JPS638735A - Photosensitive resin plate for pattern formation - Google Patents

Abstract

PURPOSE:To obtain a uniform photosensitive layer by forming the photosensitive resin material which constitutes a photosensitive resin layer of titled plate with a specific component. CONSTITUTION:The titled resin comprises a methacrylate and an unsatd. monomer contg. carboxylic group as an essential monomer component, and an unsated. vinyl compd. as a small amount of the component, and a cross-linkable monomer having an ethylenically unsated. group an a photopolymerization initiator as an essential component. The resin of the 1st. Component is preferably a copolymer of one or two or more kinds of the methacrylate and one or two or more kinds of the unsated. monomers contg. the carboxyl group such as acrylic acid. The copolymer obtd. by combining one or two or more kinds of the comonomers selected from unsated. vinyl comds. capable of copolymerizing with said comonomer such as methylacrylate may be used. The cross-linkable monomer having at least one of ethylenically unsatd. group in a molecular which is used as the 2nd. component is preferably exemplified by methyl acrylate, etc. The photopolymerization initiator is exemplified by benzophenone, such as 9,10-anthraquinone, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a photosensitive resin plate for forming a design pattern on a support.

A method using a photosensitizer has been proposed when forming a design pattern on glass, metal, or plastic film.

Such patterns are called color images and are used as samples for logos and designs.

Adhesive is applied onto the pattern and used as a transfer sheet. The design pattern at this time is formed using alcohol-soluble ink. Since the ink has a wide variety of colors, it has the advantage that the color can be freely selected and a number of design patterns of desired colors can be created from a single original film. Further, when used as a transfer sheet, it can be transferred to paper, metal plastic, etc.

Furthermore, this photosensitive resin plate for pattern formation has a high possibility of being used in other fields as well.

Prior Art Conventionally, the following photosensitive resin plates and pattern forming methods have been used to form such design patterns. Namely.

■ Plastic sheet? An alcohol-soluble ink is evenly applied to one side of the support and allowed to dry.

■ A water-developable photosensitive agent is applied to the surface coated with the alcohol-soluble ink and dried to form a photosensitive layer.

■ Expose through negative film.

■ Develop the unexposed areas of the photosensitive layer with water.

(1) Dissolve and remove the exposed surface of the alcohol-soluble ink layer with alcohol.

■ Remove the remaining photosensitive layer with a stripping solution.

The following process is used. After this, if an adhesive is applied to the ink surface, it can be used as a transfer sheet. In this case, the design pattern is first formed to be a mirror image.

Here, alcohol-soluble ink is usually used as the pattern-forming ink. The reason for this is that alcohol-soluble ink dries faster and has better weather resistance than water-soluble ink.

As a photosensitizer, a mixed composition of a diazo resin or acrylamide and polyvinyl alcohol or polyvinyl acetate has generally been used.

Problems to be Solved by the Invention However, since the above-mentioned photosensitizers are water-developable, they have poor drying properties after development and poor wettability to the ink layer, making it difficult to obtain sufficient density. There was a problem that a uniform photosensitive layer could not be obtained because the photosensitive agent was not coated or the photosensitive agent was repelled by oil from hands and the like on the surface of the ink layer.

Furthermore, since the ink layer is insoluble in water, there is a problem in that the step of developing the photosensitive layer and the step of removing the exposed ink to form an image are separate and time-consuming steps.

Means to Solve the Problems In order to solve these problems, the inventors of the present application have conducted intensive research and have developed an alcohol-developable photosensitive agent that can be suitably used in the formation of design patterns using alcohol-soluble inks. They discovered this and completed the present invention.

That is, the present invention provides a pattern-forming photosensitive resin plate in which an alcohol-soluble ink layer is provided on a support and a photosensitive resin layer is provided thereon, in which the photosensitive resin material forming the photosensitive resin layer is ( a) Contains a methacrylic acid ester and a carboxyl group-containing unsaturated monomer as essential single receptor components, and optionally contains a small amount of at least one unsaturated vinyl compound copolymerizable with these lj monomers. (b) a resin whose main component is an acrylic copolymer obtained by copolymerizing a monomer mixture contained as a component; (b) a crosslinkable monomer having at least one ethylenically unsaturated group in the molecule; .

(C) A photosensitive resin plate for pattern formation characterized by comprising a photopolymerization initiator as an essential component.

(Resin component) The resin as component (a) in the present invention includes ethyl methacrylate, ethyl methacrylate, n-propyl methacrylate, 1so-propyl methacrylate, n-methacrylate
Butyl, methacrylic m:S mebutyl, methacrylic II
One or more methacrylic acid esters such as 5ec-butyl, tart-butyl methacrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate, and acrylic acid, methacrylic acid, maleic acid,
A copolymer with one or more carboxyl group-containing unsaturated monomers such as crotonic acid and fumaric acid is preferably used. In addition, component (a) is the methacrylic acid ester and the carboxyl group-containing unsaturated monomer, and these 111
Unsaturated vinyl compounds copolymerizable with M-form, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, 1SO-propyl acrylate, n-butyl acrylate, 15O-butyl acrylate, acrylic m5ea
-Butyl, acrylic@tert-butyl, acrylic acid 2
- Acrylic acid esters such as hydroxyethyl and 2-hydroxypropyl acrylate, chlorine-containing unsaturated monomers such as vinyl chloride, allyl chloride, and acrylic acid chloride, methyl vinyl ether, ethyl vinyl ether, n-
Propyl vinyl ether, 1so-propyl vinyl ether, n-butyl vinyl ether, 1so-butyl vinyl ether, 38C-butyl vinyl ether, tert
-butyl vinyl ether, n-amyl vinyl ether,
1so-amyl vinyl ether, 2-methoxyethyl vinyl ether, 2-chloroethyl vinyl ether, 2
- Vinyl ethers such as ethylhexyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, methyl vinyl ketone, ethyl vinyl ketone, β
-Methylene-γ-ketobutal, 2-methyl-1-penten-3-one, 4,4-dimethyl-1-penten-3
-one, 2-ethyl-1-hexen-3-one, divinyl ketone, phenyl vinyl ketone, acetoxymethyl vinyl ketone, α-acetoxy vinyl methyl ethyl ketone, α-chlorovinyl methyl ketone, β-chlorovinyl methyl ketone, chlorovinyl ketone , vinyl ketones such as methyl isopropenyl ketone, styrene, vinylbenzenes such as vinyltoluene, acrylamide, acrylamide such as N-methylol acrylamide, etc., or a combination of one or more L. May be combined.

The copolymerization ratio of the resin that is component (a) of the present invention is 40 to 90 fifi% of methacrylic acid ester, 10 to 40% by weight of carboxyl group-containing unsaturated monomer, and O to 30% by weight of other unsaturated vinyl compounds. A range is preferred.

Furthermore, component (a) includes polyvinyl ethers, polyvinyl acetal, polyhinyl alcohol,
1 selected from polyvinyl butyral and polyamides
The resin may be a species or a mixture of two or more species.

In the present invention, the weight average molecular weight of the copolymer of component (a) is preferably about 20,000 to 150,000, more preferably 30,000 to 80,000.

(Crosslinkable monomer) The crosslinkable monomer having at least one ethylenically unsaturated group in the molecule, which is used as the component (b) a in the present invention, is methyl acrylate.

Acrylic acid esters such as ethyl acrylate, n-propyl acrylate, 1so-propyl acrylate, n-butyl acrylate, 1so-butyl acrylate, see-butyl acrylate, tert-butyl acrylate, methyl methacrylate, methacrylate Ethyl acid, methacrylic acid n
-propyl, 1so-propyl methacrylate, n-butyl methacrylate, 1so-butyl methacrylate, msec-butyl methacrylate, tert- methacrylate
Methacrylic acid esters such as butyl, carboxyl group-containing unsaturated monomers such as acrylic acid, methacrylic acid, male monomer, crotonic acid, fumaric acid, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, Triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,3-propanediol diacrylate, 1.3-propanediol dimethacrylate, 1.3-butanediol diacrylate acrylate,
1.3-butanediol dimethacrylate, 1.4-butanediol diacrylate, 1,4-butanediol dimethacrylate, neobentanediol diacrylate, neobentanediol dimethacrylate, 1.6-
Hexanediol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane triacrylate, tetramethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol Tetraacrylate, pentaerythritol tetramethacrylate,
Dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and the like can be suitably used.

In addition, acrylamide, N-methylolacrylamide, N,N'-methylenebisacrylamide, N,N
'-methylenebismethacrylamide, N,N'-trimethylenebismethacrylamide, N,N'-)rimethylenebismethacrylamide, N,N'-hexamethylenebismethacrylamide, N,N'-hexamethylenebismethacrylamide Acrylamides such as amide, N,N'-benzylidene bisacrylamide, N,N'-benzylidene bismethacrylamide, etc. can also be used.

The blending ratio of these crosslinkable monomers as component (b) is as follows:
25 to 20 parts by weight of resin as component (a)
It is used in an amount of 0 parts by weight, preferably in a range of 40 to 150 parts by weight. If the amount of component (b) is less than this range, sufficient sensitivity cannot be obtained. In addition, if the amount is too high, cranks are likely to occur in the photosensitive layer obtained by drying, and storage stability is further reduced.

(Photopolymerization initiator) Examples of the photopolymerization initiator as component (c) in the present invention include 7-anthraquinones such as 9.10-anthraquinone, 1-chloroanthraquinone, and 2-chloroanthraquinone, pentuphenone, p-aminobenzophenone, Benzophenones such as p-chlorobenzophenone and P-dimethylaminobenozophenone, benzoins such as benzoin, pentuin methyl ether, pentuin ethyl ether, and α-methylbenzoin, 2-chlorothioxanthone, 2,4-diethylthioxanthone, etc. Conventionally known thioxanthone compounds can be used.

These photopolymerization initiators are used in an amount of 0.1 to 10% by weight based on the crosslinkable monomer as component (b).

If it is less than this range, there will be no difference in solubility in the developer between the irradiated area and the light irradiated area after irradiation with actinic rays, and no image will be formed; if it is more than this, the irradiation required to cause a difference in solubility This takes an unreasonably long time and is not practical.

(Other components) In the present invention, the above (a), (b) and (C
) In addition to the ingredients, if necessary, photopolymerization accelerators such as Michler's ketone and ethyl p-dimethylbenzoate, and
:l Known additives such as thermal polymerization inhibitors such as quinone, tert-butylhydroquinone, benzoquinone, and catechol, colorants such as dyes and pigments, and plasticizers may be added.

The photosensitive agent of the present invention is dissolved in a solvent and applied onto the lower ink layer to form a photosensitive layer.The solvent for this purpose is an alcohol-based solvent, or an aliphatic hydrocarbon-based or aromatic hydrocarbon-based solvent. A mixed solvent containing a chlorinated hydrocarbon, ether, ketone, or S-acid ester solvent can be used.

When the photosensitive layer formed from the photosensitive agent thus obtained is closely stacked with the original film and irradiated with actinic light from the L side, only the exposed areas are cured. As a light source that emits such actinic rays, various mercury lamps, carbon arc lamps, xenon lamps, ultraviolet fluorescent lamps, etc. can be used.

(Example of use) Next, an example of use suitable for the photosensitive resin plate for pattern formation in the present invention will be shown.

Fix the base film that will serve as a support on a workbench. The support may be a transparent plastic film such as polyester or polystyrene, or a transfer film with one side of the plastic film matted.Next, alcohol-soluble ink is applied uniformly over one surface using a percoater or the like. . Special alcohol-soluble inks are commercially available from Letraset Japan Co., Ltd., Holbein Art Materials Co., Ltd., and others. The film thickness at this time is 5 to 1
It is about 5gm. After sufficiently drying with a hair dryer or the like, the photosensitive agent of the present invention is applied over one surface using a bar coater or the like, and then dried with a hair dryer or the like. The thickness of the photosensitive layer is preferably about 5 to 20 gm.

Next, the original film is attached to T: and exposed. When making a transfer sheet, attach the original film closely so that it becomes a mirror image.

After exposure, the unexposed areas of the photosensitive layer and the underlying ink layer can be easily removed by soaking a sponge, cloth, tissue, etc. in the developer and lightly rubbing the surface on which the photosensitive layer is formed. A pattern faithful to the original film is formed. As the developer, use an alcohol-based solvent, or a mixed solvent in which an aliphatic hydrocarbon-based, aromatic hydrocarbon-based, kM hydrogenated hydrocarbon-based, ketone-based, ether-based, acetate-based solvent, etc. are added to this solvent. Can be done. It is desirable to use a volatile solvent in order to prevent the solvent from penetrating into the underlying ink layer and destroying the pattern.

The desired pattern can be obtained by drying after development, but if left as is for a long time, the cured photosensitive layer may deteriorate due to ultraviolet rays and cracks may occur, so if necessary, dry it after development. The photosensitive layer can also be peeled off. In this case, the photosensitive layer is monoethanolamine,
It can be dissolved and removed with an alkaline aqueous solution of jetanolamine, triethanolamine, quaternary ammonium salt, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide, and the like.

In addition, in the case of making a transfer sheet, after forming the pattern or peeling off the photosensitive layer, an adhesive is applied using a coater or the like. As the adhesive, an aqueous solution of polyvinyl methyl ether, an alcoholic solution or a water-alcoholic solution, an alcoholic solution of polyvinyl isobutyl ether, and, for transfer sheets, those listed by Ichi Jl can be used. EXAMPLES The present invention will be explained in detail by referring to examples below, but the present invention is not limited thereby.

Example 1 (1) Methyl methacrylate/methacrylic acid/2-hydroxypropyl methacrylate copolymer (weight ratio = 70/2
0/10, weight average molecular weight 35,000) 40% by weight
250 parts by weight of ethanol solution (2) 60 parts by weight of pentaerythritol triacrylate (3) 20 parts by weight of tetraethylene glycol diacrylate (4) 4 parts by weight of benzophenone (5)
1 part by weight of p-dimethylaminobenzophenone was thoroughly mixed with a propeller mixer to prepare a photosensitizer.

A polyester film was tightly fixed on a glass plate with cellophane tape, and a white alcohol-soluble ink was applied onto the polyester film using a bar coater and dried using a dryer. The film thickness at this time was within the range of 5 to 10 lm.

The previously prepared photosensitizer was applied onto the alcohol-soluble ink layer using a bar coater, and dried using a dryer.
A photosensitive layer having a thickness of gm was obtained.

Next, the original film was placed in close contact with the original film, and a 3 kW high-pressure mercury lamp (
Exposure was carried out using Jet Light 3000 (manufactured by Saiichi Seisakusho Co., Ltd.). The average thickness of the photosensitive layer at this time was 10 gm, and the exposure amount was 45 mJ/crrr'.

1 composition after exposure is isopropyl alcohol 80% by volume,
A sponge was soaked in a developer consisting of 20% by volume of n-hexane, and the exposed surface was developed by rubbing lightly.The alcohol-soluble ink layer exposed by the development process was also removed and dried with a hair dryer. A pattern faithful to the original film was obtained.

Example 2 (1) 200 parts by volume of a 50% by weight ethanol solution of methyl methacrylate/methacrylic acid/ethyl acrylate copolymer (weight ratio = 60/20/20, weight average molecular weight 38,000) [2] Trimethyl 40 parts by weight of monopropane triacrylate (3) 40 parts by weight of 2-hydroxy-1,3-dimethacryloxypropane (4) 2,4-
A photosensitizer was prepared from 4 parts by weight of diethylthioxanthone (5) P-dimethylaminoben, 4 parts by weight of ethyl oxyfluoroate (6) 60 parts by weight of methyl ethyl ketone, and a pattern was formed in the same manner as in Example 1. Similar results were obtained. However, the average thickness of the photosensitive layer at this time was 10 gm, and the exposure amount was 45 gm.
It was mJ/crrf.

Example 3 (1) Methyl methacrylate/methacrylic acid/ethyl acrylate copolymer (1f (iB ratio = 40/4.0/20,
Weight average molecular weight% ethanol solution 200 parts by weight (2) 40 parts by weight of trimethylolpropane triacrylate (3) 50 parts by weight of tetraethylene glycol diacrylate (4) 6 parts by weight of 2,4-diethylthioxanthone (5) p-dimethylamino A photosensitizer was prepared from 4 parts by weight of ethyl benzoate (8) and 80 parts by weight of methyl ethyl ketone, and a pattern was formed in the same manner as in Example 1. The same results as in Example 1 were obtained. However, the average thickness of the photosensitive layer at this time was 10 lm, and the exposure amount was 50 lm.
mJ/crn'.

Example 4 (1) 50% by weight isopropanol solution of methyl methacrylate/methacrylic acid/ethyl acrylate copolymer (weight ratio = 60/20/201 weight average molecular weight 40,000) 180 @Okibe (2) Polyvinyl butyral resin 10 parts by weight (3) 20 parts by weight of trimethylolpropane triacrylate (4) 20 parts by weight of diethylene glycol diacrylate (5) 4 parts by weight of 2,4-diethylthioxanthone (8) 4 parts by weight of ethyl p-dimethylbenzoate (7)
A photosensitizer was prepared from 50 parts by weight of methyl ethyl ketone, and a pattern was formed in the same manner as in Example 1, and the same results as in Example 1 were obtained. However, the average film thickness of the photosensitive layer at this time was 15 cm, and the exposure amount was 60 mJ/
It was C.

Example 5 (1) Methyl methacrylate/methacrylic acid/n-butyl methacrylate/ethyl acrylate copolymer (weight ratio = 4
0/20/10/30. Weight average molecular weight 50,000)
50% ethanol solution of 2
00 parts by weight (2) Tetranityle 7 glycol diacrylate 70 parts by weight (3) 7 parts by weight of 2-tart-butylanthraquinone (4) A photosensitizer was prepared from 50 parts by weight of ethylene glycol monoethyl ether, and A pattern was formed in the same manner as in Example 1, and the same results as in Example 1 were obtained. However, the uniform film thickness of the photosensitive layer at this time was 10 pm, and the exposure amount was 70 mJ/am''.

Example 6 (1) Methyl methacrylate/methacrylic acid/is.

-Butyl vinyl ether copolymer (original paper ratio = 70/20
/10. (2) 30 parts by weight of polyethylene glycol dimethacrylate (3) 60 parts by weight of tetraethylene glycol diacrylate (4) 4.5 parts by weight of benzophenone
5) Ethyl p-dimethylaminobenzoate 2ffi seam (6) Methyl ethyl ketone 80 weight r? A photosensitizer was prepared from part L and a pattern was formed in the same manner as in Example 1, and the same results as in Example 1 were obtained. However, the average thickness of the photosensitive layer at this time was 1°m, and the exposure amount was 6.
0 mJ/am'' Example 7 (1) 50% by weight ethanol solution of methyl methacrylate/methacrylic acid/ethyl acrylate copolymer (weight ratio = 50/30/201 weight average molecular weight 39,000)
200 parts by weight (2) 30 parts by weight of trimethylolpropane triacrylate (3) 20 parts by weight of tetraethylene glycol diacrylate (4) 10 parts by weight of methacrylic acid (5)
A photosensitizer was prepared from 4 parts by weight of 2,4-diethylthioxanthone ([i) 4 parts by weight of ethyl p-dimethylbenzoate] and 40 parts by weight of methyl ethyl ketone, and a pattern was formed in the same manner as in Example 1. Similar results were obtained. However, the average thickness of the photosensitive layer at this time was 10 m, and the exposure amount was 60 mJ.
/crn'.

Next, prepare a 20% by weight aqueous solution of triethanolamine, soak it into a sponge, apply it to the patterned surface, leave it for 60 to 90 seconds, and then wash with water to remove only the photosensitive layer and remove the alcohol. A pattern remained where only the town-soluble ink was used.

Example 8 (1) Notyl methacrylate/methacrylic acid/2-hydroxypropyl methacrylate copolymer (weight ratio = 80/1
0/10, weight average molecular weight 42.000) 40% by weight
250 parts by weight of isopropanol solution (2) 80 parts by weight of pentaerythritol triacrylate (3) 10 parts by weight of tetraethylene glycol diacrylate (4) Benzphenone 4.5 parts by weight (5
) A photosensitizer was prepared from p-dimethylaminphenone 0.5 heavy tail, and a pattern was formed on a transfer film in the same manner as in Example 1, and the same results as in Example 1 were obtained. However, the average thickness of the photosensitive layer at this time was 12 m, and the exposure amount was 40 mJ/cm'.

After pattern formation, apply transfer sheet adhesive (manufactured by Letraset) to the patterned surface using a bar coater! I washed it and dried it with a hair dryer. Next, the surface coated with the adhesive was placed on a white paper, and the transfer film was pressed from the back side. When the transfer film was peeled off, the pattern was transferred onto the white paper.

Example 9 (1) 50% by weight ethanol solution of methyl methacrylate/methacrylic acid/ethyl acrylate copolymer (weight ratio = 40/40/204 weight average molecular weight 45,000)
200 parts by weight (2)) Dimethylolpropane triacrylate - 840 parts by weight (3) Tetraethylene glycol diacrylate 40f
fi parts (4) 2,4-diethylthioxanthone 4 parts by weight (5) p-dimethyl Anzuki, ethyl fragrant 4 parts by weight (8
) A photosensitive agent was prepared from 60 parts by weight of methyl ethyl ketone, and a pattern was formed on a transfer film in the same manner as in Example 1, and the same results as in Example 1 were obtained. The average film thickness of the photosensitive layer was 5 gm, and the exposure amount was 30 zJ/crn'.

Next, after removing the photosensitive layer using the circular method as in Example 5, adhesive was applied 70 in the same manner as in Example 6, and after drying, it was pressed onto white paper, and the pattern was transferred onto the white paper. I wanted it.

Effects of the Invention According to the present invention, in the step of forming a design bag using an alcohol-soluble ink on a support, the step of developing the photosensitive layer and the step of removing the exposed alcohol-soluble ink are performed simultaneously. As a result, patterns can be formed more easily and in a shorter time than before.

Claims (1)

[Scope of Claims] In a pattern-forming photosensitive resin plate in which an alcohol-soluble ink layer is provided on a support and a photosensitive resin layer is provided thereon, the photosensitive resin material forming the photosensitive resin layer is (a) Contains a methacrylic acid ester and a carboxyl group-containing unsaturated monomer as essential monomer components, and optionally contains a small amount of at least one unsaturated vinyl compound copolymerizable with these monomers. (b) a resin whose main component is an acrylic copolymer obtained by copolymerizing a monomer mixture contained as a component; (b) a crosslinkable monomer having at least one ethylenically unsaturated group in the molecule; (c) A photosensitive resin plate for pattern formation, comprising a photopolymerization initiator as an essential component.