Photosensitive film for sand blasting

Abstract

To provide a photosensitive film for sandblasting excellent in sandblasting resistance, leaving little residue on a base material after peeling a resist and ensuring a short resist peeling time.SOLUTION: A photosensitive film 10 for sandblasting includes, as photosensitive resin layers, a first photosensitive resin layer 11 containing (A) urethane (meth) acrylate, (B) a photopolymerization initiator, and (C) a cellulose derivative, and a second photosensitive resin layer 12 containing (A) urethane (meth) acrylate, (B) a photopolymerization initiator, and (D) an acrylic resin. The photosensitive film 10 for sandblasting includes a transparent film 13, a first photosensitive resin layer 11, a second photosensitive resin layer 12, and a release film 14 in this order.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a photosensitive film for sandblasting. [Background technology]

[0002] Sandblasting, in which an abrasive is blown onto the surface of a workpiece using compressed air, is a well-known processing method for glass, stone, metal, plastic, ceramic, etc. During sandblasting, a photosensitive resin layer patterned by photolithography or the like is provided on the workpiece as a mask, and the unmasked portions are removed by polishing.

[0003] Various proposals have been made regarding the photosensitive resin layer that is the mask material used in sandblasting, and the photosensitive film for transferring the photosensitive resin layer onto the object to be processed.

[0004] As a photosensitive resin layer for sandblasting, a negative photosensitive resin layer containing an alkali-soluble resin, a urethane (meth)acrylate, and a photopolymerization initiator is known.

[0005] Patent Document 1 discloses a photosensitive resin composition containing a carboxy-modified urethane (meth)acrylate compound having an acid value and glass transition point within a specific range, an alkali-soluble polymer compound having an acid value within a specific range, and a photopolymerization initiator.

[0006] Patent Document 2 discloses a photosensitive resin composition containing (A) a binder polymer having a carboxyl group, (B) a photopolymerizable monofunctional compound having an ethylenically unsaturated group, (C) a photopolymerizable polyfunctional compound having an ethylenically unsaturated group, (D) a urethane (meth)acrylate compound, and (E) a photopolymerization initiator, wherein the component (B) contains a specific (meth)acrylate compound.

[0007] Patent Document 3 discloses a photosensitive resin composition for sandblasting containing an alkali-soluble resin, a photopolymerization initiator, a urethane (meth)acrylate, and an epoxy (meth)acrylate, and lists monofunctional epoxy (meth)acrylate and acid-modified epoxy (meth)acrylate as the epoxy (meth)acrylate.

[0008] Furthermore, if the amount of urethane (meth)acrylate is increased, the photosensitive resin layer becomes more adhesive before curing, which is known to cause problems such as the photosensitive resin layer not peeling off from the support and being difficult to transfer to the substrate. To address this problem, a method has been proposed in which a release layer is formed between the support and the photosensitive resin layer. Patent Documents 4 to 6 disclose photosensitive films for sandblasting in which a release layer containing the same components as the photosensitive resin layer but not a polymerization initiator is provided between the support and the photosensitive resin layer.

[0009] The mask material used in the sandblasting process is required to have not only high sandblasting resistance but also, from the viewpoint of productivity, to be able to be removed quickly after the sandblasting process is completed. However, the above-mentioned known techniques are insufficient in these respects, and there is room for further improvement. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] Japanese Patent Application Publication No. 8-054734 [Patent Document 2] International Publication No. 2014 / 200028 [Patent Document 3] Japanese Patent Application Laid-Open No. 2017-126053 [Patent Document 4] Japanese Patent Application Laid-Open No. 2012-027357 [Patent Document 5] Japanese Patent Application Laid-Open No. 2014-206746 [Patent Document 6] Japanese Patent Application Laid-Open No. 2015-179275 Summary of the Invention [Problem to be solved by the invention]

[0011] The present invention has been made in view of the above-mentioned background art, and an object of the present invention is to provide a photosensitive film for sandblasting that has excellent sandblasting resistance, leaves little residue on the substrate after resist stripping, and requires a short resist stripping time. [Means for solving the problem]

[0012] The present inventors have conducted extensive research to solve the above problems and have discovered the following facts, which have led to the completion of the present invention.

[0013] That is, in a photosensitive film for sandblasting having a photosensitive resin layer containing urethane (meth)acrylate, by laminating two photosensitive resin layers with different compositions, the photosensitive resin layer can be made to have excellent sandblasting resistance, and after the sandblasting process is completed, the mask material (resist) can be easily and quickly removed from the substrate.

[0014] Specifically, the above-mentioned effects can be achieved by adding (A) urethane (meth)acrylate, (B) a photopolymerization initiator, and (C) a cellulose derivative to the first photosensitive resin layer, and by adding (A) urethane (meth)acrylate, (B) a photopolymerization initiator, and (D) an acrylic resin to the second photosensitive resin layer.

[0015] The present invention thus completed is as follows:

[0016] [1] A photosensitive film for sandblasting having a photosensitive resin layer, characterized in that the photosensitive resin layer comprises a first photosensitive resin layer containing (A) a urethane (meth)acrylate, (B) a photopolymerization initiator, and (C) a cellulose derivative, and a second photosensitive resin layer containing (A) a urethane (meth)acrylate, (B) a photopolymerization initiator, and (D) an acrylic resin.

[0017] [2] The photosensitive film for sandblasting according to [1], which comprises a transparent film, the first photosensitive resin layer, the second photosensitive resin layer, and a release film in this order.

[0018] [3] The photosensitive film for sandblasting according to [1] or [2], wherein the thickness of the first photosensitive resin layer is 25 μm or more and 70 μm or less, and the thickness of the second photosensitive resin layer is 1 μm or more and 40 μm or less. [Effects of the Invention]

[0019] According to the present invention, it is possible to provide a photosensitive film for sandblasting that has excellent sandblasting resistance, leaves little residue on the substrate after resist stripping, and requires a short resist stripping time. [Brief explanation of the drawings]

[0020] [Figure 1] 1 is a schematic cross-sectional view showing the structure of a photosensitive film for sandblasting of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0021] The present invention will be described below, but the present invention is not limited to the following embodiments and can be practiced with any modifications.

[0022] In this specification, "(meth)acrylate" is a general term for "acrylate" and "methacrylate."

[0023] The photosensitive film for sandblasting 10 of the present invention has a photosensitive resin layer. The photosensitive resin layer of the photosensitive film for sandblasting of the present invention has a first photosensitive resin layer 11 and a second photosensitive resin layer 12.

[0024] As shown in FIG. 1, the photosensitive film 10 for sandblasting of the present invention may have a transparent film 13, a first photosensitive resin layer 11, a second photosensitive resin layer 12, and a release film 14 in this order.

[0025] <First photosensitive resin layer> The first photosensitive resin layer of the photosensitive film for sandblasting of the present invention contains (A) a urethane (meth)acrylate, (B) a photopolymerization initiator, and (C) a cellulose derivative.

[0026] The (A) urethane (meth)acrylate contained in the first photosensitive resin layer refers to a reaction product of a compound having a terminal isocyanate group, which is formed by reacting a compound having a polyvalent hydroxy group with a polyvalent isocyanate compound, and a (meth)acrylate compound having a hydroxy group.

[0027] Examples of compounds having a polyvalent hydroxy group include polyesters having a hydroxy group at the terminal and polyethers having a hydroxy group at the terminal.

[0028] Examples of polyesters having a hydroxy group at the end include polyesters obtained by ring-opening polymerization of lactones, polycarbonates, and polyesters obtained by condensation reaction of alkylene glycol and dicarboxylic acid.

[0029] Examples of lactones include δ-valerolactone, ε-caprolactone, β-propiolactone, α-methyl-β-propiolactone, β-methyl-β-propiolactone, α,α-dimethyl-β-propiolactone, and β,β-dimethyl-β-propiolactone.

[0030] Examples of polycarbonates include reaction products of diols such as bisphenol A, hydroquinone, and dihydroxycyclohexanone with carbonyl compounds such as diphenyl carbonate, phosgene, and succinic anhydride.

[0031] Examples of alkylene glycols include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and dipropylene glycol.

[0032] Examples of dicarboxylic acids include maleic acid, fumaric acid, glutaric acid, and adipic acid.

[0033] Examples of polyethers having a hydroxy group at the end include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and polypentamethylene glycol.

[0034] Examples of polyisocyanate compounds include aliphatic or alicyclic diisocyanate compounds such as 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-trimethylhexane diisocyanate, decamethylene diisocyanate, and isophorone diisocyanate.

[0035] Examples of the (meth)acrylate compound having a hydroxy group include 2-hydroxyethyl (meth)acrylate and 3-hydroxypropyl (meth)acrylate. Furthermore, compounds in which 1 to 10 mol of ε-caprolactone is added to 1 mol of 2-hydroxyethyl (meth)acrylate or 3-hydroxypropyl (meth)acrylate are also examples of the (meth)acrylate compound having a hydroxy group.

[0036] The urethane (meth)acrylate (A) contained in the first photosensitive resin layer may have a carboxy group. When the urethane (meth)acrylate (A) contains a carboxy group, the solubility of the unexposed areas of the first photosensitive resin layer in an alkaline developer tends to be improved. The (A) urethane (meth)acrylate having a carboxy group can be obtained, for example, by first reacting a diisocyanate compound with a diol compound having a carboxy group so that isocyanate groups remain at both ends, and then reacting the terminal isocyanate groups of this reaction product with a (meth)acrylate compound having a hydroxy group.

[0037] The first photosensitive resin layer may contain one type of (A) urethane (meth)acrylate, or may contain two or more types of (A) urethane (meth)acrylate.

[0038] Examples of the photopolymerization initiator (B) contained in the first photosensitive resin layer include benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinophenyl]-2-methyl-4-methyl ... Aromatic ketones such as 1-methyl-2-propanone; 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- quinones such as naphthoquinone and 2,3-dimethylanthraquinone; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; benzoin compounds such as benzoin, methylbenzoin, and ethylbenzoin; benzil derivatives such as benzil dimethyl ketal; 2,4,5-triarylimidazole dimers such as 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer; acridine derivatives such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; N-phenylglycine and its derivatives; Coumarin compounds; thioxanthone compounds such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, and 2,4-diethylthioxanthone; and tertiary amine compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid. The aryl groups of the two 2,4,5-triarylimidazoles in the 2,4,5-triarylimidazole dimer may have a substituent. The substituents on the two aryl groups may be the same to give a symmetrical compound, or may be different to give an asymmetrical compound.

[0039] The first photosensitive resin layer may contain one type of (B) photopolymerization initiator, or may contain two or more types of (B) photopolymerization initiators. When two or more types of (B) photopolymerization initiators are contained, the combinations thereof may be, for example, a combination of an aromatic ketone and a 2,4,5-triarylimidazole dimer, or a combination of a thioxanthone compound and a tertiary amine compound.

[0040] Examples of the cellulose derivative (C) contained in the first photosensitive resin layer include cellulose acetate phthalate, hydroxypropyl methylcellulose phthalate, hydroxypropyl methylcellulose acetate phthalate, and hydroxypropyl methylcellulose acetate succinate.

[0041] The first photosensitive resin layer may contain one type of cellulose derivative (C), or may contain two or more types of cellulose derivatives (C).

[0042] The first photosensitive resin layer may contain components other than the above-mentioned components (A), (B) and (C). Examples of such components include photopolymerizable monomers, thermal polymerization inhibitors, plasticizers, dyes, pigments, photocoloring agents, photocolor-reducing agents, thermal color-development inhibitors, fillers, defoaming agents, flame retardants, adhesion promoters, leveling agents, release promoters, antioxidants, fragrances, heat curing agents, water repellents, and oil repellents.

[0043] The content of (A) urethane (meth)acrylate in the first photosensitive resin layer is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 20% by mass or more, and is preferably 90% by mass or less, more preferably 80% by mass or less, and particularly preferably 70% by mass or less.

[0044] The content of the (B) photopolymerization initiator in the first photosensitive resin layer is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and particularly preferably 0.5% by mass or more, and is preferably 15% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less.

[0045] The content of the cellulose derivative (C) in the first photosensitive resin layer is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 15% by mass or more, and is preferably 70% by mass or less, more preferably 60% by mass or less, and particularly preferably 50% by mass or less.

[0046] The content of components other than components (A), (B), and (C) in the first photosensitive resin layer is preferably 1% by mass or more, more preferably 2% by mass or more, and particularly preferably 5% by mass or more, and is preferably 30% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less.

[0047] The content of each component in the first photosensitive resin layer mentioned above means the content in a dry state.

[0048] The method for forming the first photosensitive resin layer is not particularly limited. For example, the above-mentioned components are dissolved in a solvent to prepare a coating liquid for the first photosensitive resin layer, the coating liquid for the first photosensitive resin layer is applied to a substrate for forming the first photosensitive resin layer, and the solvent is volatilized to form the first photosensitive resin layer. Examples of solvents for the coating liquid for the first photosensitive resin layer include ethyl methyl ketone, cyclohexanone, toluene, xylene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, methanol, ethanol, propanol, ethylene glycol, propylene glycol, octane, decane, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha.

[0049] The thickness of the first photosensitive resin layer is preferably 25 μm or more, more preferably 30 μm or more, and particularly preferably 35 μm or more, and is preferably 70 μm or less, more preferably 65 μm or less, and particularly preferably 60 μm or less. If the thickness of the first photosensitive resin layer is less than 25 μm, the sandblast resistance of the photosensitive film may be deteriorated, and if the thickness of the first photosensitive resin layer is more than 70 μm, the resolution during development may be deteriorated. In this specification, "thickness" means "average thickness" unless otherwise specified.

[0050] <Second photosensitive resin layer> The second photosensitive resin layer of the photosensitive film for sandblasting of the present invention contains (A) a urethane (meth)acrylate, (B) a photopolymerization initiator, and (D) an acrylic resin.

[0051] Specific examples of the urethane (meth)acrylate (A) contained in the second photosensitive resin layer are the same as the specific examples of the urethane (meth)acrylate (A) contained in the first photosensitive resin layer described above.

[0052] In the photosensitive film for sandblasting of the present invention, the (A) urethane (meth)acrylates contained in the two photosensitive resin layers (the second photosensitive resin layer and the first photosensitive resin layer) may be the same or different. Furthermore, when one or both of the two photosensitive resin layers contain a plurality of types of urethane (meth)acrylate (A), only some of them may be of the same type.

[0053] Specific examples of the (B) photopolymerization initiator contained in the second photosensitive resin layer are the same as the specific examples of the (B) photopolymerization initiator contained in the first photosensitive resin layer described above.

[0054] In the photosensitive film for sandblasting of the present invention, the (B) photopolymerization initiators contained in the two photosensitive resin layers (the second photosensitive resin layer and the first photosensitive resin layer) may be the same or different. Furthermore, when one or both of the two photosensitive resin layers contain a plurality of types of (B) photopolymerization initiators, only some of them may be of the same type.

[0055] The (D) acrylic resin contained in the second photosensitive resin layer may be an acrylic polymer containing a (meth)acrylate as a main component and copolymerized with an ethylenically unsaturated carboxylic acid. Furthermore, the (D) acrylic resin contained in the second photosensitive resin layer may be a resin obtained by copolymerizing, in addition to the ethylenically unsaturated carboxylic acid, a monomer having a copolymerizable ethylenically unsaturated group.

[0056] Examples of (meth)acrylates 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, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-(dimethylamino)ethyl (meth)acrylate, 2-(diethylamino)ethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate.

[0057] Examples of ethylenically unsaturated carboxylic acids include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; and anhydrides and half esters thereof. Among these, monocarboxylic acids are preferred, with acrylic acid and methacrylic acid being particularly preferred.

[0058] Other copolymerizable monomers having an ethylenically unsaturated group include, for example, 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 methyl ether, and vinyl-n-butyl ether.

[0059] The second photosensitive resin layer may contain one type of (D) acrylic resin, or may contain two or more types of (D) acrylic resin.

[0060] The second photosensitive resin layer may contain components other than the above-mentioned components (A), (B) and (D). Examples of such components include photopolymerizable monomers, thermal polymerization inhibitors, plasticizers, dyes, pigments, photocoloring agents, photocolor-reducing agents, thermal color-development inhibitors, fillers, defoaming agents, flame retardants, adhesion promoters, leveling agents, release promoters, antioxidants, fragrances, heat curing agents, water repellents, and oil repellents.

[0061] The content of (A) urethane (meth)acrylate in the second photosensitive resin layer is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 20% by mass or more, and is preferably 90% by mass or less, more preferably 80% by mass or less, and particularly preferably 70% by mass or less.

[0062] The content of the (B) photopolymerization initiator in the second photosensitive resin layer is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and particularly preferably 0.5% by mass or more, and is preferably 15% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less.

[0063] The content of the (D) acrylic resin in the second photosensitive resin layer is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 15% by mass or more, and is preferably 70% by mass or less, more preferably 60% by mass or less, and particularly preferably 50% by mass or less.

[0064] The content of components other than components (A), (B), and (D) in the second photosensitive resin layer is preferably 1% by mass or more, more preferably 2% by mass or more, and particularly preferably 5% by mass or more, and is preferably 30% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less.

[0065] The content of each component in the second photosensitive resin layer mentioned above means the content in a dry state.

[0066] The method for forming the second photosensitive resin layer is not particularly limited. For example, the above-mentioned components are dissolved in a solvent to prepare a coating liquid for the second photosensitive resin layer, and the coating liquid for the second photosensitive resin layer is applied to a substrate for forming the second photosensitive resin layer, and the solvent is volatilized to form the second photosensitive resin layer. Examples of the solvent for the coating liquid for the second photosensitive resin layer include the same solvents as those for the coating liquid for the first photosensitive resin layer described above.

[0067] The thickness of the second photosensitive resin layer is preferably 1 μm or more, more preferably 2 μm or more, and particularly preferably 3 μm or more, and is preferably 40 μm or less, more preferably 35 μm or less, and particularly preferably 30 μm or less. If the thickness of the second photosensitive resin layer is less than 1 μm, the peeling time may be long when peeling off the resist, and if the thickness of the second photosensitive resin layer is more than 40 μm, the resolution during development may be deteriorated.

[0068] <Transparent film> The transparent film of the photosensitive film for sandblasting of the present invention is a film that transmits ultraviolet light.

[0069] Examples of materials that can be used to form the transparent film include polypropylene, polyester, and polyvinyl alcohol. Among these, polyester, especially polyethylene terephthalate, is desirable as a material for constructing transparent films because it has excellent lamination and peelability, light transmittance, refractive index, is inexpensive, does not easily become brittle, has excellent solvent resistance, and has high tensile strength.

[0070] The thickness of the transparent film is preferably 1 μm or more, more preferably 5 μm or more, and particularly preferably 12 μm or more, and is preferably 100 μm or less, more preferably 80 μm or less, and particularly preferably 50 μm or less.

[0071] <Release film> The release film of the photosensitive film for sandblasting of the present invention plays a role in protecting the surface of the photosensitive resin layer of the photosensitive film for sandblasting during storage until use.

[0072] Examples of materials constituting the release film include polyester films laminated with release agents, such as silicone, fluorine, long-chain alkyl acrylates, long-chain alkyl-modified polymers, and non-silicone compounds.

[0073] The thickness of the release film is preferably 10 μm or more, more preferably 15 μm or more, and particularly preferably 20 μm or more, and is preferably 150 μm or less, more preferably 120 μm or less, and particularly preferably 100 μm or less. If the thickness of the release film is less than 10 μm, problems such as wrinkles may occur during storage of the photosensitive film.If the thickness of the release film is more than 150 μm, when the photosensitive film is rolled, the roll diameter becomes large, which may result in poor handling and increased costs.

[0074] <Method for producing photosensitive film for sandblasting> Examples of methods for producing the photosensitive film for sandblasting 10 of the present invention as shown in FIG. 1 include the following methods 1 and 2.

[0075] (Method 1) A coating liquid for a first photosensitive resin layer is applied onto a transparent film 13 and dried to form a first photosensitive resin layer 11. Next, a coating liquid for a second photosensitive resin layer is applied onto the first photosensitive resin layer 11 and dried to form a second photosensitive resin layer 12. Next, a release film 14 is attached onto the second photosensitive resin layer 12.

[0076] (Method 2) A coating liquid for a first photosensitive resin layer is applied onto a transparent film 13 and dried to form a first photosensitive resin layer 11 (this is referred to as film A). A coating liquid for a second photosensitive resin layer is applied onto a release film 14 and dried to form a second photosensitive resin layer 12 (this is referred to as film B). Next, films A and B are attached together so that the first photosensitive resin layer 11 and the second photosensitive resin layer 12 are in contact with each other. [Example]

[0077] The present invention will be explained in more detail below by way of examples and comparative examples, but the present invention is not limited to these examples as long as it does not depart from the gist of the invention.

[0078] <Preparation of photosensitive film> Examples 1 to 9 The components shown below were mixed to obtain a coating liquid for a first photosensitive resin layer.

[0079] (A) Shiko (registered trademark) UV-2000B (manufactured by Mitsubishi Chemical Corporation, urethane acrylate): 32 parts by mass (B-1) 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer: 1.5 parts by mass (B-2) N,N,N',N'-tetraethyl-4,4'-diaminobenzophenone: 0.2 parts by mass (C) Cellulose acetate phthalate: 17 parts by mass (Photopolymerizable monomer) Pentaerythritol triacrylate: 6 parts by mass (Pigment) Phthalocyanine Green: 0.1 parts by weight (Solvent) Methyl ethyl ketone: 43.2 parts by mass

[0080] The components shown below were mixed to obtain a coating liquid for a second photosensitive resin layer.

[0081] (A) KAYARAD (registered trademark) UXF-4001-M35 (manufactured by Nippon Kayaku Co., Ltd., solid content 65% by mass): 30.7 parts (B-1) 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer: 1.5 parts by mass (B-2) N,N,N',N'-tetraethyl-4,4'-diaminobenzophenone: 0.2 parts by mass (D) Copolymer resin (mass average molecular weight 30,000) obtained by copolymerizing methyl methacrylate / n-butyl acrylate / methacrylic acid in a mass ratio of 64 / 15 / 21: 30 parts by mass (Photopolymerizable monomer) Pentaerythritol triacrylate: 6 parts by mass (Pigment) Phthalocyanine Green: 0.1 parts by weight (Solvent) Methyl ethyl ketone: 43.2 parts by mass

[0082] The first photosensitive resin coating liquid was applied onto a polyethylene terephthalate film (thickness: 25 μm, transparent film) using an applicator, and the film was dried at 80°C for 8 minutes to volatilize the solvent, thereby forming a first photosensitive resin layer having the thickness shown in Table 1 on the polyethylene terephthalate film.

[0083] Next, the coating liquid for the second photosensitive resin layer was applied onto the first photosensitive resin layer using an applicator, and dried at 80°C for 8 minutes to volatilize the solvent, thereby forming a second photosensitive resin layer having the thickness shown in Table 1 on the first photosensitive resin layer.

[0084] A silicone-coated polyethylene terephthalate film (product name: PET-75×1-A3, manufactured by Nippa Corporation, release film) was attached to the surface of the second photosensitive resin layer to obtain photosensitive films for sandblasting of Examples 1 to 9.

[0085] Comparative Example 1 The first photosensitive resin coating liquid was applied onto a polyethylene terephthalate film (25 μm thick, transparent film) using an applicator, and dried at 80°C for 8 minutes to volatilize the solvent, forming a 50 μm thick photosensitive resin layer on the polyethylene terephthalate film.

[0086] Next, a polyethylene film (product name: GF1, thickness 30 μm, manufactured by Tamapoly Co., Ltd.) was laminated on the photosensitive resin layer to obtain a photosensitive film for sandblasting of Comparative Example 1.

[0087] Comparative Example 2 The second photosensitive resin coating liquid was applied onto a polyethylene terephthalate film (25 μm thick, transparent film) using an applicator, and dried at 80°C for 8 minutes to volatilize the solvent, forming a 30 μm thick photosensitive resin layer on the polyethylene terephthalate film.

[0088] Next, a polyethylene film (product name: GF1, thickness 30 μm, manufactured by Tamapoly Co., Ltd.) was laminated on the photosensitive resin layer to obtain a photosensitive film for sandblasting of Comparative Example 2.

[0089] <Evaluation of resolution> After peeling off the polyethylene terephthalate film on the second photosensitive resin layer side of the photosensitive films for sandblasting in Examples 1 to 9, the photosensitive films for sandblasting were attached to a glass epoxy substrate measuring 100 x 100 mm and 0.8 mm thick. Similarly, after peeling off the polyethylene film from the photosensitive films for sandblasting of Comparative Examples 1 and 2, the photosensitive films for sandblasting were attached to the glass epoxy substrates.

[0090] Next, the photosensitive resin layer was exposed to actinic rays through a photomask having hole patterns with diameters of 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, and 120 μm. Next, the polyethylene terephthalate film (transparent film) was peeled off, and alkaline development was carried out with a 0.2% by mass aqueous solution of sodium carbonate to remove the photosensitive resin layer in the unexposed areas. The smallest hole pattern opened at this time is shown in Table 2.

[0091] <Sandblasting resistance evaluation> The photosensitive resin layer with the hole pattern formed was sandblasted for 10 minutes (spray pressure: 0.2 MPa) using a SiC abrasive (manufactured by Naniwa Kenma Kogyo Co., Ltd., product name: GC Micro Powder #1200) to form dimples in the glass epoxy substrate. The opening diameter of the hole pattern in the photosensitive resin layer became larger than before the sandblasting process.

[0092] The diameter of the openings in the glass epoxy substrate after sandblasting was measured in a hole pattern with a diameter of 120 μm (Table 1). The smaller the diameter, the higher the sandblasting resistance.

[0093] <Evaluation of Resist Stripping> The glass epoxy substrate with the photosensitive resin layer after sandblasting was immersed in a 3 mass % sodium hydroxide aqueous solution (80°C) to remove the resist.

[0094] The time required for the photosensitive resin layer to be completely removed (resist removal time) was measured (Table 1). In addition, the surface of the glass epoxy substrate after resist removal was observed to check for the presence or absence of resist residue (Table 1).

[0095] <Summary of evaluation results> As shown in Table 1, all of the photosensitive films for sandblasting of Examples 1 to 9 had good sandblasting resistance, the resist stripping time was short, and no residue was generated after the resist was stripped.

[0096] In particular, in Examples 2, 3, 7, and 8, in which the thickness of the first photosensitive resin layer was 25 μm or more and 70 μm or less and the thickness of the second photosensitive resin layer was 1 μm or more and 40 μm or less, the resolution, sandblasting resistance, resist stripping time, and post-resist stripping residue were all good.

[0097] On the other hand, the photosensitive film for sandblasting of Comparative Example 1 required a long time for resist stripping, and residues were generated after resist stripping, which was a problem. Furthermore, the photosensitive film for sandblasting of Comparative Example 2 had poor sandblasting resistance, and the opening in the glass epoxy substrate widened significantly, which was a problem.

[0098] [Table 1]

[0099] [Table 2] [Industrial Applicability]

[0100] The photosensitive film for sandblasting of the present invention is used in sandblasting of glass, stone, metal, plastic, ceramic, etc. [Explanation of symbols]

[0101] 10. Photosensitive film for sandblasting 11 First photosensitive resin layer 12 Second photosensitive resin layer 13 Transparent film 14 Release film

Claims

1. A photosensitive film for sandblasting having a photosensitive resin layer, characterized in that the photosensitive resin layer comprises a first photosensitive resin layer containing (A) a urethane (meth)acrylate, (B) a photopolymerization initiator, and (C) a cellulose derivative, and a second photosensitive resin layer containing (A) a urethane (meth)acrylate, (B) a photopolymerization initiator, and (D) an acrylic resin.

2. 2. The photosensitive film for sandblasting according to claim 1, comprising a transparent film, the first photosensitive resin layer, the second photosensitive resin layer, and a release film, in this order.

3. 3. The photosensitive film for sandblasting according to claim 1 or claim 2, wherein the thickness of the first photosensitive resin layer is 25 μm or more and 70 μm or less, and the thickness of the second photosensitive resin layer is 1 μm or more and 40 μm or less.

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