JP2826331B2 - Photopolymerizable composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a photopolymerizable composition, and more particularly, to a photopolymerizable composition which can be developed with an alkali developer and has an improved peeling time of a cured film. About.

[Prior Art and Problems to be Solved by the Invention] Photopolymerizable compositions are used as printed wiring boards, printing plates, and photoresists for forming metal relief images.
This photopolymerizable composition is usually used in the form of a liquid or a dry film.For example, it is applied to a copper-clad laminate for a printed board, a support for printing or a metal substrate used for fine processing, and laminated by lamination or the like. By exposing active light through a predetermined pattern mask or the like, the exposed portion is cured, and the unexposed portion is dissolved and removed with a developer to form a resist image. After forming a resist image,
A predetermined circuit or the like corresponding to the resist image is formed by an etching process, a plating process, or the like, and then the resist image is stripped and removed with a stripping solution.

On the other hand, although an organic solvent-type developer such as 1,1,1-trichloroethane is known as the developer, this developer involves problems such as contamination of a working environment, surrounding environment, and an increase in manufacturing cost. . In view of the above, in recent years, photopolymerizable compositions that can be developed with an aqueous alkaline developer containing a basic compound such as an aqueous sodium carbonate solution have been gradually used. This photopolymerizable composition usually basically contains a thermoplastic polymer binder having a carboxyl group, an addition polymerizable compound, and a photopolymerization initiator.

However, the properties and developability of the cured film of the photopolymerizable composition are greatly affected by the properties of the thermoplastic polymer binder and the addition polymerizable compound. In addition, since the alkali-developable photopolymerizable composition has an active carboxyl group, it has many restrictions on etching and plating compared to a photopolymerizable composition that can be developed with an organic solvent-type developer, and is not suitable for use. A number of problems arise. Particularly, in the case of a photopolymerizable composition that can be alkali-developed, when the cured film is peeled with an aqueous alkali solution such as sodium hydroxide or potassium hydroxide, it takes a long time to peel the cured film. Not only does it lower, but also the so-called "alkali burn" in which the metal substrate, particularly the copper foil of the copper-clad laminate, is darkened by the alkaline aqueous solution, adversely affecting subsequent steps.

An object of the present invention is to provide a photopolymerizable composition which has a short peeling time of a cured film, can prevent alkali burning, and is excellent in productivity of a printed wiring board and the like.

[Constitution of the Invention] As a result of intensive studies, the present inventors have found that an excellent photopolymerizable composition can be obtained by combining a specific addition polymerization compound with a thermoplastic polymer binder having a carboxyl group and a photoinitiator. Was obtained. That is, the present invention provides: (1) 100 parts by weight of a thermoplastic polymer binder containing 4 to 40% by weight of units of an acidic addition-polymerizable monomer having a carboxyl group; (Wherein, R ₁ and R ₄ are the same or different and each represent a hydrogen atom or a methyl group; R ₂ and R _{3 each} represent a linear or branched alkylene group; R ₅ represents a hydrogen atom; A represents an alkyl group or a halogen atom, a and b each represent a positive integer of 1 to 10, and n represents a positive integer of 1 to 20). The above object is achieved by a photopolymerizable composition containing 0.01 to 30 parts by weight of a photopolymerization initiator.

In the photopolymerizable composition, the developability and the resistance of the resist film largely depend on the properties of the thermoplastic polymer binder.
The thermoplastic polymer binder used in the present invention comprises four units (A) of an acid addition polymerizable monomer having a carboxyl group.
-40% by weight to impart alkali developability to the photopolymerizable composition.

Acid addition polymerizable monomer having a carboxyl group (A)
Examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, propionic acid, sorbic acid, and cinnamic acid, and at least one of them is used. Among the acidic addition-polymerizable monomers having a carboxyl group, methacrylic acid, acrylic acid and a mixture of both are particularly preferred.

The thermoplastic polymer binder containing a unit of the acidic addition-polymerizable monomer (A) has a property of swelling or dissolving in an alkaline liquid. Therefore, non-acidic addition-polymerizable monomers (B) such as styrene and its derivatives, acrylates or methacrylates are effective as copolymerization components for imparting resistance to alkali developers.

Examples of the styrene monomer include styrene; α-substituted styrene in which the α-position is substituted with an alkyl group or a halogen atom, such as α-methylstyrene and α-chlorostyrene; and substituted styrene in which the hydrogen atom of a benzene ring is substituted. For example, p-methylstyrene, p-ethylstyrene and the like are exemplified, and at least one is used. Among the styrene monomers, styrene, α-methylstyrene and the like are preferred.

Examples of the acrylate include butyl acrylate, isobutyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, and 2-phenoxyethyl acrylate. Examples of the methacrylate include methacrylate corresponding to the above acrylate.

In particular, an acrylate or methacrylate having a specific structure represented by the general formula (II) is useful as the non-acidic addition polymerizable monomer (B).

(Wherein, R ₆ is a hydrogen atom or a methyl group, and R ₇ has 1 to 6 carbon atoms.
R ₈ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a halogen atom, and n represents a positive integer of 1 to 20.) In the compound represented by the general formula (II), an alkylene group represented by R ₇ Examples thereof include a methylene, ethylene, propylene, trimethylene, tetramethylene, hexamethylene group and the like. Examples of the alkyl group for R ₈ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, and octyl groups. Examples of the halogen atom for R ₈ include bromine, chlorine, fluorine and the like.

Preferred non-acid addition polymerizable monomers (B) among the compounds represented by the general formula (II) include 2-phenoxyethyl acrylate, 2-phenoxypropyl acrylate, 3-phenoxypropyl acrylate, and acrylic acid Phenoxyethoxyethyl, phenoxydiethoxyethyl acrylate, phenoxytriethoxyethyl acrylate, phenoxypropoxypropyl acrylate, phenoxydipropoxypropyl acrylate, phenoxytripropoxypropyl acrylate, ethyl (p-chlorophenoxy) acrylate, acrylic acid (P-methylphenoxy) ethyl, 2-phenoxyethyl methacrylate, 3-phenoxypropyl methacrylate, phenoxyethoxyethyl methacrylate, phenoxydiethoxyethyl methacrylate, fe-methacrylate Xitriethoxyethyl, phenoxypropoxypropyl methacrylate, phenoxydipropoxypropyl methacrylate, phenoxytripropoxypropyl methacrylate, (p-chlorophenoxy) ethyl methacrylate, (p-methylphenoxy) ethyl methacrylate and the like can be mentioned. .

The unit of these non-acidic addition-polymerizable monomers (B) is contained in the copolymer at least 5% by weight, preferably 10 to 70% by weight.

The non-acid addition polymerizable monomer (B) has the general formula (II)
And at least one of a styrene monomer, an acrylate and a methacrylate.

The acidic addition-polymerizable monomer (A) having a carboxyl group and the non-acidic addition-polymerizable monomer (B) each have a formula (II)
It is preferable to copolymerize with the non-acidic addition-polymerizable monomer (C) satisfying I).

0.25 <(QA / QC) Exp [−eA (eA−eC)] <4.00 (III) When copolymerized with the non-acidic addition-polymerizable monomer (C) satisfying the above relational formula (III), acid addition polymerization A copolymer in which the units of the functional monomer (A) are uniformly distributed is obtained, and the developability is excellent. That is, as the acid addition polymerizable monomer (A) and the non-acid addition polymerizable monomer (C), Alfrey-
In the Price (Alfrey-Price) formula, the value of Q, which is an index of copolymerizability, is similar, and the use of a monomer having the opposite sign of e and a large difference in absolute value significantly increases copolymerizability. Can be. Therefore, when a monomer that does not satisfy the above relational formula (III) is used, a copolymer or a free polymer in which the units of the acidic addition-polymerizable monomer (A) are unevenly distributed can be obtained. Poor development may occur, or in a severe case, precipitation of the copolymer may occur during polymerization or during the preparation of a coating solution containing the photopolymerizable composition.

The non-acidic addition-polymerizable monomer (C) is appropriately selected according to the properties of the acidic addition-polymerizable monomer (A). More specifically, (QA / QC) Exp [-eA (eA-eC)] of the relational expression (III)
Let X be X, for example, when methacrylic acid (QA = 2.340, eA = 0.650) is used as the acidic addition-polymerizable monomer (A), methyl methacrylate (QA = 0.740, eA = 0.400, X = 2.69), ethyl methacrylate (QA = 0.730, eA = 0.520, X = 2.59) and the like. In this case, n-butyl acrylate (QA = 0.500, eA
= 1.060, X = 6.11), methacrylic acid is consumed quickly during the polymerization, resulting in a non-uniform copolymer composition and sometimes precipitation.

When a plurality of acidic addition-polymerizable monomers (A) are used, the non-acidic addition-polymerizable monomer (C) is at least one of the acidic addition-polymerizable monomers (A). Relational expression (II
I) should be satisfied.

The non-acidic addition-polymerizable monomer (C) constitutes the remainder of the thermoplastic polymer binder other than the acidic addition-polymerizable monomer (A) and the non-acidic addition-polymerizable monomer (B). 100% by weight.

The addition polymerizable compound of the component (2) mixed with the thermoplastic polymer binder of the component (1) belongs to an acrylate or methacrylate derivative and can be represented by the general formula (I).

In the general formula (I), examples of the alkylene group for R ₂ and R ₃ include the same linear or branched alkylene group as described above, as well as a heptamethylene, octamethylene group, and the like.
Examples of the alkyl group and halogen atom for R ₅ include the same alkyl groups and halogen atoms as described above.

The compound represented by the general formula (I) may be an adduct of an aromatic dicarboxylic acid optionally having a substituent and an alkylene oxide, or an aromatic dicarboxylic acid optionally having a substituent and a divalent compound. An acrylic or methacrylic acid ester of an esterified product with an alcohol or a hydroxycarboxylic acid and having a hydroxyl group or a carboxyl group at a terminal.

In the compound represented by the above general formula (I), the carbonyl group substituted on the benzene ring is phthalic acid in which one carbonyl group is substituted with the other carbonyl group at the o-, m-, or p-position. Derivatives, isophthalic acid derivatives and terephthalic acid derivatives may be used. Preferred addition-polymerizable compounds among the compounds represented by the general formula (I) include, for example, phthalic acid derivatives shown in the following table.

At least one kind of the addition polymerizable compound represented by the general formula (I) is used.

The addition polymerizable compound represented by the general formula (I) is
It can be used by mixing with other addition polymerizable compounds. Examples of such an addition polymerizable compound include acrylates and methacrylates which are liquid or solid at normal temperature and normal pressure and have two or more acryloyl groups or methacryloyl groups in the molecule. Examples of the acrylate having two acryloyl groups in the molecule include ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, and dipropylene glycol. Diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, polypropylene glycol diacrylate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, ethylene oxide addition of bisphenol A Diacrylate, bisphenol A propylene oxide adduct dia Relate, diacrylate of ethylene oxide adduct of hydrogenated bisphenol A, diacrylate of propylene oxide adduct of hydrogenated bisphenol A,
N, N'-methylenebisacrylamide, N, N'-benzylidenebisacrylamide and the like are exemplified.

Examples of the acrylate having three or more acryloyl groups in the molecule include glycerin triacrylate,
Examples thereof include trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate.

Examples of the methacrylate having two or more methacryloyl groups in the molecule include methacrylates corresponding to the above acrylates.

The addition polymerizable compound represented by the formula (I) is used in an amount of 10 to 200 parts by weight, preferably 20 to 150 parts by weight, based on 100 parts by weight of the thermoplastic polymer binder. When the addition-polymerizable compound represented by the general formula (I) is used by being mixed with another addition-polymerizable compound, the addition-polymerizable compound represented by the general formula (I) is a thermoplastic polymer binder 100 5 parts by weight
To 150 parts by weight, preferably 10 parts by weight or more.

As the photopolymerization initiator of the component (3), various ones such as substituted or unsubstituted polynuclear quinones, aromatic ketones, benzoins, benzoin ethers, and substituted or unsubstituted thioxanthones can be used.

Examples of the substituted or unsubstituted polynuclear quinones include, for example, 2
-Methylanthraquinone, 2-ethylanthraquinone,
2-propylanthraquinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,4-dimethylanthraquinone, 2,3-dimethylanthraquinone, benz [a] anthraquinone, benz [b] anthraquinone, 2-phenylanthraquinone, 2,3 -Diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 3-chloro-2-methylanthraquinone, 1,4-naphthaquinone, 9,10-phenanthraquinone,
Examples thereof include 2-methyl-1,4-naphthaquinone, 2,3-dichloronaphthaquinone, and 7,8,9,10-tetrahydronaphthacenequinone.

As aromatic ketones, for example, benzophenone,
Examples include Michler's ketone [4,4'-bis (dimethylamino) benzophenone], 4,4'-bis (diethylamino) benzophenone, 4-methoxy-4'-diethylaminobenzophenone, and the like.

Examples of benzoins and benzoin ethers include benzoin, methyl benzoin, ethyl benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether and the like.

Examples of the substituted or unsubstituted thioxanthone include thioxanthone, 2-chlorothioxanthone,
Methylthioxanthone, 2-ethylthioxanthone, 2
-Isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dibutylthioxanthone and the like.

Examples of other photopolymerization initiators include oxime esters such as benzyl, α, α-diethoxyacetophenone, and benzophenone oxime acetate.

The photopolymerization initiator is used alone or in combination of two or more,
The same or different photopolymerization initiators may be used in combination.

The photopolymerization initiator is used in an amount of 0.01 to 30 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the thermoplastic polymer.

The photopolymerization initiator is, for example, 2,4,5-triarylimidazolyl dimer, 2-mercaptobenzoxazole, leuco crystal violet, tris (4
-Diethylamino-2-methylphenyl) methane and aliphatic or aromatic tertiary amines such as N-methyldiethanolamine, ethyl p-dimethylaminobenzoate are useful in combination.

The photopolymerizable composition of the present invention may contain a stabilizer, a coloring agent, a coloring agent for facilitating discrimination of a resist image, a plasticizer for imparting flexibility, if necessary, for suppressing a thermal polymerization reaction and for enhancing storage stability. And the like. Examples of the stabilizer include p-methoxyphenol, hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol and the like, and are used in an appropriate amount as long as the photopolymerizability is not inhibited. As the color former, a leuco compound of a triarylmethane dye is useful. For example, leuco crystal violet, leucomalachite green, mineral salts such as hydrochloride and sulfate of these leuco bodies, p-toluenesulfonate And the like. Examples of the coloring agent include crystal violet, malachite green, Victoria blue, methylene blue and the like. Examples of the plasticizer include phthalic acid esters such as diethyl phthalate, dibutyl phthalate, diheptyl phthalate, and dioctyl phthalate; fatty acid esters such as dioctyl adipate and dibutyl diglycol adipate; phosphoric acid esters such as trimethylphosphine;
Examples thereof include sulfonic acid amides such as toluenesulfonic acid amide.

The photopolymerizable composition of the present invention may be a liquid containing no organic solvent, but is usually used in the form of a dispersed liquid or a dry film which does not dissolve in the organic solvent. Examples of the organic solvent include alcohols such as methanol, ethanol, and propanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran; and halogenated hydrocarbons such as methylene chloride. And the like. The dry film is produced, for example, by applying a polymerizable composition to a base film such as a polyethylene terephthalate film, drying the film, and then laminating a cover film such as a polyethylene film with a pressure roll or the like.

The thickness of the photopolymerizable composition of the dry film is not particularly limited as long as the resolution and workability are not reduced, but is usually 5 to 100 μm, preferably 20 to 70 μm.

The photosensitive layer comprising the photopolymerizable composition of the present invention is usually prepared by printing or coating a liquid photopolymerizable composition containing an organic solvent on a support such as a printed circuit board to remove the organic solvent or dry the photopolymerizable composition. It is formed by peeling the cover film of the film and laminating the film on the support with a rubber roll or the like.

The photosensitive layer is a light source that generates chemically active radiation,
For example, exposure is performed with a light source such as a low-pressure mercury lamp, an ultra-high-pressure mercury lamp, and a xenon lamp. Exposure is usually performed by providing a cover sheet on the photosensitive layer as necessary and using a negative or positive mask pattern by a contact method or a projection method. After exposure, development with an alkaline developer containing a basic compound yields a resist image corresponding to the pattern. Examples of the basic compound in the alkali developer include inorganic bases such as potassium carbonate, sodium carbonate, sodium hydrogen carbonate, sodium silicate, and sodium phosphate; and organic compounds such as trimethylamine, triethylamine, diethanolamine, triethanolamine, morpholine, and pyridine. Bases are exemplified. The developer may contain an organic solvent such as ethylene glycol monobutyl ether.

When a circuit pattern is formed, after forming a resist image, the resist image is treated with a plating solution or an etching solution, and the resist image is peeled off with a strong alkaline aqueous solution such as sodium hydroxide or an organic solvent such as methylene chloride. .

[Effect of the Invention] According to the photopolymerizable composition of the present invention, the specific addition polymerization compound is combined with the thermoplastic polymer binder having a carboxyl group and the photopolymerization initiator, so that the cured film is peeled off. The time is short, "alkaline burning" can be prevented, and the productivity of printed wiring boards and the like can be increased. Therefore, the photopolymerizable composition of the present invention is useful as a photoresist for producing a printed wiring board, a circuit board, a metal relief image, a printing plate, and the like.

EXAMPLES Hereinafter, the present invention will be described in more detail based on examples.

In the following examples, the compound No. indicates the phthalic acid derivative No. shown in the above table.

Example 1 The following components were mixed to obtain a photopolymerizable composition.

Copolymer of 20% by weight of methacrylic acid, 60% by weight of methyl methacrylate, and 20% by weight of isobutyl acrylate 50g Compound No. 1 30g 2-Chlorothioxanthone 1g Ethyl p-dimethylaminobenzoate 2g N-methyldiethanolamine 0.1g Victoria blue GH 0.1 g Methyl ethyl ketone 70 g Tetrahydrofuran 10 g This photopolymerizable composition was applied to a 25 μm-thick polyethylene terephthalate film support and dried at 75 ° C. to obtain a photosensitive film. The thickness of the photosensitive layer was 50 μm. The photosensitive film was laminated on a copper-clad laminate polished by a rubber roller heated to 100 ° C. Laying the wiring circuit pattern mask on the photosensitive film, 50c with a 2Kw ultra-high pressure mercury lamp
After irradiating for 10 seconds from a distance of m and curing, spray-developed with 30% 1% aqueous sodium carbonate solution for 70 seconds,
A resin relief image was formed. Next, when the copper-clad laminate was etched with a cupric chloride etching solution, a good printed wiring board was obtained.

Then, when the cured film was immersed in a 2% by weight aqueous sodium hydroxide solution at a temperature of 55 ° C., the cured film was completely peeled off in 1 minute 30 seconds to 2 minutes, and no alkali burn was observed.

Example 2 The following components were mixed to obtain a photopolymerizable composition.

15% by weight of methacrylic acid, 15% by weight of acrylic acid, 40% by weight of methyl methacrylate, 20% by weight of isobutyl acrylate
50 g of compound No. 1 25 g benzophenone 2 g Michler's ketone 0.5 g N-methyldiethanolamine 0.1 g Victoria blue GH 0.1 g methyl ethyl ketone 70 g tetrahydrofuran 10 g When the above photopolymerizable composition was evaluated in the same manner as in Example 1, a good print was obtained. The wiring board was obtained, and the time required for peeling the cured film was 1 minute 30 seconds to 2 minutes, and no alkali burn was observed.

Example 3 The following components were mixed to obtain a photopolymerizable composition.

10% by weight of methacrylic acid, 15% by weight of acrylic acid, 42% by weight of methyl methacrylate, 2-ethylhexyl acrylate
23% by weight copolymer 50 g Compound No. 26 25 g 2,4-dimethylthioxanthone 1 g ethyl p-dimethylaminobenzoate 2.5 g N-methyldiethanolamine 0.1 g Victoria blue GH 0.1 g methyl ethyl ketone 70 g tetrahydrofuran 10 g The above photopolymerizable composition Was evaluated in the same manner as in Example 1. As a result, a good printed wiring board was obtained, and the peeling time of the cured film was 1 minute 30 seconds to 2 minutes, and no alkali burn was observed.

Example 4 The following components were mixed to obtain a photopolymerizable composition.

Copolymer of 12% by weight of methacrylic acid, 8% by weight of acrylic acid, 35% by weight of methyl methacrylate, 35% by weight of 2-phenoxyethyl acrylate 50g Compound No. 1 30g Benzophenone 2g Michler's ketone 0.5g Nn-butyldiethanolamine 0.1 g Victoria blue GH 0.1 g Methyl ethyl ketone 70 g Tetrahydrofuran 10 g When the above photopolymerizable composition was evaluated in the same manner as in Example 1, a good printed wiring board was obtained, and the peeling time of the cured film was 1 minute 30 seconds to 2 minutes. And no alkali burn was observed.

Example 5 The following components were mixed to obtain a photopolymerizable composition.

50 g of the copolymer of Example 2 Compound No. 17 30 g Irgacure 651 (manufactured by Merck) 3 g 2,4-dimethylthioxanthone 1 g ethyl p-dimethylaminobenzoate 2.5 g N-methyldiethanolamine 0.1 g Victoria blue GH 0.1 g methyl ethyl ketone 70 g tetrahydrofuran 10 g When the above photopolymerizable composition was evaluated in the same manner as in Example 1, a good printed wiring board was obtained, and the peeling time of the cured film was 1 minute 30 seconds to 2 minutes. I couldn't.

Example 6 The following components were mixed to obtain a photopolymerizable composition.

Copolymer of Example 2 50 g Compound No. 1 15 g Compound No. 12 15 g 2,4-dimethylthioxanthone 1 g ethyl p-dimethylaminobenzoate 3 g N-methyldiethanolamine 0.1 g Victoria blue GH 0.1 g methyl ethyl ketone 70 g tetrahydrofuran 10 g When the polymerizable composition was evaluated in the same manner as in Example 1, a good printed wiring board was obtained, and the peeling time of the cured film was 1 minute 30 seconds to 2 minutes, and no alkali burn was observed.

Example 7 The following components were mixed to obtain a photopolymerizable composition.

50 g of the copolymer of Example 2 Compound No. 1 20 g Compound No. 17 10 g Compound No. 12 10 g Trimethylolpropane triacrylate 10 g 2,4-dimethylthioxanthone 1 g Ethyl p-dimethylaminobenzoate 2.5 g N-n-butyl Diethanolamine 0.1 g Victoria blue GH 0.1 g Methyl ethyl ketone 70 g Tetrahydrofuran 10 g When the above photopolymerizable composition was evaluated in the same manner as in Example 1, a good printed wiring board was obtained, and the peeling time of the cured film was from 1 minute 30 seconds to 2 minutes, and no alkali burn was observed.

Comparative Example 1 A photopolymerizable composition was prepared in the same manner as in Example 2 except that trimethylolpropane triacrylate was used in place of compound No. 1 in Example 2, and evaluated in the same manner as in Example 1. It took 4 minutes to peel off the cured film, and alkali burning occurred on the copper surface.

Comparative Example 2 The following components were mixed to obtain a photopolymerizable composition.

50 g of the copolymer of Example 2 nonaethylene glycol dimethacrylate 30 g benzophenone 2 g Michler's ketone 0.5 g N-n-butyldiethanolamine 0.1 g Victoria blue GH 0.1 g methyl ethyl ketone 70 g tetrahydrofuran 10 g This composition was evaluated in the same manner as in Example 1. It took 4 minutes to peel off the cured film, and alkali burning occurred on the copper surface.

Continuation of the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03F 7/027 G03F 7/033 C08F 2/46

Claims (2)

(57) [Claims] (1) With respect to 100 parts by weight of a thermoplastic polymer binder containing 4 to 40% by weight of units of an acidic addition-polymerizable monomer having a carboxyl group, (2) General formula (I) (Wherein, R ₁ and R ₄ are the same or different and each represent a hydrogen atom or a methyl group; R ₂ and R _{3 each} represent a linear or branched alkylene group; R ₅ represents a hydrogen atom; Wherein a and b are each a positive integer of 2 to 10, and n is a positive integer of 1 to 20), and 10 to 200 parts by weight of an addition polymerizable compound represented by the following formula: 3) A photopolymerizable composition comprising 0.01 to 30 parts by weight of a photopolymerization initiator. 2. The thermoplastic polymer binder of the component (1) comprises: (A) an acid addition polymerizable monomer 4 having a carboxyl group.
(B) General formula (II) (Wherein, R ₆ is a hydrogen atom or a methyl group, and R ₇ has 1 to 6 carbon atoms.
R ₈ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a halogen atom, and n represents a positive integer of 1 to 20). % And (C) relational expression (III) 0.25 <(QA / QC) Exp [−eA (eA−eC)] <4.00 (III) (where Q and e are Alfrey-Pri
ce) is the stability and polarity of the monomer as defined by the formula
The symbol A or C represents an addition polymerizable monomer (A) or a non-acidic addition polymerizable monomer (C). The photopolymerizable composition according to claim 1, which is a copolymer of a non-acidic addition polymerizable monomer having a Q value and an e value satisfying the following.