JPS61188534A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having a good stavility during a storage and capable of forming an image having a high sensitivity and a high resolution by incorporating a prescribed amount of a specific photopolymerizable composition which is a liquid state at a room temp. and a prescribed amount of specific two or three kinds of compds. having a sensitizing property to the alpha, beta-unsatd. ethylenic polymer. CONSTITUTION:The titled composition is prepared by polymerizing a solution of a polymerizable mixture comprising 100-300pts.wt. of a photopolymerizable monomer which is liquid at the room temp. and is capable of cross-linking such as pentaerythritol triacrylate. 0.01-10pts.wt. thioxanthone or its derivative, and 0.01-10pts.wt. compd. shown by formula I wherein R1, R2 and R3 are a hydrogen atom or an alkyl group per 100pts.wt. the alpha, beta-unsatd. ethylenic monomer such as polymethacrylic acid methylester, if necessary adding a coloring agent and a leuco dye. in a presence of a polymerization catalyst such as benzophenone. The phtotosensitive layer is formed by coating the obtd. polymer solution on the surface of the substrate and drying. The photosensitive layer composed of the obtd. image forming material is laminated on the surface of the printed wiring board covered with copper under a pressure, and exposured the wiring pattern and then developing by peeling out the substrate, thereby obtaining a fine resist pattern with a high accuracy.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to photosensitive compositions.

(Prior art) Conventionally, a film of a photosensitive composition is formed by applying the photosensitive composition onto a transparent support film, etc., and the core film is brought into contact with the surface of the substrate on which an image is to be formed. Then, the transparent support film is left on the top layer or the support film is removed,
A solvent method in which the film surface is exposed to active light that has passed through the original image for a second and the unexposed areas are eluted with a solvent, or the unexposed areas are adhered to the film and removed when the supporting film is peeled off. An image corresponding to the original image is developed by peeling development, and this is applied to, for example, the production of printed wiring boards by the photoresist method, or to the production of relief plates.

An important problem when using conventional photosensitive compositions for the above-mentioned purposes is that it is not possible to obtain a composition that satisfies the sensitizer Φ sensitization rate and its storage stability at the same time. In addition, the adhesion to the substrate on which the image is to be formed is still insufficient, and as a result, satisfactory resolution cannot be obtained.
When mounting an IC chip on a printed wiring board, 5
A resolution of 0μ or less is sometimes required, but it is difficult to meet such requirements.Furthermore, when used for copper through-hole circuit formation, the tent strength is weak and the film thickness must be 50μ or more. If it is thinner than this, the hole portion will be torn during development and the product will be defective.

More specifically, for example, as described in Japanese Patent Publication No. 48-38403, 2,4,5-
A combination of a triarylmethaimidazolyl dimer and a P-aminophenyl ketone has been proposed, but the rate of increase is insufficient.

Furthermore, as described in Japanese Patent Publication No. 52-34490, a combination of thioxanthone or its halogenated derivative and P-diphenylaminobenzoic acid or its ester has been proposed, but the adhesion to the substrate is poor. Therefore, there was a drawback that the resolution was not sufficient and the tinting property was weak when used as a one-way resist through steel.

(Problems to be Solved by the Invention) In view of the above-mentioned current situation, the present invention has a high sensitization speed,
In addition, it has excellent storage stability, and has excellent □F9ing resistance.
There are a number of methods that have been developed for the purpose of providing a photosensitive resin composition with excellent tenting properties and plating resistance.

(Means for solving problem □) The gist of the present invention is L (a) Polymerizability of resin containing α, β-unsaturated ethylenic monomer as a constituent unit, 100 parts by weight, normally 1 liquid. Monomer 100-300 parts by weight □, □ (C) At least one kind of thioxanthone or its derivative α01-1
0 parts by weight, (d) Contains at least one type of compound represented by the formula (Is) (101 to 10 parts by weight, R1 (R+, Rs, Rs is H or an alkyl group)
A photosensitive resin composition characterized by:
'□J "specified invention"), and 2. (a)α,
Resin 1 whose constituent unit is β-unsaturated ethylenic monomer
00 parts by weight, 10 to 30 parts by weight of a room temperature liquid photopolymerizable monomer
0 parts by weight, (6) at least one kind of thioxanthone or its derivative α01-10 parts by weight, (d) at least one kind of compound represented by formula (I) (L61-1 parts by weight, E, - (R1, R spirit, R1 is E or an alkyl group) (e) a 2,4,5-triarylimidazolyl dimer consisting of a lofin dimer containing at least 1 to 10 parts by weight of α01 and A photosensitive resin composition (hereinafter referred to as the "second invention") characterized by
).

The resin component (a) used in the present invention includes α, β
A polymeric substance having an -unsaturated ethylenic monomer in the constituent position is used, and examples of the α,β-unsaturated ethylenic monomer include styrene, 0-methylstyrene, m
-Methylstyrene, P-methylstyrene, α-methylstyrene, P-ethylstyrene, 2,4-dimethylstyrene, P-n-butylstyrene, P-ter&-butylstyrene, P-n-hexylstyrene, P- Styrenes such as n-octylstyrene, P-methoxystyrene, P-phenylstyrene, 3,4-dichlorostyrene; vinylnaphthalenes; ethylene, propylene, butylene,
α-olefins of CI1 to C3° and above; Vinyl halides such as vinyl chloride, vinyl bromide, and vinyl fluoride; Vinyl esters such as vinyl acetate, vinyl propionate, and vinyl butyrate; Methyl acrylate, acrylic Ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, 2-10 ethyl acrylate, phenyl acrylate, methyl α-chloroacrylate , ethyl methacrylate, propyl methacrylate, methacrylate, ethyl', isobutyl methacrylate, n-octyl methacrylate,
α-methylene aliphatic monocarboxylic acid esters such as lauryl methacrylate, 2-ethylhexyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate; acrylic acid or methacrylic acid such as acrylonitrile, methacrylonitrile, acrylamide, etc. Derivatives; Vinyl ethers such as vinyl ethyl ether and vinyl ethyl ether; Vinyl ketones such as vinyl methyl ketone and vinyl ethyl ketone; N-vinylvirol,
N such as N-vinylcarbazole, N-vinylindole, etc.
-Vinyl compounds and the like.

As the photopolymerizable monomer ('b) used in the present invention,
Room-temperature liquid monomers that initiate polymerization and cure with light in the presence of a photopolymerization initiator are used, and are usually pentaerythritol triacrylate, polyethylene glycol diacrylate, triethylene glycol schifacrylate, ?
Examples include poly-1 acrylate or polymethacrylate monomers such as lyethylene glycol dimethacrylate, polymethylene diacrylate, #'J methylene dimethacrylate, trimethylolpropane triacrylate, and trimethylolpropane triacrylate.

Thioxanthone or its 1-alkyl or halogenated derivative (0) used in the present invention includes thioxanthone, alkylated derivatives of thioxanthone such as 2-ethylthioxanthone and 2,4-diethylthioxanthone, and 2-chlorothioxanthone. Thioxanthone alkyl derivatives such as santhone and 2,4-dichlorothioxanthone can be suitably used.

The compound (d) R1 (R1-Rt-Rs is ■ or an alkyl group) used in the present invention and represented by formula (I) is as follows:
For example, 2-methyl-1-(4-(methylthio)phenyl-2-morpholinopropan-1-one, 2-methyl-1-(4-(methylthio)phenyl-2-morpholinobutane-1- 1-(4-methylthiophenyl)-2-morpholinopropan-1-one are preferably used, and the alkyl groups of R, , R, and R are preferably short-chained rather than long-chained.

The 2-4-
As the 5-triarylimidazolyl dimer (・),
Compounds of formula (6) consisting of lophine dimers linked together by a single covalent bond, i.e. teary (optionally substituted in the phenyl group), such as 4f, 2-(0 -chlorophenyl)-4,5-diphenylimidazolyl dimer, 2-(0-fluorophenyl)-4,5-diphenylimidazolyl dimer, 2-(0-fluorophenyl)-4,5-diphenylimidazolyl dimer,
-chlorophenyl)-4,5-bis-(m-methoxyphenyl)imidazolyl dimer, or 2-(0-methoxyphenyl)-4,5-diphenylimidazolyl 21, 2-(P-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2,4-di(P-methoxyphenyl)5-phenylimidazolyl dimer, 2-(2,4-
dimethoxyphenyl)-4,5-diphenylmemidazolyl 1, 2-(p-methylmercaptophenyl)-4
-5-diphenylimidazolyl dimer, hexaphenyllophine dimer, bis(2,3,5-triphenylimidazolyl) dimer, etc. Suitable lophine dimers are described in British Patent No. 997396 and British Patent No. 1810.
No. 47569.

In the present invention, a coloring agent or a coloring agent, such as a leuco dye, may be contained, and it is more preferable to contain it. Amine-substituted leuco dyes can act together as color formers and free radical generators. Effective leuco dyes are those having at least one dialkylamino group. Also, any amine-substituted leucotriphenylmethane dye or various salts of the dye may be used, such as the hydrochloride salt of the leuco blue dye. Examples of suitable dye variants include, for example, tris-(4-N-N-diethylamino-0-)lyl)metatrihydrochloride, bis(4-
N-N-diethylamino-O-tolyl)chenylmethane, bis(4-N-N-diethylamino-〇-tolyl)-
Benzylthiophenylmethane, leucomalachite green (C, 1, basic, green 4), leuco form of crystal violet and brilliant green (C,
1, Page, Ri, Green 1), Victoria Green 3
B(C-I.

Basic, Green 4), Acid Green GG (C
, 1, Azide Green 3), Methyl Violet (C,
1, Basic Violet 1)・, Rosanine (C,
1 and basic violet 14). Salt forms of leuco dyes such as hydrochlorides, salts with Lewis acids, sulfates, P-toluenesulfonates can also be used, but the free bases are preferred.

Other free radical generating agents that can be used include, for example:
Aniline, N-methylaniline, N,N-diethylaniline, N-N-diethylcresidine, triethanolamine, 2-7lylthiourea, sarcosine, N-N-diethylglycine, trihexylamine, diethylcyclohexylamine, N -N-N'/N'-tetramethylethylenediamine, diethylaminoethanol, ethylaminoethanol, N-N-N'/N'-ethylenediaminotetraacetic acid, N-methylpyrrolidone, N-N, N
'・N#・N'-pentamethyldiethylenetriamine,
N-N-diethylxylidene, N・N'-dimethyl-1
- Amines such as 4-piperazine, N-β-hydroxyethylpiperidine, N-ethylmorpholine and related amino compounds can be mentioned.

In the specific invention, 10 to 300 parts by weight of (b1 polymerizable monomer, ((+
) Thioxane or its derivative (Lot ~ 10 parts by weight, (
d) Used in the compound represented by formula (1) in an amount of 01 to 10 parts by weight.

In the second invention, (a) 10 to 300 parts by weight of a polymerizable monomer, (C) 1 to 10 parts by weight of a thioxanthone or its derivative, ((
1) 1 to 10 parts by weight of the compound represented by formula (I), (
e) Dimer aO is used in a proportion of 1 to 10 parts by weight.

In the specified invention-ζ, by adding components (6) and (d) as essential concomitant components to components (a) and ('b), (C) and (d) are added. Adding each of the components alone produces the desired effect that cannot be predicted.

#I2 In the invention, in addition to the components of the specified invention (@
) The effect is further enhanced by adding the component as a concomitant component.

The reason for these effects has not been elucidated, but as seen in the development of spectral sensitization in photochemistry, radicals generated in the sensitizer used as a concomitant ingredient undergo complex reactions with each other. It seems that something like this will happen.

(Example) The present invention will be explained below with reference to Examples.

<Example> ? Methyl remethacrylate 60y Pentaerythritol triacrylate Tetraethylene glycol diacrylate 5p 2,4-diethylthioxanthone 1 type! 2-Methyl-1-(4-(methylthio)phenyl]-2-morpholino-propan-1-one °
22 paramethoxyphenol, αlp
Triethylene glycol diacetate □, 15F/ethyl violet α22 The above composition was dissolved in 200f of methyl ethyl ketone to prepare a photosensitive solution.
This photosensitive solution was applied onto a polyethylene terephthalate film having a thickness of 25 μm so that the dry photosensitive layer would have a thickness of 50 μm, and was dried at 80° C. for 10 minutes to prepare an image forming material.

Next, this image forming material was laminated under pressure on the surface of a double-sided steel-clad substrate for a printed wiring board having through holes whose surface had been cleaned.

A negative image with a wiring circuit pattern in the state of
．． , OZ rejoule per square centimeter.

Next, the polyethylene terephthalate film of the support was peeled off at room temperature, and spray development was performed with trichloroethane.

At this time, the image was reproduced down to a thin line of 40 μm.

Also, the sensitivity was 6 steps with Kodak Step Tablet 2.

In addition, at 15 KP/all pressure of trichloroethane, 100
Spray development was performed for seconds, but wrinkles appeared after 200 seconds.

This value was suitable for use as a tenting resist. Further, no gel was formed even when the photosensitive solution was left at 30° C. for 30 days.

<Example 2> The same test as in Example 1 was conducted on a composition in which 1 part of 2-(0-chlorophenyl)-4,5-dimethoxyphenylimidazole dimer was added to the composition of Example 1. I went.

As a result, images up to a fine pattern of 25 μm were reproduced.

Also, the sensitivity was 8 steps with the Kodak Step Tablet Iori 2.

In addition, up to 300 seconds with trichloroethane L51 species/-,
Although it was spray developed, there was no abnormality in the resist tenting the through hole part of the 5% summer, and the storage stability was 30℃.
No gel formed for 30 days.

<Example 3> Methyl methacrylate 6.0 p Pesitaerythritol triacrylate 5y Tetraethylene glycol diacrylate sy 2,4-cyclothioxanthone 122-Methyl-1-(4-(methylthio)phenyl-2-morpholinopro) Pan-1・-on
222-('0-chlorophenyl)-4.5 dimethoxyphenyl imidazole dimer 1 g! Leucomalachite Green 12.

Ethyl violet α2f paramethoxyphenol □ α12 triethylene glycol diacetate y A photosensitive solution was prepared using the above composition, and an SI test was conducted in the same manner as in Example 1.

At this time, the thickness of the photosensitive layer was 40μ, and at the time of exposure,
The exposed area was colored bright green and a sufficient latent image was obtained.

At this time, the image was reproduced up to a fine pattern of 20 μm.

Also, the sensitivity is Kodak Step Tablet.

There were 8 stages in To-2.

Also, trichloroethane L5Kf/m″tsao.

There was no abnormality in the sprayed resist up to 2 seconds, and the storage stability was excellent with no gel formation for 130 days with 3G'C.

Comparative example> Polymethyl methacrylate 60jl Pentaerythritol tri7 acrylate 5p Tetraethylene glycol diacrylate sP Paramethoxyphenol α1f Triethylene glycol diacetate F Ethyl violet a2y Benzophenone 3P Michler ketone
IP A photosensitive solution was prepared using the above composition, and the procedure of Example 1 was followed up to development.

At this time, the image was only reproduced up to the 70/l line.

Moreover, the sensitivity was as low as 4 to 5 steps with the Kodak Once Step Tablet-2.

Further, when the resist was developed using trichloroethane at a pressure of 156/sf for 100 seconds, wrinkles appeared in the resist at the through-hole portions of 5% summer.

Furthermore, when the light wave was left at 30° C. for 80 days, a gel was formed.

(Effects) Specified invention - Since the photosensitive resin composition has the above-mentioned composition, it can be used as an image forming material to quickly form a photoimage and has a ζζζ increasing effect, and the photosensitive liquid is extremely stable during storage. Moreover, the adhesion between the cured photosensitive layer and the substrate surface and the curing of the film are significantly improved, which leads to good results in peeling phenomenon and resolution in solvent development, making it suitable for use as a photoresist material. When used as a copper resist, the etching resistance of the photosensitive hardened layer is excellent, and the high resolution is excellent. When used as a one-way copper resist, it is resistant to tinting, and when used as a metal resist, there is no plating sinking and printing is possible. It is effective for applications that require precision, such as manufacturing wiring boards.

The second invention photosensitive resin composition has the above structure,
Furthermore, since it contains a 2.4.5-triarylimidazolyl dimer consisting of a lophine dimer,
-1 The photosensitive speed is faster, the resolution is higher, and even thin films are resistant to tenting.

Claims (1)

[Scope of Claims] 1. (a) 100 parts by weight of a resin containing an α,β-unsaturated ethylenic monomer as a constituent unit; (b) 10 to 300 parts by weight of a photopolymerizable monomer that is liquid at room temperature; (c) At least one type of thioxanthone or its derivative 0
．． 01 to 10 parts by weight, (d) 0.0 of at least one compound represented by formula (I)
1 to 10 parts by weight, ▲ Numerical formula, chemical formula, table, etc. ▼ A photosensitive resin composition characterized by containing the formula (I) (R_1, R_2, R_3 are H or an alkyl group). 2. (a) 100 parts by weight of a resin whose unit is an α,β-unsaturated ethylenically monomer, (b) 10 to 300 parts by weight of a photopolymerizable monomer that is liquid at room temperature, (c) thioxanthone or its derivative At least one kind of 0
．． 01 to 10 parts by weight, (d) at least one compound represented by formula (I);
01 to 10 parts by weight, ▲Mathematical formulas, chemical formulas, tables, etc. are available▼Formula (I) (R_1, R_2, R_3 are H or alkyl groups) (e)
A photosensitive resin composition comprising 0.01 to 10 parts by weight of at least one type of 2,4,5-triarylimidazolyl dimer consisting of a lophine dimer.