TWI687769B - Photo-sensitive resin composition for sandblasting and sandblasting process - Google Patents

Abstract

An object of the present invention is to provide a photosensitive resin composition for sand blasting that has high abrasion resistance and high adhesion to a workpiece, and a sand blasting method using the photosensitive resin composition for sand blasting.

The present invention relates to a photosensitive resin composition for sandblasting and a sandblasting method using the photosensitive resin composition for sandblasting, wherein the composition is characterized by containing (A) an alkali-soluble resin and (B) a photopolymerization initiator , (C) urethane (meth)acrylate compound, and (D) epoxy (meth)acrylate, preferably containing (D-1) monofunctional epoxy (meth)acrylate and/ Or (D-2) acid-modified epoxy (meth)acrylate as (D) epoxy (meth)acrylate.

Description

Photosensitive resin composition for sandblasting and sandblasting treatment method

The invention relates to a photosensitive resin composition for sandblasting and a sandblasting treatment method.

Conventionally, when cutting processed objects such as glass, stone, metal, plastic, ceramic, etc. to form a relief, sandblasting was used for processing. A photosensitive resin layer patterned by photolithography or the like is provided as a masking material on the object to be processed, and then sandblasting is performed by spraying abrasive to selectively cut the non-masking portion.

As a photosensitive resin composition that can be used as a masking material for such sandblasting, for example, it is usually a negative photosensitive resin containing an alkali-soluble resin, a urethane (meth)acrylate compound, and a photopolymerization initiator Composition. As the alkali-soluble resin, an alkali-soluble cellulose derivative or an acrylic resin containing a carboxyl group is used (for example, refer to Patent Documents 1 to 7).

Examples of the characteristics required for the photosensitive resin composition for sand blasting include high abrasion resistance, high density of processed objects such as glass, etc. Sex. In the conventional photosensitive resin composition, satisfying any one of the characteristics tends to sacrifice the other characteristic, making it difficult to produce a photosensitive resin composition satisfying both characteristics.

[Prior Art Literature] Patent Literature

[Patent Document 1] Japanese Patent No. 3449572

[Patent Document 2] Japanese Patent No. 3846958

[Patent Document 3] Japanese Patent Laid-Open No. 10-69851

[Patent Document 4] Japanese Unexamined Patent Publication No. 2012-27357

[Patent Document 5] Japanese Patent Application Publication No. 2013-156306

[Patent Document 6] International Publication No. 2014/200028 Brochure

[Patent Document 7] Japanese Patent Publication No. 2005-537514.

An object of the present invention is to provide a photosensitive resin composition for sand blasting that has high abrasion resistance and high adhesion to a workpiece, and a sand blasting method using the photosensitive resin composition for sand blasting.

The above problems can be solved by the following means.

(1) A photosensitive resin composition for sandblasting, characterized in that Contains (A) alkali-soluble resin, (B) photopolymerization initiator, (C) urethane (meth)acrylate compound, and (D) epoxy (meth)acrylate.

(2) The photosensitive resin composition for sandblasting of (1) above, which contains (D-1) monofunctional epoxy (meth)acrylate and/or (D-2) acid-modified epoxy (meth) Acrylic ester as (D) epoxy (meth)acrylate.

(3) The photosensitive resin composition for sandblasting of (1) above, which contains (D-1) monofunctional epoxy (meth)acrylate and (D-2) acid-modified epoxy (meth)acrylate As (D) epoxy (meth)acrylate.

(4) The photosensitive resin composition for sandblasting according to any one of (1) to (3) above, wherein (C) the urethane (meth)acrylate compound is such that (c1) has a polyvalent hydroxyl group The product of the reaction of the compound with (c2) polyisocyanate compound with terminal isocyanate group and (c3) the (meth)acrylate compound with hydroxyl group, wherein compound (c1) is 1,4-butanediol or poly Tetramethylene ether glycol.

(5) The photosensitive resin composition for sandblasting according to any one of (1) to (4) above, wherein (C) the urethane (meth)acrylate compound is (c1) having a polyhydroxy group The product of the reaction between the compound and the (c2) polyisocyanate compound having a terminal isocyanate group and the (c3) (meth)acrylate compound having a hydroxyl group, wherein the compound (c3) is 4-hydroxybutyl acrylate.

(6) The photosensitive resin composition for sandblasting according to any one of (1) to (5) above, wherein (D-1) the monofunctional epoxy (meth)acrylate is acrylic acid 2-hydroxy-3-benzene Propyloxypropyl ester.

(7) The photosensitive resin composition for sandblasting according to any one of (1) to (6) above, wherein (D-2) acid-modified epoxy (meth)acrylate is at least (d1) epoxy A resin, a compound obtained by reacting (d2) (meth)acrylic acid, and (d3) at least one compound selected from a carboxylic acid-containing compound and an anhydride of a carboxylic acid-containing compound.

(8) A sandblasting method, which includes: attaching a photosensitive resin layer composed of a photosensitive resin composition to the object to be processed and after exposure, rinsing the non-exposed portion with an alkali developing solution to form a resist on the object to be processed Etching the image, and then performing sandblasting to process the object to be processed; or, after exposing the photosensitive resin layer composed of the photosensitive resin composition, rinsing the non-exposed part with an alkali developer to form a resist image, The resist image is attached to the object to be processed, a resist image is formed on the object to be processed, and then sandblasting is performed to process the object to be processed; characterized in that the photosensitive resin composition used is ( 1) The photosensitive resin composition for sandblasting in any one of (7).

According to the photosensitive resin composition for sand blasting and sand blasting processing method of this invention, it is possible to coexist with the adhesiveness of a to-be-processed object and high abrasion resistance.

1‧‧‧Support

2‧‧‧ peeling layer

3‧‧‧Photosensitive resin layer

4‧‧‧covering film

[Fig. 1] A schematic cross-sectional view showing the configuration of a dry film.

[Fig. 2] A schematic cross-sectional view showing the configuration of a dry film.

[Best form for implementing the invention]

Hereinafter, the photosensitive resin composition for sand blasting of the present invention (hereinafter sometimes simply referred to as "photosensitive resin composition") will be described in detail.

The photosensitive resin composition of the present invention is characterized by comprising (A) alkali-soluble resin, (B) photopolymerization initiator, (C) urethane (meth)acrylate compound, and (D) epoxy (Meth)acrylate.

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

Examples of the alkali-soluble cellulose derivatives include cellulose acetate phthalate, hydroxypropyl methyl cellulose phthalate, hydroxypropyl methyl cellulose acetate phthalate, and hydroxypropyl succinate acetate. Methyl cellulose, etc.

As the acrylic resin containing a carboxyl group, an acrylic polymer obtained by copolymerizing an ethylenically unsaturated carboxylic acid with (meth)acrylate as a main component can be cited. In addition, other monomers having copolymerizable ethylenically unsaturated groups may also be copolymerized.

Examples of (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth) N-butyl 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, (meth)acrylic acid Glycerin, lauryl (meth)acrylate, tetrahydrofuranyl (meth)acrylate, 2-(dimethylamino)ethyl (meth)acrylate, 2-(diethylamine) (meth)acrylate Group) ethyl ester, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, etc. Furthermore, in the present invention, (meth)acrylate is a term collectively referred to as acrylate, methacrylate, and these mixtures.

As the ethylenically unsaturated carboxylic acid copolymerized with (meth)acrylate, monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, etc. are preferably used, and maleic acid, fumaric acid, itaconic acid, etc. may also be used. Dicarboxylic acids, or these anhydrides or half esters. Among them, acrylic acid and methacrylic acid are particularly preferred.

Examples of other monomers having a copolymerizable ethylenically unsaturated group include styrene, α-methylstyrene, p-methylstyrene, p-ethylstyrene, p-methoxystyrene, p-ethyl Oxystyrene, p-chlorostyrene, p-bromostyrene, (meth)acrylonitrile, (meth)acrylamide, diacetone acrylamide, vinyl toluene, vinyl acetate, vinyl n-butyl ether Wait.

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

In addition, (A) the mass average molecular weight of the alkali-soluble resin 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 the photosensitive resin composition of the present invention into a coating state. On the other hand, if it exceeds 200,000, there is a relative The solubility in alkaline developing solution tends to deteriorate.

Examples of the (B) photopolymerization initiator include benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Millerone), N,N'-tetra Ethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- Aromatic ketones such as (4-morpholinophenyl)-1-butanone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-acetone; 2 -Ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-benzoanthraquinone, 2-phenylanthraquinone, 2, 3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 2,3 -Quinones such as dimethylanthraquinone; benzoin ether compounds such as benzoin methyl ether, benzoin ether, benzoin phenyl ether, benzoin compounds such as benzoin, methyl benzoin, ethyl benzoin; benzoin dimethyl ketal, etc. Benzoyl derivatives, 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- (P-methoxyphenyl)-4,5-diphenylimidazole dimer and other 2,4,5-triarylimidazole dimer; 9-phenylacridine, 1,7-bis(9, 9'-acridinyl) acridine derivatives such as heptane; N-phenylglycine, N-phenylglycine derivatives, coumarin compounds, etc. The substituents of the two aryl groups of 2,4,5-triarylimidazole dimer in the 2,4,5-triarylimidazole dimer may be the same to provide a symmetric compound, or may be different to provide an asymmetric compound. In addition, the thioxanthone-based compound and the tertiary amine compound may be combined as in the combination of diethylthioxanthone and dimethylaminobenzoic acid. These can be used alone or in combination of two or more.

(C) Carbamate (meth)acrylate compounds include: (c3) a compound having a terminal isocyanate group and (c3) a hydroxyl group which reacts a compound having a polyvalent hydroxyl group and (c2) a polyisocyanate compound The product of the reaction of (meth)acrylate compounds.

(C1) Compounds having a polyhydric hydroxyl group include polyesters having a hydroxyl group, polyethers having a hydroxyl group, and the like.

Examples of the polyesters having a hydroxyl group include polyesters obtained by ring-opening polymerization of lactones, or polycarbonates, or ethylene glycol, propylene glycol, 1,4-butanediol, and diethylene glycol. , Polyethylene glycol, triethylene glycol, dipropylene glycol and other alkylene glycols, and maleic acid, fumaric acid, glutaric acid, adipic acid and other dicarboxylic acids and polycondensation reaction of polyesters. Specific examples of lactones include δ-valerolactone, ε-caprolactone, β-propiolactone, α-methyl-β-propiolactone, and β-methyl-β-propiolactone. , Α,α-dimethyl-β-propiolactone, β,β-dimethyl-β-propiolactone, etc. In addition, specific examples of the polycarbonates include reaction products of diols such as bisphenol A, hydroquinone, and dihydroxycyclohexanone, and carbonyl compounds such as diphenyl carbonate, carbonyl chloride, and succinic anhydride. .

In addition, specific examples of polyethers having a hydroxyl group include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and polypentamethylene ether glycol. Among them, (c1) the compound having a polyhydric hydroxyl group is preferably 1,4-butanediol or polytetramethylene ether glycol, which further improves abrasion resistance and adhesion to glass after development.

Examples of (c2) polyvalent isocyanate compounds include dimethylene diisocyanate, trimethylene diisocyanate, and tetramethylene. Methyl 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-triisocyanate Aliphatic or alicyclic diisocyanate compounds such as methylhexane diisocyanate, decamethylene diisocyanate, and isophorone diisocyanate, which can be used alone or in a mixture of two or more.

Examples of (c3) (meth)acrylate compounds having a hydroxyl group include hydroxymethyl acrylate, hydroxymethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylic acid 3-Hydroxypropyl ester, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, etc. In addition, the addition of 1 to 10 mol of ε-caprolactone to this may be mentioned. Ester-derived compounds. Among them, (c3) the (meth)acrylate compound having a hydroxyl group is preferably 4-hydroxybutyl acrylate, and the abrasion resistance and adhesion to glass after development are further improved.

The (C) urethane (meth)acrylate compound related to the present invention may contain a carboxyl group. The inclusion of a carboxyl group tends to increase the solubility in the developing solution. The carboxyl group-containing (C) carbamate (meth)acrylate compound can be obtained by the following method: First, the diisocyanate compound is reacted with the diol compound having a carboxyl group so that the isocyanate group remains at both ends, and then The (meth)acrylate compound having a hydroxyl group is reacted with the terminal isocyanate group of the reactant.

(D) Epoxy (meth) acrylate based at least epoxy compound It is obtained by reaction with (meth)acrylic acid. In the present invention, (meth)acrylic acid is a term collectively referring to acrylic acid, methacrylic acid, and mixtures of these. The epoxy compound may be an aromatic or aliphatic compound having an epoxy group. Examples of epoxy (meth)acrylates include CN104, CN104A80, CN104B80, CN104D80, CN111US, CN112C60, CN113D70, CN115, CN116, CN117, CN118, CN119, CN120, CN121, CN131B, CN132, manufactured by Sartomer. CN133, CN136, CN137, CN151, CN152, EBECRYL (registered trademark) 600, EBECRYL (registered trademark) 605, EBECRYL (registered trademark) 645, EBECRYL (registered trademark) 648, EBECRYL (registered trademark) 860 manufactured by DAICEL-ALLNEX , EBECRYL (registered trademark) 1606, EBECRYL (registered trademark) 3500, EBECRYL (registered trademark) 3603, EBECRYL (registered trademark) 3700, EBECRYL (registered trademark) 3701, EBECRYL (registered trademark) 3702, EBECRYL (registered trademark) 3703, EBECRYL (registered trademark) 3708, EBECRYL (registered trademark) 6040, EPOXYESTERM-600A, EPOXYESTER 40EM, EPOXYESTER 70PA, EPOXYESTER 200PA, EPOXYESTER 80MFA, EPOXYESTER 3002M, EPOXYESTER 1600A, EPOXYESTER 3000M, EPOXYESTER 3000A, EPOXYESTER 3000A, OX EPOXYESTER 400EA and so on.

When containing (D-1) monofunctional epoxy (meth)acrylate and/or (D-2) acid-modified epoxy (meth)acrylate as (D) epoxy (meth)acrylate The following effects can be obtained: the resolution of the photosensitive resin layer is improved, and even for a finer image, the cured photosensitive resin layer It is also difficult to peel off the object. Especially when both (D-1) monofunctional epoxy (meth)acrylate and (D-2) acid-modified epoxy (meth)acrylate are contained as (D) epoxy (meth)acrylic acid In the case of an ester, the following effects are further improved: the effect of improving the resolution of the photosensitive resin layer; and the effect of hardly peeling off the cured object of the cured photosensitive resin layer even for a finer image.

(D-1) Monofunctional epoxy (meth)acrylate refers to a compound in which (D) epoxy (meth)acrylate has one (meth)acrylate group. For example, 2-hydroxy-3-phenyloxypropyl (meth)acrylate, 2-hydroxy-3-butyloxypropyl (meth)acrylate, 2-hydroxy-(meth)acrylate can be mentioned. 3-(2-ethylhexyloxy)propyl ester, (meth)acrylic acid 2-hydroxy-3-octyloxypropyl ester, (meth)acrylic acid 2-hydroxy-3-(2-methyloctyl Oxy)propyl ester, (meth)acrylic acid 2-hydroxy-3-methyloxypropyl ester, (meth)acrylic acid 2-hydroxy-3-p-methylphenyloxypropyl ester, (meth)acrylic acid 2-hydroxy-3-stearyloxypropyl ester, etc. Among them, (D-1) monofunctional epoxy (meth)acrylate is preferably 2-hydroxy-3-phenyloxypropyl acrylate, and the abrasion resistance and adhesion to glass after development are further improved .

Examples of (D-2) acid-modified epoxy acrylate include at least (d1) epoxy resin, (d2) (meth)acrylic acid, and (d3) selected from carboxylic acid-containing compounds and carboxylic acid-containing A compound formed by reacting at least one compound of the compound's anhydride. This compound can be synthesized, for example, by adding (meth)acrylic acid (d2) to the epoxy resin (d1) and then adding the compound (d3). When acrylic acid and methacrylic acid are compared, acrylic acid is preferred because of its good abrasion resistance.

Examples of (d1) epoxy resins include phenol novolac type, cresol novolac type, bisphenol A type, bisphenol F type, triphenol type, tetraphenol type, phenol-xylylene type, and glycidyl ether type. Or these halogenated epoxy resins.

As the carboxylic acid-containing compound, maleic acid, succinic acid, itaconic acid, phthalic acid, and tetrahydrophthalic acid can be used ), Hexahydrophthalic Acid, Endomethylenetetrahydrophthalic Acid, Methylendomethylenetetrahydrophthalic Acid, Chlorendic Acid Acid), Methyltetrahydrophthalic Acid, Trimellitic Acid, Pyromellitic Acid, Benzophenonetetracarboxylic Acid, etc. Examples of the anhydride of the carboxylic acid-containing compound include the above-mentioned anhydrides of the carboxylic acid-containing compound.

(D-2) The acid value of the acid-modified epoxy acrylate affects the alkali developing speed, the resist peeling speed, the flexibility of the photosensitive resin layer, and the like. The acid value is preferably 40 to 120 mgKOH/g. If the acid value is less than 40 mgKOH/g, the alkali development time tends to become longer. On the other hand, if the acid value exceeds 120 mgKOH/g, the adhesion to the substrate to be processed may be deteriorated.

The (D-2) acid-modified epoxy acrylate preferably has a mass average molecular weight of 3,000 to 15,000. If the mass average molecular weight is less than 3,000, it may be difficult to form the photosensitive resin composition before curing into Film state. On the other hand, if it exceeds 15,000, the solubility with respect to the alkali developing solution tends to be poor.

The photosensitive resin layer of the present invention may contain components other than the components (A) to (D) as necessary. Examples of such components include photopolymerizable monomers, solvents, thermal polymerization inhibitors, plasticizers, colorants (dyes, pigments), photochromic agents, photochromic agents, thermochromic inhibitors, fillers, Defoamers, flame retardants, tackifiers, leveling agents, peeling accelerators, antioxidants, fragrances, thermosetting agents, water repellents and oil repellents, etc., can contain about 0.01 to 20% by mass, respectively. These components can be used alone or in combination of two or more.

The photopolymerizable monomer is (C) urethane (meth) acrylate compound and (D) epoxy (meth) acrylate compound and has at least one polymerizable ethylenically unsaturated group in the molecule compound of. For example, a compound obtained by reacting an α,β-unsaturated carboxylic acid with a polyhydric alcohol, a bisphenol A-based (meth)acrylate compound, an α,β-unsaturated carboxylic acid and a glycidyl group-containing compound Compound obtained by the reaction of the compound, alkyl (meth)acrylate, ethylene oxide or propylene oxide modified (meth)acrylate, etc. These photopolymerizable compounds can be used alone or in combination of two or more.

In addition, examples of the photopolymerizable monomer include trimethylolpropane tri(meth)acrylate, di(trimethylolpropane)tetra(meth)acrylate, and pentaerythritol tri(meth)acrylic acid. Ester, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane triglycidyl ether tri(meth) Base) acrylate, etc.

In the photosensitive resin composition of the present invention, the blending amount of component (A) is preferably 25 to 70% by mass relative to the total amount of components (A), (B), (C), and (D). It is more preferably 40 to 60% by mass. If the blending amount of the component (A) is less than 25% by mass, the coating property may deteriorate or the alkali developability may decrease. If the blending amount of the component (A) exceeds 70% by mass, the abrasion resistance may decrease.

The blending amount of the component (B) is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass relative to the total amount of the components (A), (B), (C), and (D). If the blending amount of the component (B) is less than 0.1% by mass, the photopolymerizability tends to be insufficient. On the other hand, if it exceeds 10% by mass, the absorption on the surface of the photosensitive resin layer during exposure increases, and the photopolymerization inside the photosensitive resin layer tends to be insufficient.

The blending amount of the component (C) is preferably 10 to 60% by mass, and more preferably 30 to 50% by mass relative to the total amount of the components (A), (B), (C), and (D). If the blending amount of the component (C) is less than 10% by mass, the abrasion resistance tends to decrease, or the light sensitivity tends to be insufficient. On the other hand, if it exceeds 60% by mass, the adhesiveness of the film surface tends to increase excessively.

The blending amount of the component (D) is preferably 1 to 30% by mass, more preferably 3 to 20% by mass relative to the total amount of the components (A), (B), (C), and (D). If the blending amount of the component (D) is less than 1% by mass, the cured film tends to swell during alkaline development, and the photosensitive resin layer cured during alkaline development tends to peel off easily. On the other hand, if it exceeds 30% by mass, the wear resistance tends to decrease.

When components (D-1) and (D-2) are contained as component (D), the blending amount of (D-1) relative to the total amount of components (D-1) and (D-2) It is more preferably 10-50% by mass. If the blending amount of the component (D-1) is less than 10% by mass, compared with the case where the component (D-1) is not included, the wear resistance may not change, and if it exceeds 50% by mass, there may be a film The tendency for surface adhesion to increase excessively.

As shown in FIG. 1, the photosensitive resin composition of the present invention may be configured as a dry film in which a support 1, a photosensitive resin layer 3, and a cover film 4 are laminated. In addition, as shown in FIG. 2, a dry film in which the support 1, the release layer 2, the photosensitive resin layer 3, and the cover film 4 are laminated may be used. In the configuration of the dry film of FIGS. 1 and 2, the cover film 4 may be omitted.

As the support 1, a transparent film that transmits active light is preferred. In terms of the thickness of the support 1, a thin support is preferred because of less light refraction, and a thick support is preferred because of excellent coating stability, preferably 10 to 100 μm. Examples of such films include films of polyethylene terephthalate and polycarbonate.

Examples of the peeling layer 2 include polyvinyl alcohol, alkali-soluble resin, mixture of alkali-soluble resin and urethane (meth)acrylate, mixture of alkali-soluble resin and epoxy (meth)acrylate, alkali A mixture of soluble resin and urethane (meth)acrylate and epoxy (meth)acrylate. The release layer 2 may or may not impart photopolymerizability. However, since it can be removed by alkali imaging, it is more preferable not to impart photopolymerizability.

As the cover film 4, as long as it can peel off uncured or cured The photosensitive resin layer may be sufficient, and a resin with high releasability is used. For example, a polyethylene film, a polypropylene film, etc. may be mentioned, and a release agent such as silicone may be coated on these films. The photosensitive resin layer 3 is a layer containing a photosensitive resin composition.

The sandblasting method of the present invention includes a direct method and an indirect method. In the direct method and the indirect method, a photosensitive resin composition made into a dry film can be used. Examples of the object to be processed include glass, stone, metal, plastic, and ceramics.

In the direct method, first, the cover film 4 of the dry film is removed, and then the object to be processed is attached by a laminator or the like with the photosensitive resin layer 3 in contact. Next, after exposing with a masking film in accordance with the relief image from the side of the support 1 with active light, the support 1 is peeled off. Alternatively, when resolution is required, after the support 1 is peeled off, exposure is performed using active light through a masking film that matches the relief image. The exposed portion of the photosensitive resin layer 3 is cured through polymerization. Next, the non-exposed part is rinsed with an alkali developing solution and washed with water to form a resist image. Next, sandblasting is performed to process the object.

In the indirect method, it is mostly used when a dry film cannot be laminated on the object to be processed or when proximity exposure cannot be performed. First, after exposing the dry film with active light through a masking film consistent with the relief image, the support 1 is peeled off. Alternatively, when resolution is required, after the support 1 is peeled off, exposure is performed using active light through a masking film that matches the relief image. The exposed portion of the photosensitive resin layer 3 is cured through polymerization. Next, the non-exposed part is rinsed with an alkali developing solution and washed with water. by This forms a resist image on the cover film 4. The resist image is attached to the object to be processed using an aqueous adhesive or the like. Next, the cover film 4 is peeled off to form a resist image on the object. Next, sandblasting is performed to process the object.

The thickness of the photosensitive resin layer is preferably 10 to 150 μm, and more preferably 20 to 120 μm. If the thickness of the photosensitive resin layer is too large, problems such as reduced resolution and high cost are likely to occur. Conversely, if it is too thin, the wear resistance tends to decrease.

[Example]

Hereinafter, the present invention will be described in more detail through examples, but the present invention is not limited to these examples.

(Examples 1 to 12, Comparative Examples 1 to 3)

The components shown in Table 1 and Table 2 were mixed to obtain a photosensitive resin composition. In addition, the unit of the blending amount of each component in Table 1 and Table 2 represents a mass part. Using a wire bar, the obtained coating liquid was coated on a polyethylene terephthalate (PET) film (support 1, trade name: R310, 25 μm thick, manufactured by Mitsubishi Resin Co., Ltd.), and dried at 80° C. 8 The solvent component was evaporated in minutes to obtain a dried resin layer 3 (dry film thickness: 50 μm) containing the photosensitive resin compositions of Examples 1 to 12 and Comparative Examples 1 to 3 on one side of the PET film. membrane.

[Table 1]

In Table 1 and Table 2, each component is as follows.

<ingredient (A)>

(A-1) Combine methyl methacrylate/n-butyl acrylate/methacrylic acid Copolymer resin obtained by copolymerization with mass ratio 64/15/21 (mass average molecular weight 30,000)

(A-2) A copolymer resin (mass average molecular weight 70,000) obtained by copolymerizing methyl methacrylate/n-butyl acrylate/methacrylic acid at a mass ratio of 58/15/27.

<ingredient (B)>

(B-1) 2-(2’-chlorophenyl)-4,5-diphenylimidazole dimer

(B-2) 4,4'-bis(diethylamino)benzophenone.

<ingredient (C)>

(C-1) KAYARAD (registered trademark) UXF-4001-M35 (manufactured by Nippon Kayaku Co., Ltd.) 65% solid content

(C-2) Art Resin (registered trademark) UN-2600 (manufactured by Negami Industrial Co., Ltd.)

(C-3) Urethane acrylate obtained by reacting polytetramethylene ether glycol 2000 (manufactured by Mitsubishi Chemical Corporation) with isophorone diisocyanate at a ratio of 5:10 moles to obtain a compound , And then react 4-hydroxybutyl acrylate with the terminal isocyanate of the compound at a ratio of 2 moles

(C-4) Urethane acrylate obtained as follows: Polyethylene glycol (average molecular weight 360-440) and isophorone diisocyanate are reacted at a ratio of 5:10 moles to obtain a compound, which is then 2 The molar ratio reacts 4-hydroxybutyl acrylate with the terminal isocyanate of the compound

(C-5) Urethane acrylate obtained as follows: polytetramethylene Ether ether glycol 1000 (manufactured by Mitsubishi Chemical Corporation) reacts with isophorone diisocyanate at a ratio of 5:10 mol to obtain a compound, and then reacts hydroxyethyl acrylate with the terminal isocyanate of the compound at a ratio of 2 mol

(C-6) The urethane acrylate obtained as follows: Polyethylene glycol (average molecular weight 360 to 440) and isophorone diisocyanate are reacted at a ratio of 5:10 moles to obtain a compound, and then 2 The molar ratio allows hydroxyethyl acrylate to react with the terminal isocyanate of the compound.

<ingredient (D)>

(D-1-a) 2-Hydroxy-3-phenyloxypropyl acrylate

(D-1-b) 2-Hydroxy-3-butyloxypropyl acrylate

(D-2-a) Acid-modified epoxy acrylate KAYARAD (registered trademark) ZAR-1035 (manufactured by Nippon Kayaku Co., Ltd.) 65% solid content

(D-2-b) acid-modified epoxy acrylate KAYARAD (registered trademark) UXE-3024 (manufactured by Nippon Kayaku) 65% solid content

(D-2-c) A bisphenol A epoxy compound (JER828, Mitsubishi Chemical Co., Ltd.) as an epoxy resin, and a compound obtained by reacting succinic acid and acrylic acid in a 1:2:2 molar ratio (D-2 -d) A bisphenol A epoxy compound (JER828, Mitsubishi Chemical Co., Ltd.) as an epoxy resin, and a compound obtained by reacting succinic acid and methacrylic acid in a 1:2:2 molar ratio.

<Photopolymerizable monomer>

(E-1) Pentaerythritol triacrylate

(E-2) 2,2-bis[4-(methacryloxypolyethoxy]phenyl]propane (EO 10mol), epoxidized bisphenol A dimethacrylate, NK ESTER BPE-500 (Produced by Shin Nakamura Chemical Industry Corporation).

The dry films of Examples 1 to 12 and Comparative Examples 1 to 3 were attached to a glass plate with a thickness of 3 mm in such a manner that the photosensitive resin layer was in contact with the glass plate (to-be-processed object), followed by 50, 70, 100, 150, 200 μm line and space (line and space) and 3cm × 3cm square pattern photomask for exposure. Next, the PET film was peeled off, and alkali development was performed with a 1.0% by mass sodium carbonate aqueous solution, and the photosensitive resin layer in the non-exposed part was removed. At this time, for those containing (D-1) monofunctional epoxy (meth)acrylate and (D-2) acid-modified epoxy (meth)acrylate as (D) epoxy (meth)acrylate In Examples 3 to 12, lines and pitches of 70 μm can be developed. For lines of 70 μm or more, the cured photosensitive resin layer is not peeled off from the object to be processed. In addition, Example 1 containing only (D-1) monofunctional epoxy (meth)acrylate as (D) epoxy (meth)acrylate and (D-2) acid-modified epoxy ( Methacrylate as (D) epoxy (meth)acrylate in Example 2 can develop a line and a pitch of 100 μm. For lines of 100 μm or more, the cured photosensitive resin layer is not peeled off from the object . That is, in Examples 1 to 12, the adhesion between the glass plate and the photosensitive resin layer is excellent. In addition, the photosensitive resin layer containing both (D-1) and (D-2) can form a thinner line.

On the other hand, in Comparative Example 1, a line and a pitch of 200 μm can be developed, but the line of 150 μm and the line below the pitch are peeled off, which shows that the adhesion is poor. In addition, for Comparative Examples 2 and 3, 100 μm can be developed For the line and the pitch, for a line of 100 μm or more, the cured photosensitive resin layer is not peeled off from the object to be processed, and the adhesion between the glass plate and the photosensitive resin layer is good.

Next, using silicon carbide powder (manufactured by NANIWA ABRASIVE MFG., GC#1200), sandblasting was performed to confirm the cutting depth of the glass around the 3 cm×3 cm square pattern. In Examples 1 to 12, it was possible to cut to a depth of 0.7 mm or more, and it was confirmed that it had good wear resistance. On the other hand, in Comparative Examples 2 and 3, the depth direction can only be cut to 0.1 mm, and if it exceeds 0.1 mm in the depth direction, the photosensitive resin layer disappears, and the wear resistance is insufficient. Thus, although the photosensitive resin compositions of Comparative Examples 2 and 3 have good adhesion to glass, the abrasion resistance is insufficient and cannot be used as a photosensitive resin composition for sandblasting.

Next, the blasting treatment is performed deeper. If Examples 5 to 8 are compared, it can be cut to 1.0 mm in Example 5, it can be cut to 0.8 mm in Examples 6 and 7, and it can be cut to 0.7 mm in Example 8. Example 5 using component (C-3) in which (c1) the compound having a polyhydroxy group is polytetramethylene ether glycol and (c3) the (meth)acrylate compound having a hydroxyl group is 4-hydroxybutyl acrylate The wear resistance is the best, followed by Example 7 using (c1) a compound having a polyhydroxy group as a component of polytetramethylene ether glycol (C-5) and using (c3) a (meth) group having a hydroxyl group Example 6 where the acrylate compound is 4-hydroxybutyl acrylate (C-4) is the second best.

Next, if Example 5 is compared with Example 9, it can be cut to 1.0 mm in Example 5 and can be cut to 0.8mm. (D-1) Example 5 where the monofunctional epoxy (meth)acrylate is 2-hydroxy-3-phenyloxypropyl acrylate has good abrasion resistance.

Next, if Example 11 is compared with Example 12, it can be cut to 1.0 mm in Example 11 and can be cut to 0.7 mm in Example 12. (D-2) The acid-modified epoxy (meth)acrylate is a compound obtained by reacting acrylic acid, and Example 11 has good abrasion resistance.

[Industry availability]

The invention can be used for processing using sandblasting.

1‧‧‧Support

3‧‧‧Photosensitive resin layer

4‧‧‧covering film

Claims (8)

A photosensitive resin composition for sand blasting, characterized by comprising (A) alkali-soluble resin, (B) photopolymerization initiator, (C) urethane (meth)acrylate compound, and (D) ring Oxygen (meth)acrylate. The photosensitive resin composition for sandblasting according to claim 1, which contains (D-1) monofunctional epoxy (meth)acrylate and/or (D-2) acid-modified epoxy (meth)acrylate as (D) Epoxy (meth)acrylate. The photosensitive resin composition for sandblasting according to claim 1, which contains (D-1) monofunctional epoxy (meth)acrylate and (D-2) acid-modified epoxy (meth)acrylate as (D ) Epoxy (meth) acrylate. The photosensitive resin composition for sandblasting according to any one of claims 1 to 3, wherein the (C) urethane (meth)acrylate compound is a compound having (c1) a polyhydroxy group and (c2) The product of the reaction of a compound having a terminal isocyanate group reacted with a polyisocyanate compound and (c3) a (meth)acrylate compound having a hydroxyl group, wherein the compound (c1) is 1,4-butanediol or polytetramethylene ether di alcohol. The photosensitive resin composition for sand blasting according to any one of claims 1 to 3, wherein the (C) urethane (meth)acrylate compound is a compound having (c1) a polyhydroxy group and (c2) The product of the reaction of a compound having a terminal isocyanate group reacted with a polyisocyanate compound and (c3) a (meth)acrylate compound having a hydroxyl group, wherein the compound (c3) is 4-hydroxybutyl acrylate. The photosensitive resin composition for sandblasting according to claim 2 or 3, wherein (D-1) the monofunctional epoxy (meth)acrylate is acrylic acid 2-hydroxy-3- Phenyloxypropyl ester. The photosensitive resin composition according to claim 2 or 3, wherein (D-2) acid-modified epoxy (meth)acrylate is at least (d1) epoxy resin and (d2) (meth)acrylic acid A compound obtained by reacting (d3) with at least one compound selected from carboxylic acid-containing compounds and anhydrides of carboxylic acid-containing compounds. A sandblasting method comprising: attaching a photosensitive resin layer composed of a photosensitive resin composition to an object to be processed and after exposure, rinsing the non-exposed portion with an alkali developing solution to form a resist pattern on the object to be processed The image is then subjected to sandblasting to process the object to be processed; or, after exposing the photosensitive resin layer composed of the photosensitive resin composition, the non-exposed portion is rinsed with an alkali developer to form a resist image, and the The resist image is attached to the object to be processed, a resist image is formed on the object to be processed, and then sandblasting is performed to process the object to be processed; characterized in that the photosensitive resin composition used is claim 1 The photosensitive resin composition for sandblasting according to any one of ~7.

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