JPS5928203B2 - Photopolymerizable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to photopolymerizable compositions, and in particular to photopolymerizable compositions that contain a photoinitiator of a novel composition and are also sensitive to, for example, argon laser radiation. be.

Conventionally, a photopolymerizable composition consisting of a polymerizable ethylenically unsaturated compound, a photopolymerization initiator, and optionally a polymer substance with film-forming ability, a thermal polymerization inhibitor, a plasticizer, etc. A photosensitive material with a photosensitive layer is prepared by coating a coating solution on a support, and the photosensitive layer is imagewise exposed based on a desired original to cause photopolymerization and hardening in the exposed areas, and then only the uncured areas are removed. There is a method in which the uncured portion is dissolved and removed by treatment with a soluble organic solvent to form an image based on the cured portion, or the above-mentioned photosensitive material is transferred to another image support (the support of the photosensitive material or the image support). Either is transparent.

) to form a laminate, imagewise exposed from the transparent support side, photopolymerization occurs in the exposed portion of the photosensitive layer, and the adhesion force of the photosensitive material to the support and the adhesion to the image support change. The photosensitive layer in the unexposed area is placed on one support and the photosensitive layer in the exposed area is placed on the other support by causing a change in the size and peeling off both supports in a manner that differs from the size relationship in the unexposed area. It is well known that images can be formed by separate photosensitive layers while still being adhered to the body. In this method, benzyl, benzoin, anthraquinone, Michler's ketone, and the like have been used as photopolymerization initiators. However, although photopolymerizable compositions using these photoinitiators are sensitive to relatively short-wavelength ultraviolet rays, they are hardly sensitive to long-wavelength ultraviolet rays or visible light such as argon lasers, and have no ability to initiate polymerization. There was a problem that it was not shown. This is because it is extremely desirable as an image forming technique to use visible light as a light source for exposure in such image formation, or to be able to use, for example, a laser beam that can perform scanning exposure. The present invention has been made to solve the above-mentioned problems in conventional photopolymerizable compositions, and consists of at least one polymerizable ethylenically unsaturated compound and the following chemical formula (1). This is a photopolymerizable composition characterized by containing a carbonyl compound or a derivative thereof represented by the following formula and a polymerizable compound consisting of a tertiary amine represented by the chemical formula 01).

(In the formula, R1, R2 and R3 are each an alkyl group,
Represents an aryl group or a hydroxyalkyl group.

) Most characteristic component 5 in the photopolymerizable composition of the present invention
is a polymerization initiator, which includes a carbonyl compound represented by the following chemical formula (1) or a derivative thereof, and a chemical formula (
) and a tertiary amine represented by

(In the formula, R1, R2 and R3 each represent an alkyl group, an aryl group or a hydroxyalkyl group.

) Among the above carbonyl compounds, those represented by the above formula are dinaphtho[2.172/.3●Furan-8.
The 13-dione represented by the following formula is dinaphtho[1.2-2'.31]furan-7.12-dione.

In addition to the above two compounds, carbonyl compounds in the present invention include derivatives thereof such as 6-(2-pyridyl)-carboxamide substituted compounds. These carbonyl compounds are synthesized by refluxing 2,3-dichloro-1,4-naphthoquinone and β-naphthol or α-naphthol in anhydrous pyridine. The melting point of the above formula is 271°C, and the melting point of the lower formula is 230~230°C.
The temperature is 231°C. Other than component 5 are amines, such as aliphatic tertiary amines such as triethylamine and tri-n-decylamine; aliphatic hydroxyalkylamines such as triethanolamine; N-N-dimethylaniline, N-
N-diethylaniline, N-N-diethanolaniline, N-methyl-N-benzylaniline, p-methyl-N
Alkyl mono- or hydroxyalkyl substituted such as -N dimethylaniline, p-nitro-N-N-dimethylaniline, bis[(p-dimethylamino)phenyl]methane, bis[(p-dibenzylamino)phenyl]methane Examples include aromatic amine compounds. The photopolymerization initiator in the present invention is a combination of the above two types of compounds, but in each compound system, one type may be used, or two or more types may be used in combination. The mixing ratio of both types of compounds is 1:9 to 9:1 (weight ratio)
The ratio is within the range of 1:3 to 3:1, preferably 1:3 to 3:1. Next, component 5 in the present invention is at least one polymerizable ethylenically unsaturated compound, which can be used in combination with monomers, prepolymers such as dimers and trimers, and oligomers with other compounds. It also includes mixtures and copolymers thereof. Specifically, there are acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid, as well as ethylene glycol, triethylene glycol, tetraethylene glycol, tetramethylene glycol, neopentyl glycol, and 1,10-decane. Diol, trimethylolethane, trimethylolpropane, 1,2-butane diol,
1,3-butanediol, propylene glycol, pentaerythritol, dipentaerythritol, tripentaerythritol, other pentaerythritol polymers,
Esters of aliphatic polyhydric alcohols such as sorbitol, diols of unsaturated fatty acids, di- and polyacrylates, di- and polymethacrylates, and di- and polyitaconates, and modified acrylates, methacrylic acids Salts and Itaconates: Acrylated, methacrylated and itaconylated prepolymers such as epoxy resins, oily and non-oily alkyd resins, urethanes and linear polyesters. The following compounds can be mentioned as typical compounds. Namely, triphmethylolpropane triacrylate, trimethyloleethane triacrylate, trimethylolpropane trimethacrylate, trimethyloleethane trimethacrylate, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate,
Pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate , tripentaerythritol octaacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, octaacrylate tripentaerythritol acid, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol tetramethacrylate, tripentaerythritol octamethacrylate, pentaerythritol diitaconate,
Dipentaerythritol trisitaconate, dipentaerythritol pentitaconate, dipentaerythritol hexitaconate, ethylene glycol dimethacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1-diitaconate 4-butanediol, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol tetramethacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, modified 1,4-butylene diacrylate, modified trimethylolpropane triacrylate, modified triacrylate Included are pentaerythritol acid, methacrylated epoxy resins, polyester acrylate oligomers, and mixtures and prepolymers thereof.

The above-mentioned component 5 and component 5 are used in a quantitative ratio of component 5 to component 5100 in a range of 0.1 to 20, preferably 0.1 to 10 (weight ratio).

The photopolymerizable composition of the present invention has the above-mentioned components as essential components, but in practice, it is usually mixed with various additives such as a binder, a thermal polymerization inhibitor, a colorant, and a plasticizer. It will be done. For example, the binder is a necessary component in order to form a strong resist film when the photopolymerizable composition of the present invention is used as a photosensitive material for photoresist, and the binder is a component necessary for forming a strong resist film. The solubility of the composition must be so good that demixing does not occur in all of the photosensitive material manufacturing processes from preparation of the coating solution to coating and drying, and the composition must be suitable for use as a photosensitive layer and a resist layer, for example, by solution development or by peeling development. However, development processing after image exposure is possible;
It is required to have characteristics such as being able to form a tough film as a resist layer. Specific examples of binders include:
Chlorinated polyethylene, chlorinated polypropylene, polymethyl methacrylate, polyacrylic acid, polymethacrylic acid, polyacrylic acid alkyl ester (alkyl groups include methyl, ethyl, butyl, etc.), acrylic acid alkyl ester (alkyl groups include (same as above) and at least one kind of monomer such as acrylonitrile, vinyl chloride, vinylidene chloride, styrene, butadiene, polyvinyl chloride, a copolymer of vinyl chloride and acrylonitrile,
Polyvinylidene chloride, copolymer of vinylidene chloride and acrylonitrile, polyvinyl acetate, copolymer of vinyl acetate and vinyl chloride, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylonitrile, copolymer of acrylonitrile and styrene, acrylonitrile and butadiene and styrene Copolymers of, polyvinyl alkyl ether (alkyl groups include methyl group, ethyl group, isopropyl group, butyl group, etc.), polymethyl vinyl ketone, polyethyl vinyl ketone, polyethylene, polypropylene,
Polybutene, polystyrene, poly-α-methylstyrene, polyamide (6-nylon, 6,6-nylon, etc.)
Homopolymers or copolymers such as poly-1,3-butadiene, polyisoprene, polyurethane, polyethylene terephthalate, polyethylene isophthalate, chlorinated rubber, cyclized rubber, ethyl cellulose, acetyl cellulose, polyvinyl butyral, polyvinyl formal, styrene-butadiene rubber, etc. There are polymers. In the case of a copolymer, the content ratio of the component ester can take a wide range of values, but it is generally preferable that the ester component is in a molar ratio of 10% or more and 50% or less. Further, polymers other than these can also be used as a binder in the present invention as long as they satisfy the above conditions. Among the above polymers,
Particularly suitable binders for the compositions of the present invention include chlorinated polyethylene, chlorinated polypropylene, polymethyl methacrylate, polyvinyl chloride, vinyl chloride monovinylidene chloride copolymer (molar content of vinyl chloride 20-80%), vinylidene chloride-acrylonitrile copolymer (molar content of acrylonitrile 10-3
0%), vinyl chloride-acrylonitrile copolymer (molar content of acrylonitrile 10-30%), styrene, polyvinyl butyral, polyvinyl formal, ethyl cellulose, acetyl cellulose, etc.

These polymers may be used alone as a binder, but two or more polymers must be compatible with each other to the extent that no demixing occurs during the manufacturing process, from preparing the coating solution to coating and drying. can be used as a binder by mixing them in suitable ratios.

The molecular weight of the polymeric substance used as the binder can vary widely depending on the type of polymer, but is generally in the range of 5,000 to 2,000,000, more preferably in the range of 10,000 to 1,000,000. .

The ratio of the total amount of binder to component 5 is determined by the type of ester,
Depending on the type of polymer, a suitable image can be obtained over a wide range of values, but in general, the amount of ester is 2 times to 0.2 times, particularly preferably 1.5 times to 0.3 times, the amount of ester by weight. range.

It is preferable to add a thermal polymerization inhibitor to the composition of the present invention as in the case of conventional compositions.

Specific examples of thermal polymerization inhibitors include paramethoxyphenol, hydroquinone, alkyl- or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, cuprous chloride, phenothiazine, chloranil, naphthylamine, β-naphthol, 2,6-di Examples include monot-butyl-p-cresol, pyridine, nitrobenzene, dinitrobenzene, p-toluidine, methylene blue, and organic acid copper (eg, copper acetate). These thermal polymerization inhibitors are used in an amount of 0.001 to 5 parts by weight per 100 parts by weight of ester.
It is contained within the range of parts by weight. Other coloring agents include
For example, there are pigments such as titanium oxide, carbon black, iron oxide, phthalocyanine pigments, and azo pigments, and dyes such as methylene blue, crystal violet, rhodamine B1 fuchsin, auramine, azo dyes, and anthraquinone dyes. It is preferable that the coloring agent used does not absorb light at the absorption wavelength of the photopolymerization initiator.

In such a coloring agent, the proportion of pigment is 0.1 to 30 parts by weight, and in the case of dye, 0.01 to 10 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the total amount of binder and component 5. It is preferable to contain it in a range of parts by weight. Plasticizers include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate,
Phthalate esters such as octyl capryl phthalate, synchrohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diaryl phthalate, dimethyl glycol phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl Glycol esters such as glycolate and triethylene glycol dicaprylate, phosphate esters such as tricresyl phosphate and triphenyl phosphate, diisobutyl adibate, dioctyl adibate,
Examples include aliphatic dibasic acid esters such as dimethyl sebacate, dibutyl sebacate, dioctyl azelate, and dibutyl maleate, triethyl citrate, glycerin triacetyl ester, and butyl laurate. The most typical practical embodiment of the composition of the present invention is as a material for a photosensitive layer coated on a support.

The image forming material having such a structure is produced by dissolving each of the above-mentioned components in a solvent to form a coating solution, coating this on a suitable support, and drying it. Examples of the solvent for the coating solution include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone, etc., such as ethyl acetate, butyl acetate, n-amyl acetate, methyl acetate, ethyl propionate,
Industrial compounds such as dimethyl phthalate, ethyl benzoate, etc., aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene, etc., such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, monochloroethane, etc. benzene, chlornaphthalene,
Examples include halogenated hydrocarbons such as dichloroethane, ethers such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, dimethylformamide, dimethyl sulfoxide, and the like.

The surface of the support may be provided with a coating layer or an antihalation layer of a necessary substance to facilitate bonding, if necessary. The support needs to have good light transmittance and a uniform surface.

Specifically, polyethylene terephthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride vinyl acetate copolymer. Various types of plastic films can be used, such as polytetrafluoroethylene, polytrifluoroethylene, and the like. Furthermore, a composite material consisting of two or more of these types can also be used. The support generally has 10 to 15
A material having a diameter of 0 μm, preferably 20 to 50 μm is used, but materials outside the above range can also be used.
The thickness of the photosensitive layer provided on the support is set so that the image finally formed will perform the desired function, but it is generally in the range of 5 to 100μ, more preferably It is in the range of 10 to 60μ.

The prepared image forming material basically has a structure in which a photosensitive layer is provided on a support, but a protective film can be provided on the photosensitive layer if necessary.

Such a protective film can be appropriately selected from those used for the support and paper such as paper laminated with polyethylene, polypropylene, etc. The thickness is generally 8-80μ, more preferably 10-50μ. The support can be surface-treated to improve adhesion to the photosensitive layer.

For example, applying an undercoat layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow discharge irradiation treatment,
Examples include active plasma irradiation treatment and laser beam irradiation treatment. In addition, the surface treatment of the protective film is generally carried out in order to reduce the adhesive force with the photosensitive layer, contrary to the surface treatment of the support described above, such as polyorganosiloxane, fluorinated polyolefin, etc. There is a method of providing an undercoat layer such as polyfluoroethylene. The image-forming material used in the present invention is prepared by sufficiently dissolving or dispersing components 5 and 5, the photopolymerization initiator, binder, and other components described above in a solvent, coating the material on a support by an appropriate method, and drying. However, if necessary, a protective film is further layered on top of the protective film.

Drying after application is generally carried out at 30°C to 11.0°C, particularly at 50°C to 90°C, for 1 to 30 minutes. The photosensitive image forming material prepared as described above may be subjected to a normal image forming process to form an image thereon, or may be further laminated by overlapping the photosensitive layer surface with another material. The support is peeled off and the surface of the photosensitive layer is imagewise exposed, or if the support is transparent, imagewise exposure is carried out through the support, and the support is peeled off and developed, or after the support is peeled off, an organic solvent is used. An image can be formed by developing or the like.

However, in general, the image formed by the photosensitive layer itself is rarely used as the final image, and the image formed by the photosensitive layer is usually used as a resist image, and the material existing inside the photosensitive layer is etched in the form of an image. and the image made from the material is the object. For example, in the case of an image forming material in which a metal layer is provided between the photosensitive layer and the support according to the present invention, the photosensitive layer is first subjected to image exposure and development to form an image on the photosensitive layer. At the same time or subsequently, the desired metal image is obtained by etching the inner metal layer using the image as a resist image, or by laminating the photosensitive layer on another material, that is, a material having a metal surface layer, as described above. A resist image is formed by applying a suitable treatment to the metal surface layer, and a desired metal image is obtained by simultaneously or subsequently etching the metal surface layer. Next, an image forming process for peeling and developing an image forming material composed of the composition of the present invention in order to obtain a metal image on other materials will be described in detail. As the substrate of other materials, various materials can be used depending on the purpose of the image, such as plastic film, paper, etc., which have adhesive strength to a photosensitive layer different from that used as the support for the image forming material. Wood, metal plates, glass plates, etc. are used.

Particularly when the material according to the invention is used in photoresist imaging for the production of printed circuits, a thin layer of metal, such as copper, aluminum, silver, etc., is deposited on or under a plastic plate, or by means of holes drilled through the plastic plate. A printed wiring board in which the inner wall surface of a through hole is glued or attached by plating, or a board in which a thin metal layer is provided on a thin plastic film by vapor deposition or plating, etc., may be used. When used for plate making, in addition to the various substrates mentioned above, for example, an aluminum plate or a plastic film provided with an aluminum layer is used. In this case, the surface of the metal such as aluminum may be subjected to treatments such as silicate treatment and anodic oxidation. Lamination of the photosensitive layer onto these substrates is carried out at room temperature (15
C. to 30.degree. C.) or under heating (30.degree. C. to 60.degree. C.).

The photosensitive layer and support thus laminated onto the substrate are then imagewise exposed through the transparent support, typically through an original document.

As a result of the imagewise exposure, component 5 in the exposed areas polymerizes to form a cured film.

As a result of this, although before exposure the photosensitive layer was, for example, more adhesive to the support than to the substrate, as a result of polymerization it becomes more adhesive to the substrate than to the support. Next, when the support is peeled off, the unexposed photosensitive layer remains attached to the support side and is removed from the substrate, while the exposed photosensitive layer (cured polymer layer) remains attached to the other substrate side. In this manner, a positive image relative to the exposed image is formed on the support, and a negative image is formed on the substrate. On the other hand, it is also possible to form a negative image on the support and a positive image on the substrate by selecting a suitable combination of adhesion forces of the support and the substrate to the photosensitive layer. At this time, the temperature at the time of peeling is not particularly limited, but a range of usually 200 to 80°C is desirable. The photopolymerizable composition of the present invention has the feature of being sensitive to radiation having a wavelength of about 500 mμ, and therefore has the advantage of being sensitive to radiation with a wavelength of about 500 mμ, and therefore has the advantage of being sensitive to radiation with a wavelength of approximately 500 mμ. In addition to high-pressure mercury lamps, high-pressure xenon-mercury lamps, high-pressure xenon lamps, halogen lamps, fluorescent lamps, etc., the ability to use argon laser beams with a wavelength of 488 mμ has superior properties compared to conventional photopolymerizable compositions. In particular, since scanning exposure can be performed using an argon laser beam, its application fields are extremely wide, including the production of printed wiring boards in the electronics industry, the production of lithographic or letterpress printing plates, the production of reliefs, etc.
It is used as a photosensitive material in various fields such as optical image reproduction,
The present invention is an extremely useful invention.

Hereinafter, the present invention will be explained specifically and in detail based on Examples of the present invention and Comparative Example 1 thereto.

The general methods and operations in Examples and Comparative Examples are as follows. (1) Preparation of sample Component 5, component 5, binder and other additives 1 are placed in a container with dichloroethane, stirred for about 3 hours to dissolve the solids, and then applied on an aluminum plate, It was left to dry for 10 minutes at a temperature of 80°C.

The dry thickness of the formed optical layer was approximately 10 μm. (
2) Method for Measuring Sample Sensitivity The sensitivity of the sample prepared as described in the previous section was measured as follows.

First, a polyethylene terephthalate film with a thickness of 25 μm is placed on the photosensitive layer of the sample, and an argon laser beam with a wavelength of 4880λ is passed through an optical system inserted with an optical wedge with 6 steps from O to 5 (light intensity at the sample surface is 2.6 W). ) to speed 2
The film surface was scanned at m/sec, then the film was removed and the photosensitive layer was treated with trichloroethane to dissolve and remove the non-polymerized portion.

The maximum number of stages of the optical wedge corresponding to the remaining relief image is taken as the sensitivity of the sample. The higher the number of stages, the higher the sensitivity of the sample. Examples 1 to 10 and Comparative Examples a to d The above general matters were carried out as shown in Table 1.

From the results in the bottom row of the table above, the samples using the photopolymerizable composition of the present invention have the sensitivity necessary for image formation even to argon laser light, and the desired image can be formed by the operations described above. I was able to form it.

However, samples using conventional photopolymerization initiators showed no sensitivity to argon laser light and no images were obtained. It is clear from these results that the composition of the present invention is useful. In the case of samples made from the compositions shown in Examples, if the polyethylene terephthalate film is strongly pressed against the photosensitive layer to form a laminate when preparing the sample, all the samples will have an optical wedge stage number of 2 to 3. Development by peeling the film was possible at the appropriate exposure level.

Claims (1)

[Scope of Claims] 1. (a) at least one polymerizable ethylenically unsaturated compound; (b) a carbonyl compound represented by the following chemical formula (I) or a derivative thereof; and chemical formula (II).
A photopolymerizable composition comprising a polymerization initiator consisting of a tertiary amine represented by: I ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or II ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1, R_2, and R_3 each represent an alkyl group, an aryl group, or a hydroxyalkyl group. 2. The photopolymerizable composition according to claim 1, wherein the tertiary amine is triethanolamine.