JP2016161875A - Etching resist composition and dry film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an etching resist composition from which an etching resist film excellent in durability against fluoric acid can be formed, and a dry film having a resin layer obtained from the composition.SOLUTION: The etching resist composition comprises an alkali-soluble resin having a biphenyl structure. The dry film has a resin layer obtained from the composition.SELECTED DRAWING: None

Description

  The present invention relates to an etching resist composition and a dry film, and more particularly to an etching resist composition capable of forming an etching resist film excellent in resistance to hydrofluoric acid, and a dry film having a resin layer obtained from the composition.

  In the processing of glass products, in recent years, fine processing and smoothness are more demanded, and glass processing tends to cause cracks in mechanical processing using a drill, so processing by glass etching has become mainstream. .

  Glass etching is a technique conventionally applied to glass housings such as electronic materials, optical materials, and measuring instruments. As a glass etching method, for example, a resin composition is applied to the surface of a glass substrate to be etched, and this is thermally dried or cured to form an etching resist film, and then the glass substrate is hydrofluoric acid-based. A method of forming a desired pattern on a glass substrate by immersing in an etching solution and removing a portion not covered with a resist is used (for example, Patent Document 1).

JP 2007-128052 A

  Since hydrofluoric acid-based etchants are highly permeable, the etchant will permeate between the glass substrate and the etching resist unless a measure such as forming a thick etching resist film is used. There was a problem that it was not possible. In addition, when the etching resist film is formed thick, it takes time to remove the etching resist after etching, and in the case of a development type etching resist, there is a problem that the resolution is lowered.

  Therefore, an object of the present invention is to provide an etching resist composition capable of forming an etching resist film excellent in hydrofluoric acid resistance, and a dry film having a resin layer obtained from the composition.

  As a result of intensive studies in view of the above, the present inventors have found that the above problems can be solved by blending an alkali-soluble resin having a specific structure into the etching resist composition, and have completed the present invention. .

  That is, the etching resist composition of the present invention contains an alkali-soluble resin having a biphenyl structure.

  The etching resist composition of the present invention preferably further contains an alkali-soluble resin having a bisphenol structure.

  The etching resist composition of the present invention preferably further contains a photocurable component.

  The etching resist composition of the present invention preferably further contains a coupling agent.

  The dry film of the present invention is characterized by having a resin layer obtained by applying the etching resist composition to the film and drying it.

  According to the present invention, an etching resist composition capable of forming an etching resist film excellent in hydrofluoric acid resistance and a dry film having a resin layer obtained from the composition can be provided.

  The etching resist composition of the present invention contains an alkali-soluble resin having a biphenyl structure. Since the etching resist film formed with the etching resist composition of the present invention is excellent in hydrofluoric acid resistance, peeling from the glass substrate hardly occurs during the etching process. As a result, the substrate can be etched with high accuracy. Further, since an etching solution having a high hydrofluoric acid concentration can be used in the etching process, the etching processing time can be shortened.

  Since the etching resist film formed with the etching resist composition of the present invention is excellent in hydrofluoric acid resistance, it is difficult to peel off with an etching solution without forming a thick film. Although the etching resist composition of the present invention may be of a development type or a heat drying type, it is not necessary to increase the thickness of the etching resist, so in the case of the development type, an etching resist film having excellent resolution is formed. can do.

  The etching resist composition of the present invention preferably contains a coupling agent, whereby adhesion to the substrate is improved, and an etching resist film having excellent hydrofluoric acid resistance can be formed. However, since an etching resist film having excellent hydrofluoric acid resistance can be formed without containing a coupling agent, the coupling agent may not be contained. When a coupling agent is not contained, it is excellent in storage stability, so that it can be stored in one liquid at room temperature. When a coupling agent is contained, it is preferable to store it in two or more liquids.

  Hereinafter, the components contained in the etching resist composition of the present invention will be described in detail.

[Alkali-soluble resin]
The alkali-soluble resin contained in the etching resist composition of the present invention has a biphenyl structure. As the alkali-soluble resin, a carboxyl group-containing resin or a phenolic hydroxyl group-containing resin can be used, and a carboxyl group-containing resin is preferable. When the curable resin composition of the present invention is a development type, the alkali-soluble resin preferably has an ethylenically unsaturated bond. Alkali-soluble resin may be used individually by 1 type, and may be used in combination of 2 or more type.

(Carboxyl group-containing resin)
As the carboxyl group-containing resin, for example, a bifunctional or higher polyfunctional epoxy resin having a biphenyl structure such as a biphenyl type epoxy resin is reacted with an unsaturated group-containing monocarboxylic acid to form a hydroxyl group present in the side chain. A carboxyl group-containing resin to which a dibasic acid anhydride is added, and a carboxyl group formed by adding a compound having one epoxy group and one or more (meth) acryloyl groups in one molecule to the resin. The (meth) acrylate-modified resin is included, but is not limited thereto.

  Examples of the bifunctional or higher polyfunctional epoxy resin having the biphenyl structure include biphenyl type epoxy resins represented by the following general formula (1).

（式中、ｎ_１は平均値を表し１．０１〜５である。）

(Wherein, _{n 1} is from 1.01 to 5 represent the mean.)

  Examples of the unsaturated group-containing monocarboxylic acid include (meth) acrylic acid, dimer of (meth) acrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, and saturated or unsaturated dibasic anhydride Half-esters which are equimolar reaction products of a product and a (meth) acrylate derivative having one hydroxyl group in one molecule, or equimolar reaction of a saturated or unsaturated dibasic acid and an unsaturated group-containing monoglycidyl compound The half-esters which are things are mentioned. In addition, in this specification, (meth) acrylate is a term which generically refers to acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.

  Examples of the dibasic acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, endomethylene-tetrahydrophthalic anhydride, Examples thereof include carboxylic acid anhydrides such as methyl-endomethyl-tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, and trimet acid.

  The acid value of the carboxyl group-containing resin is suitably in the range of 40 to 300 mgKOH / g, more preferably in the range of 45 to 120 mgKOH / g. When the carboxyl group-containing resin has an acid value of 40 mgKOH / g or more, it can be easily removed with an alkali stripping solution. On the other hand, when the acid value is 300 mgKOH / g or less, resistance to etching is improved.

  Moreover, although the weight average molecular weight (Mw) of the said carboxyl group-containing resin changes with resin frame | skeletons, what is generally in the range of 1,000-150,000, Furthermore, 5,000-100,000 is preferable. When the weight average molecular weight (Mw) is 1,000 or more, etching resistance is improved. On the other hand, when the weight average molecular weight (Mw) is 150,000 or less, it can be easily removed with an alkali stripping solution.

  Examples of commercially available products of the carboxyl group-containing resin include KAYARAD ZCR-1569H, ZCR-1601H, ZCR-1797H, ZCR-1798H (carboxyl group-containing resin having a biphenyl structure) manufactured by Nippon Kayaku Co., Ltd. and the like.

  In the etching resist composition of this invention, it is preferable to use together alkali-soluble resin which has a bisphenol structure from a peelable viewpoint. The alkali-soluble resin having a bisphenol structure is not particularly limited. For example, a bifunctional or higher polyfunctional epoxy resin having a bisphenol structure such as a bisphenol type epoxy resin is reacted with an unsaturated group-containing monocarboxylic acid to form a side chain. A carboxyl group-containing resin obtained by adding a dibasic acid anhydride to the hydroxyl group present in the compound, and a compound having one epoxy group and one or more (meth) acryloyl groups in one molecule. And a (meth) acrylate-modified resin having a carboxyl group.

  Moreover, as an alkali-soluble resin having a bisphenol structure, an epoxy group is added to the hydroxyl group of a bifunctional or higher polyfunctional bisphenol type epoxy resin having a hydroxyl group as shown below by epichlorohydrin or the like, and then an unsaturated group-containing monocarboxylic acid is added. A carboxyl group-containing resin obtained by further reacting an acid and a dibasic acid anhydride, and a compound having one epoxy group and one or more (meth) acryloyl groups in one molecule; (Meth) acrylate modified resin having a carboxyl group is also mentioned. Examples of the bifunctional or higher polyfunctional bisphenol type epoxy resin having a hydroxyl group include a bisphenol F type epoxy resin and a bisphenol A type epoxy resin represented by the following general formula (2).

（式中、ＸはＣＨ_２またはＣ（ＣＨ_３）_２を表し、ｎは１〜１２である。）

(In the formula, X represents CH ₂ or C (CH ₃ ) ₂ , and n is 1 to 12).

  When the alkali-soluble resin having a bisphenol structure is used in combination, the ratio of the alkali-soluble resin having a biphenyl structure and the alkali-soluble resin having a bisphenol structure is preferably 90:10 to 20:80, more preferably 80:20 to When blended at a ratio of 20:80, the peelability can be improved without impairing the etching resistance.

  Moreover, 80 mass% or less is preferable per solid content of an etching resist composition, and, as for content of the whole carboxyl group containing resin, 30-70 mass% is more preferable. When the content of the alkali-soluble resin is 80% by mass or less, the viscosity is stably stabilized. In addition, in this-application specification, solid content is a component except a solvent.

(Phenolic hydroxyl group-containing resin)
Examples of the phenolic hydroxyl group-containing resin include phenol novolac resin, alkylphenol volac resin, bisphenol A novolac resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, terpene modified phenol resin, polyvinylphenols, bisphenol F, and bisphenol S type. Known and commonly used phenolic hydroxyl group-containing resins such as a phenol resin, poly-p-hydroxystyrene, a condensate of naphthol and aldehydes, and a condensate of dihydroxynaphthalene and aldehydes can be used.

(Photocurable component)
In the case of the development type, the etching resist composition of the present invention preferably contains a photocurable component because the etching resist resistance is remarkably improved. The photocurable component may be any resin that can be cured by irradiation with active energy rays, and particularly in the present invention, a compound having one or more ethylenically unsaturated bonds in the molecule is preferably used. A photocurable component may be used individually by 1 type, and may be used in combination of 2 or more type.

  As the compound having an ethylenically unsaturated bond, known and commonly used photopolymerizable oligomers, photopolymerizable vinyl monomers, and the like are used. Among these, examples of the photopolymerizable oligomer include unsaturated polyester oligomers and (meth) acrylate oligomers. Examples of (meth) acrylate oligomers include phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, epoxy (meth) acrylates such as bisphenol type epoxy (meth) acrylate, urethane (meth) acrylate, epoxy urethane (meta ) Acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polybutadiene-modified (meth) acrylate, and the like.

  As the photopolymerizable vinyl monomer, known and commonly used monomers, for example, styrene derivatives such as styrene, chlorostyrene and α-methylstyrene; vinyl esters such as vinyl acetate, vinyl butyrate or vinyl benzoate; vinyl isobutyl ether, vinyl- vinyl ethers such as n-butyl ether, vinyl-t-butyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-n-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether, triethylene glycol monomethyl vinyl ether; acrylamide, Methacrylamide, N-hydroxymethyl acrylamide, N-hydroxymethyl methacrylamide, N-methoxymethyl acrylamide, N-ethoxymethyl acryl (Meth) acrylamides such as N-butoxymethylacrylamide; allyl compounds such as triallyl isocyanurate, diallyl phthalate, diallyl isophthalate; 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl Esters of (meth) acrylic acid such as (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, pentaerythritol Hydroxyalkyl (meth) acrylates such as tri (meth) acrylate; alkoxyalkylene such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate Recall mono (meth) acrylates; ethylene glycol di (meth) acrylate, butanediol di (meth) acrylates, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri Alkylene polyol poly (meth) acrylate such as (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate; diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethoxylated tri Polyoxyalkylene glycol poly (meth) acrylates such as methylolpropane triacrylate, propoxylated trimethylolpropane tri (meth) acrylate; Poly (meth) acrylates such as Dorokishipibarin acid neopentyl glycol ester di (meth) acrylate; tris [(meth) acryloxyethyl] isocyanurate rate poly (meth) acrylates such as isocyanurate.

  The content of the photocurable component is preferably 5 to 38% by mass, more preferably 10 to 20% by mass, based on the solid content of the etching resist composition. When content of a photocurable component is 5 mass% or more, photocurability improves. In the case of 38% by mass or less, tackiness is improved.

(Photopolymerization initiator)
In the case of the development type, the etching resist composition of the present invention preferably contains a photopolymerization initiator.

  Examples of the photopolymerization initiator include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- ( 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6- Trimethylbenzoyl) -phenylphosphine oxide Bisacylphosphine oxides such as BASF Japan, IRGACURE 819); 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid Monoacylphosphine oxides such as methyl ester, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (BASF Japan, DAROCUR TPO) 1-hydroxy-cyclohexyl phenyl ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1- Propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 2-hydroxy-2 -Hydroxyacetophenones such as methyl-1-phenylpropan-1-one; benzoins such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether; benzoin alkyl Ethers; benzophenones such as benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone; acetophenone, 2,2-dimeth Ci-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl) -1- [ Acetophenones such as 4- (4-morpholinyl) phenyl] -1-butanone and N, N-dimethylaminoacetophenone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethyl Thioxanthone, 2-chlorothioxanthone, 2,4 Thioxanthones such as diisopropylthioxanthone; anthraquinones such as anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone; acetophenone dimethyl Ketals such as ketal and benzyldimethyl ketal; benzoates such as ethyl-4-dimethylaminobenzoate, 2- (dimethylamino) ethylbenzoate and p-dimethylbenzoic acid ethyl ester; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]- Oxime esters such as 1- (0-acetyloxime); bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl ) Titanocenes such as titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2- (1-pyr-1-yl) ethyl) phenyl] titanium; phenyl disulfide 2-nitrofluorene, Examples include butyroin, anisoin ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, and the like. A photoinitiator may be used individually by 1 type and may be used in combination of 2 or more type.

  The content of the photopolymerization initiator is preferably 1 to 8% by mass, more preferably 2 to 5% by mass, based on the solid content of the etching resist composition. When content of a photoinitiator is 1 mass% or more, photocurability improves. In the case of 8% by mass or less, halation hardly occurs and the curing depth becomes appropriate.

(Coupling agent)
The etching resist composition of the present invention can contain a coupling agent. As the coupling agent, a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, or the like can be used. As the coupling agent, a silane coupling agent is preferable. A coupling agent may be used individually by 1 type, and may be used in combination of 2 or more type.

  The silane coupling agent is composed of an organic substance (organic group) and silicon. Generally, XnR ′ (n−1) Si—R ″ —Y (X = hydroxyl, alkoxyl, etc., Y = vinyl group, epoxy group, styryl group, A methacryloxy group, an acryloxy group, an amino group, a ureido group, a chloropropyl group, a mercapto group, a polysulfide group, an isocyanate group, etc. Since there are two or more different reactive groups in the molecule, It works as an intermediary between organic and inorganic materials, which are very difficult to bond, and is used for improving the strength of composite materials, modifying resins, and modifying surfaces.

  Examples of the silane coupling agent include N-γ- (aminoethyl) -γ-aminopropyltriethoxysilane, N-γ- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylphenyldiethoxysilane, 2-amino-1-methylethyltriethoxysilane, N-methyl- γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N-butyl-γ-aminopropylmethyldiethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -N-β- (amino Ethyl) -γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-isocyanatopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, methacryloxy Examples thereof include propyltrimethoxysilane and γ-polyoxyethylenepropyltrimethoxysilane.

  Examples of commercially available silane coupling agents include KA-1003, KBM-1003, KBE-1003, KBM-303, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM- 503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBE-603, KBM-903, KBE-903, KBE-9103, KBM-9103, KBM-573, KBM-575, Examples thereof include KBM-6123, KBE-585, KBM-703, KBM-802, KBM-803, KBE-846, KBE-9007 (all trade names; manufactured by Shin-Etsu Silicone).

  Titanium coupling agents include: tetraethoxy titanate, titanium alkoxides such as tetraisopropyl titanate and tetra-n-butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, polyhydroxy titanium stearate, titanium tetraacetylacetate Examples thereof include narate, polytitanium acetylacetonate, titanium octylene glycolate, titanium ethyl acetoacetate, titanium lactate, and titanium triethanolamate. As the zirconium-based and aluminum-based coupling agents, compounds corresponding to titanium-based compounds can be used.

  Since the etching rest composition of the present invention is excellent in resistance to hydrofluoric acid, the resist is hardly peeled off in the step of immersing in the etching solution without containing a coupling agent. Therefore, the inclusion of the coupling agent is not essential, but the preferred blending amount when containing the coupling agent is 0.5 to 5% by mass per solid content of the etching resist composition. When the content is 0.5% by mass or more, better etching resist resistance can be obtained. A stable characteristic is acquired as it is 5 mass% or less.

(Filler)
In the present invention, conventionally known inorganic fillers and organic fillers for etching resists can be used. Examples of the inorganic filler include extender colorants such as barium sulfate, barium titanate, talc, clay, aluminum oxide, aluminum hydroxide, silicon nitride, and aluminum nitride. These inorganic fillers play a role of appropriately adjusting the viscosity at the time of adjusting the resist composition, suppressing the curing shrinkage of the coating film at the time of heat drying or photocuring, and improving the adhesion to the substrate. Of these, talc is particularly preferably used in order to improve the adhesion to the substrate. A filler may be used individually by 1 type and may be used in combination of 2 or more type.

  The average primary particle size of the inorganic filler is preferably 15 μm or less, more preferably 10 μm or less. The average primary particle size (D50) can be measured by a laser diffraction / scattering method.

  The blending amount of the filler is preferably 0.01 to 70% by mass, more preferably 10 to 40% by mass, based on the solid content of the etching resist composition. When the blending amount of the filler is 0.01% by mass or more, the adhesion between the resist and the substrate is improved, and when it is 70% by mass or less, the fluidity of the composition is improved.

(Organic solvent)
You may mix | blend an organic solvent with the etching resist composition of this invention. Specific examples of the organic solvent include alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol and n-butyl alcohol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, n-propyl acetate and acetic acid. Esters such as n-butyl, ethers such as dibutyl ether, tetrahydrofuran and 1,4-dioxane, aliphatic hydrocarbons such as n-hexane, n-heptane and n-octane, and aromatics such as benzene, toluene and xylene Group hydrocarbons, and halogenated hydrocarbons such as chloroform and carbon tetrachloride. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

  20-85 mass% is preferable and, as for solid content of the etching resist composition of this invention, 30-80 mass% is more preferable.

(Other additives)
In addition, the resist composition of the present invention may be blended with other commonly known additives in the field of etching resist. Other additives include, for example, surface tension modifiers, surfactants, matting agents, polyester resins for adjusting film properties, polyurethane resins, vinyl resins, acrylic resins, rubber resins, waxes , Phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, and other known and commonly used colorants, silicone-based, fluorine-based, polymer-based antifoaming agents, and the like A leveling agent etc. are mentioned. Such an additive may be blended by appropriately adjusting the amount used within a range in which the desired effect of the additive can be obtained without impairing the effects of the present invention.

  When used as a liquid, the etching resist composition of the present invention may be one-component or two-component or more.

  Moreover, you may use the etching resist composition of this invention after making it into a dry film as follows. In the case of the development type, a desired pattern can be formed by exposure and development in the same manner as described above. In the case of the heat drying type, the pattern may be formed by laser processing or the like.

  The dry film of the present invention has a resin layer obtained by applying and drying the etching resist composition of the present invention on a film. When forming a dry film, first, after adjusting the etching resist composition of the present invention to the appropriate viscosity by diluting with the above organic solvent, comma coater, blade coater, lip coater, rod coater, squeeze coater, Apply a uniform thickness on the carrier film using a reverse coater, transfer roll coater, gravure coater, spray coater or the like. Then, the resin layer can be formed by drying the applied composition at a temperature of 50 to 130 ° C. for 1 to 30 minutes. Although there is no restriction | limiting in particular about a coating film thickness, Generally, it is 10-150 micrometers by the film thickness after drying, Preferably it selects suitably in the range of 20-60 micrometers.

  As the carrier film, a plastic film is used. For example, a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, or the like can be used. Although there is no restriction | limiting in particular about the thickness of a carrier film, Generally, it selects suitably in the range of 10-150 micrometers.

  After forming a resin layer made of the etching resist composition of the present invention on a carrier film, a peelable cover film is laminated on the film surface for the purpose of preventing dust from adhering to the film surface. It is preferable to do. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used. As a cover film, what is necessary is just a thing smaller than the adhesive force of a resin layer and a carrier film when peeling a cover film.

  In addition, in the dry film of this invention, the etching resist composition of this invention is apply | coated and dried on the said protective film, A resin layer may be formed, and a carrier film may be laminated | stacked on the surface. . That is, as the film to which the etching resist composition of the present invention is applied when producing a dry film in the present invention, either a carrier film or a protective film may be used.

  In the case of a dry film, the glass substrate is covered with the etching resist by peeling the carrier film after laminating the substrate so that the layer of the etching resist composition of the present invention is in contact with the glass substrate. can do.

  When the etching resist composition of the present invention is a development-type liquid composition, it is prepared as a uniform solution or dispersion, and then dried on a substrate such as a glass substrate using a coating method such as screen printing or curtain coater. The subsequent film thickness is preferably 20 to 100 μm, more preferably 30 to 60 μm. After the application, for example, heat drying is performed in a drying furnace or the like at 70 to 100 ° C. for 20 to 40 minutes, and then the pattern is printed by exposing the etching resist through a mask. Thereafter, development is performed with an aqueous alkaline solution to form a pattern. For example, if heat drying is performed in a drying furnace or the like at 100 to 200 ° C., preferably 120 to 150 ° C. for 20 to 60 minutes, the pattern is dried. A substrate coated with the etched resist can be obtained.

  In the case of a development type dry film, after laminating the layer of the etching resist composition of the present invention on the base material so as to come into contact with the base material, exposure and development are performed in the same manner as described above. A pattern may be formed.

  When the etching resist composition of the present invention is a heat-drying liquid composition, it is prepared as a uniform solution or dispersion, and then dried on a substrate such as a glass substrate in a desired pattern by screen printing or the like. What is necessary is just to apply | coat so that a coating film may become a film thickness of 20-100 micrometers preferably 30-60 micrometers more preferably. After printing, for example, at 100 to 200 ° C., preferably at 120 to 150 ° C., for 20 to 60 minutes, by drying in a drying furnace or the like, a substrate coated with an etching resist dried in a desired pattern can be obtained. it can.

  When the resist film after heat drying is tested according to the test method of JIS C 5400 in the state after drying, it is preferable that the resist film is heat-dried in close contact with the substrate as a film having a pencil hardness of F or higher. .

  In the case of a heat-drying dry film, after laminating, etc., the layer of the etching resist composition of the present invention is bonded onto the substrate so that the desired pattern is formed by laser processing or the like. What is necessary is just to form.

  By etching the glass substrate covered with the etching resist with an etching solution, the substrate portion not covered with the resist can be etched.

  The etching solution is not particularly limited, and a known and commonly used etching solution containing hydrofluoric acid may be used (for example, a mixture of hydrofluoric acid and mineral acid (nitric acid, phosphoric acid, etc.), and in some cases, water, acetic acid, etc. Including any one or more of weak acids). Since the etching resist film formed with the etching resist composition of the present invention has excellent resistance to hydrofluoric acid, an etching solution having a higher concentration of hydrofluoric acid than usual may be used.

  Furthermore, the etching resist film formed with the etching resist composition of the present invention can be stripped with a dilute alkaline aqueous solution, and can be easily removed with a known stripping solution such as a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution. The density | concentration of alkaline substances, such as sodium hydroxide, is 1-5 mass%, for example.

  The etching resist composition of the present invention can be applied to printing methods such as a gravure method and a gravure offset method in addition to a screen printing method. In addition, the etching resist composition can be applied in a plurality of times. As a coating method at that time, conventionally known wet-on-wet coating such as 2-coat 1-bake or dry-on-wet coating such as 2-coat 2-bake is possible.

  The etching resist composition of the present invention can be suitably used for forming an etching resist film on a glass substrate. For example, in addition to processing glass of electronic parts such as tempered glass (OGC) for tablet and smartphone, speakerphone, earphone, silicon wafer, etc., it can also be used for processing of lenses, medical instruments and optical sensors. It can also be used as an etching resist for silicon wafers. Processing by glass etching is not particularly limited, and for example, it can be used for surface processing and formation of through holes.

  EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following, “part” and “%” are based on mass unless otherwise specified.

(Alkali-soluble resin having biphenyl structure: Resin A-1)
Epoxy resin represented by the above general formula (1) (NC-3000P, Nippon Kayaku Co., Ltd., epoxy equivalent 286, softening point 67 ° C., n is 2.24) 2860 g (10 equivalents), acrylic acid 720 .6 g (10 equivalents), 5.5 g of methylhydroquinone, 1349.6 g of carbitol acetate, and 578.4 g of solvent naphtha were charged, and the mixture was heated and stirred at 90 ° C. to dissolve the reaction mixture. Next, the reaction solution was cooled to 60 ° C., charged with 16.5 g of triphenylphosphine, heated to 98 ° C., reacted for about 32 hours, and cooled when the acid value (mgKOH / g) was 3.0 or less. An epoxy acrylate resin (a-1) was obtained. 5530.6 g of epoxy acrylate resin (a-1), 1338.5 g of tetrahydrophthalic anhydride, 504.5 g of carbitol acetate, and 216.2 g of solvent naphtha were reacted at 95 ° C. for 10 hours, and an alkali-soluble resin (A- 1) was obtained. The product had a solid content concentration of 65.0%, a solid content acid value (mgKOH / g) of 100, and a viscosity (25 ° C., dPa · s) of 375.

(Alkali-soluble resin having bisphenol F structure: Resin A-2)
In the above general formula (2), 380 parts of a bisphenol F type epoxy resin (epoxy equivalent 950 g / eq, softening point 85 ° C.) having X of CH ₂ and an average polymerization degree n of 6.2 and 925 parts of epichlorohydrin are dimethyl sulfoxide 462 After dissolving in 5 parts, 60.9 parts of 98.5% NaOH was added over 100 minutes at 70 ° C. with stirring. After the addition, the reaction was further carried out at 70 ° C. for 3 hours. After completion of the reaction, 250 parts of water was added and washed with water. After the oil / water separation, most of the dimethyl sulfoxide and excess unreacted epichlorohydrin were recovered by distillation from the oil layer under reduced pressure, and the reaction product containing the remaining by-product salt and dimethyl sulfoxide was dissolved in 750 parts of methyl isobutyl ketone, and further 30% NaOH 10 Part was added and reacted at 70 ° C. for 1 hour. After completion of the reaction, washing was performed twice with 200 parts of water. After the oil-water separation, methyl isobutyl ketone was distilled and recovered from the oil layer to obtain an epoxy resin (a) having an epoxy equivalent of 310 g / eq and a softening point of 69 ° C. When the epoxy resin (a) obtained was calculated from the epoxy equivalent, about 5 of the 6.2 alcoholic hydroxyl groups in the starting material bisphenol F type epoxy resin were epoxidized. 310 parts of this epoxy resin (a) and 282 parts of carbitol acetate were charged into a flask, and heated and stirred at 90 ° C. to dissolve. The obtained solution is once cooled to 60 ° C., 72 parts (1 mol) of acrylic acid, 0.5 part of methylhydroquinone and 2 parts of triphenylphosphine are added, heated to 100 ° C., reacted for about 60 hours, and acid value Yielded a reaction of 0.2 mg KOH / g. To this, 140 parts (0.92 mol) of tetrahydrophthalic anhydride was added and heated to 90 ° C. for reaction to obtain an alkali-soluble resin (A-2). The solid content concentration of the product was 65.0%, and the solid content acid value (mgKOH / g) was 100.

(Alkali-soluble resin having bisphenol A structure: Resin A-3)
371 parts of a bisphenol A type epoxy resin (epoxy equivalent 650 g / eq, softening point 81.1 ° C.) having X of C (CH ₃ ) ₂ and an average polymerization degree n of 3.3 in the above general formula (2) and epichlorohydrin After dissolving 925 parts in 462.5 parts of dimethyl sulfoxide, 52.8 parts of 98.5% NaOH was added over 100 minutes at 70 ° C. with stirring. After the addition, the reaction was further carried out at 70 ° C. for 3 hours. After completion of the reaction, 250 parts of water was added and washed with water. After the oil / water separation, most of the dimethyl sulfoxide and excess unreacted epichlorohydrin were recovered by distillation from the oil layer under reduced pressure, and the reaction product containing the remaining by-product salt and dimethyl sulfoxide was dissolved in 750 parts of methyl isobutyl ketone, and further 30% NaOH 10 Part was added and reacted at 70 ° C. for 1 hour. After completion of the reaction, washing was performed twice with 200 parts of water. After separation of oil and water, methyl isobutyl ketone was recovered by distillation from the oil layer to obtain an epoxy resin (a) having an epoxy equivalent of 287 g / eq and a softening point of 64.2 ° C. When the epoxy resin (a) obtained was calculated from the epoxy equivalent, about 3.1 of the 3.3 alcoholic hydroxyl groups in the starting material bisphenol A type epoxy resin were epoxidized. 310 parts of this epoxy resin (a) and 282 parts of carbitol acetate were charged into a flask, and heated and stirred at 90 ° C. to dissolve. The obtained solution is once cooled to 60 ° C., 72 parts (1 mol) of acrylic acid, 0.5 part of methylhydroquinone and 2 parts of triphenylphosphine are added, heated to 100 ° C., reacted for about 60 hours, and acid value Yielded a reaction of 0.2 mg KOH / g. To this, 140 parts (0.92 mol) of tetrahydrophthalic anhydride was added and heated to 90 ° C. for reaction to obtain an alkali-soluble resin (A-3). The solid content concentration of the product was 64.0%, and the solid content acid value (mgKOH / g) was 100.

(Alkali-soluble resin having neither biphenyl structure nor bisphenol structure: Resin R-1)
A styrene-acrylic copolymer resin having a carboxyl group (Jonkrill 67 (solid content: 100%, solid content acid value: 200 mgKOH / g) manufactured by BASF Japan Ltd.) was used. Hereinafter, it is referred to as Resin R-1. )

(Alkali-soluble resin having neither biphenyl structure nor bisphenol structure: Resin R-2)
Phenol novolac resin (BRG-557 manufactured by Showa Denko KK (solid content: 100%, softening point: 85 ° C.) was used, hereinafter referred to as Resin R-2.

(Alkali-soluble resin having neither biphenyl structure nor bisphenol structure: Resin R-3)
Put 210 parts of cresol novolac type epoxy resin (DIC Epiklon N-680, epoxy equivalent: 210) into a four-necked flask equipped with a stirrer and reflux condenser, add 96.4 parts of carbitol acetate, and dissolve by heating. did. Next, 0.46 part of hydroquinone as a polymerization inhibitor and 1.38 parts of triphenylphosphine as a reaction catalyst were added. This mixture was heated to 95 to 105 ° C., 72 parts of acrylic acid was gradually added dropwise, and the mixture was allowed to react for about 16 hours until the acid value became 3.0 mgKOH / g or less. The reaction product was cooled to 80 to 90 ° C., 76 parts of tetrahydrophthalic anhydride was added and reacted for 8 hours. After cooling, the product was taken out to obtain an alkali-soluble resin (R-3). The solid content concentration of the product was 65%, and the acid value of the solid product was 85 mgKOH / g.

(Alkali-soluble resin having neither biphenyl structure nor bisphenol structure: Resin R-4)
In a 2 liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introducing tube, 900 g of diethylene glycol dimethyl ether as a solvent and t-butylperoxy 2-ethylhexanoate (NOF) as a polymerization initiator 21.4 g of Perbutyl O) was added and heated to 90 ° C. After heating, here, 309.9 g of MAA (methacrylic acid), 116.4 g of MMA (methyl methacrylate), and 109.8 g of lactone-modified 2-hydroxyethyl methacrylate (Daicel Plaxel FM1) are polymerization initiators. A carboxylic acid-containing copolymer resin is obtained by adding dropwise over 2 hours together with 21.4 g of bis (4-t-butylcyclohexyl) peroxydicarbonate (NORO Corporation Perroyl TCP), and further aging for 6 hours. It was. The reaction was performed under a nitrogen atmosphere.
Next, to the obtained carboxyl group-containing copolymer resin, 363.9 g of 3,4-epoxycyclohexylmethyl acrylate (Daicel Cyclomer M100), dimethylbenzylamine: 3.6 g as a ring-opening catalyst, and polymerization inhibitor Hydroquinone monomethyl ether: 1.80 g was added, heated to 100 ° C., and stirred to carry out epoxy ring-opening addition reaction for 16 hours to obtain an alkali-soluble resin (R-4). The solid content concentration of the product was 45%, the acid value of the solid content was 76 mgKOH / g, and the weight average molecular weight was 25,000.

  In accordance with the composition shown in the following table, each component was blended, premixed with a stirrer, dispersed with a three-roll mill, and kneaded to prepare compositions. The compounding quantity in a table | surface shows a mass part. Moreover, the compounding quantity of the resin in a table | surface shows solid content. Examples 1 to 5 and Comparative Examples 1 to 4 in Table 1 are development type etching resist compositions, and Example 6 and Comparative Examples 5 to 8 in Table 2 are heat drying type etching resists. It is a composition.

＊１：ビフェニル構造を有するアルカリ可溶性樹脂
＊２：ビスフェノールＦ構造を有するアルカリ可溶性樹脂
＊３：ビスフェノールＡ構造を有するアルカリ可溶性樹脂
＊４：ビフェニル構造およびビスフェノール構造の何れも有しないアルカリ可溶性樹脂（スチレン、アクリル共重合樹脂（ＢＡＳＦジャパン社製ジョンクリル６７））
＊５：ビフェニル構造およびビスフェノール構造の何れも有しないアルカリ可溶性樹脂（フェノールノボラック樹脂（昭和電工社製ＢＲＧ−５５７））
＊６：ビフェニル構造およびビスフェノール構造の何れも有しないアルカリ可溶性樹脂（クレゾールノボラック構造を有するアルカリ可溶性樹脂）
＊７：ビフェニル構造およびビスフェノール構造の何れも有しないアルカリ可溶性樹脂（カルボキシル基含有共重合アクリレート樹脂）
＊８：シリコーン系消泡剤（信越化学社製）
＊９：多官能アクリルモノマー（東亜合成社製）
＊１０：タルク（富士タルク社製）
＊１１：α-アミノアルキルフェノン系光重合開始剤（ＢＡＳＦジャパン社製）
＊１２：フタロシアニンブルー
＊１３：アクリレート系シランカップリング剤（信越化学社製）
＊１４：ジエチレングリコールモノエチルエーテルアセテート

* 1: Alkali-soluble resin having biphenyl structure * 2: Alkali-soluble resin having bisphenol F structure * 3: Alkali-soluble resin having bisphenol A structure * 4: Alkali-soluble resin (styrene) having neither biphenyl structure nor bisphenol structure , Acrylic copolymer resin (Joncrill 67 manufactured by BASF Japan))
* 5: Alkali-soluble resin (phenol novolak resin (BRG-557 manufactured by Showa Denko KK)) that has neither biphenyl structure nor bisphenol structure
* 6: Alkali-soluble resin having neither biphenyl structure nor bisphenol structure (alkali-soluble resin having cresol novolac structure)
* 7: Alkali-soluble resin (carboxyl group-containing copolymer acrylate resin) that has neither biphenyl structure nor bisphenol structure
* 8: Silicone defoaming agent (Shin-Etsu Chemical Co., Ltd.)
* 9: Multifunctional acrylic monomer (Toa Gosei Co., Ltd.)
* 10: Talc (manufactured by Fuji Talc)
* 11: α-Aminoalkylphenone photopolymerization initiator (BASF Japan)
* 12: Phthalocyanine blue * 13: Acrylate-based silane coupling agent (Shin-Etsu Chemical Co., Ltd.)
* 14: Diethylene glycol monoethyl ether acetate

＊１５：カーボンブラック
＊１６：エポキシ系シランカップリング剤（信越化学社製）

* 15: Carbon black * 16: Epoxy silane coupling agent (Shin-Etsu Chemical Co., Ltd.)

  The resulting etching resist compositions of the examples and comparative examples were evaluated according to the following. The results are shown in the table below.

(Development-type etching resist film formation, hydrofluoric acid etching test and peeling test)
The development type etching resist compositions of Examples 1 to 5 and Comparative Examples 1 to 4 are each 100 mm × 150 mm in size by screen printing on 1.8 mm soda lime glass, and the film thickness after drying is 30 to 30 mm. Printing was performed to a thickness of 40 μm. After printing, it was dried at 80 ° C. for 20 minutes to evaporate the organic solvent and form a tack-free coating film. After that, it is selectively exposed with active energy rays through a photomask, and the unexposed portion is developed with a 1% sodium carbonate aqueous solution to form a resist pattern, followed by heat curing at 120 ° C. for 30 minutes to obtain a test substrate. It was.

  The test substrate prepared by the above method was immersed in a 10% hydrofluoric acid etching solution, the state of the coating film was observed every 10 minutes, and the time when the liquid soaked was observed was measured as the etching resistance time.

  In addition, after the test substrate prepared by the above method is thermally cured, it is immersed in a stripping solution in which a 5% aqueous sodium hydroxide solution is heated to a liquid temperature of 60 ° C., and the etching resist film formed by the development type etching resist composition is swollen and peeled off. Since it was a mold, the time when the coating film started to be removed from the test substrate due to swelling was measured as the peeling time.

(Formation of thermal drying type etching resist film, hydrofluoric acid etching test and peeling test)
Patterns were applied so that the heat-dried etching resist compositions of Example 6 and Comparative Examples 5 to 8 had a thickness of 40 to 50 μm after drying by screen printing on 1.8 mm soda lime glass. Formed. After printing, the film was dried at 120 ° C. for 30 minutes to evaporate the organic solvent and form a tack-free coating film to obtain a test substrate.

  The test substrate prepared by the above method was immersed in a 5% hydrofluoric acid etching solution, the state of the coating film was observed every 10 minutes, and the time when the liquid soaked was observed was measured as the etching resistance time.

  Also, after the test substrate prepared by the above method is thermally cured, it is immersed in a stripping solution in which a 5% aqueous solution of caustic soda is heated to a liquid temperature of 60 ° C., and the etching resist film formed by the heat drying type etching resist composition is dissolved. Since it was a peeling type, the time when the coating film started to dissolve from the test substrate was measured as the peeling time.

  As shown in the above table, an etching resist film formed using an etching resist composition containing an alkali-soluble resin having a biphenyl structure is excellent in resistance to hydrofluoric acid, and particularly in the case of a development type, the resistance time is remarkably improved. You can see that Furthermore, it was confirmed that the peelability was improved by using an alkali-soluble resin having a bisphenol type epoxy structure. Generally, an alkali-removing type heat-drying etching resist (for example, Example 6 and Comparative Examples 5 to 8) is used rather than a development type etching resist (for example, Examples 1 to 5 and Comparative Examples 1 to 4). ) Tends to be inferior in hydrofluoric acid resistance, but as shown in Table 4, the etching resist film formed by removing the alkali-soluble resin having the biphenyl structure alone or in combination with the alkali-soluble resin having the bisphenol structure is alkali-removed. It can be seen that hydrofluoric acid resistance is improved even with the type of heat-drying type etching resist.

Claims (5)

  An etching resist composition comprising an alkali-soluble resin having a biphenyl structure.   The etching resist composition according to claim 1, further comprising an alkali-soluble resin having a bisphenol structure.   Furthermore, a photocurable component is contained, The etching resist composition of Claim 1 or 2 characterized by the above-mentioned.   Furthermore, a coupling agent is contained, The etching resist composition as described in any one of Claims 1-3 characterized by the above-mentioned. It has a resin layer obtained by apply | coating and drying the etching resist composition as described in any one of Claims 1-4 on a film, The dry film characterized by the above-mentioned.