and it is difficult to manufacture. The mass average molecular weight is a polystyrene converted value.

In the said fluorine-containing copolymer (E), an acid value is 20 mgKOH / g or more, Preferably it is 30 mgKOH / g or more. When it is less than 20 mgKOH / g, there exists a possibility that the developability of the alkali developable photosensitive resin composition containing this may deteriorate.

In addition to the fluorine-containing copolymer (E), the alkali developable resin composition of the present invention has an epoxy adduct having a structure in which unsaturated monobasic acid (G) is added to a polyfunctional epoxy resin (F), and a polybasic acid anhydride (D). It contains the reaction product (H) which esterified ''.

One of the preferable polyfunctional epoxy resins (F) is an alkylidene bisphenol polyglycidyl ether type epoxy resin represented by the following general formula (III).

(Wherein Z ⁴ is a direct bond, a methylene group, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group, O, S, SO ₂ , SS, SO, CO, OCO or the following [Formula 6] or [ And the alkylidene group may be substituted with a halogen atom. R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and a carbon atom 1 The alkoxy group of -8, the alkenyl group of 2-5 carbon atoms, or a halogen atom is represented, the alkyl group, the alkoxy group, and the alkenyl group may be substituted by the halogen atom, and n shows the integer of 0-10.)

Wherein Y ¹ represents a phenyl group which may be substituted by a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group or a cycloalkyl group having 3 to 10 carbon atoms, and Y ² represents an alkyl group having 1 to 10 carbon atoms or a carbon source The alkoxy group of embroidery 1-10, the alkenyl group of 2-10 carbon atoms, or a halogen atom may be substituted, and the alkyl group, the alkoxy group, and the alkenyl group may be substituted by the halogen atom, and p represents the number of 0-4.)

The general formula (III) wherein as the carbon source alkylidene group of atoms from 1 to 4 represented by Z ⁴ can be exemplified by methylene, ethylene, propylidene, and isopropylidene, butylidene, isobutoxy butylidene, represented by Z ⁴ Examples of the alicyclic hydrocarbon group include cyclopropylidene, cyclopentylidene, cyclohexylidene, 4-chlorocyclohexylidene, and the like.

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ¹ , R ² , R ^3, or R ⁴ are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, tertiary butyl, pentyl, isoamyl, and third Amyl etc. are mentioned, As an alkoxy group of 1-8 carbon atoms represented by R <^1> , R <^2> , R <^3> or R <^4> , methyloxy, ethyloxy, propyloxy, isopropyloxy, butyloxy, a second butyloxy, Tertiary butyloxy, isobutyloxy, amyloxy, isoamyloxy, tertiary amyloxy, hexyloxy, cyclohexyloxy, heptyloxy, isoheptyloxy, tertiary heptyloxy, n-octyloxy, isooctyloxy And third octyloxy, 2-ethylhexyloxy and the like, and examples of the alkenyl group having 2 to 5 carbon atoms represented by R ¹ , R ² , R ³ or R ⁴ include vinyl, 1-methylethenyl and 2- Methylethenyl, 2-propenyl, 1-methyl-3-propenyl, 3-butenyl, 1-methyl-3-butenyl, isobutenyl, 3-pentenyl, and the like. Examples of the halogen atom represented by R ¹ , R ² , R ³ or R ⁴ include fluorine, chlorine, bromine and iodine. Moreover, the halogen atom which may substitute the said alkylidene group, the halogen group which may substitute the said alkyl group, the alkoxy group, and the alkenyl group is mentioned as a halogen atom represented by R <^1> , R <^2> , R <^3> or R <^4> .

The [Formula 6] may be substituted with a phenyl group represented by Y ¹ number of carbon atoms of 1 to 10 alkyl group and Y carbon atoms of 1 to 10 alkyl group as methyl, ethyl, propyl, isopropyl, representing a ^2, with a cyclopropyl, butyl, Secondary butyl, tertiary butyl, isobutyl, amyl, isoamyl, tertiary amyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, bicyclohexyl, 1-methylcyclohexyl, heptyl, 2- Heptyl, 3-heptyl, isoheptyl, third heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl and the like; and the phenyl group represented by Y ¹ may be substituted. Examples of the alkoxy group having 1 to 10 carbon atoms and the alkoxy group having 1 to 10 carbon atoms represented by Y ² include methyloxy, ethyloxy, propyloxy, isopropyloxy, butyloxy, second butyloxy, tertiary butyloxy and iso Butyloxy, amyloxy, isoamyloxy, tertiary amyloxy, hexyloxy, cyclohexyloxy, heptyloxy, Isoheptyloxy, third heptyloxy, n-octyloxy, isooctyloxy, third octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy and the like; and 3 to 3 carbon atoms represented by Y ¹ . Examples of the cycloalkyl group of 10 include cyclopropyl, cyclobutyl, cyclopentyl, 2-methylcyclopentyl, cyclohexyl, 4-chlorocyclohexyl and the like. Examples of the alkenyl group having 2 to 10 carbon atoms represented by Y ² include vinyl, 1 -Methylethenyl, 2-methylethenyl, 2-propenyl, 1-methyl-3-propenyl, 3-butenyl, 1-methyl-3-butenyl, isobutenyl, 3-pentenyl, 4-hex C. may be mentioned senyl, heptenyl, octenyl, deshenyl, and the like. Examples of the halogen atom which may be substituted with the halogen atom represented by Y ² , the alkyl group, the alkoxy group and the alkenyl group include those exemplified above.

One of the preferable polyfunctional epoxy resins (F) is a phenol novolac type epoxy resin represented by the following general formula (IV).

Wherein R ⁵ represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, an alkoxy group of 1 to 8 carbon atoms, an alkenyl group of 2 to 5 carbon atoms, a halogen atom or (4-glycidyloxyphenyl) -2 A, 2-dimethylmethylidene group, an alkyl group, an alkoxy group and an alkenyl group may be substituted with a halogen atom, R ⁶ and R ⁷ each independently represent a hydrogen atom or a glycidyloxyphenyl group, and m is 0 to 10 Represents an integer.)

The alkyl group having 1 to 5 carbon atoms, the alkoxy group having 1 to 8 carbon atoms, the alkenyl group and halogen atom having 2 to 5 carbon atoms, and the alkyl group, the alkoxy group and the alkenyl group represented by R ⁵ of [Formula 8] Examples of the halogen atom which may be mentioned may include those exemplified above.

As said polyfunctional epoxy resin (F), the polyphenylmethane type epoxy resin which has a polyfunctional epoxy group can also be used.

 Examples of the polyphenylmethane type epoxy resins having an epoxy compound such as epoxy compounds represented by the general formulas (III) and (IV) and a polyfunctional epoxy group include the following compounds Nos. 1 to 20.

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, hydroxyethyl methacrylate malate, and hydroxyethylacrylic acid. Acrylate maleate, hydroxypropyl methacrylate maleate, hydroxypropyl acrylate maleate, dicyclopentadiene maleate, and the like. Among these, acrylic acid and methacrylic acid are preferable. Moreover, as polybasic acid anhydride (D '), the compound illustrated by said polybasic acid anhydride (D) is mentioned.

In the present invention, the reaction product (H) may further be reacted with a polyfunctional epoxy compound (K). The said polyfunctional epoxy compound can be used in order to adjust acid value and to improve developability of the alkali developable resin composition of this invention further. As said polyfunctional epoxy compound, glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether t-butylglycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl Ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether Propargyl glycidyl ether, p-methoxyethylglycidyl ether, phenylglycidyl ether, p-methoxyglycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methylcresylglycidyl ether, 4- Nonylphenyl glycidyl ether, benzyl glycidyl ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycy Dilbutyrate, vinylcyclohexane monooxide, 1,2-epoxy-4-vinylcyclohexane, styrene oxide, pinene oxide, methyl styrene oxide, cyclohexene oxide, propylene oxide, the following compound No. 21. Monoepoxy compounds such as No. 22; Bisphenol-type epoxy resins, such as the said polyfunctional epoxy resin (F) and a hydrogenated 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, tetra Ethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1,1 Glycises, such as 1-tri (glycidyloxymethyl) ethane, 1,1,1-tri (glycidyloxymethyl) methane, and 1,1,1,1-tetra (glycidyloxymethyl) methane Dil ethers; 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1- Alicyclic epoxy resins such as epoxyethyl-3,4-epoxycyclohexane; Glycidyl esters such as phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, and dimer acid glycidyl ester; Glycidylamines such as tetraglycidyldiaminodiphenylmethane, triglycidyl P-aminophenol and N, N-diglycidyl aniline; Heterocyclic epoxy resins such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; Dioxide compounds, such as dicyclopentadiene dioxide; Naphthalene type epoxy resin, a triphenylmethane type epoxy resin, a dicyclopentadiene type epoxy resin, etc. are mentioned.

The acid value of the solid content of the reaction product (H) is preferably in the range of 20 to 120 mgKOH / g, and the amount of the polyfunctional epoxy compound (K) is preferably selected to satisfy the acid value.

The alkali-developable resin composition of the present invention can further add a photopolymerization initiator (J) to obtain an alkali-developable photosensitive resin composition.

The alkali developable resin composition and alkali developable photosensitive resin composition of this invention are normally used as a solution composition which added the solvent which can melt | dissolve or disperse each said component as needed. Although there is no restriction | limiting in particular as said solvent, For example, ketones, such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone; Ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane and dipropylene glycol dimethyl ether; Ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate and n-butyl acetate; Cellosolve solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and propylene glycol monomethyl ether acetate; Alcohol-based solvents such as methanol, ethanol, iso-or n-propanol, iso- or n-butanol, and amyl alcohol; BTX type solvents such as benzene, toluene and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; Terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; Paraffin solvents such as mineral spirits, SWAZOL # 310 (Cosmo Matsuyama Oil Co., Ltd.), and SOLVESSO # 100 (Exxon Chemical Co., Ltd.); Halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichlorethylene and methylene chloride; Halogenated aromatic hydrocarbon solvents such as chlorobenzene; Carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, tetrahydrofuran, N, N-dimethylformamide, N-methylpyrrolidone, and the like, among which ketones or cello Solv solvents are preferred. These solvent can be used as 1 type, or 2 or more types of mixed solvent.

Content of reaction product (H) obtained by esterifying with (D ') component and reacting (K) component as needed with respect to the epoxy adduct which has a structure which added (G) component to (F) component. Silver Contents of a solvent in the said solution composition are 30-90 mass%, Especially 40-70 mass% is preferable.

As said photoinitiator (J) used for the alkali developable photosensitive resin composition of this invention, it is possible to use a conventional compound conventionally, For example, benzophenone, phenyl biphenyl ketone, 1-hydroxy-1- benzoyl cyclo Hexane, benzyl, benzyldimethyl ketal, 1-benzyl-1-dimethylamino-1- (4'-morpholinobenzoyl) propane, 2-morpholinyl-2- (4'-methylmercapto) benzoylpropane, thioke Santone, 1-chloro-4-propoxy thioxanthone, isopropyl thioxanthone, diethyl thioxanthone, ethyl anthraquinone, 4-benzoyl-4'-methyldiphenyl sulfide, benzoin butyl ether, 2- Hydroxy-2-benzoylpropane, 2-hydroxy-2- (4'-isopropyl) benzoylpropane, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, benzoyl formate, 1,7-bis (9'-acridinyl) heptane, 9-n-butyl-3,6-bis (2'-morpholinoisobutyroyl) carbazole, 2-methyl-1- [4- (methylthio) phenyl ] -2-mor Linopropan-1-one, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naph Til-4,6-bis (trichloromethyl) -s-triazine, the following compound No. 23, No. 24, etc. are mentioned. Among these, benzophenone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one are preferable.

(Wherein, Y ³ represents a halogen atom or an alkyl group, R ¹² represents R ^a , OR ^a , COR ^a , SR ^a , CONR ^a R ^b or CN, and R ¹³ represents R ^a , OR ^a , COR ^a , SR ^a or NR ^a R ^b and R ¹⁴ represents R ^a , OR ^a , COR ^a , SR ^a Or NR ^a R ^b , R ^a and R ^b represent an alkyl group, an aryl group, an aralkyl group or a heterocyclic group, which may be substituted with a halogen atom and / or a heterocyclic group, of which alkylene of an alkyl group and an aralkyl group The part may be interrupted by an unsaturated bond, an ether bond, a thioether bond, or an ester bond, and R ^a and R ^b may be bonded to form a ring, and q is 0 to 4).

Wherein Y ³ , R ¹² , R ¹³ , R ¹⁴ , R ^a and R ^b are the same as in 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 each independently represent a number of 1 to 4, R ¹² ′ is the same as R ¹² , R ¹³ ′ is the same as R ^13, and R ¹⁴ ′ is the same as R ¹⁴ , Z ¹⁰ represents a diol residue or a dithiol residue.)

In the alkali-developable photosensitive resin composition of the present invention, the content of the photopolymerization initiator (J) is from 0.1 to 30% by mass, particularly from 0.5 to 5, based on the solution-phase composition in which a solvent is added to the alkali-develotable resin composition of the present invention. Mass% is preferred.

The alkali developable resin composition and alkali developable photosensitive resin composition of this invention can also use together the monomer which has an unsaturated bond, a chain transfer agent, surfactant, etc. together.

As a monomer which has the said unsaturated bond, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, N-octyl acrylate, isooctyl acrylate, isononyl acrylate, stearyl acrylate, methoxyethyl acrylate, Dimethylaminoethyl acrylate, zinc acrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, butyl methacrylate, Butyl methacrylate, cyclohexyl methacrylate, trimethylolpropane trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, tricyclodecanedimethyl Roll diacrylate, and the like.

Examples of the chain transfer agent include thioglycolic acid, thio apple acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercapto Ethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenylether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1 Mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol, 2-mercapto Mercapto compounds such as benzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), And iodide alkyl compounds such as disulfide compounds obtained by oxidizing the mercapto compound, iodine acetic acid, iodine propionic acid, 2-iodine ethanol, 2-iodine ethanesulfonic acid and 3-iodine propanesulfonic acid.

Examples of the surfactant include fluorosurfactants such as perfluoroalkyl phosphate esters and perfluoroalkyl carbonates, anionic surfactants such as higher fatty acid alkali salts, alkylsulfonates and alkyl sulfates, higher amine halogenates, and quaternary grades. Surfactants such as cationic surfactants such as ammonium salts, polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and nonionic surfactants such as fatty acid monoglycerides, amphoteric surfactants and silicone surfactants, You may use in combination.

The alkali developable resin composition and alkali developable photosensitive resin composition of this invention can also improve the characteristic of hardened | cured material 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, and (meth) acrylic acid-methyl methacryl. And latex copolymers, polyvinyl butyral, cellulose esters, polyacrylamides, saturated polyesters, and the like.

Further, the alkali developable resin composition and the alkali developable photosensitive resin composition of the present invention include, as necessary, thermal polymerization inhibitors such as anisole, hydroquinone, pyrocatechol, tertiary butylcatechol and phenothiazine; Plasticizers; Adhesion promoters; Fillers; Defoamer; General additives, such as a leveling agent, can be added.

The alkali developable photosensitive resin composition of the present invention is applied on supporting substrates such as metal, paper, plastic, and the like by known means such as a roll coater, curtain coater, various types of printing and dipping. In addition, once applied to a supporting gas such as a film, it can also be transferred to another supporting gas, there is no limitation on the application method.

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 alkali developable photosensitive resin composition is a photocurable paint, a photocurable adhesive, a printing plate, It can be used for various uses, such as a photoresist for a printed wiring board, There is no restriction | limiting in particular in the use.

Moreover, as a light source of the active light used when hardening the alkali developable photosensitive resin composition of this invention, what emits light of wavelength 300-450 nm can be used, For example, ultra-high pressure mercury, mercury vapor arc, carbon arc, xenon arc, etc. Can be used.

Example

Hereinafter, although an Example etc. are given and this invention is demonstrated in more detail, this invention is not limited to these Examples.

Example 1 Preparation of Fluorinated Copolymer No. 1

100 g of MODIPER F-600 (fluorinated copolymer; NOF CORPORATION), a block copolymer (C), 16.4 g of 1,2,3,6-tetrahydrophthalic anhydride (D), and propylene glycol-1-mono Add 400 g of methyl ether-2-acetate, stir at 120 ° C until the peak of acid anhydride disappears, and use the fluorine-containing copolymer (E) as a propylene glycol-1-monomethyl ether-2-acetate solution. Union No. 1 was obtained. Various analyzes were performed about these. Mass average molecular weight 33000, acid value 57.9 mgKOH / g, fluorine content 12.0 mass% (EDX analysis), carbon content 64.1 mass% (EDX analysis), oxygen 24.0 mass% (EDX analysis), IR spectrum: Fig. 1.

Example 2 Preparation of Fluorinated Copolymer No. 2

Fluorinated copolymer No which is a fluorine-containing copolymer (E) as a propylene glycol-1-monomethyl ether-2-acetate solution similarly to Example 1 except having changed the polybasic acid anhydride (D) into 20.7 g of trimellitic anhydride. .2 was obtained. Various analyzes were performed about this. Mass average molecular weight 33000, acid value 116 mgKOH / g, fluorine content 11.5 mass%, carbon content 62.8 mass%, oxygen 25.3 mass% (EDX analysis), IR spectrum: Fig. 2.

Example 3 Preparation of Fluorinated Copolymer No. 3

A fluorine-containing copolymer which 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) was changed to 9.9 g of maleic anhydride. No. 3 was obtained (mass average molecular weight 35000, acid value 52.1 mgKOH / g).

Example 4 Preparation of Fluorinated Copolymer No. 4

Fluorine-containing copolymer No. which is a fluorine-containing copolymer (E) as a propylene glycol-1-monomethyl ether-2-acetate solution similarly to Example 1 except having changed the polybasic acid anhydride (D) into 15.6 g of phthalic anhydrides. 4 was obtained (mass average molecular weight 29000, acid value 56.3 mgKOH / g).

Example 5 Preparation of Fluorinated Copolymer No. 5

Propylene glycol- was prepared in the same manner as in Example 1 except that the block copolymer (C) was changed to 100 g of MODIPER F-220 (fluorinated copolymer; manufactured by NOF CORPORATION), and the polybasic acid anhydride (D) was changed to 9.9 g of succinic anhydride. As a 1-monomethyl ether-2-acetate solution, fluorine-containing copolymer No. 5 which is a fluorine-containing copolymer (E) was obtained (mass average molecular weight 36000, acid value 31.3 mgKOH / g).

Example 6 Preparation of Fluorinated Copolymer No. 6

Fluorinated copolymer which is a fluorine-containing copolymer (E) as a propylene glycol-1-monomethyl ether-2-acetate solution similarly to Example 5 except having changed the polybasic acid anhydride (D) into 19.7 g of trimellitic anhydrides. No. 6 was obtained (mass average molecular weight 36000, acid value 64.5 mgKOH / g).

Example 7 Preparation of Fluorinated Copolymer No. 7

Fluorinated copolymer No which is a fluorine-containing copolymer (E) as a propylene glycol-1-monomethyl ether-2-acetate solution similarly to Example 5 except having changed the polybasic acid anhydride (D) into 11.4 g of itaconic anhydrides. .7 was obtained (mass average molecular weight 35000, acid value 30.4 mgKOH / g).

Example 8 Preparation of Fluorinated Copolymer No. 8

A fluorine-containing copolymer which 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 15.6 g of hexahydrophthalic anhydride. No. 8 was obtained (mass average molecular weight 37000, acid value 32.6 mgKOH / g).

Example 9 Preparation of Fluorinated Copolymer No. 9

A propylene glycol-1-monomethyl ether-2-acetate solution was prepared in the same manner as in Example 5 except that the block copolymer (C) was changed to 100 g of DEFENSA MCF-350SF (fluorinated copolymer; manufactured by Dainippon Ink and Chemicals). The fluorine-containing copolymer No. 9 which is a fluorine-containing copolymer (E) was obtained (mass average molecular weight 38000, acid value 56.4 mgKOH / g).

Example 10 Preparation of Fluorinated Copolymer No. 10

A fluorine-containing copolymer which 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) was changed to 9.9 g of maleic anhydride. No. 10 was obtained (mass average molecular weight 42000, acid value 58.3 mgKOH / g).

Example 11 Preparation of Fluorinated Copolymer No. 11

Fluorine-containing copolymer No. which is a fluorine-containing copolymer (E) as a propylene glycol-1-monomethyl ether-2-acetate solution similarly to Example 9 except having changed polybasic acid anhydride (D) into 15.6 g of phthalic anhydrides. 11 was obtained (mass average molecular weight 40000, acid value 52.4 mgKOH / g).

Example 12 Preparation of Alkaline Developable Resin Composition No. 1

<Step 1> Preparation of 1,1-bis (4'-hydroxyphenyl) -1- (1 ''-biphenyl) -1-cyclohexylmethane

70.5 g of biphenylcyclohexyl ketone, 200.7 g of phenol and 10.15 g of thioacetic acid were added thereto, and 40.0 g of trifluoromethanesulfonic acid was added dropwise at 18 ° C. over 20 minutes. After reacting at 17-19 degreeC for 18 hours, 500 g of water was added and reaction was stopped, 500 g of toluene was added, and the organic layer was wash | cleaned with water until it became pH3-4, and the organic layer was isolate | separated. Toluene, water and excess phenol were distilled off. Toluene was added to the residue, and the precipitated solid was collected by filtration and dispersed and washed with toluene to obtain 59.2 g (yield 51%) of pale yellow crystals. Melting point of the pale yellow crystals was 239.5 ℃, it was confirmed that the pale yellow crystals are the target.

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

57.5 g of 1,1-bis (4'-hydroxyphenyl) -1- (1 ''-biphenyl) -1-cyclohexylmethane and 195.8 g of epichlorohydrin obtained in Step 1 were added thereto, and benzyltriethylammonium was added thereto. 0.602 g of chloride was added and stirred at 64 ° C. for 18 hours. Then, it cooled to 54 degreeC, 43.0 g of 24 mass% sodium hydroxide aqueous solutions were dripped, and it stirred for 30 minutes. Epichlorohydrin and water were distilled off, 216 g of methyl isobutyl ketones were added, and it wash | cleaned with water, and 2.2 g of 24 mass% sodium hydroxide was dripped. After stirring at 80 ° C. for 2 hours, the mixture was cooled to room temperature, neutralized with an aqueous 3% by mass sodium monophosphate solution, and washed with water. The solvent was distilled off and the yellow solid 57g (yield 79%) was obtained. (Melting point 64.2 ° C., epoxy equivalent 282, n = 0.04). It was confirmed that the yellow crystal was the target product.

<Step 3> Production of alkali developable resin composition No. 1

169.5 g of 1,1-bis (4'-epoxypropyloxyphenyl) -1- (1 ''-biphenyl) -1-cyclohexylmethane which is a polyfunctional epoxy resin (F) obtained in step 2, unsaturated monobasic acid 44.3 g of acrylic acid (G), 0.6 g of 2,6-di-tert-butyl-p-cresol, 1.1 g of tetrabutylammonium acetate, and 142.5 g of propylene glycol-1-monomethyl ether-2-acetate were added, and 120 ° C. Stirred for 16 h. After cooling to room temperature, 71.8 g of propylene glycol-1-monomethyl ether-2-acetate, 48.2 g of succinic anhydride as polybasic acid anhydride (D '), and 2.5 g of tetrabutylammonium acetate were added, followed by stirring at 100 ° C for 5 hours. Furthermore, 50.8 g of 1,1-bis (4'-epoxypropyloxyphenyl) -1- (1 ''-biphenyl) -1-cyclohexylmethane and propylene glycol-which are polyfunctional epoxy compounds (K) obtained in step 2 21.8 g of 1-monomethyl ether-2-acetate was added thereto, followed by stirring at 120 ° C. for 12 hours, 80 ° C. for 2 hours, and 40 ° C. for 2 hours, followed by 146.3 g of propylene glycol-1-monomethyl ether-2-acetate. 4.24 g of propylene glycol-1-monomethyl ether-2-acetate solution of fluorine-containing copolymer No. 1 which is the fluorine-containing copolymer (E) obtained in Example 1 was added, and propylene glycol-1-monomethyl ether-2-acetate was added. As a solution, alkali developing resin composition No. 1 which is a target object was obtained.

Example 13 Preparation of Alkaline Developable Resin Composition No. 2

Acrylic acid which is 43 g of 1,1-bis (4'-epoxypropyloxyphenyl) -1- (1 ''-biphenyl) -1-cyclohexyl methane which is a polyfunctional epoxy resin (F), and unsaturated monobasic acid (G) 33.6 g, 2,6-di-tert-butyl-p-cresol 0.04 g, 0.21 g of tetrabutylammonium acetate, and 18 g of propylene glycol-1-monomethyl ether-2-acetate were added 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, followed by stirring at 100 ° C for 3 hours. Furthermore, 8 g of bisphenol Z glycidyl ether, a polyfunctional epoxy compound (K), was added, followed by stirring at 120 ° C for 4 hours, 90 ° C for 3 hours, 60 ° C for 2 hours, and 40 ° C for 5 hours. 29 g of monomethyl ether-2-acetate and 1.28 g of propylene glycol-1-monomethyl ether-2-acetate solution of fluorine-containing copolymer No. 1 which is the fluorine-containing copolymer (E) obtained in Example 1 were added, and propylene Alkali-developable resin composition No. 2 which is a target object was obtained as a glycol-1-monomethyl ether-2-acetate solution.

Example 14 Preparation of Alkaline Developable Resin Composition No. 3

1,1-bis (4'-epoxypropyloxyphenyl) -1- (1 ''-biphenyl) -1-cyclohexylmethane as polyfunctional epoxy resin (F) is 169.5 g of unsaturated monobasic acid (G) 44.3 g of acrylic acid, 0.6 g of 2,6-di-tert-butyl-p-cresol, 1.1 g of tetrabutylammonium acetate, and 142.5 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 120 ° C. for 16 hours. It was. After cooling to room temperature, 93.1 g of propylene glycol-1-monomethyl ether-2-acetate, 74.1 g of hexahydrophthalic anhydride, which is a polybasic acid anhydride (D '), and 2.5 g of tetra-n-butylammonium acetate were added thereto, and then at 70 ° C. Stir for 4 hours. In addition, 31.3 g of ethylene glycol diglycidyl ether, which is a polyfunctional epoxy compound (K), and 146.3 g of propylene glycol-1-monomethyl ether-2-acetate, and a fluorine-containing copolymer (E) obtained in Example 1 4.31 g of propylene glycol-1-monomethyl ether-2-acetate solution of copolymer No. 1 was added, and alkali developing resin composition No. 3 which is a target object was obtained as a propylene glycol-1-monomethyl ether-2-acetate solution. .

Example 15 Preparation of Alkaline Developable Resin Composition No. 4

Step 1 Preparation of Bisphenol Z Glycidyl Ether

137 g of bisphenol Z (4,4'-cyclohexylidene bisphenol) and 406.67 g of epichlorohydrin were added thereto, and the temperature was raised to 74 ° C. 48% NaOHaq. 25.52 g was added dropwise and stirred for 3 hours. Furthermore, 48% NaOHaq at 50-60 ° C., 620-630 mmHg. 59.56 g was added dropwise and stirred for 30 minutes. It heated up to 73 degreeC as it was, and epichlorohydrin was distilled off. Subsequently, 583 g of methyl isobutyl ketone was added to form a 48% NaOHaq. 3.04g, 13.66g of ion-exchange water, and 0.16g of tetrabutylammonium bromide were added, it heated up to 80 degreeC, and hold | maintained for 2 hours. Further, 233 g of ion-exchanged water was added and stirred at 80 ° C. for 30 minutes, the organic layer was neutralized with 100 g of 3% sodium monophosphate aqueous solution, washed with water, and the organic layer was distilled off at 140 ° C. to have a cyclohexylidene group as a target. The functional epoxy resin (F) was obtained.

<Step 2> Production of alkali developable resin composition No. 4

94.78 g of bisphenol Z glycidyl ether, the polyfunctional epoxy resin (F) obtained in step 1, 0.13 g of 2,6-di-tert-butyl-p-cresol, 1.28 g of benzyltriethylammonium chloride, and methoxypropyl acetate 128.11g was added and heated up to 90 degreeC. Then, 33.33 g of acrylic acid which is unsaturated monobasic acid (G) was added, it heated up to 120 degreeC, and hold | maintained for 15 hours. Furthermore, 39.41 g of non-phthalic acid dianhydride and 0.13 g of tetrabutylammonium bromide which are polybasic acid anhydrides (D ') were added, and it hold | maintained at 120 degreeC for 3 hours. Then it cooled to 80 degreeC and hold | maintained for 10 hours. Then, it heated up to 90 degreeC, the 26.33g glycidyl methacrylate which is a polyfunctional epoxy compound (K) was added, it heated up to 120 degreeC, and hold | maintained for 10 hours. Thereafter, the mixture was cooled to 50 ° C, and 156 g of methoxypropyl acetate and 2.62 g of a propylene glycol-1-monomethyl ether-2-acetate solution of fluorine-containing copolymer No. 1, which was the fluorine-containing copolymer (E) obtained in Example 1. Was added to obtain a 35% solution of methoxypropyl acetate of alkali developable resin composition No. 4 (photopolymerizable unsaturated compound).

Example 16 Preparation of Alkaline Developable Resin Composition No. 5

184 g of bisphenol fluorene type epoxy resin (epoxy equivalent 231) which is polyfunctional epoxy resin (F), 58 g of acrylic acid which is unsaturated monobasic acid (G), 0.26 g of 2,6-di-tert- butyl-p-cresol, tetrabutyl 0.11 ammonium acetate and 23 g of propylene glycol-1-monomethyl ether-2-acetate were added, and it stirred at 120 degreeC for 16 hours. Cool to room temperature, add 35 g of propylene glycol-1-monomethyl ether-2-acetate, 59 g of non-phthalic anhydride, polybasic acid anhydride (D '), and 0.24 g of tetra-n-butylammonium bromide and stir at 120 ° C. for 4 hours. It was. Furthermore, 20 g of tetrahydro phthalic anhydride which is polybasic acid anhydride (D) is added, after stirring at 120 degreeC for 4 hours, 100 degreeC for 3 hours, 80 degreeC for 4 hours, 60 degreeC for 6 hours, and 40 degreeC for 11 hours, propylene glycol 90 g of -1-monomethyl ether-2-acetate and 4.33 g of a propylene glycol-1-monomethyl ether-2-acetate solution of fluorine-containing copolymer No. 1 which is the fluorine-containing copolymer (E) obtained in Example 1 were added. Alkali-developable resin composition No. 5 which is the target object was obtained as a propylene glycol-1-monomethyl ether-2-acetate solution.

Example 17 Preparation of Alkaline Developable Resin Composition No. 6

Bisphenol A type epoxy resin (epoxy equivalent 190) 154 g of polyfunctional epoxy resin (F), 59 g of acrylic acid which is unsaturated monobasic acid (G), 0.26 g of 2,6-di-tert- butyl-p-cresol, tetrabutylammonium 0.11 g of acetate and 23 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 120 ° C. for 16 hours. After cooling to room temperature, 365 g of propylene glycol-1-monomethyl ether-2-acetate, 67 g of non-phthalic anhydride which is a polybasic acid anhydride (D '), and 0.24 g of tetra-n-butylammonium bromide were added, and the mixture was heated at 120 ° C for 4 hours. 90 g of propylene glycol-1-monomethyl ether-2-acetate and the fluorine-containing copolymer obtained in Example 1 after stirring for 3 hours at 100 ° C, 4 hours at 80 ° C, 6 hours at 60 ° C, and 11 hours at 40 ° C. 3.78 g of propylene glycol-1-monomethylether-2-acetate solution of (E) phosphorus-containing fluorine copolymer No.1 was added, and alkali-developable resin composition No.6 which is a target object was made into propylene glycol-1-monomethyl ether- Obtained as a 2-acetate solution.

Example 18 Preparation of Alkaline Developable Resin Composition No. 7

<Step 1> Preparation of 1,1-bis (4'-hydroxyphenyl) -1- (1 ''-biphenyl) ethane

75 g of phenol and 50 g of 4-acetylbiphenyl were heated and melted at 60 DEG C, and 5 g of 3-mercaptopropionic acid was added and stirred, followed by 72 hours of blowing hydrogen chloride gas with stirring. After washing with warm water at 70 ° C, the mixture was heated to 180 ° C under reduced pressure to distill off the evaporate. Xylene was added to the residue to cool, the precipitated crystals were collected by filtration, and dried under reduced pressure to obtain 65 g (yield 68%) of pale yellow crystals. It was confirmed that the melting point of the pale yellow crystal was 184 ° C, and the pale yellow crystal was the target product.

<Step 2> Preparation of 1,1-bis (4'-epoxypropyloxyphenyl) -1- (1 ''-biphenyl) ethane

37 g of 1,1-bis (4'-hydroxyphenyl) -1- (1 ''-biphenyl) ethane and 149.5 g of epichlorohydrin obtained in Step 1 were added, and 0.45 g of benzyltriethylammonium chloride was added. It stirred at 64 degreeC for 18 hours. Then, it cooled to 54 degreeC, 32.6 g of 24 mass% sodium hydroxide aqueous solutions were dripped, and it stirred for 30 minutes. Epichlorohydrin and water were distilled off, and 140 g of methyl isobutyl ketones were added and the water washed, 1.7 g of 24 mass% sodium hydroxide was dripped. After stirring at 80 ° C. for 2 hours, the mixture was cooled to room temperature, neutralized with an aqueous 3% by mass sodium monophosphate solution, and washed with water. The solvent was distilled off and 38.7 g (yield 80%) of yellow viscous liquids were obtained (epoxy equivalent 248, n = 0.04). The yellow viscous liquid was confirmed to be the target product.

<Step 3> Production of alkali developable resin composition No. 7

49.6 g of 1,1-bis (4'-epoxypropyloxyphenyl) -1- (1 ''-biphenyl) ethane which is the polyfunctional epoxy resin (F) obtained by step 2, and acrylic acid which is unsaturated monobasic acid (G) 14.4 g, 2,6-di-tert-butyl-p-cresol, 0.05 g, tetrabutylammonium acetate 0.14 g and propylene glycol-1-monomethyl ether-2-acetate were added thereto, and the mixture was stirred at 120 ° C. 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 as a polybasic acid anhydride (D) were added, followed by stirring at 120 ° C for 8 hours. In addition, 7.9 g of tetrahydrophthalic anhydride, a polybasic acid anhydride (D '), was added, followed by stirring at 120 ° C for 4 hours, 100 ° C for 3 hours, 80 ° C for 4 hours, 60 ° C for 6 hours, and 40 ° C for 11 hours. 34 g of glycol-1-monomethyl ether-2-acetate and 1.14 g of propylene glycol-1-monomethyl ether-2-acetate solution of fluorine-containing copolymer No. 1 which is the fluorine-containing copolymer (E) obtained in Example 1 It added and obtained alkali developing resin composition No. 7 which is a target object as a propylene glycol-1-monomethyl ether-2-acetate solution.

Example 19 Preparation of Alkaline Developable Resin Composition No. 8

Alkali developability in the same manner as in Example 12 except that the fluorinated copolymer (E) was changed to 4.10 g of the propylene glycol-1-monomethylether-2-acetate solution of the fluorinated copolymer No. 2 obtained in Example 2. Resin composition No. 8 was obtained.

Example 20 Preparation of Alkaline Developable Resin Composition No. 9

Alkali developability in the same manner as in Example 13 except that the fluorinated copolymer (E) was changed to 1.28 g of the propylene glycol-1-monomethylether-2-acetate solution of Fluorinated Copolymer No. 3 obtained in Example 3. Resin composition No. 9 was obtained.

Example 21 Preparation of Alkaline Developable Resin Composition No. 10

Alkali developability in the same manner as in Example 14 except that the fluorinated copolymer (E) was changed to 3.91 g of a propylene glycol-1-monomethylether-2-acetate solution of the fluorinated copolymer No. 4 obtained in Example 4. Resin composition No. 10 was obtained.

Example 22 Preparation of Alkaline Developable Resin Composition No. 11

Alkali developability was carried out in the same manner as in Example 12, except that the fluorinated copolymer (E) was changed to 3.84 g of the propylene glycol-1-monomethylether-2-acetate solution of the fluorinated copolymer No. 5 obtained in Example 5. Resin composition No. 11 was obtained.

Example 23 Preparation of Alkaline Developable Resin Composition No. 12

Alkali developability in the same manner as in Example 16 except that the fluorinated copolymer (E) was changed to 3.93 g of a propylene glycol-1-monomethylether-2-acetate solution of the fluorinated copolymer No. 6 obtained in Example 6. Resin composition No. 12 was obtained.

Example 24 Preparation of Alkali Developable Resin Composition No. 13

Alkali developability was carried out in the same manner as in Example 15, except that the fluorinated copolymer (E) was changed to 2.22 g of a propylene glycol-1-monomethylether-2-acetate solution of the fluorinated copolymer No. 7 obtained in Example 7. Resin composition No. 13 was obtained.

Example 25 Preparation of Alkaline Developable Resin Composition No. 14

Alkali developability was carried out in the same manner as in Example 18, except that the fluorinated copolymer (E) was changed to 3.38 g of the propylene glycol-1-monomethylether-2-acetate solution of the fluorinated copolymer No. 8 obtained in Example 8. Resin composition No. 14 was obtained.

Example 26 Preparation of Alkali Developable Resin Composition No.15

Alkali developability was carried out in the same manner as in Example 12 except that the fluorinated copolymer (E) was changed to 3.84 g of a propylene glycol-1-monomethylether-2-acetate solution of the fluorinated copolymer No. 9 obtained in Example 9. Resin composition No. Got 15.

Example 27 Preparation of Alkaline Developable Resin Composition No. 16

Alkali developability in the same manner as in Example 13 except that the fluorinated copolymer (E) was changed to 1.28 g of the propylene glycol-1-monomethylether-2-acetate solution of Fluorinated Copolymer No. 10 obtained in Example 10. Resin composition No. 16 was obtained.

Example 28 Preparation of Alkaline Developable Resin Composition No. 17

Alkali developability in the same manner as in Example 16 except that the fluorinated copolymer (E) was changed to 3.93 g of a propylene glycol-1-monomethylether-2-acetate solution of the fluorinated copolymer No. 11 obtained in Example 11. Resin composition No. 17 was obtained.

Example 29 Preparation of Alkali Developable Photosensitive Resin Composition No.1

To 14 g of alkali developable resin composition No. 1 obtained in Example 12, 5.9 g of trimethylolpropane triacrylate, 2.1 g of benzophenone, and 78 g of ethyl cellosolve were added and stirred well, and the alkali developable photosensitive resin composition No. 1 was obtained.

Example 30 Preparation of Alkali Developable Photosensitive Resin Composition No.2

To 14 g of alkali developable resin composition No. 2 obtained in Example 13, 5.9 g of trimethylolpropane triacrylate, 2.1 g of benzophenone, and 78 g of ethyl cellosolve were added and stirred well, and the alkali developable photosensitive resin composition No. 2 was obtained.

Example 31 Preparation of Alkaline Developable Photosensitive Resin Composition No. 3

To 14 g of alkali developable resin composition No. 3 obtained in Example 14, 5.9 g of trimethylolpropane triacrylate, 2.1 g of benzophenone, and 78 g of ethyl cellosolve were added and stirred well, and the alkali developable photosensitive resin composition No. Got 3.

Example 32 Preparation of Alkali-developable Photosensitive Resin Composition No. 4

To 14 g of alkali developable resin composition No. 4 obtained in Example 15, 5.9 g of trimethylolpropane triacrylate, 2.1 g of benzophenone, and 78 g of ethyl cellosolve were added and stirred well, and the alkali developable photosensitive resin was added. Composition No. Got 4.

Example 33 Preparation of Alkaline Developable Photosensitive Resin Composition No. 5

To 14 g of alkali developable resin composition No. 5 obtained in Example 16, 5.9 g of trimethylolpropane triacrylate, 2.1 g of benzophenone, and 78 g of ethyl cellosolve were added and stirred well, and the alkali developable photosensitive resin composition No. Got 5.

Example 34 Preparation of Alkaline Developable Photosensitive Resin Composition No. 6

To 14 g of alkali developable resin composition No. 6 obtained in Example 17, 5.9 g of trimethylolpropane triacrylate, 2.1 g of benzophenone, and 78 g of ethyl cellosolve were added and stirred well, and the alkali developable photosensitive resin composition No. 6 was obtained.

Example 35 Preparation of Alkaline Developable Photosensitive Resin Composition No. 7

To 14 g of alkali developable resin composition No. 7 obtained in Example 18, 5.9 g of trimethylolpropane triacrylate, 2.1 g of benzophenone, and 78 g of ethyl cellosolve were added and stirred well, and the alkali developable photosensitive resin composition No. 7 was obtained.

Example 36 Preparation of Alkali-developable Photosensitive Resin Composition No. 8

To 14 g of alkali developable resin composition No. 8 obtained in Example 19, 5.9 g of trimethylolpropane triacrylate, 2.1 g of benzophenone, and 78 g of ethyl cellosolve were added and stirred well, and the alkali developable photosensitive resin composition No. 8 was obtained.

Example 37 Preparation of Alkaline Developable Photosensitive Resin Composition No. 9

To 14 g of alkali developable resin composition No. 9 obtained in Example 20, 5.9 g of trimethylolpropane triacrylate, 2.1 g of benzophenone, and 78 g of ethyl cellosolve were added and stirred well, and the alkali developable photosensitive resin was added. Composition No. Got 9

Example 38 Preparation of Alkali-developable Photosensitive Resin Composition No. 10

To 14 g of alkali developable resin composition No. 10 obtained in Example 21, 5.9 g of trimethylolpropane triacrylate, 2.1 g of benzophenone, and 78 g of ethyl cellosolve were added and stirred well, and the alkali developable photosensitive resin composition No. 10 was obtained.

Example 39 Preparation of Alkaline Developable Photosensitive Resin Composition No. 11

To 14 g of alkali developable resin composition No. 11 obtained in Example 22, 5.9 g of trimethylolpropane triacrylate, 2.1 g of benzophenone, and 78 g of ethyl cellosolve were added and stirred well, and the alkali developable photosensitive resin composition No. 11 was obtained.

Example 40 Preparation of Alkali Developable Photosensitive Resin Composition No.12

To 14 g of alkali developable resin composition No. 12 obtained in Example 23, 5.9 g of trimethylolpropane triacrylate, 2.1 g of benzophenone, and 78 g of ethyl cellosolve were added and stirred well, and the alkali developable photosensitive resin composition No. 12 was obtained.

Example 41 Preparation of Alkaline Developable Photosensitive Resin Composition No.13

To 14 g of alkali developable resin composition No. 13 obtained in Example 24, 5.9 g of trimethylolpropane triacrylate, 2.1 g of benzophenone, and 78 g of ethyl cellosolve were added and stirred well, and the alkali developable photosensitive resin composition No. 13 was obtained.

Example 42 Preparation of Alkali-developable Photosensitive Resin Composition No. 14

To 14 g of alkali developable resin composition No. 14 obtained in Example 25, 5.9 g of trimethylolpropane triacrylate, 2.1 g of benzophenone, and 78 g of ethyl cellosolve were added and stirred well, and the alkali developable photosensitive resin was added. Composition No. 14 was obtained.

Example 43 Preparation of Alkali Developable Photosensitive Resin Composition No.15

To 14 g of alkali developable resin composition No. 15 obtained in Example 26, 5.9 g of trimethylolpropane triacrylate, 2.1 g of benzophenone, and 78 g of ethyl cellosolve were added and stirred well, and the alkali developable photosensitive resin composition No. Got 15.

Example 44 Preparation of Alkali-developable Photosensitive Resin Composition No. 16

To 14 g of alkali developable resin composition No. 16 obtained in Example 27, 5.9 g of trimethylolpropane triacrylate, 2.1 g of benzophenone, and 78 g of ethyl cellosolve were added and stirred well, and the alkali developable photosensitive resin composition No. 16 was obtained.

Example 45 Preparation of Alkali Developable Photosensitive Resin Composition No. 17

To 14 g of alkali developable resin composition No. 17 obtained in Example 28, 5.9 g of trimethylolpropane triacrylate, 2.1 g of benzophenone, and 78 g of ethyl cellosolve were added and stirred well, and the alkali developable photosensitive resin composition No. 17 was obtained.

Example 46 Preparation of Alkali-developable Photosensitive Resin Composition No. 18

To 12 g of alkali developable resin composition No. 1 obtained in Example 12, 8.1 g of dipentaerythritol hexaacrylate, 1.9 g of benzophenone, 47 g of ethyl cellosolve, and 31 g of cyclohexanone were added and stirred well, and alkali Developable Photosensitive Resin Composition No. 18 was obtained.

Example 47 Preparation of Alkali Developable Photosensitive Resin Composition No.19

To 7.2 g of alkali developable resin composition No. 1 obtained in Example 12, 4.3 g of trimethylolpropane triacrylate and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane 1.5 g of -1-one and 87 g of ethyl cellosolve were added, and the mixture was stirred well, and the alkali developable photosensitive resin composition No. 19 was obtained.

Example 48 Preparation of Alkaline Developable Photosensitive Resin Composition No. 20

To 20 g of alkali developable resin composition No. 1 obtained in Example 12, 8.7 g of trimethylolpropane triacrylate, 4.6 g of an acrylic copolymer, and 2-methyl-1- [4- (methylthio) phenyl] -2 1.7 g of morpholino propane-1-one and 65 g of ethyl cellosolve were added and stirred well, and the alkali developable photosensitive resin composition No. 20 was obtained.

Moreover, the said acryl-type copolymer melt | dissolves 20 mass parts of methacrylic acid, 15 mass parts of hydroxyethyl methacrylate, 10 mass parts of methyl methacrylates, and 55 mass parts of butyl methacrylates in 300 mass parts of ethylcellose, and nitrogen It is obtained by adding 0.75 mass part of azobisisobutylnitrile in an atmosphere, and making it react at 70 degreeC for 5 hours.

Comparative Example 1 Preparation of Alkaline Developable Resin Composition No. 18

Alkali-developable resin composition No. 18 was obtained like Example 12 except having changed the fluorine-containing copolymer into 0.95 g of the compound represented by following formula (33).

[Comparative Example 2] Preparation of alkali developable resin composition No.19

Alkali-developable resin composition No. 19 was obtained like Example 12 except not having added the fluorine-containing copolymer.

[Comparative Example 3] Preparation of alkali developable photosensitive resin composition No.21

To 14 g of alkali-developable resin composition No. 18 obtained in Comparative Example 1, 5.9 g of trimethylolpropane triacrylate, 2.1 g of benzophenone, and 78 g of ethyl cellosolve were added and stirred well to alkali-developable photosensitive resin composition No. .21 was obtained.

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

To 14 g of alkali developable resin composition No. 19 obtained in Comparative Example 2, 5.9 g of trimethylolpropane triacrylate, 2.1 g of benzophenone, and 78 g of ethyl cellosolve were added and stirred well, and the alkali developable photosensitive resin composition No. 22 was obtained.

Evaluation of obtained alkali developable photosensitive resin composition No.1-22 was performed as follows.

That is, after spin-coating well-dried γ-glycidoxypropylmethylethoxysilane on a glass substrate, the alkali developable photosensitive resin composition was spin-coated (1300 r.p.m, 50 seconds) and dried. After prebaking at 70 ° C. for 20 minutes, a 5% by mass solution of polyvinyl alcohol was coated to form an oxygen barrier film. After drying for 20 minutes at 70 ° C, using a high-pressure mercury lamp as a light source, the solution was immersed in a 2.5% by mass sodium carbonate solution at 25 ° C for 30 seconds to develop and washed well with water. After washing with water and drying, it was baked at 230 ° C. for 1 hour to obtain a test substrate. The contact angle was measured about the obtained test board. The results are shown in Table 1.

Alkali-developable photosensitive resin composition Contact angle No.1 (Example 29) 41 ° No.2 (Example 30) 42 ° No.3 (Example 31) 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.10 (Example 38) 43 ° No.11 (Example 39) 39 ° No.12 (Example 40) 37 ° No.13 (Example 41) 38 ° No.14 (Example 42) 34 ° No.15 (Example 43) 37 ° No.16 (Example 44) 35 ° No.17 (Example 45) 36 ° No.18 (Example 46) 44 ° No.19 (Example 47) 42 ° No.20 (Example 48) 43 ° No.21 (Comparative Example 3) 10 ° or less No.22 (Comparative Example 4) 10 ° or less

The alkali developable photosensitive resin composition of Examples 29-48 was 30 degree or more in contact angle, and was excellent in ink repellency. Moreover, the obtained coating film is excellent in adhesiveness with a board | substrate and alkali resistance.

In contrast, the alkali developable photosensitive resin compositions of Comparative Examples 3 to 4 had a low contact angle of 10 ° or less and poor ink repellency.

[Comparative Example 5] Preparation of alkali developable photosensitive resin composition No. 23

An alkali developable resin composition was obtained in the same manner as in Example 12 except that the fluorinated copolymer (E) was changed to the same mass MODIPER F-600 (fluorinated copolymer; manufactured by NOF CORPORATION).

Alkali-developable photosensitive resin composition No. 23 was obtained like Example 29 except having changed alkali-developable resin composition No. 1 into the obtained alkali-developable resin composition.

Evaluation of alkali developable photosensitive resin composition No. 1 and No. 23 was performed as follows.

After spin-coating well-dried γ-glycidoxypropylmethylethoxysilane on a glass substrate, the alkali developable photosensitive resin composition was spin-coated (1300 r.p.m, 50 seconds) and dried. After prebaking for 20 minutes at 70 degreeC, it immersed in 2.5 mass% sodium carbonate solution at 25 degreeC for 30 second, and developed, and it wash | cleaned well with water. After washing with water and drying, it was baked at 230 ° C. for 1 hour to obtain a test substrate. The residual film was visually checked with respect to the obtained test substrate. Although the residual film was not observed in the board | substrate using alkali-developable photosensitive resin composition No. 1, the residual film was observed for the board | substrate using alkali-developable photosensitive resin composition No.23. This shows that alkali-developable photosensitive resin composition No. 1 had favorable alkali developability, and alkali-developable photosensitive resin composition No. 23 was hard to alkali develop.

The alkali developable photosensitive resin composition using the alkali developable resin composition containing the fluorine-containing copolymer of the present invention is excellent in ink repellency, alkali developability, sensitivity, resolution, transparency, adhesion, and alkali resistance, and fine patterns are precisely formed. Can be formed.

Claims (12)

As block copolymer (C) which consists of A segment and B segment, A segment is a fluorine-containing segment obtained from the 1 or more types of fluorine-type monomer (A) represented by following [Formula 1] or [Formula 2], and B segment is 1 It is a non-fluorine segment obtained from the non-fluorine-type monomer (B) more than a kind, and one or more of the hydroxyl groups of the said block copolymer (C) which has a hydroxyl group in one or more of A segment and B segment is polybasic acid anhydride (D). It is obtained by modifying the fluorine-containing copolymer (E). [Formula 1]

(Wherein, R _f ¹ and R _f ² represent a perfluoroalkyl group which may have a hydroxyl group having 1 to 30 carbon atoms.) [Formula 2]

Wherein R ′ represents a hydrogen atom or a methyl group, Z ¹ represents a direct bond, -R ''-NR-SO _2- , -R ''-NR-CO-, -CH ₂ -CH (OH)- CH ₂ — or —CH ₂ —CH (OH) —CH ₂ —O— represents a group selected from R ₂ represents an alkylene group having 1 to 4 carbon atoms, and R _f ³ represents the general formula (I) Is the same as R _f ^2. R represents an alkyl group which may have a hydrogen atom or a hydroxyl group having 1 to 30 carbon atoms.) delete delete The fluorine-containing copolymer (E) according to claim 1, wherein the non-fluorine monomer (B) is a (meth) acrylic acid monomer. The fluorine-containing copolymer (E) according to claim 1 or 4, wherein a mass ratio of the fluorine monomer (A) and the non-fluorine monomer (B) is 10/90 to 80/20. The fluorine-containing copolymer (E) according to claim 1 or 4, wherein the mass average molecular weight is 10000 to 100,000. The fluorine-containing copolymer (E) according to claim 1 or 4, wherein the acid value is 20 mgKOH / g or more. The hydroxyl group of the said block copolymer (C) is modified with polybasic acid anhydride (D), The manufacturing method of the fluorine-containing copolymer (E) of Claim 1 or 4 characterized by the above-mentioned. The reaction product (H) obtained by esterifying an epoxy adduct which has a structure which added unsaturated monobasic acid (G) to the polyfunctional epoxy resin (F), and polybasic acid anhydride (D '), and Claim 1 or Claim An alkali developable resin composition comprising the fluorine-containing copolymer (E) according to claim 4. The alkali developable resin composition according to claim 9, wherein the polyfunctional epoxy resin (F) is an alkylidene bisphenol polyglycidyl ether type epoxy resin represented by the following general formula (III). (3)

(Wherein Z ⁴ is a direct bond, a methylene group, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group, O, S, SO ₂ , SS, SO, CO, OCO or the following [Formula 4] or [ And the alkylidene group may be substituted with a halogen atom. R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and 1 carbon atom. The alkoxy group of -8, the alkenyl group of 2-5 carbon atoms, or a halogen atom is represented, the alkyl group, the alkoxy group, and the alkenyl group may be substituted by the halogen atom, and n shows the integer of 0-10.) [Formula 4]

Wherein Y ¹ represents a phenyl group which may be substituted by a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group or a cycloalkyl group having 3 to 10 carbon atoms, and Y ² represents an alkyl group having 1 to 10 carbon atoms or a carbon source The alkoxy group of embroidery 1-10, the alkenyl group of 2-10 carbon atoms, or a halogen atom may be substituted, and the alkyl group, the alkoxy group, and the alkenyl group may be substituted by the halogen atom, and p represents the number of 0-4.) [Chemical Formula 5]

The alkali developable resin composition according to claim 9, wherein the polyfunctional epoxy resin (F) is a phenol novolac epoxy resin represented by the following general formula (IV). [Formula 6]

Wherein R ⁵ represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, an alkoxy group of 1 to 8 carbon atoms, an alkenyl group of 2 to 5 carbon atoms, a halogen atom or (4-glycidyloxyphenyl) -2 And a 2-dimethylmethylidene group, an alkyl group, an alkoxy group and an alkenyl group may be substituted with a halogen atom, each of R ⁶ and R ⁷ independently represents a hydrogen atom or a glycidyloxyphenyl group, and m is 0-10. Represents an integer.) The alkali-developable photosensitive resin composition formed by containing a photoinitiator (J) in the alkali-developable resin composition of Claim 9.

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