JPS59166944A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive composition having improved adhesive strength to a substrate on which an image is formed and capable of forming an image with superior resolution by adding a specified copolymer to a base resin having constituent units of an alpha,beta-unsatd. ethylenic monomer. CONSTITUTION:A copolymer consisting of 5-70wt% glycidyl ester of unsatd. carboxylic acid (anhydride) and 95-30wt% other alpha,beta-unsatd. ethylenic monomer as constituent units, e.g., a glycidyl methacrylate-styrene-methyl methacrylate copolymer is used. A photosensitive composition is obtd. by blending 100pts.wt. resin (A) having constituent units of an alpha,beta-unsatd. ethylenic monomer such as polymethyl methacrylate or chlorinated polyethylene with 0.1-40pts.wt. said copolymer (B), 10-300pts.wt. photopolymerizable monomer (C) which is liq. at ordinary temp. such as pentaerythritol acrylate and 0.1-20pts.wt. photopolymn. initiator (D) such as benzophenone.

Description

[Detailed description of the invention] The present invention relates to photosensitive compositions.

Conventionally, a film of a photosensitive composition is formed by applying the photosensitive composition onto a transparent support film, etc., and the film is brought into contact with the surface of the substrate on which an image is to be drawn, and then heat-sealed. With the transparent support film left on the top layer or with the support film removed, the surface of the film is exposed to active light that has passed through the original image, and the unexposed areas are exposed with a solvent. An image corresponding to the original image is developed using a solvent elution method or a peeling development method in which unexposed areas are attached to and removed from the support film when the support film is peeled off, and this is then applied to a printed wiring board using a photoresist method. It is being applied to manufacturing, or to the manufacturing of relief plates.

One of the important problems when using photosensitive compositions for the above applications is that their adhesion to the substrate on which images are to be formed is still insufficient, making it difficult to obtain satisfactory resolution. One point is that it cannot be done. In particular, when used as a resist material for printed wiring, for example when mounting IC chips on printed wiring boards, high resolution may be required, but it is difficult to meet such demands. .

In addition, various methods have been tried to improve this point, such as providing an adhesive layer between the photosensitive composition layer and the substrate to improve adhesion, and using a peel development method. It has also been proposed to add sulbonyl chloride, phosphate, etc. to the composition, but in the former case, the process of uniformly applying and drying the adhesive layer is necessary when creating the image forming material. In the latter case, the additives may bleed, resulting in poor long-term shelf life, and the resolution is also not satisfactory. I can not say.

In view of the current situation as described above, the present invention has been made with the object of providing a photosensitive composition that has improved resolution by improving adhesion to a substrate and can be easily processed into an image forming material. The gist is α, β−
Resin component 10 having an unsaturated ethylenic monomer as a constituent unit
A composition containing 10 to 300 parts by weight of a photopolymerizable monomer that is liquid at room temperature and 0.1 to 20 parts by weight of a photopolymerization initiator in 100 parts by weight of the resin component. A copolymer whose constituent units are 5 to 70% by weight of a glinodylester monomer of a saturated carboxylic acid or seven acid anhydrides and 95 to 30% by weight of other α,β-unsaturated ethylenically monomers. A photosensitive composition characterized by containing 0.1 to 40 parts by weight of a polymer.

As the resin component in the present invention, a polymer containing an α,β-unsaturated ethyne monomer as a constituent unit is used, and examples of the α,β-unsaturated ethyne monomer include styrene. , 0-methylstyrene, m-methylstyrene, P-methylstyrene, α-methylstyrene, P-ethylstyrene, 2,4-dimethylstyrene, P-n-methylstyrene, Ptert-7'tylstyrene, P-n-
Styrenes such as hex/rustyrene, P-n-octylstyrene, P-methylstyrene, P-phenylstyrene, 3-4-dichlorostyrene; vinylnaphthalenes; ethylene, propylene, butylene, C5-c3o and the like; The above α-onfins; vinyl chloride, vinyl bromide,
Vinyl halides such as vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate; methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, inbutyl acrylate, n-acrylate -Octyl, lauryl acrylate, 2-ethylhexyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, ethyl methacrylate, globil methacrylate, n-butyl methacrylate, methacrylic acid inbutyl,
α-Methylene aliphatic monocarboxylic acid esters such as n-octyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate; acrylonitrile, methacrylonitrile, acrylamide, etc. Acrylic acid or methacrylic acid derivatives; vinyl methyl ether, vinyl ethyl ether, vinyl x
vinylketone M; N-vinylpyrol, N
-N such as vinylcarbazole, N-vinylindole, etc.
-vinyl compounds, etc.

In addition, the polymeric substance having the above unsaturated monomer as a constituent unit is
For example, it may be modified with halogen or the like, and halogenated α-polyolefins such as chlorinated polyethylene are preferably used.

The photopolymerizable monomer used in the present invention is a room-temperature liquid monomer that initiates photopolymerization and cures in the presence of a photopolymerization initiator, and is usually a monomer that is liquid at room temperature. Tri-a-ri-ri-to,
Polyethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene dalycol dimethacrylate, polymethylene diacrylate,
Polyacrylate or polymethacrylate monomers such as polymethylene dimethacrylate, trimethylolpropane triacrylate, and trimethylolpropane triacrylate, and oligomers of these monomers are preferably used.

Among the oligoesters mentioned above, one containing multiple ester bonding moieties in the main chain of the molecule is Oligo Acrylate T manufactured by Toagosei Co., Ltd.

-1, TO-2, TO-3, TO-4, etc., which have multiple wonton bonding moieties in the molecular main chain, include Takuyasei Co., Ltd.'s product name acrylic oligomer NI)-3, etc. Examples of products containing an Epoquin compound include the product name Riboki/RT-802, L; N-ool, manufactured by Showa Kobunshi Co., Ltd.
The product name is Light Ester BP-4 manufactured by Kyoei Yushi Kagaku Co., Ltd., and the product name NK Ester 4G manufactured by Shin-Nakamura Chemical Co., Ltd. has a polyglycol incorporated in the main chain of the molecule.

3G, P-2G, TMPT, A-TMPT, A-TMM
T, etc. can be mentioned.

If the amount of the photopolymerizable monomer used is too small, the exposed area will not be cured sufficiently and the uncured area will tend to stick to the surface of the substrate such as a copper plate. The amount of monomer used depends on the type of the monomer, but is preferably 10 to 300 parts by weight, preferably 10 to 300 parts by weight of the resin component. is set at 50 to 200 parts by weight.

Next, the photopolymerization initiator may be any one having the property of activating the above-mentioned polymerizable monomer with actinic rays and initiating polymerization. For example, the following compounds are effectively used.

Namely, iodine compounds such as sodium dimethyl dithiocarbamate sulfur, tetramethylthiuram monosulfide, diphenyl monosulfide, dibenzothiazoyl monosulfide and disulfide; hydrazone, azobisinbutyronitrile, benzenediazonicum chloride, etc. Azo and diazo compounds; inorganic compounds such as zinc oxide, magnesium oxide, tetraethyl lead;
Biacetyl, benzoin methyl ether, benzoin ethyl ether, benzophenone, P, P'-bis (dimethylamino)benzophenone (hereinafter referred to as Michler's ketone), benzaldehyde, benzoin, benzyl anthraquinone, 2-methyl anthraquinone, 2-ethyl anthraquinone, 2 - Aromatic carbonyl compounds such as tertiarybutyl anthraquinone, 2-aminoanthraquinone, 2-chloroanthraquinone, terephthalaldehyde; benzoyl peroxide, ditertiarybutyl peroxide, dicumyl peroxide, cume/hydroper Examples include peroxides such as Okinodo, inorganic ions such as cobalt chloride, cobalt acetate, copper acetate, iron chloride, iron L 9ate, cobalt acetylacetonate, cobalt nanthenate, zinc naphthenate, and complex compounds. .

It is also possible to use a combination of two or more types of photopolymerization initiators, and in particular, when a mixture of benzophenone and Michler's ketone is used, the efficiency of polymerization initiation by irradiation light is excellent and the exposure time is further shortened. suitable.

If the amount of the photopolymerization initiator used is less than 0.1 part by weight based on 100 parts by weight of the resin component, the photosensitivity will decrease, and if it is more than 20 parts by weight, the initiator will tend to precipitate from the composition. 0.1 to 20 parts by weight, preferably 0.5 parts by weight.
It is used in a range of 10 parts by weight.

Therefore, in the present invention, in 100 parts by weight of the resin component, 5 to 70% by weight of a glyceptidyl ester monomer of an unsaturated carboxylic acid or its acid anhydride and other α,
It is characterized in that it contains 0.1 to 40 parts by weight of a copolymer whose constitutional unit is 95 to 30 weight % of a β-unsaturated ethylenic monomer.

Examples of the glycidyl ester monomer of carboxylic acid or seven acid anhydrides include acrylic acid, methacrylic acid,
Examples include gly/dyl esters such as itaconic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, vinyl acetic acid, and α-ethyl acrylic acid; preferred are gly/dyl esters of acrylic acid, methacrylic acid, and maleic acid. used for.

The copolymer used in the present invention contains 5 to 70% by weight of the above glinodyl ester monomer, preferably 10 to 50% by weight.
and other α,β-unsaturated ethylenic monomers copolymerizable with said monomer. This can be carried out by adding the following and polymerizing by a conventional polymerization method such as a solution method or a suspension method.

The glyc/dyle ester monomer component in the above copolymer is
When the composition of the present invention is applied to a support film and dried, or when the film is laminated onto a substrate by heating and pressurizing, the epoxy/group opens the ring and acts like a crosslinking agent, so that it is cured afterwards. It is presumed that it contributes to improving the adhesion between the photosensitive layer and the substrate surface. If the amount is too large, phase separation with other resin components tends to occur, and as a result, sufficient resolution cannot be obtained, so it is limited to the above range.

In addition, if the content of the copolymer in the present invention is too small, the adhesion between the cured layer and the substrate surface will be significantly improved upon exposure, and if it is too large, phase separation will occur, resulting in a decrease in resolution. The content of the resin component in 100 parts by weight of the resin component is limited to 0.1 to 40 parts by weight, since this leads to disadvantages such as a decrease in the etching resistance of the cured layer.

Preferred examples of the copolymer used in the present invention include:
Copolymers of gly/dyle esters of acrylic acid, methacrylic acid, or maleic acid with the above-mentioned styrenes, such as gly7lyl acrylate/styrene, ivy gly/lyl acrylate/styrene, phosphorysyl maleate half ester/styrene These are not limited to binary copolymers; for example, terpolymers such as glyc/zyl(meth)acrylate/styrene/methyl(meth)acrylate can be used to form a photosensitive layer and a substrate surface. It is particularly preferred that the adhesion is good at Hiko point.

As described above, the photosensitive composition of the present invention comprises 100 parts by weight of a copolymer containing 01 to 40 parts by weight of a glyc/dyle ester monomer of an unsaturated carboxylic acid or its acid anhydride. The photosensitive composition is prepared by adding predetermined parts of a photopolymerizable monomer and a photopolymerization initiator that are liquid at room temperature to parts by weight, and the photosensitive composition is usually dissolved in a solvent in the form of a polyethylene terephthalate film or the like. A photosensitive layer is formed by coating the film on a support film and drying it, which is then used as an image-forming material.

The present image-forming material can then be used for forming photoresist images or relief images in the same manner as conventional products.

When the composition of the present invention is used in the formation of these various optical images, a pre-image contained in the composition is obtained.

This is considered to be because the addition of the above-mentioned copolymer improves the adhesion between the cured photosensitive layer and the surface of the substrate, which brings about favorable results in peeling phenomenon or resolution in solvent development.

Furthermore, when the composition of the present invention is used as a photoresist material, the improved adhesion improves the etching resistance of the photosensitive hardened layer, and highly accurate etching can be performed. Furthermore, when the composition of the present invention is made into an image forming material as described above, it has good compatibility with the resin components. Therefore, no component bleeds from the photosensitive layer, and it has excellent long-term storage stability.

Hereinafter, the present invention will be explained based on Examples. In addition, in the following, parts mean parts by weight.

Copolymerization weight ratio of glycidyl methacrylate/styrene/methyl methacrylate copolymer in the above order: 5°:25:25
, oil product side [Premmar Copolymer #50J)
10 parts chlorinated polyethylene (manufactured by Sanyo Kokusaku Valve [Super Kun CPE907L
TAJ) 70 parts polymethyl methacrylate (manufactured by Mitsubishi Rayon [Diatol BR-80J)
30 parts pentaerythritol triacrylate 150 parts benyne isophylloyl acetate 7 parts 5 parts ethyl violet
03 part parametoki/phenol
A photosensitive liquid was prepared by adding 01 parts of the above compound and 400 parts of toluene and uniformly mixing and dissolving them.

This photosensitive liquid was applied onto a polyethylene terephthalate film having a thickness of 25/I so that the thickness of the photosensitive layer after drying was 507 mm, and was dried at 80° C. for 10 minutes to prepare an image forming material.

Next, this image forming material was applied to the surface of a double-sided copper-clad board for a printed wiring board having through-holes whose surface had been cleaned.
Lamination was carried out by heating and pressurizing at a temperature of 0' to 110°C. In this state, the negative image with the wiring circuit pattern was brought into close contact with the support and exposed to 300 millijoules of senna per square meter at a distance of 1 m from a 400 W high-pressure mercury lamp. Then, by simply peeling off the polyethylene/terephthalate film support at room temperature, a copper-clad substrate with a faithfully reproduced negative image (60 fi) was etched with a copper layer at a temperature of 40°C using an aqueous cupric chloride solution. Even during this etching process, the 60p thin line photosensitive layer adhered strongly to the copper and did not peel off, and no phenomenon other than tearing of the tenting portion occurred.

Comparative Example 1 Copolymer “Blemmer G” in the photopolymerizable composition of Example 1
The same experiment as in Example 1 was conducted except that 10 copies were removed. In this case, an image up to a fine line of 150/I was obtained, but a phenomenon in which the exposed portion was partially peeled off from the substrate was observed. Further peeling of the resist pattern was observed in some areas due to the subsequent etching process. Furthermore, a portion of the tenting part was torn.

Example 2 The copolymer used in Example 1 “Blemmer Copolymer 4”
#-50'' 10 parts, polymethyl methacrylate 60 parts, trimethylolbromine triac 1) L/-t 33 parts,
A photosensitive solution was prepared by mixing and dissolving 4 parts of benzophenone, 2 parts of Michler's ketone (photopolymerization initiator), 1 part of crystalline (Ioresotho) and 900 parts of methyl ethyl ketone, and after drying on a 25 mm thick polyethylene terephthalate V- film. An image forming material was prepared by coating the film to a thickness of 50 tones.

Next, this image forming material was heated to 110°C, 140°C,
A laminated copper clad plate was laminated at a temperature of 160° C., and exposed to light at a dose of 90 millijoules/cm 2 in the same manner as in Example 1. After exposure, the support was peeled off, the exposed layer was immersed in trichloroethane, developed, and dried. As shown in the following table, it was found that the higher the lamination temperature, the thinner the lines that can be developed and the higher the resolution.

It was also found that when the copper clad plate was etched, the higher the lamination temperature, the better the adhesion.

Table 1 Comparative Example 2 An image forming material was prepared in the same manner as in Example 2 except that 10 parts of the copolymer [Glenmar G copolymer + 50J] used in Example 2 was not used, and this was laminated on a laminated copper clad board (laminate). (Temperature: 110°C) Peeling development was carried out in the same manner as in Example 2, but it was difficult to form fine lines of 150 μm or less, and peeling was observed in some parts of the resist layer during subsequent etching. .

patent applicant Sekisui Chemical Co., Ltd. Representative Mototoshi Fujinuma

Claims (1)

[Scope of Claims] 10 parts by weight of a resin component containing a 1,05β-unsaturated ethylenic monomer as a constituent unit and 10 parts by weight of a photopolymerizable monomer that is liquid at room temperature.
~300 parts by weight and 10.1 to 20 parts by weight of a photopolymerization initiator, and in 100 parts by weight of the resin component, a glyc/dyl ester based unsaturated carboxylic acid or its acid anhydride is added. Monomer 5-70% by weight and other α
, 0.1 to 40 parts by weight of a copolymer having a constituent unit of 95 to 30% by weight of a β-unsaturated ethylenic monomer. 2. The photosensitive composition according to item 1, wherein the unsaturated carboxylic acid is acrylic acid or methacrylic acid. 3. The photosensitive composition according to item 1 or 2, wherein the copolymer is a copolymer of a styrene monomer and glycidyl methacrylate ester.