KR20160108160A - Etching resist composition and dry film - Google Patents

Abstract

The present invention provides an etching resist composition which can form an etching resist film having excellent hydrofluoric acid resistance, and to a dry film having a resin layer obtained from the composition and, more specifically, to an etching resist composition, comprising an alkali-soluble resin having a biphenyl structure, and to a dry film having a resin layer obtained from the composition.

Description

ETCHING RESIST COMPOSITION AND DRY FILM [0002]

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 hydrofluoric acid resistance and a dry film having a resin layer obtained from the composition.

In the processing of glass products, recently, fine processing and smoothness are more required. In addition, machining by glass etching is becoming mainstream in that machining using a drill is liable to cause cracks in the glass .

Glass etching is a method conventionally applied to glass bodies such as electronic materials, optical materials, and measuring instruments. As a method of glass etching, for example, a method of applying a resin composition to the surface of a glass substrate to be etched and thermally drying or curing the same to form an etching resist film, immersing the glass substrate in a fluoric acid etching solution, A method of forming a desired pattern on a glass substrate by removing the uncoated portion is used (for example, Patent Document 1).

Japanese Patent Application Laid-Open No. 2007-128052

The fluoric acid etchant has a strong permeability. Therefore, unless the etchant resist film is designed to be thick, the etchant penetrates between the glass substrate and the etch resist, and a desired pattern can not be obtained. Further, if the etching resist film is formed thick, it takes time to peel off the etching resist after the etching, and in the case of the developing type etching resist, the resolution is deteriorated.

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.

DISCLOSURE OF THE INVENTION The present inventors have intensively studied in view of the above, and as a result, they found that the above problems can be solved by adding an alkali-soluble resin having a specific structure to an etching resist composition, and have completed the present invention.

That is, the etching resist composition of the present invention is characterized by containing 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 a film and drying the film.

According to the present invention, it is possible 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.

The etching resist composition of the present invention is characterized by containing an alkali-soluble resin having a biphenyl structure. Since the etching resist film formed of the etching resist composition of the present invention is excellent in hydrofluoric acid resistance, peeling from the glass substrate during the etching process is unlikely to occur. Thereby, the substrate can be etched with high accuracy. In addition, since an etching liquid having a high hydrofluoric acid concentration can be used in the etching step, the etching processing time can be shortened.

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

The etching resist composition of the present invention preferably contains a coupling agent, whereby adhesion with the substrate can be improved, and an etching resist film having more 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, a coupling agent may not be contained. In the case of not containing a coupling agent, since the storage stability is excellent, it is also possible to store one solution at room temperature. When a coupling agent is contained, it is preferable to divide it into two or more liquids and store them.

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, but a carboxyl group-containing resin is preferable. When the curable resin composition of the present invention is a developing type, it is preferable that the alkali-soluble resin has an ethylenic unsaturated bond. The alkali-soluble resin may be used singly or in combination of two or more.

(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 or the like is reacted with a monocarboxylic acid containing an unsaturated group to form 2 (Meth) acrylate-modified resin having a carboxyl group formed by adding a carboxylic acid group anhydride and a compound having one epoxy group and at least one (meth) acryloyl group in addition to the resin, But are not limited to these.

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

(Wherein n < ₁ > represents an average value and 1.01 to 5)

Examples of the unsaturated group-containing monocarboxylic acid include (meth) acrylic acid, a dimer of (meth) acrylic acid,? -Styryl acrylic acid,? -Furfuryl acrylic acid, and a saturated or unsaturated dibasic acid anhydride (Meth) acrylate derivatives having one hydroxyl group, or half esters, which are equimolar reactants of a saturated or unsaturated dibasic acid and an unsaturated group-containing monoglycidyl compound. Further, in the present specification, (meth) acrylate is a generic term for acrylate, methacrylate, and mixtures 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-methylhexahydrophthalic anhydride, endomethylene-tetrahydrophthalic anhydride, methyl -Carboxylic anhydrides such as endomethyl-tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride and trimellitic 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 acid value of the carboxyl group-containing resin is 40 mgKOH / g or more, it can be easily removed by an alkaline removing solution. On the other hand, when the acid value is 300 mgKOH / g or less, resistance to etching is improved.

The weight average molecular weight (Mw) of the carboxyl group-containing resin varies depending on the resin skeleton, but is generally in the range of 1,000 to 150,000, more preferably 5,000 to 100,000. When the weight average molecular weight (Mw) is 1,000 or more, the 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 by an alkaline peeling liquid.

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

In the etching resist composition of the present invention, an alkali-soluble resin having a bisphenol structure is preferably used in combination from the viewpoint of releasability. The alkali-soluble resin having a bisphenol structure is not particularly limited. For example, an unsaturated group-containing monocarboxylic acid is reacted with a bifunctional or higher polyfunctional epoxy resin having a bisphenol structure such as a bisphenol-type epoxy resin, (Meth) acrylate having a carboxyl group-containing resin obtained by adding a dibasic acid anhydride to an existing hydroxyl group and a carboxyl group formed by adding a compound having one epoxy group and at least one (meth) acryloyl group in one molecule to the resin, Acrylate-modified resins.

As the alkali-soluble resin having a bisphenol structure, an epoxy group is added to a hydroxyl group of a bifunctional or higher polyfunctional bisphenol type epoxy resin having a hydroxyl group as described below with epichlorohydrin or the like, and then an unsaturated group-containing monocarboxylic acid (Meth) acrylate having a carboxyl group obtained by addition reaction of a carboxyl group-containing resin obtained by further reacting a carboxyl group-containing acid anhydride and a dibasic acid anhydride and a compound having an epoxy group and at least one (meth) acryloyl group in one molecule, Acrylate-modified resins. 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).

(Wherein 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 to the alkali-soluble resin having a bisphenol structure is preferably from 90:10 to 20:80, more preferably from 80 : 20 to 20:80, the etching resistance is not deteriorated and the peelability can be improved.

The content of the entire carboxyl group-containing resin is preferably 80% by mass or less, more preferably from 30 to 70% by mass, based on the solid content of the etching resist composition. When the content of the alkali-soluble resin is 80 mass% or less, the viscosity is stabilized well. Further, in the present specification, the solid content is a component excluding the solvent.

(Phenolic hydroxyl group-containing resin)

Examples of the phenolic hydroxyl group-containing resin include phenol novolac resins, alkylphenol novolak resins, bisphenol A novolak resins, dicyclopentadiene type phenol resins, Xylok type phenol resins, terpene modified phenol resins, polyvinyl phenols, bisphenol F, Phenolic hydroxyl group-containing resins such as bisphenol S-type phenol resin, poly-p-hydroxystyrene, condensates of naphthol and aldehydes, and condensation products of dihydroxynaphthalene and aldehydes.

(Photocurable component)

In the case of the development type of the etching resist composition of the present invention, since the etching resist resistance is remarkably improved, it is preferable that the etching resist composition contains a photocurable component. The photocurable component may be a resin which is cured by irradiation with active energy rays, and in the present invention, a compound having at least one ethylenic unsaturated bond in the molecule is preferably used. The photo-curable component may be used singly or in combination of two or more.

As the compound having an ethylenically unsaturated bond, a photopolymerizable oligomer and a photopolymerizable vinyl monomer for publicly known generations are used. Examples of the photopolymerizable oligomer include unsaturated polyester oligomers and (meth) acrylate oligomers. (Meth) acrylate oligomers include epoxy (meth) acrylates such as phenol novolac epoxy (meth) acrylate, cresol novolak epoxy (meth) acrylate and bisphenol epoxy Acrylate, epoxy urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, and polybutadiene modified (meth) acrylate.

Examples of the photopolymerizable vinyl monomers include known ones such as styrene derivatives such as styrene, chlorostyrene, and? -Methylstyrene; Vinyl esters such as vinyl acetate, vinyl butyrate and vinyl benzoate; N-butyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-n-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether Vinyl ethers such as ether and triethylene glycol monomethyl vinyl ether; Acrylamides such as acrylamide, methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide and N-butoxymethylacrylamide Meth) acrylamides; Allyl compounds such as triallyl isocyanurate, diallyl phthalate and diallyl isophthalate; (Meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tetra Esters of (meth) acrylic acid such as acrylate; Hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and pentaerythritol tri (meth) acrylate; Alkoxyalkylene glycol mono (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; Acrylates such as ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri , Alkylpolyol poly (meth) acrylates such as pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate; Polyoxyalkylene glycol poly (meth) acrylates such as diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethoxylated trimethylolpropane triacrylate and propoxylated trimethylolpropane tri (meth) Meth) acrylates; Poly (meth) acrylates such as hydroxypivalic acid neopentyl glycol ester di (meth) acrylate; And isocyanurate type poly (meth) acrylates such as tris [(meth) acryloxyethyl] 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 the content of the photocurable component is 5% by mass or more, the photocurability is improved. When it is 38% by mass or less, the tackiness is improved.

(Photopolymerization initiator)

In the case of the developing type, the etching resist composition of the present invention preferably contains a photopolymerization initiator.

As the photopolymerization initiator, for example, bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine 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- 6-trimethylbenzoyl) -phenylphosphine oxide (IRGACURE 819 manufactured by BASF Japan); 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, Monoacylphosphine oxides such as valylphenylphosphinic acid isopropyl ester and 2,4,6-trimethylbenzoyldiphenylphosphine oxide (DAROCUR TPO manufactured by BASF Japan); 1-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy- 2-methyl-1-phenyl-propan-1-one, 2-hydroxy- Hydroxyacetophenones such as 1-one; Benzoin such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether and benzoin n-butyl ether; Benzoin alkyl ethers; Benzophenones such as benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, and 4,4'-bisdiethylaminobenzophenone; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2- Acetophenones such as (dimethylamino) -2 - [(4-methylphenyl) methyl) -1- [4- (4-morpholinyl) phenyl] -1-butanone and N, N-dimethylaminoacetophenone; Thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-di Thioxanthones such as isopropylthioxanthone; Anthraquinones such as anthraquinone, chloroanthraquinone, 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-tert-butyl anthraquinone, 1-chloro anthraquinone, 2-amylanthraquinone and 2-aminoanthraquinone; Ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2- (dimethylamino) ethylbenzoate and p-dimethylbenzoic acid ethyl ester; Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbaldehyde, 1- Oxazol-3-yl] -, 1- (0-acetyloxime); Bis (cyclopentadienyl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium, bis (cyclopentadienyl) Titanocenes such as bis [2,6-difluoro-3- (2- (1-phenyl-1-yl) ethyl) phenyl] titanium; Phenyldisulfide, 2-nitrofluorene, butyroin, anisooin ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, and the like. The photopolymerization initiator may be used singly or in combination of two or more.

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 the content of the photopolymerization initiator is 1% by mass or more, the photocurability is improved. When it is 8% by mass or less, the halation hardly occurs and the curing depth becomes appropriate.

(Coupling agent)

The etching resist composition of the present invention may contain a coupling agent. As the coupling agent, a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent and the like can be used. As the coupling agent, a silane coupling agent is preferable. The coupling agent may be used singly or in combination of two or more kinds.

The silane coupling agent is composed of an organic material (organic group) and silicon and is generally represented by XnR '(n-1) Si-R "-Y (X = hydroxyl, alkoxyl, etc., Y = vinyl group, , A methacryloxy group, an acryloxy group, an amino group, an ureido group, a chloropropyl group, a mercapto group, a polysulfide group, an isocyanate group, etc. Since they have two or more different reactors in a molecule, It serves as an intermediary for connecting an organic material and an inorganic material that are hardly combined with each other, and is used for strength improvement of a composite material, modification of a resin, and surface modification.

Examples of the silane coupling agent include N-γ- (aminoethyl) -γ-aminopropyltriethoxysilane, N-γ- (aminoethyl) -γ-aminopropyltrimethoxysilane, Aminopropyltrimethoxysilane,? -Aminopropylmethyldiethoxysilane,? -Aminopropylmethyldimethoxysilane,? -Aminopropylphenyldiethoxysilane, 2-amino-1-methylethyltriethoxy Silane, N-methyl- gamma -aminopropyltriethoxysilane, N-phenyl- gamma -aminopropyltriethoxysilane, N-butyl- gamma -aminopropylmethyldiethoxysilane, N- aminopropyltriethoxysilane,? - (aminoethyl) -N-? - (aminoethyl) -? - aminopropyltrimethoxysilane,? -ureidopropyltriethoxysilane,? -glycidyl Isopropyltriethoxysilane,? -Glycidoxypropylmethyldimethoxysilane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane,? -Mercapto Vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane, Silane, methacryloxypropyltrimethoxysilane, and? -Polyoxyethylene propyltrimethoxysilane.

Examples of commercial products of silane coupling agents include KA-1003, KBM-1003, KBE-1003, KBM-303, KBM-403, KBE-402, KBE-403, KBM-1403, KBM- KBM-573, KBM-603, KBM-903, KBE-903, KBE-9103, KBM-9103, KBM-573, KBM- 6123, KBE-585, KBM-703, KBM-802, KBM-803, KBE-846 and KBE-9007 (all trade names; manufactured by Shinetsu Silicone Co., Ltd.).

Examples of the titanium-based coupling agent include titanium alkoxides such as tetraethoxytitanate, tetraisopropyl titanate and tetra-n-butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) Titanium tetraacetylacetonate, polythiethylacetyl acetonate, titanium octyleneglycolate, titanium ethylacetoacetate, titanium lactate, titanium triethanolaminate, and the like can be exemplified. As the zirconium-based and aluminum-based coupling agents, compounds corresponding to titanium-based compounds can be used.

Since the etching resist composition of the present invention is excellent in hydrofluoric acid resistance, it is difficult for the resist to peel off in the immersion step in the etching solution without containing a coupling agent. Therefore, the content of the coupling agent is not essential, but when the coupling agent is contained, the preferable amount is 0.5 to 5% by mass per solid fraction of the etching resist composition. If it is 0.5% by mass or more, more excellent etching resist resistance is obtained. When it is 5 mass% or less, stable characteristics are obtained.

(Filler)

In the present invention, conventionally known inorganic fillers for etching resists and organic fillers can be used. Examples of the inorganic filler include sieving agents such as barium sulfate, barium titanate, talc, clay, aluminum oxide, aluminum hydroxide, silicon nitride, aluminum nitride and the like. The inorganic filler plays a role of adjusting the viscosity at the time of adjusting the resist composition appropriately, suppressing the curing shrinkage of the coating film upon thermal drying or photo-curing, and improving adhesion with the substrate. Of these, talc is particularly preferably used in order to improve adhesion with the substrate. The fillers may be used singly or in combination of two or more.

The average primary particle diameter of the inorganic filler is preferably 15 占 퐉 or less, more preferably 10 占 퐉 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, per solid fraction of the etching resist composition. When the compounding amount of the filler is 0.01 mass% or more, the adhesion between the resist and the substrate is improved, and when it is 70 mass% or less, the fluidity of the composition is improved.

(Organic solvent)

The etching resist composition of the present invention may contain an organic solvent. 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, N-hexane, n-heptane, n-octane and the like, aliphatic hydrocarbons such as benzene, toluene, xylene And halogenated hydrocarbons such as chloroform and carbon tetrachloride. The organic solvent may be used singly or in combination of two or more kinds.

The solid content of the etching resist composition of the present invention is preferably 20 to 85% by mass, and more preferably 30 to 80% by mass.

(Other additives)

In addition, other additives known in the field of etching resists may be added to the resist composition of the present invention. Examples of other additives include surface tension modifiers, surfactants, matting agents, polyester resins for adjusting physical properties of membranes, polyurethane resins, vinyl resins, acrylic resins, rubber resins, waxes, phthalocyanine blue, phthalocyanine Colorants such as green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black and naphthalene black; antifoaming agents and leveling agents such as silicone type, fluorine type and high molecular type; and the like. Such an additive can be compounded by appropriately adjusting the amount of the additive to such an extent that the effect of the present invention is not impaired and a desired effect of the additive is obtained.

In the case of using the etching resist composition of the present invention as a liquid phase, it may be one-liquid or two-liquid or more.

The etching resist composition of the present invention may be used as a dry film as described below. In the case of the developing type, a desired pattern can be formed by exposure in the same manner as described above. In the case of the heat drying type, a pattern can be formed by laser machining or the like.

The dry film of the present invention has a resin layer obtained by applying the etching resist composition of the present invention to a film and drying it. In forming the dry film, first, the etching resist composition of the present invention is diluted with the above-mentioned organic solvent and adjusted to an appropriate viscosity. Thereafter, a resist composition such as a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, A gravure coater, a spray coater or the like to a uniform thickness on the carrier film. Thereafter, the coated composition is dried at a temperature of usually 50 to 130 DEG C for 1 to 30 minutes to form a resin layer. The thickness of the coating film is not particularly limited, but is generally appropriately selected in the range of 10 to 150 占 퐉, preferably 20 to 60 占 퐉 in film thickness after drying.

As the carrier film, a plastic film is used, and for example, a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film and the like can be used. The thickness of the carrier film is not particularly limited, but is generally appropriately selected in the range of 10 to 150 mu m.

It is preferable to laminate a peelable cover film on the surface of the film for the purpose of preventing the adhesion of dust to the surface of the film after the resin layer containing the etching resist composition of the present invention is formed on the carrier film Do. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface treated paper and the like can be used. The cover film may be one that is smaller than the adhesive force between the resin layer and the carrier film when the cover film is peeled off.

In the dry film of the present invention, it is also possible to form a resin layer by coating and drying the etching resist composition of the present invention on the protective film, and laminating a carrier film on the surface of the resin layer. That is, in the present invention, as the film to which the etching resist composition of the present invention is applied when producing the dry film, either a carrier film or a protective film may be used.

In the case of a dry film, it is possible to coat the glass substrate with an etching resist by joining the layer of the etching resist composition of the present invention to the substrate so as to be in contact with the glass substrate with a laminator or the like and then peeling off the carrier film.

In the case where the etching resist composition of the present invention is a liquid composition of a developing type, it is preferable to use a coating method such as screen printing or a curtain coater on a substrate such as a glass substrate after adjustment as a uniform solution or dispersion, Is preferably 20 to 100 占 퐉, more preferably 30 to 60 占 퐉. After the application, the resist is thermally dried in a drying furnace or the like at 70 to 100 ° C for 20 to 40 minutes, and then the resist is exposed to light through a mask to bake the pattern. Thereafter, development is carried out with an aqueous alkali solution to form a pattern, and the resultant structure is thermally dried, for example, at 100 to 200 DEG C, preferably 120 to 150 DEG C for 20 to 60 minutes in a drying furnace, Can be obtained.

In the case of a dry type film of a developing type, after the layer of the etching resist composition of the present invention is bonded to a substrate so as to be in contact with the substrate by a laminator or the like, a pattern can be formed by exposure and development in the same manner as described above .

When the etching resist composition of the present invention is a thermally drying liquid composition, it is preferable that the substrate after being adjusted as a uniform solution or dispersion is coated with a desired pattern by screen printing or the like on a substrate such as a glass substrate, Mu m, more preferably 30 to 60 mu m. After printing, the substrate is thermally dried in a drying furnace at a temperature of, for example, 100 to 200 DEG C, preferably 120 to 150 DEG C for 20 to 60 minutes to obtain a substrate coated with an etching resist dried in a desired pattern.

When the resist coating film after the heat drying is tested in accordance with the test method of JIS C 5400 in the state after drying, it is preferable that the resist coating film is brought into close contact with the substrate as a film having a hardness of not less than F and is thermally dried.

In the case of the dry dry type dry film, a desired pattern can be formed by laser processing after the layer of the etching resist composition of the present invention is bonded to a substrate so as to be in contact with the substrate by a laminator or the like.

The glass substrate coated with the etching resist is etched by an etching solution to etch the substrate portion which is not covered with the resist.

The etching solution is not particularly limited and an etching solution containing a known acid such as hydrofluoric acid can be used (for example, a mixture of hydrofluoric acid and inorganic acid (nitric acid, phosphoric acid, etc.) Including more than species. Since the etching resist film formed of the etching resist composition of the present invention is excellent in hydrofluoric acid resistance, an etching solution having a higher hydrofluoric acid concentration than usual can be used.

In addition, the etching resist film formed from the etching resist composition of the present invention can be peeled off with a dilute alkali aqueous solution, and can be easily removed with a known peeling solution such as an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, or the like. The concentration of the alkali substance such as sodium hydroxide is, for example, 1 to 5 mass%.

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

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 glass processing for electronic parts such as tempered glass (OGC), speaker phone, earphone, and silicon wafer for tablet or smart phone, it can be used for processing lenses, medical instruments, and optical sensors. It can also be used as an etching resist for a silicon wafer. The processing by glass etching is not particularly limited, and it can be used, for example, for processing of a surface and formation of a through-hole.

[Example]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following, " parts " and "% " are based on mass unless otherwise specified.

(Alkali-soluble resin having biphenyl structure: resin A-1)

2860 g (10 eq.) Of an epoxy resin represented by the above general formula (1) (NC-3000P, epoxy equivalent 286, softening point 67 ° C, n 2.24), 720.6 g (10 eq.) Of acrylic acid, methylhydroquinone 5.5 1349.6 g of carbitol acetate, and 578.4 g of solvent naphtha were charged, and the mixture was heated and stirred at 90 DEG C to dissolve the reaction mixture. Subsequently, the reaction solution was cooled to 60 DEG C and 16.5 g of triphenylphosphine was added thereto. The mixture was heated to 98 DEG C and allowed to react for about 32 hours. When the acid value (mgKOH / g) To obtain a late resin (a-1). Soluble resin (A-1) was obtained by charging 5530.6 g of the epoxy acrylate resin (a-1), 1338.5 g of tetrahydrophthalic anhydride, 504.5 g of carbitol acetate and 216.2 g of solvent naphtha at 95 ° C for 10 hours, . The solid content concentration of the product was 65.0%, the solid acid value (mgKOH / g) was 100, and the viscosity (25 캜, dPa s) was 375.

(Alkali-soluble resin having a bisphenol F structure: resin A-2)

380 parts of a bisphenol F epoxy resin (epoxy equivalent weight 950 g / eq, softening point 85 캜) having X of CH ₂ and an average degree of polymerization n of 6.2 in the above-mentioned formula (2) and 925 parts of epichlorohydrin were added to 462.5 parts of dimethyl sulfoxide , And then 60.9 parts of 98.5% NaOH was added over 100 minutes at 70 DEG C under stirring. After the addition, the reaction was further carried out at 70 ° C for 3 hours. After the completion of the reaction, 250 parts of water was added to the reaction solution, followed by washing with water. After the water separation, most of the dimethyl sulfoxide and excess unreacted epichlorohydrin were distilled off under reduced pressure, and the reaction product containing the remaining unsubstituted salt and dimethyl sulfoxide was dissolved in 750 parts of methyl isobutyl ketone , And further, 10 parts of 30% NaOH was added and reacted at 70 DEG C for 1 hour. After completion of the reaction, the reaction mixture was washed twice with 200 parts of water. After the water separation, methyl isobutyl ketone was distilled off 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 캜. The epoxy resin (a) obtained was epoxidized with about 5 of the 6.2 alcoholic hydroxyl groups in the starting bisphenol F epoxy resin as calculated from the epoxy equivalent. 310 parts of the epoxy resin (a) and 282 parts of carbitol acetate were placed in a flask, and the mixture was heated and stirred at 90 DEG C to dissolve. The obtained solution was once cooled to 60 占 폚, and 72 parts (1 mole) of acrylic acid, 0.5 part of methylhydroquinone and 2 parts of triphenylphosphine were added and heated to 100 占 폚 for about 60 hours to obtain an acid value of 0.2 mgKOH / g Was obtained. Thereto was added 140 parts (0.92 mol) of tetrahydrophthalic anhydride and heated at 90 占 폚 to carry out the reaction to obtain an alkali-soluble resin (A-2). The solid content concentration of the product was 65.0% and the solid acid value (mgKOH / g) was 100.

(Alkali-soluble resin having a bisphenol A structure: resin A-3)

Wherein in the formula (2) X is C (CH _{3) 2,} the average degree of polymerization of n is 3.3 Bisphenol A type epoxy resin (epoxy equivalent 650g / eq, softening point 81.1 ℃) 371 part and the epichlorohydrin, 925 parts of dimethyl After dissolving in 462.5 parts of sulfoxide, 52.8 parts of 98.5% NaOH was added over 100 minutes at 70 DEG C under stirring. After the addition, the reaction was further carried out at 70 ° C for 3 hours. After the completion of the reaction, 250 parts of water was added to the reaction solution, followed by washing with water. After the water separation, most of the dimethyl sulfoxide and excess unreacted epichlorohydrin were distilled off under reduced pressure, and the reaction product containing the remaining unsubstituted salt and dimethyl sulfoxide was dissolved in 750 parts of methyl isobutyl ketone , And further, 10 parts of 30% NaOH was added and reacted at 70 DEG C for 1 hour. After completion of the reaction, the reaction mixture was washed twice with 200 parts of water. After the water separation, methyl isobutyl ketone was distilled and collected 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 占 폚. The epoxy resin (a) obtained was epoxidized with about 3.1 of the 3.3 alcoholic hydroxyl groups in the starting bisphenol A epoxy resin as calculated from the epoxy equivalent. 310 parts of the epoxy resin (a) and 282 parts of carbitol acetate were put into a flask, and heated and stirred at 90 캜 to dissolve. The obtained solution was once cooled to 60 占 폚, and 72 parts (1 mole) of acrylic acid, 0.5 part of methylhydroquinone and 2 parts of triphenylphosphine were added and heated to 100 占 폚 for about 60 hours to obtain an acid value of 0.2 mgKOH / g Was obtained. Thereto was added 140 parts (0.92 mol) of tetrahydrophthalic anhydride, and the mixture was heated to 90 DEG C to carry out a reaction to obtain an alkali-soluble resin (A-3). The solid content concentration of the product was 64.0% and the solid acid value (mgKOH / g) was 100.

(Alkali-soluble resin having neither a biphenyl structure nor a bisphenol structure: Resin R-1)

Acrylic acid copolymer resin having a carboxyl group (Joncryl 67 (solid content: 100%, solid acid value: 200 mgKOH / g) manufactured by BASF Japan) was used. Hereinafter, it is referred to as Resin R-1.

(Alkali-soluble resin having neither a biphenyl structure nor a bisphenol structure: resin R-2)

Phenol novolac resin (BRG-557 (solid content 100%, softening point 85 캜) manufactured by Showa Denko KK) was used. Hereinafter, it is referred to as Resin R-2.

(Alkali-soluble resin having neither a biphenyl structure nor a bisphenol structure: Resin R-3)

210 parts of cresol novolak type epoxy resin (Epiclon N-680, manufactured by DIC Corporation, epoxy equivalent: 210) were placed in a four-necked flask equipped with a stirrer and a reflux condenser, and 96.4 parts of carbitol acetate was added and heated to dissolve. Then, 0.46 part of hydroquinone as a polymerization inhibitor and 1.38 parts of triphenylphosphine as a reaction catalyst were added. The mixture was heated to 95 to 105 DEG C, and 72 parts of acrylic acid was slowly added dropwise, and the mixture was reacted for about 16 hours until the acid value became 3.0 mgKOH / g or less. The reaction product was cooled to 80 to 90 占 폚, and 76 parts of tetrahydrophthalic anhydride was added and reacted for 8 hours. After cooling, the reaction product was taken out to obtain an alkali-soluble resin (R-3). The solid content of the product was 65% and the acid value of the solid was 85 mgKOH / g.

(Alkali-soluble resin having neither a biphenyl structure nor a bisphenol structure: resin R-4)

To 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 21.4 g of perbutyl O) was added and heated to 90 占 폚. After heating, 309.9 g of MAA (methacrylic acid), 116.4 g of MMA (methyl methacrylate), and 109.8 g of lactone-modified 2-hydroxyethyl methacrylate (Flaxel FM1 manufactured by Daicel) (4-t-butylcyclohexyl) peroxydicarbonate (Nitrate-like ferulic TCP) was added dropwise over 3 hours and further aged for 6 hours to obtain a carboxyl group-containing copolymer resin . The reaction was carried out in a nitrogen atmosphere.

Subsequently, 363.9 g of 3,4-epoxycyclohexylmethyl acrylate (Cyclomer M100 manufactured by Daicel Chemical Industries, Ltd.), 3.6 g of dimethylbenzylamine as a ring opening catalyst, 1.80 g of hydroquinone monomethyl ether as polymerization inhibitor And the mixture was heated to 100 占 폚 and stirred to carry out a ring-opening addition reaction of epoxy for 16 hours to obtain an alkali-soluble resin (R-4). The product had a solid content concentration of 45%, an acid value of solid content of 76 mgKOH / g and a weight average molecular weight of 25,000.

Each component was blended according to the formulation shown in the following table, premixed in a stirrer, dispersed with a three-axis roll mill, and kneaded to prepare a composition. The amount in the table indicates the parts by mass. The amount of the resin in the table indicates the solid content. Examples 1 to 5 and Comparative Examples 1 to 4 in Table 1 are the development type etching resist compositions, and Example 6 and Comparative Examples 5 to 8 in Table 2 are heat drying type etching resist compositions.

* 1: Alkali-soluble resin having biphenyl structure

* 2: Alkali-soluble resin having a bisphenol F structure

* 3: Alkali-soluble resin having a bisphenol A structure

* 4: Alkali-soluble resin having no biphenyl structure and bisphenol structure (styrene, acrylic copolymer resin (John Krill 67 manufactured by BASF Japan))

* 5: Alkali-soluble resin having no biphenyl structure and bisphenol structure (phenol novolak resin (BRG-557 manufactured by Showa Denko KK))

* 6: An alkali-soluble resin having neither a biphenyl structure nor a bisphenol structure (alkali-soluble resin having a cresol novolak structure)

* 7: Alkali-soluble resin having no biphenyl structure and bisphenol structure (carboxyl group-containing copolymer acrylate resin)

* 8: Silicone antifoaming agent (manufactured by Shinetsu Chemical Co., Ltd.)

* 9: Polyfunctional acrylic monomer (manufactured by Toa Kose Co., Ltd.)

* 10: Talc (manufactured by Fuji Talc)

* 11:? -Aminoalkylphenone-based photopolymerization initiator (manufactured by BASF Japan)

* 12: Phthalocyanine blue

* 13: Acrylate-based silane coupling agent (manufactured by Shinetsu Chemical Co., Ltd.)

* 14: Diethylene glycol monoethyl ether acetate

* 15: Carbon black

* 16: Epoxy-based silane coupling agent (manufactured by Shinetsu Chemical Co., Ltd.)

The etching resist compositions of each of the obtained examples and comparative examples were evaluated as follows. The results are shown in the following table.

(Formation of a developing type etching resist film, hydrofluoric acid etching test and peeling test)

Resistive etching resist compositions of Examples 1 to 5 and Comparative Examples 1 to 4 were dried to a size of 100 mm x 150 mm on a soda lime glass of 1.8 mm by screen printing to have a thickness of 30 to 40 m As shown in FIG. After printing, the substrate was dried at 80 DEG C for 20 minutes, and the organic solvent was evaporated to form a non-stick coating film. Thereafter, the resist film was selectively exposed through an active energy ray through a photomask, the unexposed portion was developed with a 1% aqueous solution of sodium carbonate to form a resist pattern, and the resist pattern was thermally cured at 120 DEG C for 30 minutes to obtain a test substrate .

The test substrate produced 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 at which the immersion of the solution was observed was measured as the etching resistance time.

In addition, the test substrate prepared by the above method is thermally cured and immersed in a 5% caustic soda aqueous solution in a peeling solution heated at a temperature of 60 캜, and the etching resist film formed by the developing type etching resist composition is swollen and peelable, The time at which the coating film was started from the substrate due to the swelling was measured as the peeling time.

(Formation of a heat drying type etching resist film, hydrofluoric acid etching test and peeling test)

The dry-type etching resist compositions of Example 6 and Comparative Examples 5 to 8 were formed on soda lime glass of 1.8 mm by screen printing to form a pattern having a thickness of 40 to 50 占 퐉 Respectively. After printing, the substrate was dried at 120 DEG C for 30 minutes, and the organic solvent was evaporated to form a tack-free coating film, and a test substrate was obtained.

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

Further, the test substrate produced by the above method is thermally cured and then the 5% caustic soda aqueous solution is immersed in a peeling solution heated to a temperature of 60 ° C, and the etching resist film formed by the heat-drying type etching resist composition is dissolved and peeled, The time at which the coating film started dissolving from the test substrate was measured as the peeling time.

As shown in the above table, an etching resist film formed by using an etching resist composition containing an alkali-soluble resin having a biphenyl structure is excellent in hydrofluoric acid resistance, and particularly in the case of the developing type, the resistance time is remarkably improved Able to know. Further, by using an alkali-soluble resin having a bisphenol-type epoxy structure in combination, it was confirmed that the peelability was also improved. Further, in general, it is preferable to use an alkali removal type heat-drying type etching resist (for example, the resist composition of Example 6 and Comparative Example 5 (for example, To 8) tend to be poor in hydrofluoric acid resistance. However, as shown in Table 4, the etching resist film formed by using an alkali-soluble resin having a biphenyl structure alone or in combination with an alkali-soluble resin having a bisphenol structure is heat- Type etching regulator also shows improved hydrofluoric acid resistance.

Claims (5)

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. The etching resist composition according to claim 1 or 2, further comprising a photocurable component. The etching resist composition according to any one of claims 1 to 3, further comprising a coupling agent. A dry film comprising a resin layer obtained by applying the etching resist composition according to any one of claims 1 to 4 to a film and drying the resist film.