JPS62180356A - 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 of a thermoplastic org. polymer binder, an addition-polymerizable comps. having at least two ethylenic double bonds in a molecule, and a photopolymn. initiator as primary components, and a specified compd. as additive component. CONSTITUTION:A photopolymerizable compsn. consists of a thermoplastic org. polymer binder, an addition-polymerizable unsatd. compd. having at least two ethylenic double bonds in a molecule, and a photopolymn. initiator as primary components, wherein a compd. expressed by the formula is added. Specific examples for the compds. expressed by the formula providing improved adhesion and resistance to plating are octadecylamine, hexadecylamine, etc. The content basing on the whole weight (dry basis) of the compsn. is pref. 0.006-6.0wt%. Suitable thermoplastic org. polymer binder is polymer or copolymer of vinyl monomer such as polyacrylic acid, etc. The amt. of the binder to be used is pref. 35-70wt% basing on the weight (dry basis) of the photopolymerizable compsn. Suitable photopolymn. initiator is one suitable for the polymn. of ethylenic unsatd. compds.

Description

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

[Conventional technology]

Many proposals have been made to improve the adhesion between a coating formed from a photopolymerizable composition and a substrate. That is, dry film photoresists used in the manufacture of printed wiring boards have weaker adhesion to metal surfaces than 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
7-26285, Special Publication No. 54-5292, Special Publication No. 55
-22481, JP-A-51-64919, JP-A-5
(See Japanese Patent Publication No. 1-64920, Japanese Patent Publication No. 57-46053, Japanese Patent Publication No. 57-46054, Japanese Patent Publication No. 57-21697, Japanese Patent Publication No. 57-40500, etc.) [Problems to be solved by the invention] However, these conventional proposals These compounds exhibit the following drawbacks, especially when used as photoresists. 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 and It has an unfavorable effect on post-processing such as etching. Alternatively, an increase in the amount of adhesion promoter added may have an adverse effect 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 development process.

The purpose of the present invention is to eliminate the above-mentioned problems with coating materials of photopolymerizable compositions, improve adhesion to metal surfaces, reproduce faithful image images to the original, and achieve high resolution. 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).

R2 R, -N-H (I) (Here, R1 is a hydrogen atom, an alkyl group or an aromatic derivative substituent, and "Bird" is an alkyl group having 4 or more carbon atoms.) The above general formula (I) of the present invention Specific examples of compounds that improve adhesion and plating resistance represented by are octadecylamine and hexadecylamine.

Octylamine, N-octyl-N-methylamine, cyclohexylamine, dicyclohexylamine, di-n
-octylamine, N-cyclooxyl-N-dodecylamine, N-phenyl-N-dodecylamine, N-(4
-methylphenyl)-N-)"decylamine, N-benzyl-N-dodecylamine, and the like.

Further, the content of the above compound is preferably 0.5% based on the total weight (dry residue) of the photopolymerizable composition. OO6~6.0
It is preferably 0.03 to 2.5% by weight, preferably 0.03 to 2.5% by weight.

Thermoplastic organic polymer binders suitably used in the photopolymerizable composition of the present invention include, for example, polymethyl methacrylate, polystyrene, chlorinated polyethylene, polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, and polyvinyl futhysil. Examples include polymers and copolymers of vinyl monomers such as polyacrylic acid. 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 may be any compound that can be addition-polymerized. One or more kinds of these compounds can be used. Examples include acrylic esters, methacrylic esters, acrylamide, methacrylamide, allyl compounds, vinyl ether compounds, and the like. Specifically, acrylic esters and methacrylic esters include polyhydric alcohols such as polyacrylate and polymethacrylate (polyacrylate and the like referred to here are compounds that are higher than diacrylate); Examples include polyethylene glycol, polypropylene glycol, neopentyl glycol, trimethylolpropane, pentaerythritol, butanediol, and trimethylolethane. Examples of acrylamide and methacrylamide include methylenebisacrylamide and methacrylamide, as well as polyacrylamide and polymethacrylamide such as ethylenediamine and hexamethylenediamine. Examples of allyl compounds include diallyl esters such as 7-talic acid, adipic acid, and malonic acid.

Examples include diallylamide, diallyl esters of anthraquinone disulfonic acid, benzenedisulfonic acid, and naphthalene disulfonic acid, and diallylamide. Examples of vinyl ether compounds include polyvinyl ethers of the above-mentioned polyhydric alcohols, such as ethylene glycol divinyl ether,
Examples include glycerol trivinyl ether. Examples of the vinyl ester compound include divinyl succinate, divinyl adipate, and divinyl heptatalate.

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, - anthraquinone derivatives such as ethyl anthraquinone, benzoin, benzoin ether, benzoin alkyl ether such as penzoin inglobil ether, benzopheno/, aceto7dinone, phenanthrenequinone, oxime ester,
Aminophenyl ketone, thioxanthone, etc. are used alone or in combination.

The content of the photoinitiator or photoinitiator system is preferably 0.006 based on the total weight (dry residue) of the photopolymerizable composition.
~6. Oi amount is preferably 0.06~
It is 3.0% 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 and plating resistance after curing were evaluated.

(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,
Development was performed with chlorocene, and the resolution was determined by reading the width of the resist where fine lines were formed.

(Evaluation of adhesion after curing) The thickness of the polyester film obtained above was 50
Pressure is applied to a full copper-clad 9-layer laminate with a photopolymerizable layer of μm.

Laminated by heating. Using a fine-line turn mask on this laminate, an ultra-high-pressure mercury lamp was applied to two levels of exposure (60,
100-J/ca). Next ri o.

I developed it using a sen. The obtained resist pattern substrate was immersed in a potassium hydroxide aqueous solution (pH 10, 60° C.) for 1 hour and air-dried. After that, adhesion was evaluated by observing changes in the state of the resist pattern substrate (color change on the resist surface, penetration of alkaline aqueous solution into the formed fine lines, peeling of the resist at the copper interface, etc.). .

Example 1 As a photopolymerizable composition, the compound shown below was used as the main component, and the blended photopolymerizable composition was dissolved in methyl ethyl ketone and applied to a thickness of 50 μm on a polyester film. The evaluation was performed according to the procedure for adhesion evaluation.

Triacrylate 31.2 #Tetraethylene glycol diacrylate 25.0 #Chlorothioxanthone 021 Octadecylamine 0.91 Example 2 Except for using hexa7”/L/amine (0.8 mfit part) instead of octadecylamine The evaluation was carried out in the same manner as in Example 1.

Example 3 N-octyl-N-1f instead of octadecylamine
Evaluation was carried out in the same manner as in Example 1, except that ruamine (0.4 parts by weight) was used.

Example 4 Cyclohexylamine (
Evaluation was carried out in the same manner as in Example 1, except that 0.3 parts by weight) was used.

Example 5 Evaluation was carried out in the same manner as in Example 1, except that dicyclohexylamine (0.6 parts by weight) was used instead of octadecylamine.

Example 6 Evaluation was carried out in the same manner as in Example 1, except that di-n-octylamine (1.8 parts by weight) was used instead of octadecylamine.

Example 7 N-cyclohexyl-N instead of octadecylamine
Evaluation was carried out in the same manner as in Example 1, except that -dodecylamine (0.9 parts by weight) was used.

Example 8 Evaluation was carried out in the same manner as in Example 1, except that N-7enyl-N-dodecylamine (0.9 parts by weight) was used instead of octadecylamine.

Example 9 Evaluation was carried out in the same manner as in Example 1, except that N-(4-methylphenyl)-N-dodecylamine (o, 9 it parts) was used instead of octadecylamine.

Example 10 Evaluation was carried out in the same manner as in Example 1, except that N-benzyl-N-doa'zylamine (0.9 parts by weight) was used instead of octadecylamine.

Comparative 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 1-10. The results of Comparative Example 1 are summarized in Table 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 a hydrogen atom, an alkyl group, or an aromatic derivative substituent, and R_2 is an alkyl group having 4 or more carbon atoms.)