JPS62180355A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To obtain a photopolymerizable compsn. having high resolving power capable of reproducing faithfully lines of a picture image of an original plate by using a compsn. consisting primarily of a thermoplastic org. polymer binder, an addition-polymerizable unsatd. compd. having two ethylenic double bonds in a molecule, and a photopolymn. initiator as primary components, and specified compds. as additive components. CONSTITUTION:A photopolymerizable compsn. consists of a thermoplastic org. polymer binder, an addition-polymerizable unsatd. compd. having two ethylenic double bonds in a molecule, and a photopolymn. initiator, as primary components and a compd. expressed by the formula sa an additive component. Specific examples for the compd. expressed by the formula providing improved adhsion are 2-amino-oxazole, 2-amino-5-phenyloxazole, etc. The content basing on the whole weight (dry basis) of the photopolymerizable compsn. is pref. 0.006-6.0wt%. Suitable thermoplastic org. polymer binder is polymer or copolymer of vinyl monomer such as polyacrylic acid, etc. Suitable photopolymn. initiator is one suitable for the polymn. of ethylenic unsatd. compds.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a novel photopolymerizable composition, and more specifically, its adhesion to metals (adhesiveness or 'adhesion').
The present invention relates to a photopolymerizable composition with improved properties.

[Conventional technology]

Many proposals have been made to improve the adhesion between a coating formed from a photopolymerizable composition and a substrate. Dry film photoresists used in the manufacture of printed wiring boards have poor adhesiveness to metal surfaces compared to solution-type photoresists, and various undesirable phenomena occur during etching or plating. . For example, phenomena such as undercutting during spraying of an etching solution and penetration of the plating solution into the resist interface when immersed in a plating solution occur, and as a result, it is often experienced that the expected wiring cannot be obtained.

In order to solve these problems, various proposals have been made to improve adhesion by adding various compounds to the photosensitive resin layer. (For example, Tokuko Sho 5
No. 0-9177, Special Publication No. 57-49894, Special Publication No. 57
No. 7-26285, Special Publication No. 1983. -5292, Special Publication No. 55-22481, Sai, No. 51-64919,
Japanese Patent Publication No. 51-6 ll 920, Special Publication No. 57-460
No. 53, Special Publication No. 57-46054, Special Publication No. 57-21
697, Japanese Patent Publication No. 57-40500, etc.) [Problems to be Solved by the Invention] However, these conventionally proposed compounds exhibit the following drawbacks, especially when used as photoresists. be. For example, when a photopolymerizable composition containing a heterocyclic nitrogen-containing compound such as benzimidazole or benzotriazole, which is known as an adhesion promoter, is used, red discoloration of the exposed copper surface of the substrate after development is observed, and plating, It has an unfavorable effect on post-processing such as etching. Alternatively, an increase in the amount of the density/density promoter added may cause negative effects such as a decrease in sensitivity.

In addition, in recent years, there has been a desire for higher density printed wiring, which has created a need for dry film photoresists that have good original reproducibility, high resolution, and reliable tenting. It is desired to have good adhesion, wide latitude when exposed to light, good resolution, and stability against fluctuations in the developing process.

The purpose of the present invention is to eliminate the above-mentioned gap between the photopolymerizable composition and the target material, to improve the adhesion to the metal surface, to reproduce a faithful image to the original plate, and to achieve high resolution. 3
The object of the present invention is to provide a photopolymerizable composition that can be

[Means for solving problems]

The present inventors have discovered that these objects can be achieved by using the following photopolymerizable composition, and have completed the present invention.

That is, the present invention mainly comprises a thermoplastic organic polymer binder, an addition polymerizable unsaturated compound having at least two ethylenically unsaturated double bonds in the molecule, and a photopolymerization initiator, and has the following general formula ( The present invention provides a photopolymerizable composition containing a compound represented by I).

(Here, R1 is an amine group, a (mono- or di)n-substituted amine group, or a carboxylic acid alkyl ester group.

It is an alkyl group, an aromatic derivative substituent, or an allyl derivative substituent. 112. R3 is a hydrogen atom or a halogen.

It is an alkyl group or an aromatic derivative substituent. ) Specific examples of compounds that improve adhesion represented by the above general formula (1) of the present invention include 2-aminoxazole, 2-
Amino-5-phenyloxazole, 2.5-diphenyloxazole, 2.4.5-)liphenyloxazole, 2-ethyl-4,5-diphenyloxazole,
2-styryl-5-7enyloxazole, 2-acetylamino-5-phenyloxazole, 2-benzoylamino-5-phenyloxazole, N'-(4,5-
Dimethyloxazole-2-yl)sulfanilamide 5-7enyloxazole-2-carboxylic acid ethyl ester, 2,5-dimethyloxazole-4-carboxylic acid ethyl ester, and the like.

In addition, the content jik of the above compound is preferably 0.00 based on the total car jil (dry and residual amount) of the photopolymerizable composition.
6-6.0% by weight, preferably 0.03-6.0% by weight
It is 2.5% by weight.

Examples of thermoplastic organic binders suitably used in the photopolymerizable composition of the present invention include polymethyl methacrylate, polystyrene, chlorinated polyethylene, polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, and polyacrylic acid. Polymers and copolymers of vinyl monomers are exemplified. The amount used is preferably 0.1 to 80% by weight, more preferably 35 to 70% by weight, based on the total weight (dry residue) of the photopolymerizable composition.

The addition-polymerizable unsaturated compound suitably used in the photopolymerizable composition of the present invention has at least two ethylenically unsaturated double bonds in the molecule, and any compound capable of addition polymerization is sufficient. One or more kinds of these compounds can be used.

For example, acrylic ester, methacrylic ester,
Examples include acrylamide, methacrylamide, allyl compounds, and vinyl ether compounds.

Specifically, acrylic acid esters and meccrylic acid esters include polyhydric alcohols polyacrylate and polymethacrylate (polyacrylate and the like referred to here are compounds that are higher than diacrylate); , polyethylene glycol, polypropylene glycol, neopentyl glycol, trimethylolpropane, pentaerythritol, butanediol.

Such as trimethylolethane. Examples of acrylamide and methacrylamide include methylenebisacrylamide and methacrylamide, as well as polyacrylamide and polymethacrylamide such as ethylenediamine and hexamethylenediamine. As an allyl compound,
Diallyl esters, diallylamides, such as phthalic acid, adipic acid, malonic acid, or anthraquinone disulfonic acid.

Examples include diallyl esters and diallylamides of benzene disulfonic acid and naphthalene disulfonic acid.

Examples of vinyl ether compounds include polyvinyl ethers of the polyhydric alcohols, such as ethylene glycol divinyl ether and glycerol trivinyl ether. Examples of the vinyl ester compound include divinyl succinate, divinyl adipate, divinyl phthalate, and the like.

Among these, glycol esters such as tetraethylene glycol diacrylate and methacrylate, and pentaerythritol triacrylate.

Acrylic polyfunctional monomers such as methacrylate, trimethylolpropane triacrylate, and methacrylate are preferred.

The content of the addition polymerizable unsaturated compound is preferably about 10 to 90% by weight, more preferably about 20 to 55% by weight, based on the total weight (dry residue) of the photopolymerizable composition. .

The photopolymerization initiator preferably used in the composition of the present invention is an initiator suitable for polymerizing ethylenically unsaturated compounds, and for acrylic polyfunctional monomers, anthraquinone, 2-methylanthraquinone, 2-methylanthraquinone, -Ethylani/
Anthraquinone xi forms such as traquinone, benzoin,
Benzoin alkyl ethers such as benzoin ether and benzoin isopropyl ether, benzophenone, acetophenone, phenanthrenequinone, oxime ester, aminophenyl ketone, thioxanthone, etc. are used alone or in combination.

The content of the photoinitiator or photoinitiator system is preferably O, OO6 based on the total weight (dry residue) of the photopolymerizable composition.
-6.0% by weight, preferably 0.06-3
．． It is 0% by weight.

As mentioned above, the photopolymerizable composition of the present invention contains as essential components a thermoplastic organic polymer binder, an ethylenically unsaturated compound, a photopolymerization initiator, and a compound that improves adhesion.
Dyes and pigments to make it easier to check thermal polymerization inhibitors and resist if necessary.

A plasticizer or the like may also be used.

The photopolymerizable composition of the present invention is a composition useful for forming photoresists, but is not necessarily limited to this use, and can be used for UV inks, solder resists, printing plates, etc.
It can also be applied to UV-curable paints, UV-curable adhesives, etc.

〔Example〕

The present invention will be further explained below by showing Examples and Comparative Examples.

In Examples and Comparative Examples, resolution and
Adhesion was evaluated after curing.

(Preparation of photopolymerizable layer) A photopolymerizable composition dissolved in a solvent was applied onto a polyester film and dried at 75° C. for 15 minutes to obtain a photopolymerizable layer with a thickness of 50 μm.

(resolution) This photopolymerizable layer was laminated on a copper plate under pressure and heating.

The obtained laminate was exposed to light at several levels of exposure using an ultra-high pressure mercury lamp using a thin line pattern mask. next,
The image was developed with chlorocene, and the resolution was determined by reading the width of the resist where fine lines were formed.

(Evaluation of adhesion after curing) Thickness 50 coated on the polyester film obtained above
A µm photopolymerizable layer is pressed onto a copper-clad laminate.

Laminated by heating. This laminate was exposed to two layers of water using a fine line pattern mask using a four-layer high-pressure mercury lamp: ", '
C (60,100rrJ/ff1). Next, I developed it with chlorocene. The obtained resist pattern was coated with a potassium hydroxide aqueous solution (pH 10).

60° C.) for 1 hour and air-dried. After that, changes in the state of the resist pattern substrate (color change on the resist surface,
Infiltration of alkaline aqueous solution into the formed thin line parts,
Adhesion was evaluated by observing resist peeling, bumps, etc. at the copper interface.

Example 1 A photopolymerizable composition using the compound shown below as the main component was dissolved in methyl ethyl ketone and deposited on a polyester film with a thickness of 15 Q lt.
The film was coated on a surface of 100 ml, and evaluated according to the above-mentioned procedure for resolution and adhesion value after curing.

Polymethyl methacrylate 100 parts by weight (weight average molecular weight 70,000) Trimethylolpropane 31.2#1/IJ acrylate tetraethylene glycol 25.0 parts by weight, '(Hf
i% diacrylate p-methylacetophenone oxime 3,0〃-
〇-acetate chlorothioxanthone 0.2〃2-amineoxazole 0.3〃Example 2 Example 1 except that 2-amino-5-phenyloxazole (0.4 parts by weight) was used instead of 2-aminoxazole. The evaluation was performed using the same procedure.

Example 3 Example 1 except that 2.57 diphenyloxazole (0.4 parts by weight) was used for 2 instead of 2-aminoxazole.
The evaluation was performed using the same procedure.

Example 4 2.4.5-triphenyloxazole (0.8 parts by weight) was used instead of 2-aminoxazole.
Evaluation was performed using the same procedure as in Example 1.

Example 5 2-ethyl-445 instead of 2-aminoxazole
Evaluation was carried out in the same manner as in Example 1, except that 0.6 parts by weight of Schifmori nyloxazole was used.

Example 6 2-styryl-5- instead of 2-aminoxazole
Besides using phenyloxazole (0.6 parts by weight),
Evaluation was performed using the same procedure as in Example 1.

Example 7 2-acetylamino-5-phenyloxazole (0.4 parts! 71 parts)'f instead of 2-aminoxazole
i: The pond used was evaluated in the same manner as in Example 1.

Example 8 2-benzoylamino-5-7enyloxazole (0.6m:11
) was used, but the evaluation was performed in the same manner as in Example 1.

Example 9 Instead of 2-aminoxazole, N'-(45-dimethyloxazol-2-yl)sulfanilamide (
Evaluation was carried out in the same manner as in Example 1 except that 0.7 parts by weight) was used.

Example 10 Evaluation was carried out in the same manner as in Example 1, except that 5-phenyloxazole-2-carboxylic acid ethyl ester (0.4 parts by weight) was used instead of 2-aminooxazole.

Example 11 Evaluation was carried out in the same manner as in Example 1, except that 2,5-dimethyloxazole-4-carboxylic acid ethyl ester (0.4 parts by weight) was used instead of 2-aminoxazole.

Ratio Example 1 Except for not using an adhesion promoter as a photopolymerizable composition,
Evaluation was performed using the same procedure as in Example 1.

Examples 1-11. Table 1 summarizes the results of ratio 1 bite case 1.

Claims (1)

[Claims] Thermoplastic organic polymer binder, containing at least two
1. A photopolymerizable composition comprising as main components an addition-polymerizable unsaturated compound having ethylenically unsaturated double bonds and a photopolymerization initiator, and to which a compound represented by the following general formula (I) is added. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (Here, R_1 is an amino group, a (mono- or di-)substituted amino group, a carboxylic acid alkyl ester group, an alkyl group, an aromatic derivative substituent, or an allyl derivative substituent. (R_2 and R_3 are hydrogen atoms, halogens, alkyl groups, or aromatic derivative substituents.)