JPS6410057B2 - - 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.
In more detail, the unexposed portion is removed together with the support by adhesion to the image forming substrate, exposed, and peeled off, and the exposed portion is bonded to the substrate when an image is formed using the exposed portion left on the substrate. The present invention relates to an image forming material that has good properties, high development reliability, and little change in characteristics over time. 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. For these, there is a method of forming an image by peeling utilizing the difference in adhesion between the exposed and unexposed areas to the substrate and the 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 of the photosensitive layer, b ₂ , then a ₁ <b, a ₂ > b ₂ . Minimum required. 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, 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 the structure becomes more complex and complex, it is necessary to increase the difference between b ₁ and a ₁ in order to satisfy the above relational expression. 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. Alternatively, when forming a complex 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. On the other hand, even if some means are taken to improve the above-mentioned drawbacks, such as adding additives to increase the adhesive strength between the substrate and the exposed portion of the photosensitive layer, the peeling of the exposed portion during peel development may be suppressed. When applied to fine or complicated image patterns, there is a problem that unexposed portions of the photosensitive layer tend to remain on the substrate. In other words, while the image forming material is being stored, especially when the image forming material is bonded to a substrate and being stored at a relatively high temperature, the photosensitive layer may undergo gelation, resulting in changes in properties, and this may be peeled off by exposure. Unexposed portions of the photosensitive layer that should be removed together with the support during development tend to adhere and remain on the substrate, and this becomes more noticeable as the image pattern becomes finer or more complex. As a result of extensive research in order to solve the above problems, the inventors discovered that by combining two specific compounds in a photosensitive layer made of a photopolymerizable composition, fine to complex image patterns can be created. Even when applied to a substrate, peeling development can be performed reliably without causing peeling of the exposed areas of the photosensitive layer, and the photosensitive layer remains intact even when stored for a long period of time while bonded to a substrate at relatively high temperatures. It has been found that there is little change in properties and unexposed areas are less likely to remain on the substrate during peel development, leading to the present invention. That is, this invention provides a photopolymerizable composition layer containing a film-forming polymer substance, a compound containing 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 a heterocyclic compound residue, R ₂ is a halogen or CHmYn (Y is a halogen, m + n = 3 and n
is 1 or more)] and a compound represented by the general formula; (However, k + l = 3, l is 1 or 2, X is a hydrogen atom or CH ₃ group, and R ₃ is an alkylene group). This relates to an image forming material in which the compound is added in an amount of 0.01 to 5% by weight. By blending the compound represented by the above general formula (A), the adhesion of the exposed portion of the photosensitive layer comprising the photopolymerizable composition layer to the substrate can be greatly improved. 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. Compounds represented by such general formula (A) include:

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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. By blending the compound represented by the general formula (B), the compound represented by the general formula (A) can be added to the photosensitive layer of the photopolymerizable composition during storage of the image forming material without impairing the blending effect of the compound represented by the general formula (A). This shows a function that greatly suppresses changes in characteristics. Examples of the compound represented by the general formula (B) include 2-hydroxyethyl acryloyl phosphate, 2-hydroxyethyl methacryloyl phosphate, bis-(2-hydroxyethyl acryloyl) phosphate, and bis-(2-hydroxyethyl methacryloyl). ) phosphate, 2-hydroxypropyl acryloyl phosphate, 2-
Hydroxypropyl methacryloyl phosphate, bis-(2-hydroxypropyl acryloyl) phosphate, bis-(2-hydroxypropyl methacryloyl) phosphate, etc.
As mentioned above, for the total photopolymerizable composition (solid content)
It is recommended that it be added in an amount of 0.01 to 5% by weight, and in particular, that the amount added is approximately the same as that of the compound of general formula (A). The transparent support constituting the image-forming material of the present invention can be photopolymerized with a photopolymerizable composition layer.
A material with good transmittance to 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 supports having a thickness 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-
alkylacrylamide (such alkyl groups include, for example, methyl, ethyl, butyl, isopropyl, t-butyl, ethylhexyl, etc.), methacrylamide, 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 caprate, 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 polyhydric alcohol mentioned above is
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-diol
Examples include propanediol, triethanolamine, decalindiol, 3-chloro-1,2-propanediol, and the like. 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. As the photopolymerization initiator used in this invention, conventionally known ones can be suitably used, and these include carbonyl compounds, organic sulfur compounds, peroxides, redox compounds, azo and diazo compounds, and photoreducible initiators. There are pigments, etc. Typical specific examples of carbonyl compounds include benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, benzophenone, anthraquinone, 2-methylanthraquinone, 2-t-butylanthraquinone, 9. Ten
-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-az-bis-cyclohexanecarbonitrile, and diazonium salt of P-aminodiphenylamine. There is. 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. In this invention, the photosensitive layer of the image forming material is composed of a film-forming polymeric substance, an addition polymerizable unsaturated compound, a photopolymerization initiator, a specific adhesion improver, and a preservability improver as described above. However, if necessary, various additives such as thermal polymerization inhibitors, colorants, fillers, and plasticizers can be added. 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 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 more 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. can do. The present invention will be specifically explained below using Examples, but the present invention is not limited to these Examples. Example 1 Chlorinated polyethylene (Superchron CPE907HA manufactured by Sanyo Kokusaku Pulp Co., Ltd.) 70 (parts by weight) Polymethyl methacrylate (Dyanal BR-75 manufactured by Mitsubishi Rayon Co., Ltd.) 30 Pentaerythritol triacrylate
50 Oligoester acrylate (Aronix M-6300 manufactured by Toagosei Kagaku Kogyo Co., Ltd.) 80 Benzophenone 2.0 Micher's ketone 2.0 Paramethoxyphenol 0.1 2-naphthalenesulfonyl chloride
0.5 2-Hydroxyethyl acryloyl phosphate
0.5 Paramethoxyphenol 0.1 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 20 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 was laminated under pressure on the copper surface of a copper-clad glass epoxy laminate whose surface had been cleaned, and a negative original having various line width patterns of 75 to 300 μm was adhered 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 is 75μm or 100μm
It was confirmed that even thin line width patterns such as the above pattern did not peel off and faithfully corresponded to the negative original. Furthermore, images were formed on nine substrates by the same operation, and exactly the same results were obtained. On the other hand, a substrate laminated with image forming material in the same manner was
℃ and 80% atmosphere for 1 day and 3 days were similarly exposed and peeled and developed, and in both cases good image patterns were obtained that were as good as those that were not left. Each copper-clad substrate having the resist pattern thus obtained was treated with a ferrous chloride aqueous solution.
The copper layer was etched at a temperature of 40°C, and it was confirmed that the resist resist adhered strongly to the copper surface even during this process, and no peeling or pinholes occurred. 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 2-naphthalenesulfonyl chloride and 2-hydroxyethyl acryloyl phosphate in the photopolymerizable composition of Example 1 were 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 5 substrates. Comparative Example 2 An image forming material was obtained in the same manner as in Example 1 except that 2-hydroxyethyl acryloyl phosphate 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, relatively good image patterns were obtained. When the sample was exposed to light and peeled and developed after being left in an RH atmosphere for one day, it was confirmed that the unexposed portion remained on the substrate in a half-gelled state. 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.) 40 Oligoester acrylate (Manufactured by Toagosei Chemical Industry Co., Ltd.) Aronix M-6100) 100 2-t-butylanthraquinone 2.0 4,4'-bisdiethylaminobenzophenone
2.0 Tribromomethylphenylsulfone
1.0 2-Hydroxyacryloyl phosphate
1.0 Paramethoxyphenol 0.1 Ethyl biolate 0.3 Toluene 400 An image forming material was obtained in the same manner as in Example 1 using the above materials. When a resist pattern was formed using this in the same manner as in Example 1, a good image pattern with no peeling was obtained.
When the sample was left to stand in the same manner as above, no change in characteristics was observed and a good image pattern was obtained. Comparative Example 3 An image forming material was obtained in the same manner as in Example 2 except that tribromophenyl sulfone and 2-hydroxyethyl acryloyl phosphate in the photopolymerizable composition of Example 2 were 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, 100 μm, and 125 μm was confirmed in the resist patterns of 8 substrates. Comparative Example 4 An image forming material was obtained in the same manner as in Example 1 except that 2-hydroxyethyl acryloyl phosphate 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, relatively good image patterns were obtained on all of them. When the sample was exposed and developed after being left in an 80% RH atmosphere for one day, it was confirmed that, as in Comparative Example 2, the unexposed portion remained on the substrate in a half-gelled state.

Claims (1)

[Scope of Claims] 1. A photopolymerizable composition layer containing a film-forming polymer substance, a compound containing at least one addition-polymerizable unsaturated bond, and a photopolymerization initiator as essential components on a transparent support. In an image forming material provided with the above photopolymerizable composition layer, the general formula; [However, R ₁ is a substituted or unsubstituted aromatic residue or a heterocyclic compound residue, R ₂ is a halogen or CHmYn (Y is a halogen, m + n = 3 and n
is 1 or more)] and a compound represented by the general formula; (However, k + l = 3, l is 1 or 2, X is a hydrogen atom or CH ₃ group, and R ₃ is an alkylene group). The image forming material is added in an amount of 0.01 to 5% by weight.