CN106154749B - Photosensitive resin composition for sandblasting and sandblasting method - Google Patents
Photosensitive resin composition for sandblasting and sandblasting method Download PDFInfo
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- CN106154749B CN106154749B CN201610311217.3A CN201610311217A CN106154749B CN 106154749 B CN106154749 B CN 106154749B CN 201610311217 A CN201610311217 A CN 201610311217A CN 106154749 B CN106154749 B CN 106154749B
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24C—ABRASIVE OR RELATED BLASTING WITH PARTICULATE MATERIAL
- B24C1/00—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods
- B24C1/10—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods for compacting surfaces, e.g. shot-peening
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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- Mechanical Engineering (AREA)
- Materials For Photolithography (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
本发明的课题在于提供：在具有高耐磨性的同时与被处理物的粘附性高的喷砂用感光性树脂组合物，和使用该喷砂用感光性树脂组合物的喷砂处理方法。本发明涉及喷砂用感光性树脂组合物和使用该喷砂用感光性树脂组合物的喷砂处理方法，所述组合物的特征在于，含有(A)碱可溶性树脂、(B)光聚合引发剂、(C)氨基甲酸酯(甲基)丙烯酸酯化合物和(D)环氧(甲基)丙烯酸酯，优选含有(D‑1)单官能环氧(甲基)丙烯酸酯和/或(D‑2)酸改性环氧(甲基)丙烯酸酯作为(D)环氧(甲基)丙烯酸酯。
An object of the present invention is to provide a photosensitive resin composition for sandblasting having high abrasion resistance and high adhesion to an object to be treated, and a sandblasting method using the photosensitive resin composition for sandblasting . 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, (B) a photopolymerization initiator agent, (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
Technical Field
The present invention relates to a photosensitive resin composition for sandblasting and a sandblasting method.
Background
Conventionally, when a material to be processed such as glass, stone, metal, plastic, or ceramic is cut to form a relief, the material is processed by sandblasting. A photosensitive resin layer patterned by photolithography or the like is provided as a masking material on an object to be processed, and then sandblast processing is performed in which an abrasive is sprayed to selectively cut off a non-masked portion.
As a photosensitive resin composition usable as such a masking material for sandblasting, for example, a negative photosensitive resin composition containing an alkali-soluble resin, a urethane (meth) acrylate compound and a photopolymerization initiator is generally used. As the alkali-soluble resin, an alkali-soluble cellulose derivative or a carboxyl group-containing acrylic resin is used (for example, see patent documents 1 to 7).
Examples of the properties required for the photosensitive resin composition for sandblasting include high abrasion resistance and high adhesion to an object to be treated such as glass. In the conventional photosensitive resin compositions, when one property is satisfied, the other property tends to be sacrificed, and it is difficult to prepare a photosensitive resin composition satisfying both properties.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 3449572
Patent document 2: japanese patent No. 3846958
Patent document 3: japanese laid-open patent publication No. 10-69851
Patent document 4: japanese patent laid-open No. 2012 and 27357
Patent document 5: japanese patent laid-open publication No. 2013-156306
Patent document 6: international publication No. 2014/200028 pamphlet
Patent document 7: japanese patent application laid-open No. 2005-537514.
Disclosure of Invention
Problems to be solved by the invention
The subject of the invention is to provide: a photosensitive resin composition for sandblasting having high abrasion resistance and high adhesion to an object to be treated, and a sandblasting method using the photosensitive resin composition for sandblasting.
Means for solving the problems
The above problems can be solved by the following means.
(1) The photosensitive resin composition for sandblasting is characterized by containing (A) an alkali-soluble resin, (B) a photopolymerization initiator, (C) a urethane (meth) acrylate compound and (D) an epoxy (meth) acrylate.
(2) The photosensitive resin composition for sandblasting described in the above (1), which comprises (D-1) a monofunctional epoxy (meth) acrylate and/or (D-2) an acid-modified epoxy (meth) acrylate as the (D) epoxy (meth) acrylate.
(3) The photosensitive resin composition for sandblasting described in the above (1), which comprises (D-1) a monofunctional epoxy (meth) acrylate and (D-2) an acid-modified epoxy (meth) acrylate as the (D) epoxy (meth) acrylate.
(4) The photosensitive resin composition for sandblasting as described in any one of (1) to (3), wherein the urethane (meth) acrylate compound (C) is: a product obtained by reacting (c1) a compound having a polyvalent hydroxyl group with (c2) a polyvalent isocyanate compound to obtain a compound having a terminal isocyanate group with (c3) a (meth) acrylate compound having a hydroxyl group, wherein the compound (c1) is 1, 4-butanediol or polytetramethylene ether glycol.
(5) The photosensitive resin composition for sandblasting as described in any one of (1) to (4), wherein the urethane (meth) acrylate compound (C) is a product obtained by reacting a compound having a terminal isocyanate group obtained by reacting a compound having a polyvalent hydroxyl group (C1) with a polyvalent isocyanate compound (C2), and a (meth) acrylate compound having a hydroxyl group (C3), wherein the compound (C3) is 4-hydroxybutyl acrylate.
(6) The photosensitive resin composition for sandblasting as described in any one of (1) to (5), wherein the (D-1) monofunctional epoxy (meth) acrylate is 2-hydroxy-3-phenoxypropyl acrylate.
(7) The photosensitive resin composition for sandblasting as described in any one of (1) to (6), wherein the (D-2) acid-modified epoxy (meth) acrylate is a compound obtained by reacting at least (D1) an epoxy resin, (D2) (meth) acrylic acid and (D3) at least 1 compound selected from a carboxylic acid-containing compound and an anhydride of the carboxylic acid-containing compound.
(8) A method of grit blasting comprising: applying a photosensitive resin layer comprising a photosensitive resin composition to an object to be treated, exposing the photosensitive resin layer to light, washing a non-exposed portion with an alkali developer to form a resist image on the object, and then performing a blast treatment to process the object; or, after exposing a photosensitive resin layer composed of a photosensitive resin composition to light, washing a non-exposed portion with an alkali developer to form a resist image, attaching the resist image to an object to be treated to form a resist image on the object to be treated, and then performing sandblasting to process the object to be treated;
characterized in that the photosensitive resin composition used is the photosensitive resin composition for sandblasting described in any one of (1) to (7).
Effects of the invention
According to the photosensitive resin composition for sandblasting and the sandblasting method of the present invention, both adhesiveness to the object to be treated and high abrasion resistance can be achieved.
Drawings
Fig. 1 is a schematic sectional view showing the constitution of a dry film.
Fig. 2 is a schematic sectional view showing the constitution of the dry film.
Detailed Description
The photosensitive resin composition for sandblasting of the present invention (hereinafter, may be simply referred to as "photosensitive resin composition") will be described in detail below.
The photosensitive resin composition of the present invention is characterized by containing (a) an alkali-soluble resin, (B) a photopolymerization initiator, (C) a urethane (meth) acrylate compound, and (D) an epoxy (meth) acrylate.
Examples of the alkali-soluble resin (a) include alkali-soluble cellulose derivatives and carboxyl group-containing acrylic resins.
Examples of the alkali-soluble cellulose derivative include cellulose acetate phthalate, hydroxypropylmethylcellulose acetate succinate and the like.
Examples of the carboxyl group-containing acrylic resin include acrylic polymers containing a (meth) acrylate as a main component and obtained by copolymerizing an ethylenically unsaturated carboxylic acid with the acrylic polymer. In addition, other monomers having copolymerizable ethylenically unsaturated groups may also be copolymerized.
Examples of the (meth) acrylic acid ester 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, tetrahydrofuryl (meth) acrylate, 2- (dimethylamino) ethyl (meth) acrylate, 2- (diethylamino) ethyl (meth) acrylate, 2,2, 2-trifluoroethyl (meth) acrylate, and mixtures thereof, 2,2,3, 3-tetrafluoropropyl (meth) acrylate, and the like. It is to be noted that, in the present invention, (meth) acrylate is a term collectively referred to as acrylate, methacrylate and a mixture thereof.
As the ethylenically unsaturated carboxylic acid to be copolymerized with the (meth) acrylic ester, 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, or anhydrides or half-esters thereof may also be used. Among them, acrylic acid and methacrylic acid are particularly preferable.
Examples of the other monomer having a copolymerizable ethylenically unsaturated group include styrene, α -methylstyrene, p-ethylstyrene, p-methoxystyrene, p-ethoxystyrene, p-chlorostyrene, p-bromostyrene, (meth) acrylonitrile, (meth) acrylamide, diacetone acrylamide, vinyltoluene, vinyl acetate, and vinyl n-butyl ether.
(A) The acid value of the alkali-soluble resin is preferably 30 to 500mgKOH/g, more preferably 100 to 300 mgKOH/g. When the acid value is less than 30mgKOH/g, the alkali development time tends to be long, while when it exceeds 500mgKOH/g, the abrasion resistance may be lowered.
The alkali-soluble resin (A) preferably has a mass average molecular weight of 10,000 to 200,000, more preferably 10,000 to 150,000. When 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 film, while when it exceeds 200,000, the solubility in an alkali developing solution tends to be poor.
Examples of the photopolymerization initiator (B) include benzophenone, N ' -tetramethyl-4, 4 ' -diaminobenzophenone (Millerone), N ' -tetraethyl-4, 4 ' -diaminobenzophenone, 4-methoxy-4 ' -dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, aromatic ketones such as 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-propanone, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1, 2-benzoanthraquinone, 2, 3-benzoanthraquinone, 2-phenylanthraquinone, and the like, Quinones such as 2, 3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1, 4-naphthoquinone, 9, 10-phenanthrenequinone, 2-methyl-1, 4-naphthoquinone, 2, 3-dimethylanthraquinone, benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether, benzoin compounds such as benzoin, methyl benzoin and ethyl benzoin, benzil derivatives such as benzil dimethyl ketal, 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, 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, 2,4, 5-triarylimidazole dimers such as 2- (p-methoxyphenyl) -4, 5-diphenylimidazole dimer, acridine derivatives such as 9-phenylacridine and 1, 7-bis (9, 9' -acridinyl) heptane, N-phenylglycine derivatives, coumarin-based compounds, and the like. The substituents for the aryl groups of 2,4, 5-triarylimidazoles in the 2,4, 5-triarylimidazole dimer may be the same to provide symmetrical compounds or different to provide asymmetrical compounds. Further, the thioxanthone-based compound may be combined with the tertiary amine compound as in the combination of diethylthioxanthone and dimethylaminobenzoic acid. These may be used alone or in combination of 2 or more.
(C) The urethane (meth) acrylate compound may be exemplified by: a product obtained by reacting (c1) a compound having a polyvalent hydroxyl group with (c2) a polyvalent isocyanate compound to obtain a compound having a terminal isocyanate group with (c3) a (meth) acrylate compound having a hydroxyl group.
Examples of the compound having a polyvalent hydroxyl group (c1) 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, polycarbonates, and polyesters obtained by polycondensation of an alkylene glycol such as ethylene glycol, propylene glycol, 1, 4-butanediol, diethylene glycol, triethylene glycol, or dipropylene glycol with a dicarboxylic acid such as maleic acid, fumaric acid, glutaric acid, or adipic acid. Specific examples of the lactones include delta-valerolactone, epsilon-caprolactone, beta-propiolactone, alpha-methyl-beta-propiolactone, beta-methyl-beta-propiolactone, alpha-dimethyl-beta-propiolactone, beta-dimethyl-beta-propiolactone, and the like. Specific examples of the polycarbonate include reaction products of diols such as bisphenol a, hydroquinone and dihydroxycyclohexanone with carbonyl compounds such as diphenyl carbonate, phosgene and succinic anhydride.
Specific examples of the polyether having a hydroxyl group include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and polypentamethylene ether glycol. Among them, (c1) the compound having a polyvalent hydroxyl group is preferably 1, 4-butanediol or polytetramethylene ether glycol, and the abrasion resistance and the adhesion to glass after development are further improved.
Specific examples of the (c2) polyisocyanate compound include dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, 2-dimethylpentane-1, 5-diisocyanate, aliphatic or alicyclic diisocyanate compounds such as octamethylene diisocyanate, 2, 5-dimethylhexane-1, 6-diisocyanate, 2, 4-trimethylpentane-1, 5-diisocyanate, nonamethylene diisocyanate, 2, 4-trimethylhexane diisocyanate, decamethylene diisocyanate and isophorone diisocyanate, and these compounds may be used alone or in a mixture of 2 or more.
Specific examples of the (meth) acrylate compound having a hydroxyl group (c3) include hydroxymethyl acrylate, hydroxymethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate, and further include compounds obtained by adding 1 to 10mol of epsilon-caprolactone thereto. Among them, the (meth) acrylate compound having a hydroxyl group (c3) is preferably 4-hydroxybutyl acrylate, and the abrasion resistance and the adhesion to glass after development are further improved.
The (C) urethane (meth) acrylate compound according to the present invention may contain a carboxyl group. The carboxyl group tends to improve the solubility in a developer. The (C) urethane (meth) acrylate compound having a carboxyl group can be obtained by the following method or the like: first, a diisocyanate compound is reacted with a diol compound having a carboxyl group so that an isocyanate group remains at both ends, and then a (meth) acrylate compound having a hydroxyl group is reacted with a terminal isocyanate group of the reactant.
(D) The epoxy (meth) acrylate is obtained by reacting at least an epoxy compound with (meth) acrylic acid. It is to be noted that, in the present invention, (meth) acrylic acid is a term collectively referring to acrylic acid, methacrylic acid and a mixture thereof. As the epoxy compound, aromatic or aliphatic compounds having an epoxy group can be exemplified. Examples of the epoxy (meth) acrylate include CN104, CN104A80, CN104B80, CN104D80, CN111US, CN112C60, CN113D70, CN115, CN116, CN117, CN118, CN119, CN120, CN121, CN131B, CN132, 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, EBECRYL (registered trademark) 1606, EBECRYL (registered trademark) 3500, EBECRYL (registered trademark) 3603, EBRYL (registered trademark) 0, EBECRRYL (registered trademark) 3701, EBECRYL 3702, EBECRYL (registered trademark) 37040, EBRYL (registered trademark) 6060, and XYRYL (registered trademark) 6060, EBRYL (registered trademark) and XYRYR) 60, and XYRYR (registered trademark) 60, and XYRYR) available from Sar, Epoxymester 80MFA, epoxymester 3002M, EPOXYESTER 1600A, EPOXYESTER 3000M, EPOXYESTER 3000A, EPOXYESTER 200EA, epoxymester 400EA, and the like.
When (D-1) monofunctional epoxy (meth) acrylate and/or (D-2) acid-modified epoxy (meth) acrylate is contained as the (D) epoxy (meth) acrylate, the following effects can be obtained: the resolution of the photosensitive resin layer is improved, and the cured photosensitive resin layer is less likely to peel off from the object to be processed even in a finer image. In particular, when both (D-1) monofunctional epoxy (meth) acrylate and (D-2) acid-modified epoxy (meth) acrylate are contained as the (D) epoxy (meth) acrylate, the following effects are further enhanced: the effect of improving the resolution of the photosensitive resin layer; and the cured photosensitive resin layer is less likely to peel off from the object to be processed even in a finer image.
The (D-1) monofunctional epoxy (meth) acrylate means a compound in which the number of (meth) acrylate groups in the (D) epoxy (meth) acrylate is 1. Examples thereof include 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-butoxypropyl (meth) acrylate, 2-hydroxy-3- (2-ethylhexyloxy) propyl (meth) acrylate, 2-hydroxy-3-octyloxypropyl (meth) acrylate, 2-hydroxy-3- (2-methyloctyloxy) propyl (meth) acrylate, 2-hydroxy-3-methyloxypropyl (meth) acrylate, 2-hydroxy-3-p-methylphenoxypropyl (meth) acrylate, and 2-hydroxy-3-stearyloxypropyl (meth) acrylate. Among them, the (D-1) monofunctional epoxy (meth) acrylate is preferably 2-hydroxy-3-phenoxypropyl acrylate, and the abrasion resistance and the adhesion to glass after development are further improved.
The (D-2) acid-modified epoxy acrylate includes a compound obtained by reacting at least (D1) an epoxy resin, (D2) (meth) acrylic acid, and (D3) at least 1 compound selected from a carboxylic acid-containing compound and an anhydride of a carboxylic acid-containing compound. The compound can be synthesized, for example, by the following method: the epoxy resin (d1) was added with (meth) acrylic acid (d2), and further with the compound (d 3). When acrylic acid and methacrylic acid are compared, acrylic acid is preferable because of its good abrasion resistance.
Examples of the (d1) epoxy resin include phenol novolac type, cresol novolac type, bisphenol a type, bisphenol F type, triphenol type, tetraphenol type, phenol-xylylene type, glycidyl ether type, and halogenated epoxy resins thereof.
As the carboxylic Acid-containing compound, Maleic Acid (Maleic Acid), Succinic Acid (Succinic Acid), Itaconic Acid (Itaconic Acid), Phthalic Acid (Phthalic Acid), Tetrahydrophthalic Acid (Tetrahydrophthalic Acid), Hexahydrophthalic Acid (Hexahydrophthalic Acid), Endomethylenetetrahydrophthalic Acid (Endomethylenetetrahydrophthalic Acid), Methylendomethylenetetrahydrophthalic Acid (methylmethylenetetrahydrophthalic Acid), Chlorendic Acid (Chlorendic Acid), Methyltetrahydrophthalic Acid (Methyltetrahydrophthalic Acid), Trimellitic Acid (trimesic Acid), Pyromellitic Acid (pyrotitanic Acid), benzophenone tetracarboxylic Acid (Benzophenonetetracarboxylic Acid), and the like can be used. Examples of the anhydride of the carboxylic acid-containing compound include anhydrides of the above-mentioned carboxylic acid-containing compounds.
(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. When the acid value is less than 40mgKOH/g, the alkali development time tends to be long, while when it exceeds 120mgKOH/g, the adhesion to the substrate as the object to be treated may be poor.
The mass average molecular weight of the (D-2) acid-modified epoxy acrylate is preferably 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 a film. On the other hand, if it exceeds 15,000, the solubility in the alkali developer tends to be poor.
The photosensitive resin layer of the present invention may contain components other than the components (a) to (D) as required. Examples of such components include photopolymerizable monomers, solvents, thermal polymerization inhibitors, plasticizers, colorants (dyes and pigments), photocolorants, photobleachers, thermal bleachers, fillers, antifoaming agents, flame retardants, tackifiers, leveling agents, peeling accelerators, antioxidants, perfumes, thermal curing agents, water-proofing agents, and oil-proofing agents, and the components may be contained in amounts of about 0.01 to 20 mass% respectively. These components can be used alone in 1 or a combination of 2 or more.
The photopolymerizable monomer is a compound having at least 1 polymerizable ethylenically unsaturated group in the molecule other than (C) the urethane (meth) acrylate compound and (D) the epoxy (meth) acrylate compound. Examples thereof include compounds obtained by reacting an α, β -unsaturated carboxylic acid with a polyhydric alcohol, bisphenol a-based (meth) acrylate compounds, compounds obtained by reacting an α, β -unsaturated carboxylic acid with a glycidyl group-containing compound, alkyl (meth) acrylates, ethylene oxide-or propylene oxide-modified (meth) acrylates, and the like. These photopolymerizable compounds may be used alone or in combination of 2 or more.
Examples of the photopolymerizable monomer include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, and the like.
In the photosensitive resin composition of the present invention, the amount of the component (a) to be blended is preferably 25 to 70% by mass, and more preferably 40 to 60% by mass, based on the total amount of the components (a), (B), (C), and (D). If the blending amount of the component (a) is less than 25% by mass, the film forming property may be deteriorated or the alkali developability may be lowered. If the amount of the component (a) exceeds 70 mass%, the abrasion resistance may be lowered.
The amount of the component (B) blended is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, based on the total amount of the components (A), (B), (C) and (D). When the amount of the component (B) is less than 0.1% by mass, the photopolymerization tends to be insufficient. On the other hand, if the amount exceeds 10 mass%, absorption at the surface of the photosensitive resin layer increases during exposure, and photopolymerization inside the photosensitive resin layer tends to become insufficient.
The amount of the component (C) blended is preferably 10 to 60% by mass, more preferably 30 to 50% by mass, based on the total amount of the components (A), (B), (C) and (D). If the amount of the component (C) is less than 10% by mass, the abrasion resistance tends to be lowered and the photosensitivity tends to be insufficient. On the other hand, if it exceeds 60 mass%, the tackiness of the film surface tends to increase excessively.
The amount of the component (D) blended is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, based on the total amount of the components (A), (B), (C) and (D). When the blending amount of the component (D) is less than 1 mass%, the cured film tends to swell during alkali development, and the cured photosensitive resin layer tends to peel off during alkali development. On the other hand, if it exceeds 30 mass%, the wear resistance tends to be lowered.
When the components (D-1) and (D-2) are contained as the component (D), the amount of the component (D-1) is more preferably 10 to 50% by mass based on the total amount of the components (D-1) and (D-2). When the amount of the component (D-1) is less than 10% by mass, the abrasion resistance may be unchanged as compared with the case where the component (D-1) is not contained, and when it exceeds 50% by mass, the tackiness of the film surface tends to be excessively increased.
As shown in fig. 1, the photosensitive resin composition of the present invention may be a dry film in which a support 1, a photosensitive resin layer 3, and a cover film 4 are laminated. As shown in fig. 2, the support 1, the release layer 2, the photosensitive resin layer 3, and the cover film 4 may be laminated to form a dry film. In the dry film configuration of fig. 1 and 2, the cover film 4 may be absent.
The support 1 is preferably a transparent film that transmits active light. The thickness of the support 1 is preferably 10 to 100 μm, because a thin support is preferable because refraction of light is small, and a thick support is preferable because coating stability is excellent. Examples of such films include films of polyethylene terephthalate, polycarbonate, and the like.
Examples of the release layer 2 include polyvinyl alcohol, alkali-soluble resins, mixtures of alkali-soluble resins and urethane (meth) acrylates, mixtures of alkali-soluble resins and epoxy (meth) acrylates, and mixtures of alkali-soluble resins, urethane (meth) acrylates and epoxy (meth) acrylates. The release layer 2 may or may not be provided with photopolymerization. However, since the photopolymerization initiator can be removed by alkali development, it is more preferable not to impart photopolymerization.
As the cover film 4, a resin having high releasability can be used as long as it can peel off an uncured or cured photosensitive resin layer. For example, a polyethylene film, a polypropylene film, and the like are mentioned, and a release agent such as silicone may be applied to these films. The photosensitive resin layer 3 is a layer containing a photosensitive resin composition.
The sand blasting method of the present invention includes a direct method and an indirect method. In the direct method and indirect method, a photosensitive resin composition having a dry film structure can be used. Examples of the object to be treated include glass, stone, metal, plastic, and ceramic.
In the direct method, the cover film 4 of the dry film is first removed, and then the photosensitive resin layer 3 is attached to the object to be treated by a laminator or the like so as to be in contact with the object. Next, the support 1 is peeled after exposure to actinic light through a masking film conforming to the relief image from the support 1 side. Alternatively, when resolution is required, the support 1 is peeled off, and then exposed to actinic light through a masking film conforming to the relief image. The exposed portion of the photosensitive resin layer 3 is cured by polymerization. Subsequently, the unexposed portion is washed with an alkali developer and then washed with water to form a resist image. Subsequently, the blast treatment is performed to process the object to be treated.
In the indirect method, a dry film cannot be laminated on a target object or proximity exposure cannot be performed in many cases. First, the support 1 is peeled after exposing the dry film to active light through a masking film conforming to the relief image. Alternatively, when resolution is required, the support 1 is peeled off, and then exposed to actinic light through a masking film conforming to the relief image. The exposed portion of the photosensitive resin layer 3 is cured by polymerization. Subsequently, the unexposed portion is developed with an alkali developer and washed with water. Thereby forming a resist image on the cover film 4. The resist image is attached to the object to be treated with an aqueous adhesive or the like. Subsequently, the cover film 4 is peeled off to form a resist image on the object. Subsequently, the blast treatment is performed to process the object to be treated.
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 a decrease in resolution and high cost are likely to occur. Conversely, if the thickness is too small, the wear resistance tends to be low.
Examples
The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
Examples 1 to 12 and comparative examples 1 to 3
The components shown in tables 1 and 2 were mixed to obtain a photosensitive resin composition. The unit of the amount of each component blended in tables 1 and 2 represents parts by mass. The obtained coating liquid was applied to a polyethylene terephthalate (PET) film (support 1, trade name: R310, 25 μm thick, manufactured by Mitsubishi resin Co., Ltd.) using a wire bar, dried at 80 ℃ for 8 minutes, and the solvent component was volatilized to obtain a dry film in which a photosensitive resin layer 3 (dry film thickness: 50 μm) comprising the photosensitive resin composition of examples 1 to 12 and comparative examples 1 to 3 was provided on one surface of the PET film.
In tables 1 and 2, the components are shown below.
< ingredient (A) >)
(A-1) a copolymer resin (mass-average molecular weight 30000) obtained by copolymerizing methyl methacrylate/n-butyl acrylate/methacrylic acid at a mass ratio of 64/15/21
(A-2) a copolymer resin (mass-average molecular weight 70000) 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 Chemicals) solid content 65%
(C-2) Art Resin (registered trademark) UN-2600 (manufactured by Kokai Co., Ltd.)
(C-3) urethane acrylate obtained as follows: polytetramethylene ether glycol 2000 (manufactured by Mitsubishi chemical corporation) and isophorone diisocyanate were reacted at a ratio of 5:10 mol to obtain a compound, and 4-hydroxybutyl acrylate and the terminal isocyanate of the compound were reacted at a ratio of 2 mol
(C-4) urethane acrylate obtained as follows: reacting polyethylene glycol (average molecular weight 360-440) with isophorone diisocyanate at a ratio of 5:10 mol to obtain a compound, and reacting 4-hydroxybutyl acrylate with a terminal isocyanate of the compound at a ratio of 2 mol
(C-5) urethane acrylate obtained as follows: polytetramethylene ether glycol 1000 (manufactured by Mitsubishi chemical corporation) and isophorone diisocyanate were reacted at a ratio of 5:10 mol to obtain a compound, and hydroxyethyl acrylate was reacted at a ratio of 2 mol with a terminal isocyanate of the compound
(C-6) urethane acrylate obtained as follows: a compound is obtained by reacting polyethylene glycol (average molecular weight 360-440) and isophorone diisocyanate at a ratio of 5:10 mol, and hydroxyethyl acrylate is reacted with a terminal isocyanate of the compound at a ratio of 2 mol.
< ingredient (D) >)
(D-1-a) acrylic acid 2-hydroxy-3-phenoxypropyl ester
(D-1-b) acrylic acid 2-hydroxy-3-butyloxypropyl ester
(D-2-a) acid-modified epoxy acrylate KAYARAD (registered trademark) ZAR-1035 (manufactured by Nippon Kagaku Co., Ltd.) solid content 65%
(D-2-b) acid-modified epoxy acrylate KAYARAD (registered trademark) UXE-3024 (manufactured by Nippon Chemicals) 65% in solid content
(D-2-c) bisphenol A epoxy Compound (JER828, Mitsubishi chemical corporation) as an epoxy resin, and a Compound obtained by reacting succinic acid and acrylic acid in a molar ratio of 1:2:2
(D-2-D) bisphenol A epoxy compound (JER828, Mitsubishi chemical corporation) as an epoxy resin, and a compound obtained by reacting succinic acid and methacrylic acid in a molar ratio of 1:2: 2.
< 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 (New Zhongcun chemical Co., Ltd.).
The dry films of examples 1 to 12 and comparative examples 1 to 3 were attached to a glass plate having a thickness of 3mm so that the photosensitive resin layer was in contact with the glass plate (object to be treated), and then exposed through a photomask having a line and space (line and space) of 50, 70, 100, 150, 200 μm and a square pattern of 3cm × 3 cm. Subsequently, the PET film was peeled off, and alkali development was performed with a 1.0 mass% aqueous solution of sodium carbonate to remove the photosensitive resin layer in the non-exposed portion. In this case, in examples 3 to 12 containing (D-1) monofunctional epoxy (meth) acrylate and (D-2) acid-modified epoxy (meth) acrylate as the (D) epoxy (meth) acrylate, the development was carried out at a line-to-pitch of 70 μm, and the cured photosensitive resin layer did not peel off from the object to be treated at a line of 70 μm or more. Further, in example 1 containing only (D-1) monofunctional epoxy (meth) acrylate as (D) epoxy (meth) acrylate and example 2 containing only (D-2) acid-modified epoxy (meth) acrylate as (D) epoxy (meth) acrylate, development of 100 μm lines and pitches was possible, and in the case of 100 μm or more lines, the cured photosensitive resin layer did not peel off from the object to be treated. That is, in examples 1 to 12, the adhesion between the glass plate and the photosensitive resin layer was excellent. Further, the photosensitive resin layer containing both (D-1) and (D-2) can form a finer scribe line.
On the other hand, comparative example 1 was able to develop 200 μm lines and pitches, but was found to be inferior in adhesion to 150 μm lines and pitches or less, which resulted in peeling. In comparative examples 2 and 3, the development was carried out at a line and pitch of 100 μm, and the cured photosensitive resin layer did not peel off from the object to be treated at a line of 100 μm or more, and the adhesion between the glass plate and the photosensitive resin layer was good.
Next, sand blasting was performed using silicon carbide powder (manufactured by nanwa ABRASIVE mfg. GC #1200), and the depth of the glass that can be cut around the 3cm × 3cm square pattern was confirmed. In examples 1 to 12, the cutting depth was 0.7mm or more, and the wear resistance was confirmed to be good. On the other hand, in comparative examples 2 and 3, the depth direction was only cut to 0.1mm, and when it exceeded 0.1mm, the photosensitive resin layer disappeared and the abrasion resistance was insufficient. Thus, the photosensitive resin compositions of comparative examples 2 and 3 had good adhesion to glass, but had insufficient abrasion resistance, and could not be used as a photosensitive resin composition for sandblasting.
Subsequently, the sandblasting process is performed more deeply. If comparing examples 5 to 8, the cutting can be made to 1.0mm in example 5, 0.8mm in examples 6 and 7, and 0.7mm in example 8. The abrasion resistance was most excellent in example 5 using (C1) the component (C-3) in which the compound having a polyvalent hydroxyl group was polytetramethylene ether glycol and (C3) the (meth) acrylate compound having a hydroxyl group was 4-hydroxybutyl acrylate, and secondly, in example 7 using (C1) the component (C-5) in which the compound having a polyvalent hydroxyl group was polytetramethylene ether glycol and example 6 using (C3) the component (C-4) in which the (meth) acrylate compound having a hydroxyl group was 4-hydroxybutyl acrylate were the second best.
Next, if comparing example 5 with example 9, it can be cut to 1.0mm in example 5 and 0.8mm in example 9. (D-1) the abrasion resistance of example 5 in which the monofunctional epoxy (meth) acrylate was 2-hydroxy-3-phenoxypropyl acrylate was good.
Next, when comparing example 11 with example 12, it can be cut to 1.0mm in example 11 and 0.7mm in example 12. (D-2) acid-modified epoxy (meth) acrylate the compound obtained by reacting acrylic acid showed good abrasion resistance in example 11.
Industrial applicability
The invention can be used for machining by sandblasting.
Description of the marks
1 support body
2 peeling off layer
3 photosensitive resin layer
4 covering the film.
Claims (6)
1. A photosensitive resin composition for sandblasting, characterized by comprising (A) an alkali-soluble resin, (B) a photopolymerization initiator, (C) a urethane (meth) acrylate compound and (D) an epoxy (meth) acrylate,
wherein (A) the alkali-soluble resin is not the component (C) or the component (D),
the (D) epoxy (meth) acrylate includes (D-1) monofunctional epoxy (meth) acrylate and (D-2) acid-modified epoxy (meth) acrylate,
(D) the amount of the epoxy (meth) acrylate blended is 1 to 30% by mass based on the total amount of the components (A), (B), (C) and (D).
2. The photosensitive resin composition for sandblasting as claimed in claim 1, wherein the (C) urethane (meth) acrylate compound is a product obtained by reacting (C1) a compound having a polyvalent hydroxyl group with (C2) a polyvalent isocyanate compound to obtain a compound having a terminal isocyanate group, and (C3) a (meth) acrylate compound having a hydroxyl group, wherein the compound (C1) is 1, 4-butanediol or polytetramethylene ether glycol.
3. The photosensitive resin composition for sandblasting as claimed in claim 1 or 2, wherein the (C) urethane (meth) acrylate compound is a product obtained by reacting (C1) a compound having a polyvalent hydroxyl group with (C2) a polyvalent isocyanate compound to obtain a compound having a terminal isocyanate group, and (C3) a (meth) acrylate compound having a hydroxyl group, wherein the compound (C3) is 4-hydroxybutyl acrylate.
4. The photosensitive resin composition for sandblasting as claimed in claim 1 or 2, wherein the (D-1) monofunctional epoxy (meth) acrylate is 2-hydroxy-3-phenoxypropyl acrylate.
5. The photosensitive resin composition for sandblasting as claimed in claim 1 or 2, wherein the (D-2) acid-modified epoxy (meth) acrylate is a compound obtained by reacting at least the (D1) epoxy resin, the (D2) (meth) acrylic acid and (D3) at least 1 compound selected from the group consisting of a carboxylic acid-containing compound and an anhydride of the carboxylic acid-containing compound.
6. A method of grit blasting comprising: applying a photosensitive resin layer comprising a photosensitive resin composition to an object to be treated, exposing the photosensitive resin layer to light, washing a non-exposed portion with an alkali developer to form a resist image on the object, and then performing a blast treatment to process the object; or, after exposing a photosensitive resin layer composed of a photosensitive resin composition to light, washing a non-exposed portion with an alkali developer to form a resist image, attaching the resist image to an object to be treated to form a resist image on the object to be treated, and then performing sandblasting to process the object to be treated;
characterized in that the photosensitive resin composition used is the photosensitive resin composition for sandblasting of any one of claims 1 to 5.
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| JP2015097114 | 2015-05-12 | ||
| JP2015-097114 | 2015-05-12 | ||
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| JP2016-001465 | 2016-01-07 |
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| JP2020106581A (en) * | 2018-12-26 | 2020-07-09 | 三菱製紙株式会社 | Photosensitive resin composition for sandblasting |
| KR20230021011A (en) | 2020-06-05 | 2023-02-13 | 미쓰비시 세이시 가부시키가이샤 | Photosensitive resin composition for sandblasting and photosensitive film for sandblasting |
| JP2024070237A (en) * | 2022-11-10 | 2024-05-22 | 住友化学株式会社 | Curable resin composition and film |
| CN118393813B (en) * | 2024-07-01 | 2024-11-05 | 湖南初源新材料股份有限公司 | Dry film for electroplating copper pillars and IC substrate copper pillars |
| CN118393814B (en) * | 2024-07-01 | 2024-11-05 | 湖南初源新材料股份有限公司 | Dry film resist and preparation method and application thereof |
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| CN106154749A (en) | 2016-11-23 |
| KR102640456B1 (en) | 2024-02-23 |
| JP6684147B2 (en) | 2020-04-22 |
| TWI687769B (en) | 2020-03-11 |
| TW201704867A (en) | 2017-02-01 |
| KR20160133362A (en) | 2016-11-22 |
| JP2017126053A (en) | 2017-07-20 |
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