JPH0145899B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to an image forming material comprising a specific photopolymerizable composition layer provided on a transparent support.
More specifically, when the unexposed part is removed together with the support by pasting it on an image forming substrate and exposing it, and then peeling it off, and forming an image on the exposed part left on the substrate, the exposed part adheres to the substrate. The invention relates to an image forming material that has good properties and high development reliability. Conventionally, solution-type photoresists and film-type photoresists have been commercially available for use in producing printed wiring boards, but both of these utilize the difference in solubility between exposed and unexposed areas in a solution to form images. It was something to do. However, in recent years, the operation of using a developer has become complicated, and the waste liquid from using a developer may harm public health. 1977-
No. 7728, Japanese Patent Publication No. 48-43126, Japanese Patent Publication No. 47-33623
Peelable and developable image forming materials and image forming methods as described in Japanese Patent Publication No. 51-48516, Japanese Patent Publication No. 40537, Japanese Patent Publication No. 53-19205, and Japanese Patent Publication No. 53-35722. is proposed. These are methods of forming images by peeling by utilizing the difference in adhesion between exposed and unexposed areas to the base material and support, but the following conditions are required to enable peel development. That is, the adhesion force per unit area between the support and the exposed part of the photosensitive layer is a ₁ , and that with the unexposed part is a 1 .
If a ₂ is the adhesion force per unit area between the substrate and the exposed part of the photosensitive layer, b ₁ is that of the unexposed part, b ₂ , then a ₁ < b ₁ , a ₂ > b _{2 .} is required as a minimum. Furthermore, in actual peeling development, consideration must be given to the force required to cut the interface between the exposed and unexposed areas of the photosensitive layer. Here, if the force required to cut the interface per unit length is c, then for example, in order for the exposed portion of the independent pattern with area A and total length of the interface to remain on the substrate after peeling development, A・b ₁
It is necessary to satisfy the relationship: >A・a ₁ +L・c.
If both sides of this inequality are divided by A, b ₁ > a ₁ + L・
c/A→b ₁ −a ₁ >L・c/A, and the right side varies depending on L and A. As is clear from this, the smaller the area A and the longer the interface length, the finer the image pattern. As things become more complex and complex, it is necessary to increase the difference between b ₁ and a ₁ in order to satisfy the above relationship. However, although various photosensitive layer compositions and materials have been proposed for forming images by peel development, none of them have a sufficiently large difference between the adhesion forces b ₁ and a ₁ , so that fine particles cannot be formed. When forming a complicated image pattern, the exposed portion of the photosensitive layer is likely to be removed along with the peeling support, resulting in poor reliability of the image. As a result of extensive research in order to solve the above-mentioned conventional drawbacks, the inventors have discovered that by further blending a specific compound into a photosensitive layer with a specific composition, it is possible to apply it to fine to complex image patterns. The present inventors have also discovered that peel development can be reliably performed without peeling of the photosensitive layer, leading to the present invention. That is, the present invention provides a layer of a photopolymerizable composition containing a film-forming polymer substance, a compound having at least one addition-polymerizable unsaturated bond, and a photopolymerization initiator as essential components on a transparent support. In the image forming material comprising the photopolymerizable composition layer, the general formula; [However, R ₁ is a substituted or unsubstituted aromatic residue or heterocyclic compound residue, R ₂ is a halogen or CHmYn (Y is a halogen, m + n = 3 and n is 1 or more)] The photopolymerization initiator is blended in an amount of 0.01 to 5% by weight based on the amount of the photopolymerizable composition (solid content), and the photopolymerization initiator has the following general formula; (However, R ₃ is H or Cx, x is CH ₃ or C ₂ H ₅ , R ₄ is OCH ₃ , OC ₂ H ₅ , OC ₃ H ₇ or OC ₄ H ₉ ) , organic sulfur compounds, peroxides, redox compounds,
The present invention relates to an image forming material that is at least one selected from azo and diazo compounds, and photoreducible dyes. The compound represented by the above general formula greatly improves the adhesion of the exposed portion of the photosensitive layer made of the photopolymerizable composition layer to the substrate by its blending. Although the reason is not clear, halogen radicals are generated from this compound upon exposure to light, which further abstracts hydrogen and becomes hydrogen halides, which activate the surface of substrates, such as copper-clad laminates for printed wiring boards. It is presumed that this improves the adhesive strength between the exposed portion and the substrate. As such compounds represented by the above general formula,

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[Formula] etc., and as mentioned above, it is added in an amount of 0.01 to 5% by weight based on the total photopolymerizable composition (solid content). If the amount added is less than the above range, a sufficient effect of improving adhesion cannot be obtained, and if it is too much, physical properties such as cohesive force of the photosensitive layer may be changed, leading to a decrease in image accuracy. The transparent support constituting the image-forming material of the present invention can be photopolymerized with a photopolymerizable composition layer.
A material with good transparency for light in the wavelength range of 300 to 500 nm and a uniform surface is selected. Specific examples of such supports include polyethylene terephthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide ( For example 6-
Various types of plastic films can be used, such as nylon, 6.6-nylon, 6.10-nylon, etc.), polyimide, vinyl chloride-vinyl acetate copolymer, polytetrafluoroethylene, and polytrifluoroethylene. Furthermore, a composite material consisting of two or more of these types can also be used. The support generally has a thickness of 10 to 150 μm, preferably 20 to 50 μm, but thicknesses outside the above range can also be used. The film-forming polymeric substance that can be used in this invention can be selected from a wide variety of polymeric substances, but those that have extremely poor compatibility with other constituents are not preferred. Examples of preferred film-forming polymeric substances include:
Chlorinated polyolefins (e.g. chlorinated polyethylene, chlorinated polypropylene), polymethyl methacrylate, polymethyl acrylate, polyvinyl chloride, polyvinylidene chloride, polyvinyl butyral, polyvinyl acetate, vinyl chloride.
Vinyl acetate copolymer, vinylidene chloride-acrylonitrile copolymer, polyisoprene, chlorinated rubber,
Examples include polychloroprene, polychlorosulfonated ethylene and polychlorosulfonated propylene, and solvent-soluble linear saturated polyesters. Two or more of these polymeric substances can be used in combination. The compound having at least one addition-polymerizable unsaturated bond used in this invention includes a wide range of addition-polymerizable compounds. For example,
Acrylic esters, acrylamides, methacrylic esters, methacrylamides,
Examples include allyl compounds, vinyl ethers, vinyl esters, N-vinyl compounds, styrenes, and crotonic acid esters. Specific examples of compounds having one addition-polymerizable unsaturated bond include acrylic esters, such as acrylic acid, alkyl acrylates (such as propyl acrylate, butyl acrylate, amyl acrylate, ethylhexyl acrylate, octyl acrylate). ), methacrylic esters, such as methacrylic acid, alkyl methacrylates (such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate),
Acrylamides, such as acrylamide, N-
alkylacrylamides (such alkyl groups include, for example, methyl, ethyl, butyl, isopropyl, t-butyl, ethylhexyl, etc.), methacrylamides, such as methacrylamide, N-alkylmethacrylamide (such as methacrylamide, N-alkylmethacrylamide), Examples of alkyl groups include methyl group, ethyl group, isopropyl group, t-butyl group, and ethylhexyl group), allyl compounds such as allyl esters (such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate), vinyl ethers such as alkyl vinyl ethers (e.g. hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether),
Vinyl esters such as vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, and the like. Other styrenes include styrene, methylstyrene, chloromethylstyrene, alkoxystyrene, halogenated styrene, and styrene benzoate. Examples of crotonate esters include methyl crotonate, ethyl crotonate, butyl crotonate, hexyl crotonate, and isopropyl crotonate. Next, specific examples of compounds having two or more addition-polymerizable unsaturated bonds are illustrated, and these are more preferably used than the above-mentioned compounds having one addition-polymerizable unsaturated bond. First, acrylic esters and methacrylic esters include polyacrylates and polymethacrylates (herein, "poly" refers to diacrylate or higher) of polyhydric alcohols. The above polyhydric alcohols include polyethylene glycol, polypropylene oxide,
Polybutylene oxide, (β-hydroxyethoxy)benzene, glycerin, diglycerin, neopentyl glycol, trimethylolpropane,
Triethylolpropane, pentaerythritol, dipentaerythritol, sorbitan, sorbitol, 1,4-butanediol, 1,2,4
-Butanetriol, 2-butene-1,4-diol, 2-butyl-2-ethyl-propanediol, 2-butene-1,4-diol, 1,3-propanediol, triethanolamine, decalindiol, 3 -Chlor-1,2-propanediol, etc. In addition, oligoester acrylate, oligoester methacrylate, epoxy acrylate,
Acrylates and methacrylates commercially available under names such as urethane acrylate can also be suitably used. Two or more kinds of such compounds having at least one addition-polymerizable unsaturated bond can also be used in combination. These compounds are film-forming polymeric substances.
It is used in an amount of 10 to 500 parts by weight, preferably 30 to 200 parts by weight per 100 parts by weight. The photopolymerization initiator used in this invention includes:
The following general formula; (However, R ₃ is H or Cx, x is CH ₃ or C ₂ H ₅ , R ₄ is OCH ₃ , OC ₂ H ₅ , OC ₃ H ₇ or OC ₄ H ₉ ) , organic sulfur compounds, peroxides, redox compounds,
These include azo and diazo compounds, photoreducible dyes, etc. To give typical specific examples, examples of carbonyl compounds include benzoin, benzophenone,
anthraquinone, 2-methylanthraquinone, 2
-t-butylanthraquinone, 9,10-phenanthrenequinone, diacetyl, benzyl, Micher's ketone, 4,4'-bisdiethylaminobenzophenone and the like. Examples of organic sulfur compounds include dibutyl disulfide, dioctyl disulfide, dibenzyl disulfide, diphenyl disulfide, dibenzoyl disulfide, and diacetyl disulfide. Examples of peroxides include hydrogen peroxide, di-t-butyl peroxide, benzoyl peroxide, and methyl ethyl ketone peroxide. Redox compounds consist of a combination of a peroxide and a reducing agent, and include ferrous ions and hydrogen peroxide, ferrous ions and persulfate ions, ferric ions and peroxides, and the like. Examples of azo and diazo compounds include α・α-azobisisobutyronitrile, 2-azobis-2-methylbutyronitrile, 1-azobis-cyclohexanecarbonitrile, and diazonium salt of p-aminodiphenylamine. be. Photoreducible pigments include rose bengal, erythrosin, eosin, acriflavin, riboflavin, and thionin. These photopolymerization initiators can be used alone or in combination of two or more types as required. These photopolymerization initiators can be used generally in an amount of 0.1 to 20 parts by weight per 100 parts by weight of the unsaturated compound. The photosensitive layer of the image forming material of the present invention is composed of the film-forming polymeric substance, addition polymerizable unsaturated compound, photopolymerization initiator, and specific adhesion improver as described above. Depending on the situation, various additives such as thermal polymerization inhibitors, colorants, fillers, and plasticizers can also be included. Each component forming the photosensitive layer used in the present invention is dissolved in a solvent to form a coating solution, which is coated onto a support and dried. Solvents for the coating solution include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, aromatic hydrocarbons such as toluene, benzene, and xylene, esters such as ethyl acetate, butyl acetate, and amyl acetate, carbon tetrachloride, chloroform,
Examples include halogenated hydrocarbons such as trichloroethylene and methylene chloride, ethers such as diethyl ether, tetrahydrofuran, dioxane, and ethylene glycol monomethyl ether, dimethylformamide, and dimethyl sulfoxide. The photosensitive layer can have a thickness in the range of 5 to 100 μm after coating a coating solution on the support and drying it, but from the viewpoint of application to fine image patterns, the thinner the photosensitive layer is, the smaller the exposed area is. The thickness is preferably 5 to 25 μm because less force is required to cut the interface between the layer and the unexposed portion. The image forming material of the present invention has a structure in which a photosensitive layer is provided on a support, but a protective film may be provided on the photosensitive layer if necessary. As the protective film, polyethylene, polypropylene, various films treated with non-adhesive treatment, paper, etc. can be used. A method for forming an image using the image forming material of the present invention will be described. When the image forming material of the present invention has a protective film, the protective film is peeled off and then the photosensitive layer is pressure-bonded to a desired substrate. The image is then exposed through the transparent support. As the light source, a light source containing light with a wavelength in the range of 350 to 500 nm, such as a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a carbon arc lamp, etc., can be used. In addition, laser beams, electron beams, X-rays, etc. may be used as the light source. If necessary, heat treatment may be applied after image exposure (50℃ to 120℃).
(about 1 minute to 120 minutes), when the support is peeled off from the substrate, the exposed part in the image exposure is cured and remains on the substrate, and the unexposed part is removed together with the support without being cured, thus forming the desired image on the substrate. It is formed. The image forming material of the present invention can be suitably used as a photoresist for producing printed wiring boards, but it can also be used for producing printing plates such as lithographic printing and letterpress printing, and producing other relief images. be able to. The present invention will be specifically explained below using Examples, but the present invention is not limited to these Examples. Example 1 Chlorinated polyethylene (Super Chron CPE907HA manufactured by Sanyo Kokusaku Pulp Co., Ltd.) 60 (parts by weight) Polymethyl methacrylate (Dyanal BR-83 manufactured by Mitsubishi Rayon Co., Ltd.) 40 Pentaerythritol triacrylate 50 Oligoester acrylate (Toagosei Chemical Industry Co., Ltd.) Aronix M-6100) 70 Benzophenone 2.0 4,4′-Bisdiethylaminobenzophenone
2.0 Para-methoxyphenol 0.1 p-Toluenesulfonyl chloride 1.0 Ethyl violet 0.3 Toluene 400 A solution of the photopolymerizable composition was created by uniformly dissolving and mixing the above materials, and this solution was spread to a thickness of 25 μm.
It was coated on a polyethylene terephthalate film so that the thickness after drying was 15 μm, and it was heated at 80℃ for 5 minutes.
An image forming material was obtained by drying for a minute. This image-forming material is laminated under pressure on the copper surface of a copper-clad glass epoxy laminate whose surface has been cleaned, and negative originals with various line width patterns of 75 to 300 μm are closely attached to the surface of the image-forming material. Exposure was performed for 10 seconds using a high-pressure mercury lamp from a distance of 60 cm. Next, when the polyethylene terephthalate film that is the support for the image forming material was peeled off from the substrate while the substrate was heated to 35°C, the unexposed areas were removed from the substrate along with the film, and the copper surface of the substrate was hardened. A positive image was formed consisting of the exposed areas that remained. This image was confirmed to be a pattern that faithfully corresponds to a negative original without peeling off even with thin line width patterns such as 75 μm or 100 μm. Furthermore, images were formed on nine substrates by the same operation, and exactly the same results were obtained. A copper-clad substrate having the resist pattern obtained in this manner was coated with a ferrous chloride aqueous solution for 40 minutes.
The copper layer was etched at a temperature of
It was confirmed that the resist adhered strongly to the copper surface even during this treatment, and no peeling or pinholes were observed. Furthermore, the resist after etching could be easily removed using methylene chloride. Comparative Example 1 An image forming material was obtained in the same manner as in Example 1 except that p-toluenesulfonyl chloride in the photopolymerizable composition of Example 1 was removed. When resist patterns were formed on 10 substrates using this in the same manner as in Example 1, peeling of line width patterns of 75 μm and 100 μm was confirmed in the resist patterns of 4 substrates. Example 2 Chlorinated rubber (Super Chron manufactured by Sanyo Kokusaku Pulp Co., Ltd.)
CR-5) 80 (parts by weight) Polymethyl methacrylate (Dyanal BR-80 manufactured by Mitsubishi Rayon Co., Ltd.) 20 Oligoester acrylate (Aronix M-8060 manufactured by Toagosei Chemical Industry Co., Ltd.) 50 Triethylene glycol diacrylate 80 2-t -Butylanthraquinone 2.0 Miherazketone 1.0 Paramethoxyphenol 0.1 Tribromomethylphenylsulfone 1.0 Ethyl violet 0.3 Toluene 400 An image forming material was obtained in the same manner as in Example 1 using the above materials. When resist patterns were formed on 10 substrates in the same manner as in Example 1, none of the resist patterns peeled off and faithfully corresponded to the negative original. Comparative Example 2 An image forming material was obtained in the same manner as in Example 2 except that tribromomethylphenyl sulfone in the photopolymerizable composition of Example 2 was removed. When resist patterns were formed on 10 substrates using this in the same manner as in Example 2, peeling of line width patterns of 75 μm and 100 μm was confirmed in the resist patterns of 5 substrates.

Claims (1)

[Scope of Claims] 1. A photopolymerizable composition layer containing a film-forming polymer substance, a compound having at least one addition-polymerizable unsaturated bond, and a photopolymerization initiator as essential components on a transparent support. In the image forming material provided in the photopolymerizable composition layer, the general formula; [However, R ₁ is a substituted or unsubstituted aromatic residue or heterocyclic compound residue, R ₂ is a halogen or CHm Yn (Y is a halogen, m + n = 3 and n is 1 or more)] The photopolymerization initiator is added in an amount of 0.01 to 5% by weight based on the total amount of the photopolymerizable composition (solid content), and the photopolymerization initiator has the following general formula; (However, R ₃ is H or Cx, x is CH ₃ or C ₂ H ₅ , R ₄ is OCH ₃ , OC ₂ H ₅ , OC ₃ H ₇ or OC ₄ H ₉ ) , organic sulfur compounds, peroxides, redox compounds,
An image forming material that is at least one selected from azo and diazo compounds, and photoreducible dyes.