CN106154749A - Sandblasting photosensitive polymer combination and grit-blasting treatment process - Google Patents
Sandblasting photosensitive polymer combination and grit-blasting treatment process Download PDFInfo
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- CN106154749A CN106154749A CN201610311217.3A CN201610311217A CN106154749A CN 106154749 A CN106154749 A CN 106154749A CN 201610311217 A CN201610311217 A CN 201610311217A CN 106154749 A CN106154749 A CN 106154749A
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- methyl
- acrylate
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- polymer combination
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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
-
- 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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- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials For Photolithography (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
The problem of the present invention is to provide: sandblasting photosensitive polymer combination high with the adhesiveness of treated object while having high-wearing feature, and uses the grit-blasting treatment process of this sandblasting photosensitive polymer combination.The present invention relates to sandblasting photosensitive polymer combination and use the grit-blasting treatment process of this sandblasting photosensitive polymer combination, described compositions is characterised by, containing (A) alkali soluble resin, (B) Photoepolymerizationinitiater initiater, (C) carbamate (methyl) acrylate compounds and (D) epoxy (methyl) acrylate, preferably comprise (D 1) monofunctional epoxy (methyl) acrylate and/or (D 2) acid modified epoxy (methyl) acrylate as (D) epoxy (methyl) acrylate.
Description
Technical field
The present invention relates to sandblasting photosensitive polymer combination and grit-blasting treatment process.
Background technology
In the past, when the treated objects such as glass-cutting, stone material, metal, plastics, pottery are to form embossment, blasting treatment was utilized to be processed.Treated object is arranged by photoetching process etc. carried out pattern formed photo-sensitive resin as masking material, then carry out spray grinding agent optionally to cut the blasting treatment of non-shelter.
As the photosensitive polymer combination of the masking material that can be used as this blasting treatment, such as usually containing alkali soluble resin, carbamate (methyl) acrylate compounds and the negative light-sensitive resin combination of Photoepolymerizationinitiater initiater.As alkali soluble resin, use alkali-soluble cellulose derivative or carboxylic acrylic resin (referring for example to patent documentation 1 ~ 7).
As the characteristic required by the photosensitive polymer combination of blasting treatment, the high-adhesiveness of the treated object such as high-wearing feature and glass can be listed.In conventional photosensitive polymer combination, have and meet any one characteristic and then sacrifice the tendency of another kind of characteristic, it is difficult to preparation meets the photosensitive polymer combination of two kinds of characteristics.
Prior art literature
Patent documentation
Patent documentation 1: No. 3449572 publications of Japanese Patent No.
Patent documentation 2: No. 3846958 publications of Japanese Patent No.
Patent documentation 3: Japanese Unexamined Patent Publication 10-69851 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2012-27357 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2013-156306 publication
Patent documentation 6: No. 2014/200028 pamphlet of International Publication
Patent documentation 7: Japanese Unexamined Patent Application Publication 2005-537514 publication.
Summary of the invention
Invent problem to be solved
The problem of the present invention is to provide: sandblasting photosensitive polymer combination high with the adhesiveness of treated object while having high-wearing feature, and uses the grit-blasting treatment process of this sandblasting photosensitive polymer combination.
Solve the means of problem
Above-mentioned problem can solve by the following means.
(1) sandblasting photosensitive polymer combination, it is characterised in that containing (A)
Alkali soluble resin, (B) Photoepolymerizationinitiater initiater, (C)
Carbamate (methyl) acrylate compounds and (D)
Epoxy (methyl) acrylate.
(2) the sandblasting photosensitive polymer combination described in above-mentioned (1), it contains (D-1)
Monofunctional epoxy (methyl) acrylate and/or (D-2)
Acid modified epoxy (methyl) acrylate is as (D)
Epoxy (methyl) acrylate.
(3) the sandblasting photosensitive polymer combination described in above-mentioned (1), it contains (D-1)
Monofunctional epoxy (methyl) acrylate and (D-2)
Acid modified epoxy (methyl) acrylate is as (D)
Epoxy (methyl) acrylate.
(4) the sandblasting photosensitive polymer combination according to any one of above-mentioned (1) ~ (3), wherein, (C)
Carbamate (methyl) acrylate compounds is: make (c1)
Have the compound of multi-hydroxy and (c2) polyhydric isocyanate compound react obtained by there is compound and (c3) of terminal isocyanate group
Having product obtained by (methyl) acrylate compounds reaction of hydroxyl, wherein compound (c1) is BDO or polytetramethylene ether diol.
(5) the sandblasting photosensitive polymer combination according to any one of above-mentioned (1) ~ (4), wherein, (C)
Carbamate (methyl) acrylate compounds is for making (c1)
Have the compound of multi-hydroxy and (c2) polyhydric isocyanate compound react obtained by there is compound and (c3) of terminal isocyanate group
Having product obtained by (methyl) acrylate compounds reaction of hydroxyl, wherein compound (c3) is acrylic acid 4-hydroxybutyl.
(6) the sandblasting photosensitive polymer combination according to any one of above-mentioned (1) ~ (5), wherein, (D-1)
Monofunctional epoxy (methyl) acrylate is acrylic acid 2-hydroxyl-3-phenyl epoxide propyl ester.
(7) the sandblasting photosensitive polymer combination according to any one of above-mentioned (1) ~ (6), wherein, (D-2)
Acid modified epoxy (methyl) acrylate is at least to make (d1) epoxy resin, (d2)
(methyl) acrylic acid and (d3)
Compound selected from least one compound reaction of the compound containing carboxylic acid and the acid anhydride of the compound containing carboxylic acid.
(8) grit-blasting treatment process, comprising: after attaching the photo-sensitive resin being made up of photosensitive polymer combination on treated object and exposing, rinse non-exposed portion with alkali imaging liquid, treated object forms resist pattern picture, then implement blasting treatment, treated object is processed；Or, after the photo-sensitive resin exposure being made up of photosensitive polymer combination, rinse non-exposed portion with alkali imaging liquid, form resist pattern picture, this resist pattern picture is attached on treated object, treated object is formed resist pattern picture, then implement blasting treatment, treated object is processed；
It is characterized in that, the photosensitive polymer combination of use sandblasting photosensitive polymer combination according to any one of (1) ~ (7).
Invention effect
Sandblasting photosensitive polymer combination according to the present invention and grit-blasting treatment process, can make the adhesiveness with treated object and high-wearing feature and deposit.
Accompanying drawing explanation
Fig. 1 is the schematic cross-section of the composition illustrating dry film.
Fig. 2 is the schematic cross-section of the composition illustrating dry film.
Detailed description of the invention
Hereinafter, the sandblasting photosensitive polymer combination (being the most sometimes called for short " photosensitive polymer combination ") of the present invention is described in detail.
The photosensitive polymer combination of the present invention is characterised by, containing (A)
Alkali soluble resin, (B) Photoepolymerizationinitiater initiater, (C)
Carbamate (methyl) acrylate compounds and (D)
Epoxy (methyl) acrylate.
As (A) alkali soluble resin, alkali-soluble cellulose derivative, carboxylic acrylic resin etc. can be listed.
As alkali-soluble cellulose derivative, cellulose acetate phthalate, Hydroxypropyl Methylcellulose Phathalate, cellulose acetate phthalate hydroxypropyl methyl cellulose, acetic acid succinic acid hydroxypropyl methyl cellulose etc. can be listed.
As carboxylic acrylic resin, can list using (methyl) acrylate as main component and the acrylic acid series polymeric compounds that makes ethylenically unsaturated carboxylic acids and its copolymerization.It addition, the most copolymerizable other has the monomer of copolymerizable ethylenically unsaturated group.
nullAs (methyl) acrylate，Include, for example out (methyl) acrylic acid methyl ester.、(methyl) ethyl acrylate、(methyl) n-propyl、(methyl) isopropyl acrylate、(methyl) n-butyl acrylate、(methyl) Isobutyl 2-propenoate、The most own ester of (methyl) acrylic acid、(methyl) 2-EHA、(methyl) cyclohexyl acrylate、(methyl) benzyl acrylate、(methyl) acrylic acid 2-hydroxy methacrylate、(methyl) acrylic acid 2-hydroxy propyl ester、(methyl) glycidyl acrylate、(methyl) lauryl acrylate、(methyl) acrylic acid tetrahydrofuran base ester、(methyl) acrylic acid 2-(dimethylamino) ethyl ester、(methyl) acrylic acid 2-(diethylamino) ethyl ester、(methyl) acrylic acid 2,2,2-trifluoro ethyl ester、(methyl) acrylic acid 2,2,3,3-tetrafluoro propyl ester etc..It should be noted that, in the present invention, (methyl) acrylate is to be referred to as acrylate, methacrylate and the term of their mixture.
As the ethylenically unsaturated carboxylic acids with (methyl) acrylic ester copolymer, the monocarboxylic acids such as acrylic acid, methacrylic acid .beta.-methylacrylic acid is preferably used, it is possible to use the dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid or their acid anhydride or half ester.Wherein, particularly preferred acrylic acid, methacrylic acid.
The monomer that there is copolymerizable ethylenically unsaturated group as other, include, for example out styrene, α-methyl styrene, p-methylstyrene, p-ethyl-styrene, to methoxy styrene, to ethoxystyrene, to chlorostyrene, to bromstyrol, (methyl) acrylonitrile, (methyl) acrylamide, N-[2-(2-methyl-4-oxopentyl), vinyltoluene, vinyl acetate, vinyl n-butyl ether etc..
(A) acid number of alkali soluble resin is preferably 30 ~ 500mgKOH/g, more preferably 100 ~ 300mgKOH/g.If the tendency that this acid number time of less than 30mgKOH/g, then having alkali image is elongated, if another aspect is more than 500mgKOH/g, then there is the situation that wearability reduces.
It addition, the matter average molecular weight of (A) alkali soluble resin is preferably 10,000 ~ 200,000, more preferably 10,000 ~ 150,000.If matter average molecular weight is less than 10,000, the most sometimes it is difficult to be formed as the photosensitive polymer combination of the present invention tunicle state, on the other hand, if more than 200,000, then there is the tendency being deteriorated relative to the dissolubility of alkali imaging liquid.
nullAs (B) Photoepolymerizationinitiater initiater，Benzophenone can be listed、N,N '-tetramethyl-4,4 '-diaminobenzophenone (Miller ketone)、N,N '-tetraethyl-4,4 '-diaminobenzophenone、4-methoxyl group-4 '-dimethylamino benzophenone、2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-1-butanone、The aromatic ketones such as 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino-1-acetone，2-ethyl-anthraquinone、Phenanthrenequione、2-tert-butyl group anthraquinone、Prestox anthraquinone、1,2-benzo anthraquinone、2,3-benzo anthraquinone、2-phenyl anthraquinone、2,3-diphenyl anthraquinone、1-chloroanthraquinone、2-methylanthraquinone、1,4-naphthoquinone、9,10-phenanthrenequione、2-methyl isophthalic acid,4-naphthoquinone、2,The quinones such as 3-dimethyl anthraquinone，Benzoin methyl ether、Benzoin ethyl ether、The benzoin ether compounds such as Benzoinum phenylate，Benzoinum、Benzoin methyl、The Benzoinum compounds such as ethyl Benzoinum，The benzil derivatives such as benzil dimethyl ketal，2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dimer、2-(Chloro-O-Phenyl)-4,5-bis-(methoxyphenyl) imidazoles dimer、2-(adjacent fluorophenyl)-4,5-diphenyl-imidazole dimer、2-(o-methoxyphenyl)-4,5-diphenyl-imidazole dimer、2-(p-methoxyphenyl)-4,5-diphenyl-imidazole dimer etc. 2,4,5-triarylimidazoles dimer，9-phenylacridine、1,7-double (9,9 '-acridinyl) acridine derivatives such as heptane，N-phenylglycine、N-phenylglycine derivant、Coumarin series compounds etc..In 2,4,5-triarylimidazoles dimers, the substituent group of the aryl of 22,4,5-triarylimidazoles can be identical to provide the compound of symmetry, it is possible to different to provide asymmetrical compound.Additionally, it is possible to as diethyl thioxanthone and the combination of dimethylaminobenzoic acid, thiaxanthone based compound is combined with tertiary amine compound.They may be used alone or in combination and use two or more.
(C) carbamate (methyl) acrylate compounds can list: makes (c1)
Have the compound of multi-hydroxy and (c2) polyhydric isocyanate compound react obtained by there is compound and (c3) of terminal isocyanate group
There is product obtained by (methyl) acrylate compounds reaction of hydroxyl.
There is the compound of multi-hydroxy as (c1), the polyethers etc. that the polyesters with hydroxyl can be listed, there is hydroxyl.
As the polyesters with hydroxyl, polyesters obtained by lactone ring-opening polymerisation can be listed, polycarbonate-based, or by polyesters obtained by the polycondensation reaction of the dicarboxylic acids such as the aklylene glycols such as ethylene glycol, propylene glycol, BDO, diethylene glycol, 2,2'-ethylenedioxybis(ethanol)., dipropylene glycol and maleic acid, fumaric acid, 1,3-propanedicarboxylic acid, adipic acid.As lactone, δ-valerolactone, 6-caprolactone, beta-propiolactone, Alpha-Methyl-beta-propiolactone, Beta-methyl-beta-propiolactone, α, alpha-alpha-dimethyl-beta-propiolactone, β, beta-dimethyl-beta-propiolactone etc. specifically can be listed.It addition, as polycarbonate-based, the product of the carbonyl compounds such as the glycol such as bisphenol-A, hydroquinone, dihydroxy Ketohexamethylene and diphenyl carbonate, phosgene, succinic anhydrides specifically can be listed.
It addition, as having the polyethers of hydroxyl, Polyethylene Glycol, polypropylene glycol, polytetramethylene ether diol, poly-5-methylene ether glycol etc. specifically can be listed.Wherein, (c1)
There is the adhesiveness with glass after the compound of multi-hydroxy is preferably BDO or polytetramethylene ether diol, wearability and imaging improve further.
As (c2) polyhydric isocyanate compound, specifically can list dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, 2, 2-dimethyl pentane-1, 5-diisocyanate, eight methylene diisocyanates, 2, 5-dimethylhexane-1, 6-diisocyanate, 2, 2, 4-trimethylpentane-1, 5-diisocyanate, nine methylene diisocyanates, 2, 2, 4-trimethylhexane diisocyanate, decamethylene diisocyanate, the aliphatic series such as isophorone diisocyanate or the diisocyanate cpd of ester ring type, this compound can be used alone or use mixture of more than two kinds.
There is (methyl) acrylate compounds of hydroxyl as (c3), specifically can list dihydroxypropyl methyl ester, methacrylic acid hydroxyl methyl ester, acrylic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, acrylic acid 3-hydroxy propyl ester, methacrylic acid 3-hydroxy propyl ester, acrylic acid 4-hydroxybutyl, methacrylic acid 4-hydroxybutyl etc., the most also can list compound obtained by the 6-caprolactone to they addition 1 ~ 10mol etc..Wherein, (c3)
There is the adhesiveness with glass after (methyl) acrylate compounds of hydroxyl is preferably acrylic acid 4-hydroxybutyl, wearability and imaging improve further.
(C) involved in the present invention
Carbamate (methyl) acrylate compounds can contain carboxyl.By containing carboxyl, having the tendency improved relative to the dissolubility of imaging liquid.(C) containing carboxyl
Carbamate (methyl) acrylate compounds can obtain by the following method etc.: first to make diisocyanate cpd in the way of double end residual isocyanate bases and the diol compound with carboxyl reacts, then makes the terminal isocyanate group of (methyl) acrylate compounds and this reactant with hydroxyl react.
(D) epoxy (methyl) acrylate is at least to make epoxide react with (methyl) acrylic acid and obtain.It should be noted that, in the present invention, (methyl) acrylic acid is to be referred to as acrylic acid, methacrylic acid and the term of their mixture.Epoxide can list the compound of aromatics or the aliphatic series with epoxy radicals.As epoxy (methyl) acrylate, include, for example out CN104, CN104A80, CN104B80, CN104D80, CN111US, CN112C60, CN113D70, CN115, CN116, CN117, CN118, CN119, CN120, CN121, CN131B, CN132, CN133, CN136, CN137, CN151, CN152 of Sartomer Company, the EBECRYL of DAICEL-ALLNEX company
(registered trade mark) 600, EBECRYL (registered trade mark)
605, EBECRYL (registered trade mark)
645, EBECRYL (registered trade mark)
648, EBECRYL (registered trade mark)
860, EBECRYL (registered trade mark)
1606, EBECRYL (registered trade mark)
3500, EBECRYL (registered trade mark)
3603, EBECRYL (registered trade mark)
3700, EBECRYL (registered trade mark)
3701, EBECRYL (registered trade mark)
3702, EBECRYL (registered trade mark)
3703, EBECRYL (registered trade mark)
3708, EBECRYL (registered trade mark)
6040, EPOXYESTER M-600A, EPOXYESTER of chemistry society of common prosperity society
40EM、EPOXYESTER 70PA、EPOXYESTER
200PA、EPOXYESTER 80MFA、EPOXYESTER
3002M、EPOXYESTER 1600A、EPOXYESTER
3000M、EPOXYESTER 3000A、EPOXYESTER
200EA, EPOXYESTER 400EA etc..
Containing (D-1) monofunctional epoxy (methyl) acrylate and/or (D-2)
Acid modified epoxy (methyl) acrylate is as (D)
In the case of epoxy (methyl) acrylate, available following effect: the resolution of photo-sensitive resin improves, even and finer and closely woven image, the photo-sensitive resin of solidification is also difficult to peel off from treated object.Particularly containing (D-1)
Monofunctional epoxy (methyl) acrylate and (D-2)
Acid modified epoxy (methyl) both acrylate are as (D)
In the case of epoxy (methyl) acrylate, following effect improves further: the effect that photo-sensitive resin resolution improves；Even with finer and closely woven image, the photo-sensitive resin of solidification is also difficult to the effect peeled off from treated object.
(D-1) monofunctional epoxy (methyl) acrylate refers to (D)
In epoxy (methyl) acrylate, (methyl) is acrylate-based is the compound of 1.Such as, (methyl) acrylic acid 2-hydroxyl-3-phenyl epoxide propyl ester can be listed, (methyl) acrylic acid 2-hydroxyl-3-butyl epoxide propyl ester, (methyl) acrylic acid 2-hydroxyl-3-(2-ethylhexyl epoxide) propyl ester, (methyl) acrylic acid 2-hydroxyl-3-octyl group epoxide propyl ester, (methyl) acrylic acid 2-hydroxyl-3-(2-Methyl Octyl epoxide) propyl ester, (methyl) acrylic acid 2-hydroxy-3-methyl epoxide propyl ester, (methyl) acrylic acid 2-hydroxyl-3-p-methylphenyl epoxide propyl ester, (methyl) acrylic acid 2-hydroxyl-3-stearyl epoxide propyl ester etc..Wherein, (D-1)
The adhesiveness with glass after monofunctional epoxy (methyl) acrylate is preferably acrylic acid 2-hydroxyl-3-phenyl epoxide propyl ester, wearability and imaging improves further.
As (D-2) acid modified epoxy acrylic ester, can list and at least make (d1)
Epoxy resin, (d2) (methyl) acrylic acid and (d3)
Compound selected from least one compound reaction of the compound containing carboxylic acid and the acid anhydride of the compound containing carboxylic acid.This compound such as can synthesize by the following method: to epoxy resin (d1) addition (methyl) acrylic acid (d2), and then additive compound (d3).If comparing acrylic acid and methacrylic acid, then the preferred acrylic acid because wearability is good.
As (d1) epoxy resin, phenol novolak type, cresol novolak type, bisphenol A-type, bisphenol-f type, triphen phenolic, four phenol types, phenol-xylylene type, diglycidyl ether type or their halogenated epoxy resin can be listed.
As the compound containing carboxylic acid, maleic acid (Maleic Acid), succinic acid (Succinic Acid), itaconic acid (Itaconic Acid), phthalic acid (Phthalic Acid), tetrahydrophthalic acid (Tetrahydrophthalic Acid), hexahydrophthalic acid (Hexahydrophthalic Acid), endo-methylene group tetrahydrophthalic acid (Endomethylenetetrahydrophthalic can be used
Acid), methylendomethylene tetrahydrophthalic acid (Methylendomethylenetetrahydrophthalic
Acid), chlorendic acid (Chlorendic Acid), methyl tetrahydrophthalic acid (Methyltetrahydrophthalic
Acid), trihemellitic acid (Trimellitic Acid), PMA (Pyromellitic Acid), benzophenone tetracarboxylic (Benzophenonetetracarboxylic
Acid) etc..As the acid anhydride of the compound containing carboxylic acid, the acid anhydride of the above-mentioned compound containing carboxylic acid can be listed.
(D-2) acid number of acid modified epoxy acrylic ester affects alkali imaging speed, peeling rate against corrosion, the flexibility etc. of photo-sensitive resin.Acid number is preferably 40 ~ 120mgKOH/g.If this acid number is less than 40mgKOH/g, then there is the tendency that alkali time of developing is elongated, on the other hand, if more than 120mgKOH/g, then having the situation attaching variation with the i.e. base material of treated object.
It addition, the matter average molecular weight of (D-2) acid modified epoxy acrylic ester is preferably 3,000 ~ 15,000.If matter average molecular weight is less than 3,000, the photosensitive polymer combination before being the most sometimes difficult to solidification is formed as tunicle state.On the other hand, if more than 15,000, then there is the tendency being deteriorated relative to the dissolubility of alkali imaging liquid.
The composition beyond composition (A) ~ (D) can be contained as required in the photo-sensitive resin of the present invention.As such composition, can list photopolymerization monomer, solvent, thermal polymerization inhibitor, plasticizer, coloring agent (dyestuff, pigment), light colour former, light lose lustre agent, hot color development inhibitor, filler, defoamer, fire retardant, viscosifier, levelling agent, stripping accelerator, antioxidant, spice, thermal curing agents, waterproofing agent and oil-proofing agent etc., can contain respectively about 0.01 ~ 20 mass %.These compositions can be used alone a kind or be applied in combination two or more.
Photopolymerization monomer is (C)
Carbamate (methyl) acrylate compounds and (D)
Intramolecular beyond epoxy (methyl) acrylate compounds has the compound of at least 1 polymerisable ethylenically unsaturated group.Such as, the α that sends as an envoy to can be enumerated, compound, bisphenol-A system (methyl) acrylate compounds obtained by beta-unsaturated carboxylic acid and polyol reaction, make α, beta-unsaturated carboxylic acid and the compound containing glycidyl react obtained by compound, (methyl) alkyl acrylate, ethylene oxide or propylene oxide modification (methyl) acrylate etc..These photopolymerizable compound may be used alone or in combination and use two or more.
Additionally, as photopolymerization monomer, trimethylolpropane tris (methyl) acrylate, two (trimethylolpropane) four (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, trihydroxymethylpropanyltri diglycidyl ether three (methyl) acrylate etc. the most also can be listed.
In the photosensitive polymer combination of the present invention, relative to composition (A), (B), (C), the total amount of (D), the blending amount of composition (A) is preferably 25 ~ 70 mass %, more preferably 40 ~ 60 mass %.If the blending amount of composition (A) less than 25 mass %, then has the situation or the situation of the resulting visualization reduction of alkali that tunicle is deteriorated.If the blending amount of composition (A) is more than 70 mass %, wearability reduces the most sometimes.
Relative to composition (A), (B), (C), the total amount of (D), the blending amount of composition (B) is preferably 0.1 ~ 10 mass %, more preferably 0.2 ~ 5 mass %.If the blending amount of composition (B) less than 0.1 mass %, then has optical polymerism to become insufficient tendency.On the other hand, if more than 10 mass %, then when exposure, Surface absorption at photo-sensitive resin increases, and has the photopolymerization within photo-sensitive resin to become insufficient tendency.
Relative to composition (A), (B), (C), the total amount of (D), the blending amount of composition (C) is preferably 10 ~ 60 mass %, more preferably 30 ~ 50 mass %.If the blending amount of composition (C) less than 10 mass %, then has wearability to reduce and luminous sensitivity becomes insufficient tendency.On the other hand, if more than 60 mass %, then having the tendency that the cohesiveness on film surface excessively increases.
Relative to composition (A), (B), (C), the total amount of (D), the blending amount of composition (D) is preferably 1 ~ 30 mass %, more preferably 3 ~ 20 mass %.If the blending amount of composition (D) is less than 1 mass %, then during alkali imaging, cured film becomes the most swelling, has the photo-sensitive resin that have cured when alkali images to hold flaky tendency.On the other hand, if more than 30 mass %, then having the tendency that wearability reduces.
In the case of containing composition (D-1) and (D-2) as composition (D), relative to composition (D-1) and the total amount of (D-2), the blending amount of (D-1) is more preferably 10 ~ 50 mass %.If the blending amount of composition (D-1) is less than 10 mass %, then compared with the situation not containing composition (D-1), there is the situation that wearability is constant, if more than 50 mass %, then having the tendency that the cohesiveness on film surface excessively increases.
As it is shown in figure 1, the photosensitive polymer combination of the present invention can be set to be laminated with the composition of the dry film of support 1, photo-sensitive resin 3, cover film 4.It addition, as shown in Figure 2, it is possible to it is set to be laminated with the composition of the dry film of support 1, peel ply 2, photo-sensitive resin 3, cover film 4.In the composition of the dry film of Fig. 1 and Fig. 2, can be without cover film 4.
As support 1, preferably through the transparent membrane of active ray.For the thickness of support 1, thin support is preferred less because of the refraction of light, and the support of thickness is preferred because of coating excellent in stability, preferably 10 ~ 100 μm.As such thin film, the thin film of polyethylene terephthalate, Merlon etc. can be listed.
As peel ply 2, polyvinyl alcohol can be listed, alkali soluble resin, alkali soluble resin and the mixture of carbamate (methyl) acrylate, alkali soluble resin and the mixture etc. of the mixture of epoxy (methyl) acrylate, alkali soluble resin, carbamate (methyl) acrylate and epoxy (methyl) acrylate.Peel ply 2 can give or not give optical polymerism.But, remove owing to can be imaged by alkali, so the most not giving optical polymerism.
As cover film 4, as long as photo-sensitive resin that is peelable uncured or that have cured, use the resin that release property is high.Such as, polyethylene film, polypropylene film etc. can be listed, these thin film also can be coated with the releasing agents such as silicone.Photo-sensitive resin 3 is the layer containing photosensitive polymer combination.
The grit-blasting treatment process of the present invention has direct method and indirect method.In direct method and indirect method, the photosensitive polymer combination of the composition making dry film can be used.As treated object, glass, stone material, metal, plastics, pottery etc. can be listed.
In direct method, first remove the cover film 4 of dry film, then utilize laminating machine etc. to attach in the way of photo-sensitive resin 3 contact on treated object.Then, from support 1 side across the shelter thin film consistent with camegraph, after using active ray to be exposed, peel off support 1.Or, in the case of requiring resolution, after peeling off support 1, across the shelter thin film consistent with camegraph, use active ray to be exposed.The part of the exposure of photo-sensitive resin 3 is solidified by polymerization.Then, rinse non-exposed portion with alkali imaging liquid, implement washing, form resist pattern picture.Then implement blasting treatment, treated object is processed.
In indirect method, it is used for maybe cannot to implement the situation of proximity printing in the situation of treated object overlaminate dry film.First, sheltering after thin film uses active ray to be exposed by dry film across consistent with camegraph, peeling off support 1.Or, in the case of requiring resolution, after peeling off support 1, across the shelter thin film consistent with camegraph, use active ray to be exposed.The part of the exposure of photo-sensitive resin 3 is solidified by polymerization.Then, rinse non-exposed portion with alkali imaging liquid, implement washing.On cover film 4, thus form resist pattern picture.Aqueous binder etc. is utilized to be attached on treated object by resist pattern picture.Then, peel off cover film 4, treated object is formed resist pattern picture.Then implement blasting treatment, treated object is processed.
The thickness of photo-sensitive resin is preferably 10 ~ 150 μm, more preferably 20 ~ 120 μm.If the thickness of this photo-sensitive resin is excessive, then become easily to produce resolution reduction, high in cost of production problem.Otherwise, if the thinnest, then have the tendency that wearability reduces.
Embodiment
Hereinafter, illustrate in greater detail the present invention by embodiment, but the invention is not restricted to these embodiments.
(embodiment 1 ~ 12, comparative example 1 ~ 3)
Each composition shown in Tables 1 and 2 is mixed, obtains photosensitive polymer combination.It should be noted that, the unit of each composition blending amount in Tables 1 and 2 represents mass parts.Use bar by the coating solution that obtains at polyethylene terephthalate (PET) thin film (support 1, trade name: R310,25 μ m-thick, Rhizoma Sparganii resin society system) on, it is dried 8 minutes in 80 DEG C, it is vaporized solvent composition, obtains being provided with in the one side of PET film containing embodiment 1 ~ 12, the photo-sensitive resin 3 of the photosensitive polymer combination of comparative example 1 ~ 3
The dry film of (dry film thickness: 50 μm).
In Tables 1 and 2, each composition is as follows.
＜ composition (A) ＞
(A-1) by methyl methacrylate/acrylic acid N-butyl/methacrylic acid with copolymer resins (matter average molecular weight 30000) obtained by mass ratio 64/15/21 copolymerization
(A-2) by methyl methacrylate/acrylic acid N-butyl/methacrylic acid with copolymer resins (matter average molecular weight 70000) obtained by mass ratio 58/15/27 copolymerization.
＜ composition (B) ＞
(B-1) 2-(2 '-chlorphenyl)-4,5-diphenyl-imidazole dimer
(B-2) 4,4 '-bis-(diethylamino) benzophenone.
＜ composition (C) ＞
(C-1) KAYARAD (registered trade mark)
UXF-4001-M35 (chemical medicine society of Japan system) solid constituent 65%
(C-2) Art Resin (registered trade mark)
UN-2600 (industry society system on root)
(C-3) urethane acrylate obtained as follows: make polytetramethylene ether diol 2000
(society of Mitsubishi Chemical system) and isophorone diisocyanate are reacted with the ratio of 5:10 mole and are obtained compound, then make acrylic acid 4-hydroxybutyl react with the terminal isocyanate of this compound with the ratio of 2 moles
(C-4) urethane acrylate obtained as follows: make Polyethylene Glycol (mean molecule quantity 360 ~ 440) and isophorone diisocyanate react with the ratio of 5:10 mole and obtain compound, then make acrylic acid 4-hydroxybutyl react with the terminal isocyanate of this compound with the ratio of 2 moles
(C-5) urethane acrylate obtained as follows: make polytetramethylene ether diol 1000
(society of Mitsubishi Chemical system) and isophorone diisocyanate are reacted with the ratio of 5:10 mole and are obtained compound, then make the terminal isocyanate of Hydroxyethyl Acrylate and this compound react with the ratio of 2 moles
(C-6) urethane acrylate obtained as follows: make Polyethylene Glycol (mean molecule quantity 360 ~ 440) and isophorone diisocyanate react with the ratio of 5:10 mole and obtain compound, then make the terminal isocyanate of Hydroxyethyl Acrylate and this compound react with the ratio of 2 moles.
＜ composition (D) ＞
(D-1-a) acrylic acid 2-hydroxyl-3-phenyl epoxide propyl ester
(D-1-b) acrylic acid 2-hydroxyl-3-butyl epoxide propyl ester
(D-2-a) acid modified epoxy acrylic ester KAYARAD
(registered trade mark) ZAR-1035 (chemical medicine society of Japan system) solid constituent 65%
(D-2-b) acid modified epoxy acrylic ester KAYARAD
(registered trade mark) UXE-3024 (chemical medicine society of Japan system) solid constituent 65%
(D-2-c) as the Bisphenol A epoxides (JER828, Mitsubishi chemical Co., Ltd) of epoxy resin, succinic acid with acrylic acid with compound obtained by 1:2:2 molar reactive
(D-2-d) as the Bisphenol A epoxides (JER828, Mitsubishi chemical Co., Ltd) of epoxy resin, succinic acid with methacrylic acid with compound obtained by 1:2:2 molar reactive.
＜ photopolymerization monomer ＞
(E-1) pentaerythritol triacrylate
(E-2) 2,2-pair [4-(methacryloxy polyethoxy] phenyl] propane (EO 10mol), epoxidation bisphenol a dimethacrylate, NK ESTER BPE-500 (chemical industry society of Xin Zhong village system).
In the way of photo-sensitive resin contacts with glass plate (treated object), the dry film of embodiment 1 ~ 12 and comparative example 1 ~ 3 is attached on the glass plate of thickness 3mm, then across line and the spacing (line with 50,70,100,150,200 μm
And space) and the photomask of square pattern of 3cm × 3cm be exposed.Then, peel off PET film, implement alkali imaging with 1.0 mass % aqueous sodium carbonates, remove the photo-sensitive resin in non-exposed portion.Now, for containing (D-1)
Monofunctional epoxy (methyl) acrylate and (D-2)
Acid modified epoxy (methyl) acrylate is as (D)
The embodiment 3 ~ 12 of epoxy (methyl) acrylate, can image line and the spacing of 70 μm, and for lines more than 70 μm, the photo-sensitive resin that have cured does not peels off from treated object.It addition, for comprising only (D-1)
Monofunctional epoxy (methyl) acrylate is as (D)
The embodiment 1 of epoxy (methyl) acrylate and comprise only (D-2)
Acid modified epoxy (methyl) acrylate is as (D)
The embodiment 2 of epoxy (methyl) acrylate, can image line and the spacing of 100 μm, and for lines more than 100 μm, the photo-sensitive resin that have cured does not peels off from treated object.That is, in embodiment 1 ~ 12, glass plate is excellent with the adhesiveness of photo-sensitive resin.Additionally, thinner setting-out can be formed containing (D-1) and (D-2) both photo-sensitive resin.
On the other hand, comparative example 1 can image line and the spacing of 200 μm, but produce for the line below line and the spacing of 150 μm and peel off, it is known that poor adhesion.It addition, for comparative example 2 and 3, can image line and the spacing of 100 μm, for lines more than 100 μm, the photo-sensitive resin that have cured does not peels off from treated object, glass plate and the good adhesion of photo-sensitive resin.
Then, use carborundum powder (NANIWA ABRASIVE MFG. system, GC#1200), implement blasting treatment, it is thus identified that the machinable degree of depth of glass around the square pattern of 3cm × 3cm.In embodiment 1 ~ 12, more than 0.7mm can be cut to depth direction, can confirm that good wearability.On the other hand, for comparative example 2 and 3, depth direction only machinable is to 0.1mm, if exceeding depth direction 0.1mm, then photo-sensitive resin disappears, and wearability is insufficient.Thus, although the photosensitive polymer combination of comparative example 2 and 3 and the good adhesion of glass, but wearability is insufficient, it is impossible to as sandblasting photosensitive polymer combination.
Then, blasting treatment is deeper implemented.If comparing embodiment 5 ~ 8, then in embodiment 5, machinable is to 1.0mm, and in embodiment 6 and 7, machinable is to 0.8mm, and in embodiment 8, machinable is to 0.7mm.Use (c1)
The wearability of embodiment 5 with the composition (C-3) that (methyl) acrylate compounds is acrylic acid 4-hydroxybutyl that the compound of multi-hydroxy is polytetramethylene ether diol and (c3) has hydroxyl is the best, secondly, (c1) is used
There is the embodiment 7 of the composition that compound is polytetramethylene ether diol (C-5) of multi-hydroxy and use (c3)
The embodiment 6 second of the composition (C-4) that (methyl) acrylate compounds is acrylic acid 4-hydroxybutyl with hydroxyl is good.
Then, if comparing embodiment 5 and embodiment 9, then in embodiment 5, machinable is to 1.0mm, and in embodiment 9, machinable is to 0.8mm.(D-1)
Monofunctional epoxy (methyl) acrylate is that the wearability of the embodiment 5 of acrylic acid 2-hydroxyl-3-phenyl epoxide propyl ester is good.
Then, if comparing embodiment 11 and embodiment 12, then in embodiment 11, machinable is to 1.0mm, and in embodiment 12, machinable is to 0.7mm.(D-2)
Acid modified epoxy (methyl) acrylate is to make the wearability of the embodiment 11 of compound obtained by acrylic acid reaction good.
Industrial applicability
The present invention can be used for utilizing the processing of blasting treatment.
Description of symbols
1 support
2 peel plies
3 photo-sensitive resins
4 cover films.
Claims (8)
1. sandblasting photosensitive polymer combination, it is characterized in that, containing (A) alkali soluble resin, (B) Photoepolymerizationinitiater initiater, (C) carbamate (methyl) acrylate compounds and (D) epoxy (methyl) acrylate.
2. the sandblasting photosensitive polymer combination of claim 1, it contains (D-1) monofunctional epoxy (methyl) acrylate and/or (D-2) acid modified epoxy (methyl) acrylate as (D) epoxy (methyl) acrylate.
3. the sandblasting photosensitive polymer combination of claim 1, it contains (D-1) monofunctional epoxy (methyl) acrylate and (D-2) acid modified epoxy (methyl) acrylate as (D) epoxy (methyl) acrylate.
4. the sandblasting photosensitive polymer combination any one of claim 1 ~ 3, wherein, (C) carbamate (methyl) acrylate compounds for make (c1) have the compound of multi-hydroxy and (c2) polyhydric isocyanate compound react obtained by have the compound of terminal isocyanate group and (c3) have (methyl) acrylate compounds of hydroxyl react obtained by product, wherein compound (c1) is BDO or polytetramethylene ether diol.
5. the sandblasting photosensitive polymer combination any one of claim 1 ~ 4, wherein, (C) carbamate (methyl) acrylate compounds for make (c1) have the compound of multi-hydroxy and (c2) polyhydric isocyanate compound react obtained by have the compound of terminal isocyanate group and (c3) have (methyl) acrylate compounds of hydroxyl react obtained by product, wherein compound (c3) is acrylic acid 4-hydroxybutyl.
6. the sandblasting photosensitive polymer combination any one of claim 1 ~ 5, wherein, (D-1) monofunctional epoxy (methyl) acrylate is acrylic acid 2-hydroxyl-3-phenyl epoxide propyl ester.
7. the sandblasting photosensitive polymer combination any one of claim 1 ~ 6, wherein, (D-2) acid modified epoxy (methyl) acrylate is at least to make (d1) epoxy resin, (d2)
The compound that at least one compound of the acid anhydride that (methyl) acrylic acid is selected from the compound containing carboxylic acid and the compound containing carboxylic acid with (d3) reacts.
8. grit-blasting treatment process, comprising: after attaching the photo-sensitive resin being made up of photosensitive polymer combination on treated object and exposing, rinse non-exposed portion with alkali imaging liquid, treated object forms resist pattern picture, then implement blasting treatment, treated object is processed；Or, after the photo-sensitive resin exposure being made up of photosensitive polymer combination, rinse non-exposed portion with alkali imaging liquid, form resist pattern picture, this resist pattern picture is attached on treated object, treated object is formed resist pattern picture, then implement blasting treatment, treated object is processed；
It is characterized in that, the photosensitive polymer combination of use is the sandblasting photosensitive polymer combination any one of claim 1 ~ 7.
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| TW202200631A (en) | 2020-06-05 | 2022-01-01 | 日商三菱製紙股份有限公司 | Photosensitive resin composition for sandblasting use and photosensitive film for sandblasting use |
| JP2024070237A (en) * | 2022-11-10 | 2024-05-22 | 住友化学株式会社 | Curable resin composition and film |
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| TW201704867A (en) | 2017-02-01 |
| JP2017126053A (en) | 2017-07-20 |
| JP6684147B2 (en) | 2020-04-22 |
| CN106154749B (en) | 2021-10-12 |
| TWI687769B (en) | 2020-03-11 |
| KR20160133362A (en) | 2016-11-22 |
| KR102640456B1 (en) | 2024-02-23 |
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