JP2023148940A - Photosensitive film for sand blasting - Google Patents

Abstract

To provide a photosensitive film for sand blasting which enables a support to be easily peeled from a photosensitive resin layer, and enables only a cover film to be peeled from the photosensitive resin layer without making peeling between the support and the peeling layer progress when the cover film is peeled.SOLUTION: A photosensitive film for sand blasting has a support, a peeling layer, a photosensitive resin layer and a cover film in this order, wherein the photosensitive resin layer contains (A) an alkali-soluble resin, (B) a photopolymerization initiator, (C) urethane (meth)acrylate, and (D) a fluorine-based surface active agent.SELECTED DRAWING: Figure 1

Description

The present invention relates to a photosensitive film for sandblasting.

Conventionally, when glass, stone, metal, plastic, ceramic, etc. are cut to form a relief, processing by sandblasting is performed. Sandblasting is a process in which a photosensitive resin layer patterned by photolithography or the like is provided as a mask material on the object to be processed, and then an abrasive is sprayed to selectively cut non-mask parts.

A photosensitive film for sandblasting used to provide a photosensitive resin layer serving as a mask material for sandblasting generally has a support, a photosensitive resin layer, and a cover film in this order. In addition, the photosensitive resin layer contains an alkali-soluble resin, urethane (meth)acrylate, and a photopolymerization initiator, and known examples of the alkali-soluble resin include cellulose derivatives and carboxy group-containing acrylic resins ( For example, see Patent Documents 1 to 3).

A surfactant is generally added to such a photosensitive resin layer in order to improve defoaming and leveling properties during coating, and to improve the antistatic properties of the photosensitive resin layer. ing. Patent Document 4 describes a specific example in which a fluorine-based surfactant is added to a photosensitive resin layer that serves as a mask material for sandblasting.

On the other hand, in order to increase the sandblasting resistance of the photosensitive resin layer for sandblasting, it is necessary to increase the elasticity of the cured film, and to achieve this, the amount of urethane (meth)acrylate blended should be as large as possible. There was a need. However, when the amount of urethane (meth)acrylate compounded is increased, the adhesive strength of the photosensitive resin layer increases before curing, making it impossible to peel the support from the photosensitive resin layer. It was difficult to transfer the layer to the object to be processed. Therefore, it was necessary to lower the blending amount of urethane (meth)acrylate at the expense of sandblasting resistance.

To solve this problem, a water-soluble resin layer made of polyvinyl alcohol, partially saponified polyvinyl acetate, ethylene glycol, propylene glycol, polyethylene glycol, etc. is added as a release layer between the support and the photosensitive resin layer. (for example, Patent Documents 5 and 6), or providing a peeling layer containing an alkali-soluble resin similar to the alkali-soluble resin contained in the photosensitive resin layer between the photosensitive resin layer and the support (for example, Patent Documents 5 and 6). 7) is generally practiced. This allows the support to be peeled off from the photosensitive resin layer.

However, when the above-mentioned water-soluble resin layer is used as a release layer, there is a problem that repellency is likely to occur when coating the photosensitive resin layer on the release layer, and the water-soluble resin contained in the release layer Depending on the type, the support cannot be peeled off from the photosensitive resin layer unless the release layer is heated to a temperature of 60° C. or higher when the support is peeled off, resulting in an additional heating step. In addition, when the photosensitive resin layer and the release layer contain similar alkali-soluble resins, heating is not necessary when removing the support, and although the occurrence of repelling can be suppressed, the adhesive strength between the photosensitive resin layer and the cover film is is maintained, therefore, there is a problem that peeling occurs between the support and the release layer when the cover film is peeled off, increasing the risk that the photosensitive film for sandblasting will no longer be usable.

Japanese Patent Application Publication No. 8-54734 Japanese Patent Application Publication No. 10-239840 Japanese Patent Application Publication No. 10-69851 Japanese Patent Application Publication No. 2006-065000 Japanese Unexamined Patent Publication No. 59-137948 Japanese Patent Application Publication No. 6-161098 Japanese Patent Application Publication No. 2012-27357

The problem of the present invention is to make it possible to easily peel off the support from the photosensitive resin layer, and to make only the cover film photosensitive without further peeling between the support and the release layer when the cover film is peeled off. An object of the present invention is to provide a photosensitive film for sandblasting that can be peeled off from a resin layer.

As a result of intensive studies to solve the above problems, the present inventors have found that in a photosensitive film for sandblasting, which has a support, a release layer, a photosensitive resin layer, and a cover film in this order, the photosensitive resin layer ( The above problems were solved by a photosensitive film for sandblasting, which is characterized by containing A) an alkali-soluble resin, (B) a photopolymerization initiator, (C) urethane (meth)acrylate, and (D) a fluorine-based surfactant. .

The support can be easily peeled off from the photosensitive resin layer, and only the cover film can be peeled off from the photosensitive resin layer without further peeling between the support and the release layer when the cover film is peeled off. A photosensitive film for sandblasting can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing of the photosensitive film for sandblasting of this invention.

Hereinafter, the photosensitive film for sandblasting of the present invention will be explained in detail.

As shown in FIG. 1, the photosensitive film for sandblasting of the present invention has a structure in which a support 1, a release layer 2, a photosensitive resin layer 3, and a cover film 4 are laminated. To use it, first, the cover film 4 is peeled off, and then the photosensitive resin layer 3 is attached onto the object to be processed using a laminator or the like so that it comes into contact with the object. Next, the support 1 is exposed from the side of the support 1 through a mask film that corresponds to the relief image, and then the support 1 is peeled off from the interface between the release layer 2 and the support 1. Alternatively, when high resolution is required, in order to reduce light refraction, after peeling off the support 1, exposure is performed from the peeling layer 2 side through a mask film that matches the relief image. The exposed portions of the photosensitive resin layer 3 are cured. At this time, since the release layer 2 is non-photosensitive, curing does not occur. Next, the release layer 2 and the unexposed areas are washed away with an alkaline developer, and then washed with water. Next, the object to be processed is processed by sandblasting.

As the support, a transparent film that transmits actinic rays is preferable. The transparent film preferably has a haze value of 10% or less. Regarding the thickness, a thinner one is preferable because it causes less light refraction, and a thicker one is preferable because the coating stability is excellent, so it is preferably 10 to 100 μm. Examples of such transparent films include films of polyethylene terephthalate, polycarbonate, and the like.

The cover film only needs to be able to peel off the uncured or cured photosensitive resin layer, and a resin with high mold releasability is used. Examples include films such as polyethylene film and polypropylene film. Furthermore, films obtained by coating these films with a release agent such as silicone may be mentioned.

The photosensitive resin layer contains at least (A) an alkali-soluble resin, (B) a photopolymerization initiator, (C) a urethane (meth)acrylate compound, and (D) a fluorine-based surfactant. In addition, in this specification, these components are expressed as component (A), component (B), component (C), component (D), or simply (A), (B), (C), ( D) etc.

Examples of the alkali-soluble resin (A) include the alkali-soluble cellulose derivatives and carboxyl group-containing acrylic resins described below.

Examples of the alkali-soluble cellulose derivatives include cellulose acetate phthalate, hydroxypropylmethylcellulose phthalate, hydroxypropylmethylcellulose acetate phthalate, hydroxypropylmethylcellulose acetate succinate, and the like.

Examples of carboxy group-containing acrylic resins include acrylic resins made by copolymerizing (meth)acrylates such as methyl (meth)acrylate and ethyl (meth)acrylate with ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid. Examples include polymers. It also contains dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid, their anhydrides and half esters, and other copolymerizable ethylenically unsaturated groups such as styrene, (meth)acrylonitrile, and (meth)acrylamide. Also included are polymers obtained by copolymerizing monomers.

Examples of the (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate Acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-(dimethylamino)ethyl (meth)acrylate, 2-(diethylamino)ethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, ) acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, and the like.

As the ethylenically unsaturated carboxylic acid, monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid are preferably used, and dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid, and their anhydrides and half esters are preferably used. It can also be used. Among these, acrylic acid and methacrylic acid are particularly preferred.

Examples of the other copolymerizable monomers having an ethylenically unsaturated group include styrene, α-methylstyrene, p-methylstyrene, p-ethylstyrene, p-methoxystyrene, p-ethoxystyrene, p- -chlorostyrene, p-bromostyrene, (meth)acrylonitrile, (meth)acrylamide, diacetone acrylamide, vinyltoluene, vinyl acetate, vinyl-n-butyl ether and the like.

The acid value of the alkali-soluble resin (A) is preferably 30 to 500 mgKOH/g, more preferably 100 to 300 mgKOH/g. If this acid value is less than 30 mgKOH/g, the time for alkaline development tends to be longer, while if it exceeds 500 mgKOH/g, sandblasting resistance may decrease.

Furthermore, the weight average molecular weight of the alkali-soluble resin (A) is preferably 10,000 to 200,000, more preferably 10,000 to 150,000. If the mass average molecular weight is less than 10,000, it may be difficult to form a photosensitive resin layer in the present invention, while if it exceeds 200,000, the solubility in an alkaline developer tends to deteriorate.

The photosensitive resin layer in the present invention contains (B) a photopolymerization initiator. (B) As the photopolymerization initiator, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2- Aromatic ketones such as morpholinopropan-1-one; 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone , 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, etc. quinones; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; benzoin compounds such as benzoin, methylbenzoin, and ethylbenzoin; benzyl dimethyl ketal, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2- Methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methylpropan-1-one, 2-hydroxy-1-{4-[4- (2-hydroxy-2-methyl-propionyl)benzyl]phenyl}-2-methylpropan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-( Alkylphenones such as 4-morpholinyl)phenyl]-1-butanone; acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide Class; 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(o-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H- 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4, 5-bis(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimers such as 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer; 9-phenylacridine, 1,7-bis(9,9'-acridinyl) ) Acridine derivatives such as heptane; N-phenylglycine, N-phenylglycine derivatives; Coumarin compounds; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4 '-Methyldiphenyl sulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, etc. Examples include benzophenone compounds. The substituents on the aryl groups of the two 2,4,5-triarylimidazole in the above 2,4,5-triarylimidazole dimer may be the same and give a symmetrical compound, or they may be different. Asymmetric compounds may also be provided. Furthermore, a thioxanthone compound and a tertiary amine compound may be combined, such as a combination of diethylthioxanthone and dimethylaminobenzoic acid. These may be used alone or in combination of two or more.

The photosensitive resin layer in the present invention contains (C) a urethane (meth)acrylate compound. (C) Urethane (meth)acrylate compound is a reaction product of a compound having a terminal isocyanate group and a (meth)acrylate compound having a hydroxy group, which is the reaction between a compound having a polyvalent hydroxy group and a polyvalent isocyanate compound. means. Examples of the compound having a polyvalent hydroxyl group include polyesters and polyethers having a hydroxyl group at the end; examples of the polyester include polyesters obtained by ring-opening polymerization of lactones, polycarbonates, ethylene glycol, Examples include polyesters obtained by condensation reactions of alkylene glycols such as propylene glycol, diethylene glycol, triethylene glycol, and dipropylene glycol with dicarboxylic acids such as maleic acid, fumaric acid, glutaric acid, and adipic acid. Specifically, the lactones include δ-valerolactone, ε-caprolactone, β-propiolactone, α-methyl-β-propiolactone, β-methyl-β-propiolactone, α,α-dimethyl -β-propiolactone, β,β-dimethyl-β-propiolactone, and the like. Specific examples of the polycarbonates include reaction products of diols such as bisphenol A, hydroquinone, and dihydroxycyclohexanone and carbonyl compounds such as diphenyl carbonate, phosgene, and succinic anhydride. Further, specific examples of the polyethers include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polypentamethylene glycol, and the like.

Specific examples of the polyvalent isocyanate compound that reacts with the compound having a polyvalent hydroxy group include dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, 2,2- Dimethylpentane-1,5-diisocyanate, octamethylene diisocyanate, 2,5-dimethylhexane-1,6-diisocyanate, 2,2,4-trimethylpentane-1,5-diisocyanate, nonamethylene diisocyanate, 2,2,4 - Aliphatic or alicyclic diisocyanate compounds such as trimethylhexane diisocyanate, decamethylene diisocyanate, and isophorone diisocyanate can be mentioned, and these compounds can be used alone or in a mixture of two or more types.

Further, as (meth)acrylate compounds having a hydroxy group, specifically, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, and ε- Compounds containing 1 to 10 mol of caprolactone can be mentioned, and these compounds can be used alone or in combination of two or more.

Component (C) may contain a carboxy group. Containing a carboxyl group tends to improve solubility in an alkaline developer. Component (C) containing a carboxyl group is obtained by first reacting a diisocyanate compound and a diol compound having a carboxyl group so that isocyanate groups remain at both ends, and then adding a hydroxy group to the terminal isocyanate group of the reaction product. It can be obtained by reacting (meth)acrylate compounds that have.

The photosensitive resin layer in the present invention contains (D) a fluorosurfactant. (D) Fluorine-based surfactants include polyalkylene oxide (polyethylene oxide, polypropylene oxide, etc.) adducts of alcohols having perfluoroalkyl groups, and polyalkylene oxide (polyethylene oxide, polypropylene oxide, etc.) adducts of perfluoropolyethers. This includes things such as things. Note that the fluorine-based surfactant may have a hydroxyl group, an alkoxy group, an alkyl group, an amino group, a thiol group, etc. in a part of its molecular structure (for example, a terminal group).

As the fluorine-based surfactant, commercially available products may be used. Commercially available products include, for example, Megafac (registered trademark) F114, F142D, F172, F173, F183, F251, F253, F281, F444, F445, F470, F475, F477, F478, F479, F486, F-553, F -555, F556, F559, F562, RS-75, TF-2066, TF-2067, TF-2068, pentadecaethylene glycol mono 1H, 1H, 2H, 2H-perfluorooctyl ether (manufactured by DIC Corporation) ), Florado FC-430, FC-431 (manufactured by 3M Japan Ltd.), Surflon (registered trademark) S-382 (manufactured by AGC Ltd.), EFTOP EF-122A, 122B, 122C, EF-121, EF-126, EF-127, MF-100 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), PF-636, PF-6320, PF-656, PF-6520 (manufactured by OMNOVA Solutions Inc.), Unidyne (Registered trademark) DS-401, DS-403, DS-451 (manufactured by Daikin Industries, Ltd.), Ftergent (registered trademark) 250, 251, 222F, 208G (manufactured by Neos Corporation), etc. Can be mentioned.

The photosensitive resin layer may contain components other than the above components (A) to (D), if necessary. Such components include photopolymerizable monomers, solvents, thermal polymerization inhibitors, plasticizers, colorants (dyes, pigments), photocoloring agents, photoreducing agents, thermal coloration inhibitors, fillers, and antifoaming agents. agents, flame retardants, adhesion-imparting agents, leveling agents, peel accelerators, antioxidants, fragrances, thermosetting agents, water repellents, oil repellents, etc., each of which is the sum of the above components (A) to (C). It can be contained in an amount of about 0.01 to 20% by mass based on the amount. These components can be used alone or in combination of two or more.

The photopolymerizable monomer is a compound having at least one polymerizable ethylenically unsaturated group in the molecule, other than component (C) urethane (meth)acrylate. For example, a compound obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid; a bisphenol A-based (meth)acrylate compound; a compound obtained by reacting a glycidyl group-containing compound with an α,β-unsaturated carboxylic acid. Compound; Nonylphenoxypolyethyleneoxyacrylate; γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, β-hydroxyalkyl-β'-(meth)acryloyloxyalkyl-o-phthalate, etc. Examples include phthalic acid compounds; (meth)acrylic acid alkyl esters, EO-modified and/or PO-modified nonylphenyl (meth)acrylates, and the like. Here, EO and PO represent ethylene oxide and propylene oxide, and are nonylphenyl (meth)acrylates having an ethylene oxide block structure and/or a propylene oxide block structure. These photopolymerizable monomers can be used alone or in combination of two or more types.

In the present invention, the release layer preferably contains (A) an alkali-soluble resin of the same compound as the photosensitive resin layer. In addition, the release layer may contain (C) urethane (meth)acrylate in order to reduce repellency that occurs when applying the photosensitive resin layer described above. Further, if necessary, a plasticizer, a dispersant, a heat stabilizer, a light stabilizer, an antistatic agent, an antioxidant, a surfactant, a lubricant, a solvent, etc. may be included.

The thickness of the release layer is preferably 0.5 to 15 μm, more preferably 1 to 10 μm. If the thickness of the release layer is too large, resolution tends to decrease and costs tend to increase. On the other hand, if it is too thin, releasability tends to decrease. Further, the thickness of the photosensitive resin layer described above is preferably 10 to 150 μm, more preferably 30 to 120 μm. If the thickness of the photosensitive resin layer is too large, problems such as decreased resolution, increased cost, and edge fusion are likely to occur. On the other hand, if it is too thin, the sandblasting resistance tends to decrease.

Examples of methods for applying the release layer of the present invention include doctor blade coating method, Meyer bar coating method, roll coating method, screen coating method, spinner coating method, inkjet coating method, spray coating method, dip coating method, and gravure coating method. , curtain coating method, and die coating method. There are no particular restrictions on the drying conditions for the coating solution for the release layer, but the drying temperature is preferably 55° C. to 130° C., and the drying time is preferably 30 seconds to 30 minutes.

Further, as the photopolymerizable monomer described above, a compound having three or more polymerizable ethylenically unsaturated groups in the molecule may be used. Examples of photopolymerizable compounds having three or more polymerizable ethylenically unsaturated groups in the molecule include trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and pentaerythritol tri(meth)acrylate. acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane triglycidyl ether tri(meth)acrylate, etc., and these may be used alone or Two or more types can be used.

In the photosensitive resin layer of the present invention, the content of (A) is preferably 20 to 50% by mass based on the total amount of (A), (B), (C), and (D), and 25% by mass. More preferably, it is 35% by mass. If the content of (A) is less than 20% by mass, film properties may deteriorate or developability may deteriorate. If the content of (A) exceeds 50% by mass, the resolution of the resist pattern may decrease.

The content of (B) is preferably 0.1 to 10% by mass, and 0.2 to 5% by mass based on the total amount of (A), (B), (C), and (D). It is more preferable that there be. If the content of (B) is less than 0.1% by mass, photopolymerizability may become insufficient. On the other hand, if it exceeds 10% by mass, absorption may increase on the surface of the photosensitive resin layer during exposure, resulting in insufficient photocrosslinking within the photosensitive resin layer.

The content of (C) is preferably 40 to 75% by mass, more preferably 55 to 70% by mass based on the total amount of (A), (B), (C), and (D). preferable. If the content of (C) is less than 40% by mass, crosslinking properties may decrease and photosensitivity may become insufficient. On the other hand, if it exceeds 75% by mass, the tackiness of the film surface of the photosensitive resin layer 3 may increase.

The content of (D) is preferably 0.03 to 0.15% by mass, and 0.04 to 0.04% by mass based on the total amount of (A), (B), (C), and (D). More preferably, it is 1% by mass. If the content of (D) is less than 0.03% by mass, the adhesion of the photosensitive resin layer 3 to the cover film 4 will not decrease sufficiently, and when peeling the cover film 4 from the photosensitive film for sandblasting, the support Peeling tends to progress between the body 1 and the peeling layer 2, and the photosensitive film for sandblasting may become unusable. On the other hand, if it exceeds 0.15% by mass, the coating surface may become rough due to repellency during the formation of the photosensitive resin layer by coating, and the adhesion between the photosensitive resin layer and the object to be processed may deteriorate when using the photosensitive film for sandblasting. May cause inhibition.

The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited to these Examples.

(Examples 1 to 10, Comparative Examples 1 to 4)
The components shown in Table 1 were mixed to obtain a coating solution for a release layer. In addition, the unit of the amount of each component in Table 1 represents parts by mass. The resulting coating solution was applied onto a polyethylene terephthalate (PET) film (25 μm thick, haze value 3.7%) using a wire bar, and dried at 80° C. for 4 minutes to remove the solvent component. Release layers 1 to 4 (dry film thickness: 4 μm) were obtained on one side of the PET film.

Next, the components shown in Table 2 were mixed to obtain coating solutions 1 to 13 for photosensitive resin layers. Note that the unit of the amount of each component in Table 2 represents parts by mass. Next, using an applicator, apply the coating solution for the photosensitive resin layer onto the release layer using the combination of the coating solution for the release layer and the coating solution for the photosensitive resin layer shown in Table 3, It was dried at 80° C. for 8 minutes to remove the solvent component, and photosensitive resin layers 1 to 13 (dry film thickness: 70 μm) were obtained on the release layer. After drying, a polyethylene film (30 μm thick) was laminated as a cover film on the photosensitive resin layer to obtain the photosensitive films for sandblasting of Examples 1 to 10 and Comparative Examples 1 to 4.

In Tables 1 and 2, each component is as follows.
(A-1); Cellulose acetate phthalate (mass average molecular weight 61000, acid value 200mgKOH/g)
(A-2); Hydroxypropyl methyl cellulose phthalate (manufactured by Shin-Etsu Chemical Co., Ltd., mass average molecular weight 45,000, acid value 120 mgKOH/g)
(A-3); Copolymer resin made by copolymerizing methyl methacrylate/n-butyl acrylate/methacrylic acid at a mass ratio of 58/15/27 (mass average molecular weight 30,000, acid value 176 mgKOH/g)
(B-1) 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (B-2) 4,4'-bis(diethylamino)benzophenone (C-1) Shiko (registered trademark) UV-3000B (Urethane acrylate manufactured by Mitsubishi Chemical Corporation)
(C-2) DURA-167 (carboxy group-containing urethane acrylate manufactured by Kyoeisha Chemical Co., Ltd.) (solid content ratio 53%)
(D-1); Surfactant "Megafac" F-556 (manufactured by DIC Corporation)
(D-2); Surfactant "Megafac" F-559 (manufactured by DIC Corporation)
(D-3); Surfactant "Megafac" F-251 (manufactured by DIC Corporation)

Next, OPP adhesive tape (manufactured by Nitto Denko CS System Co., Ltd., trade name "EA-3925") was attached to the cover film of the photosensitive film for sandblasting of Examples 1 to 10 and Comparative Examples 1 to 4, and the cover film was I tried to peel off the film. As a result, in Examples 1, 3 to 10, and Comparative Example 4, only the cover film could be easily peeled off, but in Comparative Examples 1 to 3, the cover film was not peeled off from the photosensitive resin layer. Peeling progressed between the PET film as a support and the release layer, and the photosensitive film could no longer be used in subsequent steps. In Example 2, the adhesion of the photosensitive resin layer to the cover film was higher than in other Examples, and in 2 out of 10 cases, the adhesive strength of the photosensitive resin layer to the cover film was higher than that of the area around which the OPP adhesive tape was attached when the cover film was peeled off. Although there were some parts where the photosensitive resin layer and release layer were lifted off the support, the cover film could be peeled off from other parts without any problems. The results are shown in Table 4. The evaluation criteria were as follows: ◯ if the cover film could be peeled off without any problem, △ if the peeling layer was partially lifted but there was no practical problem, and × if there was a practical problem.

The photosensitive resin layer surfaces of the sandblasting photosensitive films of Examples 1 to 10 and Comparative Example 4 from which the cover films had been peeled were bonded to a 3 mm thick glass plate, and laminated using a laminator at a temperature of 100° C. and a pressure of 0.2 MPa. . Subsequently, the photosensitive film for sandblasting bonded to the glass plate was exposed to light using a high-pressure mercury lamp (85 mJ/cm ² ) through a photomask having 16 circular patterns each having a diameter of 300 μm and a diameter of 250 μm. Next, the PET film of the photosensitive film for sandblasting was peeled off at room temperature. Examples 1 to 10 and Comparative Example 4 could be easily peeled off by hand. Alkaline development was performed using a 0.2% aqueous sodium carbonate solution to remove the release layer and the photosensitive resin layer in the non-exposed areas. At this time, in Examples 2 to 5 and 7 to 10, all 16 circular patterns of the cured photosensitive resin layer with a diameter of 250 μm and a diameter of 300 μm remained on the glass plate. On the other hand, in Examples 1 and 6, all 16 circular patterns with a diameter of 300 μm remained on the glass plate, but half of the circular patterns with a diameter of 250 μm were directly peeled off from the glass during development. Regarding Example 4, no circular pattern remaining on the glass plate after development was observed for both circular patterns with a diameter of 250 μm and a diameter of 300 μm. The results are shown in Table 4. The evaluation criteria were as follows: ○ when all the circular patterns remained, △ when more than half of the circular patterns remained, and × when more than half of the patterns were peeled off.

The photosensitive film of the present invention can be widely applied to photosensitive films for sandblasting.

1 Support 2 Release layer 3 Photosensitive resin layer 4 Cover film

Claims (1)

In a photosensitive film for sandblasting that has a support, a release layer, a photosensitive resin layer, and a cover film in this order, the photosensitive resin layer contains (A) an alkali-soluble resin, (B) a photopolymerization initiator, and (C) urethane ( A photosensitive film for sandblasting, comprising meth)acrylate and (D) a fluorosurfactant.