KR200494511Y1 - Photo-sensitive resin structure for sandblasting - Google Patents

Abstract

(Problem) The subject of this invention is providing the photosensitive resin structural body for sandblasting which has high blast resistance and does not easily generate wrinkles in the photosensitive resin layer before hardening at the time of preservation|save.
(Solution) In the photosensitive resin construction for sandblasting in which a support, a photosensitive resin layer, and a cover film are laminated in this order, the photosensitive resin layer is (A) alkali-soluble resin, (B) photoinitiator and (C) urethane ( A photosensitive resin composition for sand blasting, characterized in that it contains a meth)acrylate compound and is a polyethylene film or polypropylene film having a cover film thickness of 50 to 150 µm.

Description

Photosensitive resin composition for sandblasting {PHOTO-SENSITIVE RESIN STRUCTURE FOR SANDBLASTING}

The present invention relates to a photosensitive resin composition for sand blasting.

Conventionally, in cutting glass, stone, metal, plastic, ceramic, etc. and forming a relief, the process by a sandblasting process is implemented. A photosensitive resin layer patterned by a photolithography method or the like is formed on an object to be processed as a mask material, and then sandblasting is performed in which an abrasive is sprayed to selectively cut a non-masked portion.

The photosensitive resin structural body for sandblasting used in order to form the photosensitive resin layer which is a mask material for this sandblasting process generally has a structure which laminated|stacked the support body, the photosensitive resin layer, and the cover film in this order. And the photosensitive resin layer contains the negative photosensitive resin composition containing alkali-soluble resin, urethane (meth)acrylate, and a photoinitiator, for example. Moreover, as alkali-soluble resin, a cellulose derivative or a carboxyl group-containing acrylic resin is used (for example, patent documents 1-3).

In order to increase the blast resistance of the photosensitive resin composition, it is necessary to increase the elasticity of the photosensitive resin layer after curing. there was However, if the compounding amount of urethane (meth)acrylate is increased or the film thickness is increased, the viscosity of the photosensitive resin layer before curing increases. This problem occurred. As a countermeasure, in order to make peeling strength with a photosensitive resin layer low, the polyethylene terephthalate (PET) film which laminated|stacked release agents, such as silicone, is used as a cover film (for example, patent document 4). However, since the release agent cannot be used for an object to be treated which is reluctant to transfer, countermeasures by other means have been demanded.

Japanese Patent Publication No. 3449572 Japanese Patent Publication No. 3846958 Japanese Patent Application Laid-Open No. 10-69851 Japanese Patent Application Laid-Open No. 2014-206746

An object of the present invention is to provide a photosensitive resin construct for sandblasting that has high blast resistance and is less prone to wrinkles in the photosensitive resin layer before curing during storage.

The present inventors, as a result of earnest examination to solve the above problems, in the photosensitive resin construction for sandblasting in which a support, a photosensitive resin layer, and a cover film are laminated in this order, the photosensitive resin layer is (A) alkali-soluble resin, ( B) a photopolymerization initiator and (C) a urethane (meth) acrylate compound, and the cover film is a polyethylene film or a polypropylene film having a thickness of 50 to 150 μm. In a photosensitive resin composition for sandblasting The above problem was solved by

Since the photosensitive resin composition for sandblasting of the present invention improves sandblast resistance, when the viscosity of the photosensitive resin layer increases or when the thickness of the photosensitive resin layer is thickened, which has been a problem in the past, before curing during storage The effect which can suppress the problem which wrinkles generate|occur|produce in the photosensitive resin layer is acquired. Moreover, since the PET cover film which laminated|stacked the release agent, such as silicone, is not used, use with respect to the to-be-processed object which is reluctant to transfer of a release agent becomes possible.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which showed the structure of the photosensitive resin structural body for sandblasting.
It is sectional drawing which showed the structure of the photosensitive resin structural body for sandblasting.

Hereinafter, the photosensitive resin composition for sandblasting of the present invention will be described in detail. The photosensitive resin composition for sandblasting of the present invention is a photosensitive resin composition for sandblasting in which a support, a photosensitive resin layer, and a cover film are laminated in this order, wherein the photosensitive resin layer is (A) alkali-soluble resin, (B) photoinitiator and (C) a urethane (meth)acrylate compound, and is characterized in that it is a polyethylene film or a polypropylene film having a thickness of 50 to 150 µm of the cover film.

(A) As alkali-soluble resin, the alkali-soluble cellulose derivative described below, a carboxyl group-containing acrylic resin, etc. are mentioned.

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

As a carboxyl group-containing acrylic resin, the acrylic polymer which has (meth)acrylate as a main component and copolymerizes this with ethylenically unsaturated carboxylic acid is mentioned. Moreover, you may copolymerize the monomer which has another copolymerizable ethylenically unsaturated group.

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

As the ethylenically unsaturated carboxylic acid, monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid are preferably used, dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid, anhydrides and half esters thereof are used. may be Among these, acrylic acid and methacrylic acid are particularly preferable.

Examples of the other copolymerizable monomer having an ethylenically unsaturated group include styrene, α-methylstyrene, p-methylstyrene, p-ethylstyrene, p-methoxystyrene, p-ethoxystyrene, and p-chloro Styrene, p-bromostyrene, (meth)acrylonitrile, (meth)acrylamide, diacetoneacrylamide, vinyltoluene, vinyl acetate, vinyl-n-butyl ether, etc. are mentioned.

(A) It is preferable that it is 30-500 mgKOH/g, and, as for the acid value of alkali-soluble resin, it is more preferable that it is 100-300 mgKOH/g. When this acid value is less than 30 mgKOH/g, the time for alkali development tends to become long, on the other hand, when it exceeds 500 mgKOH/g, blast resistance may fall.

Moreover, it is preferable that it is 10,000-200,000, and, as for the mass average molecular weight of (A) alkali-soluble resin, it is more preferable that it is 10,000-150,000. When the mass average molecular weight is less than 10,000, it may become difficult to form the photosensitive resin composition of the present invention in a film state.

(B) Photoinitiators include benzophenone, N,N,N',N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N,N,N',N'- Tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 aromatic ketones such as ,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1; 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-di Phenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl1,4-naphthoquinone, 2,3-dimethylanthraquinone quinones such as; 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; benzyl derivatives such as benzyl dimethyl ketal; 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 2,4,5-triaryl imidazole dimers, such as a 5-diphenyl imidazole dimer; acridine derivatives such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; and N-phenylglycine, N-phenylglycine derivatives, and coumarin-based compounds. The substituents of the aryl groups of two 2,4,5-triaryl imidazole in the said 2,4,5- triaryl imidazole dimer may provide the same and symmetric compound, and are different and asymmetric You may provide a phosphorus compound. Moreover, you may combine a thioxanthone type compound and a tertiary amine compound like the combination of diethyl thioxanthone and dimethylamino benzoic acid. These are used individually or in combination of 2 or more types.

(C) Examples of the urethane (meth)acrylate include a reaction product of a compound having a terminal isocyanate group in which a compound having a polyvalent hydroxyl group and a polyvalent isocyanate compound reacted, and a (meth)acrylate compound having a hydroxyl group. have. Examples of the compound having a polyvalent hydroxyl group include polyesters and polyethers having a hydroxyl group. Examples of the polyesters include polyesters obtained by ring-opening polymerization of lactones, polycarbonates, and ethylene. Polyesters obtained by condensation reaction of alkylene glycols such as glycol, propylene glycol, diethylene glycol, triethylene glycol, and dipropylene glycol with dicarboxylic acids such as maleic acid, fumaric acid, glutaric acid, and adipic acid can be heard Specific examples of the lactones include δ-valerolactone, ε-caprolactone, β-propiolactone, α-methyl-β-propiolactone, β-methyl-β-propiolactone, α,α- dimethyl-β-propiolactone, β,β-dimethyl-β-propiolactone, and the like. Specific examples of the polycarbonates include reaction products of diols such as bisphenol A, hydroquinone and dihydroxycyclohexanone, and carbonyl compounds such as diphenyl carbonate, phosgene, and succinic anhydride. Moreover, as said polyether, polyethyleneglycol, polypropylene glycol, polytetramethylene glycol, polypentamethylene glycol, etc. are mentioned specifically,.

Examples of the polyvalent isocyanate compound that reacts with the compound having a polyvalent hydroxyl group include dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, 2,2-dimethylpentane-1,5-diisocyanate, octamethylene diisocyanate, 2,5-dimethylhexane-1,6-diisocyanate, 2,2,4-trimethylpentane-1,5-diisocyanate, nona and aliphatic or alicyclic diisocyanate compounds such as methylene diisocyanate, 2,2,4-trimethylhexane diisocyanate, decamethylene diisocyanate and isophorone diisocyanate. can

In addition, as a (meth)acrylate compound which has a hydroxyl group, specifically, hydroxymethyl acrylate, hydroxymethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3 -Hydroxypropyl acrylate and 3-hydroxypropyl methacrylate are mentioned, The compound etc. which added 1-10 mol of epsilon caprolactone to them are mentioned.

(C) Urethane (meth)acrylate which concerns on this invention may contain the carboxyl group. By containing a carboxyl group, there exists a tendency for the solubility with respect to a resin layer removal liquid to improve. (C) urethane (meth)acrylate containing a carboxyl group is first reacted with a diisocyanate compound and a diol compound having a carboxyl group so that an isocyanate group remains at both terminals, and then the terminal isocyanate group of this reactant has a hydroxyl group It can obtain by making a (meth)acrylate compound react.

You may make the photosensitive resin layer of this invention contain components other than the said component (A)-(C) as needed. Such components include a photopolymerizable monomer, a solvent, a thermal polymerization inhibitor, a plasticizer, a colorant (dye, a pigment), a photochromic agent, a photochromic agent, a thermal color development inhibitor, a filler, an antifoaming agent, a flame retardant, an adhesion imparting agent, a leveling agent. , a peeling accelerator, an antioxidant, a fragrance, a thermosetting agent, a water repellent, an oil repellent, etc., and can contain about 0.01-20 mass %, respectively. These components can be used individually by 1 type or in combination of 2 or more types.

The said photopolymerizable monomer is a compound which has at least 1 superposition|polymerization ethylenically unsaturated group in a molecule|numerator other than component (C) urethane (meth)acrylate. For example, a compound obtained by reacting an α,β-unsaturated carboxylic acid with a polyhydric alcohol, a bisphenol A (meth)acrylate compound, or a compound obtained by reacting an α,β-unsaturated carboxylic acid with a glycidyl group-containing compound , (meth)acrylic acid alkylester, ethylene oxide or propylene oxide modified (meth)acrylate, etc. are mentioned. These photopolymerizable compounds can be used individually or in combination of 2 or more types.

Moreover, as said photopolymerizable monomer, you may use the compound which has 3 or more superposition|polymerizable ethylenically unsaturated groups in a molecule|numerator. Examples of the photopolymerizable compound having three or more polymerizable ethylenically unsaturated groups in the molecule include trimethylolpropane tri(meth)acrylate, ditrimethylolpropanetetra(meth)acrylate, pentaerythritol tri(meth) ) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate The thing containing at least 1 type is mentioned.

Photosensitive resin layer WHEREIN: It is preferable that it is 15-65 mass % with respect to the total amount of components (A), (B), and (C), and, as for the compounding quantity of component (A), it is more preferable that it is 25-45 mass %. . If the compounding quantity of a component (A) is less than 15 mass %, film property may worsen and alkali developability may fall. When the compounding quantity of a component (A) exceeds 65 mass %, blast resistance may fall.

It is preferable that it is 0.1-10 mass % with respect to the total amount of components (A), (B), and (C), and, as for the compounding quantity of a component (B), it is more preferable that it is 0.2-5 mass %. If the compounding quantity of a component (B) is less than 0.1 mass %, there exists a tendency for photopolymerization to become inadequate. On the other hand, when it exceeds 10 mass %, absorption increases on the surface of the photosensitive resin layer at the time of exposure, and there exists a tendency for the photocrosslinking inside the photosensitive resin layer to become inadequate.

It is preferable that it is 30-80 mass % with respect to the total amount of components (A), (B), and (C), and, as for the compounding quantity of a component (C), it is more preferable that it is 40-70 mass %. If the compounding quantity of a component (C) is less than 30 mass %, there exists a tendency for blast resistance to fall, and there exists a tendency for a photosensitivity to become inadequate. On the other hand, when it exceeds 80 mass %, there exists a tendency for the adhesiveness of the film|membrane surface to increase.

The photosensitive resin structural body for sandblasting of this invention is a structural body of the dry film in which the support body 1, the photosensitive resin layer 3, and the cover film 4 were laminated|stacked, as shown in FIG. Moreover, as shown in FIG. 2, it is good also as a structure of the dry film in which the support body 1, the peeling layer 2, the photosensitive resin layer 3, and the cover film 4 were laminated|stacked.

As the support body 1, the transparent film which transmits an actinic light is preferable. As for the thickness of the support body 1, since the thin one has little refraction of light, it is preferable, and since the thick one is excellent in coating stability, 10-100 micrometers is preferable. As a film suitable for the support body 1, films, such as a polyethylene terephthalate and a polycarbonate, are mentioned. As the peeling layer 2, polyvinyl alcohol, the mixture of alkali-soluble resin, and urethane (meth)acrylate, etc. are mentioned. The photosensitive resin layer 3 is a layer which consists of a photosensitive resin composition. As for the dry film thickness of the photosensitive resin layer 3, since the thicker one is excellent in sand blast resistance, it is preferable, and when it is too thick, it is preferable that it is 10-150 micrometers at the point which resolution falls, and it is 30-120 micrometers. more preferably. With the cover film 4, what is necessary is just to be able to peel the non-hardened or hardened|cured photosensitive resin layer 3, and resin with high releasability is used. In this invention, a polyethylene film or a polypropylene film is used at the point with high peelability and adhesiveness with the photosensitive resin layer 3 being favorable.

As for the thickness of the cover film 4, the thicker one is preferable at the point which the effect of suppressing the generation|occurrence|production of wrinkles at the time of storage of the photosensitive resin structure is acquired, and when it is too thick, the roll diameter becomes large when it is set as the roll form of arbitrary length, and handleability is It is 50-150 micrometers, and 75-120 micrometers is more preferable at the point which also becomes easy to generate|occur|produce problems, such as a fall and cost becoming high. When it is too thin, it is unpreferable from the point which wrinkles become easy to generate|occur|produce at the time of storage. In addition, when the cover film 4 is a polyester film or the like laminated with a release agent such as silicone that lowers the peel strength with the photosensitive resin layer 3, the release agent may be transferred to the exposure mask film (photomask) or the object to be processed. It is not preferable in terms of possibility.

Example

Hereinafter, the present invention will be described in more detail by way of Examples, but the present invention is not limited to these Examples.

(Examples 1 to 10, Comparative Examples 1 to 4)

The photosensitive resin composition shown below is coated on a polyethylene terephthalate (PET) film (support body (1), trade name: R310, 25 micrometers thickness, Mitsubishi Chemical Corporation make) using a wire bar, and dried at 80 degreeC for 8 minutes. and blow off the solvent component, apply the photosensitive resin layer 3 (dry film thickness: 100 µm) on one side of the PET film, and apply the cover film 4 shown in Table 1 on the photosensitive resin layer 3 It laminated and adhered, and the photosensitive resin structural body for sandblasting of Examples 1-10 and Comparative Examples 1-4 was manufactured.

(Preparation of photosensitive resin composition)

The components shown below were mixed, and the photosensitive resin composition was obtained. The unit of each component compounding quantity represents a mass part.

(A) 17 parts of cellulose acetate phthalate (manufactured by Wako Pure Chemical Industries, Ltd.)

(B-1) 1.5 parts of 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer

(B-2) 0.2 parts of N,N,N',N'-tetraethyl-4,4'-diaminobenzophenone

(C) SIKO (registered trademark) UV-3000B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 32 copies

(Photopolymerizable monomer) 6 parts of pentaerythritol triacrylate

(pigment) phthalocyanine green 0.1 part

43.2 parts of methyl ethyl ketone (MEK)

In order to investigate the occurrence of wrinkles during storage, the photosensitive resin construct for sandblasting was cut to 20 cm x 20 cm, placed in a black polybag, and stored at 30 DEG C, 60% R.H. was stored for 8 days in an atmosphere of As a result of taking out after storage and confirming the wrinkles of the photosensitive resin layer 3, although there was some wavy in the photosensitive resin structures for sandblasting of Examples 1 and 6, generation|occurrence|production of wrinkles was not seen in the photosensitive resin layer 3. As for the photosensitive resin structural body for sandblasting of Examples 2-4 and Examples 7-9, generation|occurrence|production of the wrinkle did not exist in the photosensitive resin layer 3. In the photosensitive resin structural body for sandblasting of Example 5 and Example 10, although wrinkles did not generate|occur|produce in the photosensitive resin layer 3, the cost became slightly high. On the other hand, in the photosensitive resin structural body for sandblasting of the comparative example 1 and the comparative example 3, generation|occurrence|production of wrinkles was seen in the photosensitive resin layer 3 . Moreover, although the wrinkle did not generate|occur|produce in the photosensitive resin layer 3 in the comparative example 2 and the comparative example 4, cost became high, and improvement was not seen compared with Example 5 and Example 10. Therefore, when the cover film 4 is a 50-150 micrometers-thick polyethylene film or a polypropylene film, it turns out that the wrinkle generation of the photosensitive resin structural body for sandblasting can be suppressed.

After peeling off the cover film 4, the photosensitive resin structure for sandblasting after said preservation|save is affixed on the glass plate of 3 mm thickness so that the photosensitive resin layer 3 may contact, Next, 50, 70, 100, 150 , exposed through a photomask having a pattern of 200 μm line & space. Next, the support body 1 was peeled off, alkali development was performed with 1.0 mass % sodium carbonate aqueous solution, and the photosensitive resin layer 3 of a non-exposure part was removed. At this time, about Examples 1-10 and Comparative Example 2 and Comparative Example 4, it turned out that 100 micrometers line & space can be resolved. On the other hand, in Comparative Example 1 and Comparative Example 3, under the influence of wrinkles of the photosensitive resin layer 3, the photomask could not be brought into close contact, and the formation of a relief image was impossible.

Next, it sandblasted using silicon carbide powder (the Naniwa Abrasive Industry make, GC#1200). About Examples 1-10 and Comparative Example 2 and Comparative Example 4, it was possible to cut to 1 mm in the depth direction, and the blast resistance was favorable.

The present invention can be widely used as a photosensitive resin structural body for sandblasting.

1: support
2: release layer
3: photosensitive resin layer
4: cover film

Claims (1)

In the photosensitive resin construction for sandblasting in which a support, a photosensitive resin layer, and a cover film are laminated in this order, the photosensitive resin layer is (A) alkali-soluble resin, (B) photoinitiator, and (C) urethane (meth) acrylate A photosensitive resin composition for sand blasting, characterized in that it is a polyethylene film or polypropylene film containing a compound and having a cover film thickness of 50 to 150 µm.

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