JPH0610223B2 - Photocurable polymerization composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a photopolymerizable curable composition which is cured by irradiation with light and can be developed with an alkaline aqueous solution. More specifically, it relates to a photopolymerizable curable composition having improved resistance to etching, plating and the like after development.

[Conventional technology and problems]

In general, a photopolymerization cured product is a substrate, for example, a copper clad laminate, is coated on a metal surface to be subjected to microfabrication, is laminated by lamination, etc., and is exposed to actinic light to cure the exposed portion,
The unexposed area is dissolved by a solvent having an appropriate solubility. The solvent is roughly classified into one using an organic solvent such as 1,1,1-trichloroethane and one using an aqueous solvent such as an aqueous sodium carbonate solution.

In recent years, a photopolymerizable composition that develops with an aqueous solvent has been gradually used in terms of work environment, surrounding environment, and manufacturing cost.

However, as compared with the case of using a conventional organic solvent developing type photopolymerization / curing composition, there are many restrictions on the treatment of etching and plating, and this often causes a problem in use.

[Means for solving problems]

As a result of intensive studies to solve such problems, the present inventors have found that an addition-polymerizable compound-type thermoplastic polymer binder obtained by copolymerizing an addition-polymerized monomer having a specific structure is more resistant. The present invention has been found to be improved.

That is, the present invention, (1) the addition polymerization monomer (A) having a carboxyl group, the following non-acidic addition polymerization monomer (B) and the following non-acidic addition polymerization monomer (C) Based on 100 parts by weight of the polymerized thermoplastic polymer binder, a non-acidic addition-polymerized monomer (B): an acrylic acid ester represented by the following general formula (I) (R ₁ is an alkylene group having 1 to 5 carbon atoms, R ₂ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, a halogen atom) Non-acidic addition polymerization monomer (C): having 1 to 5 carbon atoms Methacrylic acid alkyl ester consisting of alkyl group (2) As an addition polymerizable compound, an unsaturated compound having a molecular weight of 350 to 2000, which has at least three ethylenically unsaturated groups represented by the following formula (II) in one molecule, or 20 to 200 parts by weight of an addition-polymerizable compound having a boiling point of 50 ° C. or higher at atmospheric pressure, containing at least 2 parts by weight of the compound, (In the formula, R ₁ , R ₂ , and R ₃ are hydrogen atoms or methyl groups, and n is 1 to
An integer of 6) (3) A photoinitiator and / or a photoinitiator system 0.01 to 30 parts by weight, and a photocurable polymer composition.

First, the polymer binder used in the present invention will be described in detail. In the photopolymerizable cured composition of the addition polymerizable compound type according to the present invention, the resistance of the resist film is largely dependent on the properties of the polymer binder. The acidic addition-polymerizable monomer (A) having a carboxyl group in the copolymer forming the polymer binder of the present invention imparts developability to the copolymer, and accounts for a proportion of the polymer binder. Is in the range of 4 to 40 weight percent. The appropriate ratio varies depending on the type of the developing solution. For example, the so-called semi-aqueous solution developing type containing ethylene glycol monobutyl ether and the like is 4 to 15% by weight, and the complete aqueous solution developing type is 15 to 40% by weight. can do. Of course, the optimum copolymerization rate of the acid addition polymerization monomer of the semi-aqueous solution type or the complete aqueous solution type varies depending on the developing solution and the developing conditions. In the present invention, the addition polymerization monomer having a carboxyl group (A) is preferably crotonic acid, itaconic acid, maleic acid, or an anhydride thereof, maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester. , P-vinylbenzoic acid, and these may be used alone or in combination.

Since the acidic addition-polymerized monomer is copolymerized, the thermoplastic polymer binder essentially swells and dissolves in an alkaline liquid. Therefore, it is essential to copolymerize a non-acidic addition monomer in order to impart resistance.

Particularly, the non-acidic addition-polymerized monomer (B), which is an acrylate ester having a specific structure, is effective for improving the resistance to an alkaline aqueous solution.

Examples of such substances include benzyl acrylate, phenethyl acrylate, 3-phenylbutyl acrylate, 2-phenylbutyl acrylate, p-chlorobenzyl acrylate, p-methylbenzyl acrylate, and 2 acrylate.
-Phenylpropyl, p-ethylbenzyl acrylate and the like can be mentioned, but the invention is not limited thereto.

The non-acidic addition-polymerized monomer (C) serves as a component that imparts resistance together with the addition-polymerized monomer (B), and additionally has a role of controlling the glass transition point (Tg) of the copolymer. A suitable copolymer has a Tg between 40 ° C. and 120 ° C., and at 40 ° C. or lower, the photosensitive layer flows out with time when used as a “dry film” that sandwiches the photosensitive layer with a support film and a protective film. "Cold flow" development occurs and 120
If the temperature is above ℃, the adhesiveness of the photosensitive layer will be significantly impaired.

Next, a molecular weight having at least 3 or more ethylenically unsaturated groups represented by the general formula (II) in one molecule as the addition-polymerizable compound (2) blended in the photocurable polymerization composition of the present invention.
As the unsaturated compound of 350 to 2000, for example, glyceryl ethoxy triacrylate, glyceryl propoxy trimethacrylate, glyceryl propoxy triacrylate, trimethylol propane ethoxy triacrylate, trimethylol propane propoxy triacrylate, pentaerythritol ethoxy triacrylate,
Pentaerythritol ethoxy tetraacrylate, pentaerythritol propoxy triacrylate, glyceryl diethoxy triacrylate, glyceryl triethoxy triacrylate, glyceryl dipropoxy triacrylate, glyceryl dipropoxy trimethacrylate, trimethylol propane diethoxy triacrylate, trimethylol propane dipropoxy triacrylate Examples thereof include acrylate, pentaerythritol diethoxytriacrylate, pentaerythritol triethoxytriacrylate and pentaerythritol triethoxytrimethacrylate. Further, as the addition polymerizable compound (2), an addition polymerizable compound having at least 2 parts by weight of these unsaturated compounds and having a boiling point of 50 ° C. or higher at atmospheric pressure is also used.

Examples of the addition-polymerizable compound having a boiling point of 50 ° C. or higher at normal pressure include, for example, styrene, α-methylstyrene,
Styrene compounds such as chlorostyrene, methyl (meth) acrylate (meaning methyl acrylate and methyl methacrylate, the same applies hereinafter), ethyl (meth) acrylate, n- and i-propyl (meth) acrylate, n-, sec -And t-butyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, butoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate , Phenoxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate DOO, one such functional (meth)
Acrylate compound, (meth) allylonitrile, or
(Meth) acrylamides, (meth) acrylamides such as N-methylol (meth) acrylamide, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) Acrylate, dipropylene glycol di (meth)
Acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
Bifunctional (meth) acrylates such as 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and other trifunctional Bifunctional such as functional (meth) acrylates, di (meth) acrylate of ethylene oxide and / or propylene oxide adduct of bisphenol A, and di (meth) acrylate of ethylene and / or propylene oxide adduct of hydrogenated bisphenol A Examples thereof include, but are not limited to, bisacrylamides such as (meth) acrylate, N, N′-methylenebis (meth) acryamide, and N, N′-benzylidenebis (meth) acrylamide.

In the composition of the present invention, the addition-polymerizable compound (2) as described above is 20 to 100 parts by weight of the thermoplastic polymer binder.
Used in 200 parts by weight.

The photoinitiators and / or photoinitiator systems that can be used in the compositions of the present invention include:

That is, there are substituted or unsubstituted polynuclear quinones, for example, 2
-Ethyl anthraquinone, 2-tert-butyl anthraquinone, octamethyl anthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone,
1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthaquinone,
9,10-phenanthraquinone, 2-methyl-1,4-naphthaquinone, 2,3-dichloronaphthaquinone, 1,4-dimethylanthraquinone, 2,3-dimethylanthraquinone, 3-chloro-2-methylanthraquinone, Examples include 7,8,9,10-tetrahydrophthalcenequinone. Other aromatic ketones such as benzophenone, Michler's ketone [4,4-
Bis (dimethylamino) benzophenone], 4,4′-bis (diethylamino) benzophenone], 4-methoxy-4′-dimethylaminobenzophenone and the like. Other examples include benzoin and benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin and ethylbenzoin. Furthermore, 2,4,5-triarylimidazole dimer and 2-mercaptobenzoxazole, leuco crystal violet, tris (4-diethylamino-
Combinations with 2-methylphenyl) methane and the like can also be used.

In addition, there are substituted or unsubstituted thioxanthones, such as 2-chlorothioxanthone, 2,4-diethylthioxanthone, and 2,4-dimethylthioxanthone. Further, a combination of these thioxanthones with an aliphatic or aromatic tertiary amine such as N-methyldiethanolamine, P-dimethylaminobenzoic acid ethyl ester and the like can be used, and a combination of thioxanthones with an alkylaminobenzophenone such as Michler's ketone can be used. Combinations of thioxanthones and oxime esters such as benzophenone oxime acetate are also effective. These addition-polymerizable initiators that can be activated by light may be used alone or in combination of two or more. The present invention is not limited to these.

These are 0.01 per 100 parts by weight of the thermoplastic polymer binder.
-30 parts by weight, preferably 0.1-15 parts by weight.

In the present invention, in addition to the above essential elements, stabilizers, dyes and the like can be added if necessary. Examples of the stabilizer include hydroquinone, hydroquinone monomethyl ether, t-butylcatechol and the like. These can be added within a range that does not inhibit the photopolymerization reaction. Also, a plasticizer for imparting appropriate flexibility can be added. For example, 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 and sulfone such as toluene sulfonic acid amide. Examples thereof include acid amides.

In the present invention, when the photopolymerization curable composition is solvent-free, a usual printing method or coating method is used, and when it is dissolved or dispersed in a solvent, it is coated or impregnated on a suitable support, and then, A photopolymer layer can be formed by evaporating the solvent. In this case, the support may be any one that does not adversely affect photopolymerization, and examples thereof include various plastics, various films, paper, glass, various metals, and ceramic products.

Such a photopolymer layer is cured by light from a suitable light source such as a low pressure mercury lamp or an ultrahigh pressure mercury lamp. The composition of the present invention can be used as a photopolymer or a photoresist when producing a printing plate or the like.

〔Example〕

Next, the present invention will be specifically described with reference to examples. The present invention is not limited to the embodiment.

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

Copolymer of crotonic acid 25 wt%, methyl methacrylate 35 wt%, benzyl acrylate 45 wt% 50 g Glyceryl propoxytriacrylate 30 g Benzophenone 1.5 g Michler's ketone 0.15 g Victoria blue 0.05 g Methyl ethyl ketone 80 g Thick polyethylene glycol terephthalate film It was coated on a support and dried at 75 ° C to obtain a photosensitive film. The thickness of the photosensitive layer was 25 μm. This 10
It was laminated on a copper clad laminate that had been polished by a rubber roller heated to 0 ° C. A wiring circuit pattern mask was placed on it, irradiated with an ultra-high pressure mercury lamp from a distance of 50 cm for 10 seconds to cure, and then developed with a 1% sodium carbonate aqueous solution at 30 ° C. to obtain a resin relief image on a copper clad laminate. .

Next, copper was etched with an alkaline etchant to obtain a good printed wiring board.

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

Copolymer of 20 wt% itaconic acid, 40 wt% ethyl methacrylate, 40 wt% benzyl acrylate 50 g Trimethylolpropane diethoxy triacrylate 30 g Benzophenone 1.5 g Michler's ketone 0.15 g Victoria blue 0.05 g Methyl ethyl ketone 80 g Evaluation similar to Example 1 Then, a good printed wiring board was obtained.

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

Copolymer of 40 wt% p-vinylbenzoic acid, 25 wt% propyl methacrylate and 35 wt% benzyl acrylate 50 g Glycerylpropoxytriacrylate 20 g Trimethylolpropane triacrylate 10 g 2-Chlorthioxanthone 0.5 g Methyldiethanolamine 0.05 g Victoria blue 0.05 g Methylethylketone 80 g When evaluated in the same manner as in Example 1, a good printed wiring board was obtained.

Comparative Example 1 The following components were mixed to obtain a photocurable polymerization composition.

Copolymer of 25% by weight of crotonic acid, 35% by weight of methyl methacrylate and 45% by weight of n-butyl acrylate 50 g Glyceryl propoxytriacrylate 30 g Benzophenone 1.5 g Michler's ketone 0.15 g Victoria blue 0.05 g Methyl ethyl ketone 80 g The same evaluation as in Example 1 However, disconnection was observed in the obtained printed wiring board.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location G03F 7/038 501 H05K 1/03 7011-4E

Claims (2)

[Claims] (1) Copolymerization of an addition polymerization monomer (A) having a carboxyl group with the following non-acidic addition polymerization monomer (B) and the following non-acidic addition polymerization monomer (C) Based on 100 parts by weight of the resulting thermoplastic polymer binder, the non-acidic addition-polymerized monomer (B): an acrylic acid ester represented by the following general formula (I) (R ₁ is an alkylene group having 1 to 5 carbon atoms, R ₂ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, a halogen atom) Non-acidic addition polymerization monomer (C): having 1 to 5 carbon atoms Methacrylic acid alkyl ester consisting of alkyl group (2) As an addition polymerizable compound, an unsaturated compound having a molecular weight of 350 to 2000, which has at least three ethylenically unsaturated groups represented by the following formula (II) in one molecule, or 20 to 200 parts by weight of an addition-polymerizable compound having a boiling point of 50 ° C. or higher at atmospheric pressure, containing at least 2 parts by weight of the compound, (In the formula, R ₁ , R ₂ , and R ₃ are hydrogen atoms or methyl groups, and n is 1 to
(3 an integer of 6) (3) Photoinitiator and / or 0.01 to 30 parts by weight of a photoinitiator system. 2. An addition polymerization monomer having a carboxyl group
(A) is crotonic acid, itaconic acid, maleic acid, or anhydride thereof, maleic acid monoalkyl ester, fumaric acid,
The photocurable polymerization composition according to claim 1, which is at least one compound selected from fumaric acid monoalkyl ester and p-vinylbenzoic acid.