TWI698712B - Etching resist composition and dry film - Google Patents

Abstract

To provide an etching resist composition capable of forming an etching resist film with excellent hydrogen fluoride resistance, and a dry film having a resin layer obtained from the composition.

An etching resist composition characterized by containing an alkali-soluble resin having a biphenyl structure, and a dry film having a resin layer obtained from the composition.

Description

Etching resist composition and dry film

The present invention relates to an etching resist composition and a dry film, and specifically relates to an etching resist composition capable of forming an etching resist film excellent in hydrogen fluoride resistance, and a dry film having a resin layer obtained from the composition.

In the processing of glass products, in recent years, due to the pursuit of fine processing or smoothness, and the use of drills for mechanical processing, glass has become prone to cracks, and glass etching has become the mainstream.

Glass etching is a technique that is more applicable to glass frames of electronic materials, optical materials, and measuring instruments than before. The glass etching method can be used, for example, by coating the surface of the glass substrate to be etched with a resin composition, thermally drying or curing, and forming an etching resist film, and then immersing the glass substrate in a hydrogen fluoride etching solution to remove A method of forming a desired pattern on the glass substrate for the part that is not covered by the resist (for example, Patent Document 1).

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2007-128052 A

Because the hydrogen fluoride-based etching solution is highly permeable, if no effort is made to form a thick etching resist film, etc., the etching solution penetrates between the glass substrate and the etching resist and the desired pattern cannot be obtained. In addition, the formation of a thick etching resist film also takes time to peel off the etching resist after etching, and there is a problem that the resolution is lowered in the case of a development type etching resist.

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

In view of the above situation, the inventors of the present invention worked hard to review the results, and found that the above-mentioned problems can be solved by combining the etching resist composition with an alkali-soluble resin having a specific structure and 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 further preferably contains an alkali-soluble resin having a bisphenol structure.

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

The etching resist composition of the present invention further contains Coupling agent is better.

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

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

[Best form to implement invention]

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 with the etching resist composition of the present invention is excellent in hydrogen fluoride resistance, it is difficult to peel off from the glass substrate during the etching process. Thereby, the substrate can be etched with high precision. In addition, since an etching solution with a high hydrogen fluoride concentration can be used in the etching step, the etching process time can be shortened.

Since the etching resist film formed with the etching resist composition of the present invention is excellent in hydrogen fluoride resistance, even if a thick film thickness is not formed, it is not easily peeled off by an etching solution. Although the etching resist composition of the present invention may be a developing type or a thermal drying type, the film thickness of the etching resist may not be thick. In the case of the developing type, an etching resist film with excellent resolution can be formed.

The etching resist composition of the present invention preferably contains a coupling agent, whereby the adhesion to the substrate is improved, and an etching resist film with more excellent hydrogen fluoride resistance can be formed. However, because even without coupling agent, it can still form An etching resist film with excellent hydrogen fluoride resistance, so no coupling agent is required. When the coupling agent is not included, the storage stability is also excellent, so it can be stored in one-component form at room temperature. When it contains a coupling agent, it is better to store it in two or more solutions.

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, although a carboxyl group-containing resin or a phenol-based hydroxyl resin can be used, a carboxyl group-containing resin is preferred. When the curable resin composition of the present invention is a developing type, the alkali-soluble resin preferably has an ethylenically unsaturated bond. Alkali-soluble resin can be used individually by 1 type or in combination of 2 or more types.

(Carboxyl-containing resin)

The aforementioned carboxyl group-containing resins include, for example, biphenyl type epoxy resins, such as biphenyl type epoxy resins, which have bifunctional or more multifunctional epoxy resins having a biphenyl structure and react with an unsaturated group-containing monocarboxylic acid to form a hydroxyl group in the side chain. A carboxyl group-containing resin added with a dibasic acid anhydride, and a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule is added to the resin and a (methyl) group having a carboxyl group Acrylate modified resin, but not limited to these.

The bifunctional or more polyfunctional epoxy resin having a biphenyl structure includes, for example, a biphenyl type epoxy resin represented by the following general formula (1).

(式中，n₁表示平均值，為1.01~5)。

(In the formula, n ₁ represents the average value, which is 1.01 to 5).

The aforementioned unsaturated group-containing monocarboxylic acids include, for example, (meth)acrylic acid, (meth)acrylic acid dimers, β-styryl acrylic acid, β-furfuryl acrylic acid, and saturated or unsaturated diprotic acid anhydrides With half esters of molar reactants such as (meth)acrylate derivatives having one hydroxyl group in one molecule, or between saturated or unsaturated diprotic acids and unsaturated group-containing monoglycidyl compounds Half esters of ear reactants. In addition, in this specification, the general terminology and other similar expressions of (meth)acrylate acrylate, methacrylate, and their mixtures are also the same.

The aforementioned dibasic acid anhydrides include, for example, anhydrous phthalic acid, tetrahydroanhydrous phthalic acid, hexahydroanhydrous phthalic acid, 3-methyl-tetrahydroanhydrous phthalic acid, 4-methyl-hexahydroanhydrous phthalic acid , Endomethyl-tetrahydroanhydrous phthalic acid, methyl-endomethyl-tetrahydroanhydrous phthalic acid, anhydrous succinic acid, anhydrous maleic acid, trimellitic acid and other carboxylic anhydrides.

The acid value of the aforementioned carboxyl group-containing resin is preferably 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 aforementioned carboxyl group-containing resin is more than 40 mgKOH/g, it can be easily removed with an alkaline stripping solution. On the other hand, when the acid value is less than 300 mgKOH/g, the resistance during etching improves.

In addition, although the weight average molecular weight (Mw) of the aforementioned carboxyl group-containing resin varies depending on the resin skeleton, it is generally 1,000 to 150,000, and more preferably in the range of 5,000 to 100,000. When the weight average molecular weight (Mw) is 1,000 or more, the etching resistance improves. On the other hand, when the weight average molecular weight (Mw) is 150,000 or less, it can be easily removed with an alkaline stripping liquid.

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

In the etching resist composition of the present invention, from the viewpoint of releasability, it is preferable to use an alkali-soluble resin having a bisphenol structure in combination. Alkali-soluble resins having a bisphenol structure are not particularly limited, and examples include bisphenol type epoxy resins such as bisphenol-based epoxy resins that have bifunctional or more multifunctional epoxy resins having a bisphenol structure react with unsaturated group-containing monocarboxylic acids, A carboxyl group-containing resin in which a dibasic acid anhydride is added to the hydroxyl group present in the side chain, and the resin is then added to a compound having one epoxy group and one or more (meth)acrylic groups in one molecule. Carboxyl (meth)acrylate modified resin.

In addition, alkali-soluble resins having a bisphenol structure may also include, for example, the following bifunctional or more multifunctional bisphenol-type epoxy resins having hydroxyl groups. After the hydroxyl groups are added to epoxy groups with epichlorohydrin, etc. A carboxyl group-containing resin obtained by reacting with an unsaturated group-containing monocarboxylic acid and a dibasic acid anhydride, and a resin having 1 epoxy group and 1 or more (meth)acrylic groups in 1 molecule (Meth)acrylate modified resin with carboxyl group composed of compound. The aforementioned bifunctional or more multifunctional bisphenol with hydroxyl The type epoxy resins include, for example, bisphenol F type epoxy resins and bisphenol A type epoxy resins represented by the following general formula (2).

(式中，X為CH₂或C(CH₃)₂，n為1~12)。

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

When the alkali-soluble resin with a bisphenol structure is used in combination, the ratio of the alkali-soluble resin with a biphenyl structure to the alkali-soluble resin with a bisphenol structure is preferably 90:10-20:80, more preferably 80: The ratio of 20-20:80 can improve the peelability without compromising the etching resistance.

In addition, the total content of the carboxyl group-containing resin per unit solid content of the etching resist composition is preferably 80% by mass or less, and more preferably 30 to 70% by mass. When the content of the alkali-soluble resin is 80% by mass or less, the viscosity is good and stable. In addition, in the specification of the present invention, the solid content refers to the component from which the solvent is removed.

(Containing phenolic hydroxyl resin)

As the aforementioned phenolic hydroxyl resin, phenolic novolak resin, alkylphenol novolak resin, bisphenol A novolak resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, terpene modified phenol resin, Polyvinylphenols, bisphenol F, bisphenol S type phenol resin, poly-p-hydroxystyrene, naphthol and Conventionally used phenolic hydroxyl-containing resins such as condensation products of aldehydes and condensation products of dihydroxynaphthalene and aldehydes.

(Light-curing ingredients)

In the case of the development type, the etching resist composition of the present invention preferably contains a photocurable component in order to greatly improve the resistance of the etching resist. The photocurable component may be a resin that is cured by active energy ray irradiation. In the present invention, it is particularly preferable to use a compound having at least one ethylenic unsaturated bond in the molecule. The photocurable component can be used singly or in combination of two or more kinds.

As the compound having an ethylenically unsaturated bond, conventionally used photopolymerizable oligomers, photopolymerizable vinyl monomers, and the like can be used. Here, the photopolymerizable oligomer includes, for example, an unsaturated polyester-based oligomer, a (meth)acrylate-based oligomer, and the like. (Meth)acrylate oligomers, for example, phenol novolac epoxy (meth)acrylate, cresol novolac epoxy (meth)acrylate, bisphenol epoxy (meth)acrylate Epoxy (meth)acrylate, urethane (meth)acrylate, epoxy urethane (meth)acrylate, polyester (meth)acrylate such as acrylate Ester, polyether (meth)acrylate, polybutadiene modified (meth)acrylate, etc.

Photopolymerizable vinyl monomers, for example, conventionally used ones, such as styrene derivatives such as styrene, chlorostyrene, α-methylstyrene, etc.; vinyl acetate, vinyl butyrate or vinyl benzoate Vinyl esters such as esters; vinyl isobutyl ether, vinyl-n-butyl ether, vinyl-t-butyl ether, vinyl-n-pentyl ether, vinyl isoamyl ether, ethyl Alkenyl-n-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether, triethylene glycol monomethyl vinyl ether and other vinyl ethers; acrylamide, methpropylene Amide, N-hydroxymethacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethacrylamide, N-ethoxymethacrylamide, N-butoxy (Meth)acrylamides such as methacrylamide; allyl esters of triallyl isocyanurate, diallyl phthalate, diallyl isophthalate, etc. Compound; 2-Ethylhexyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth) Acrylate, phenoxyethyl (meth)acrylate and other (meth)acrylic acid esters; hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, pentaerythritol tris(methyl) ) Hydroxyalkyl (meth)acrylates such as acrylates; alkoxyalkyl (meth)acrylates such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate Base) acrylic esters; ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di (Meth) acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate and other alkylene polyols poly(meth) Acrylate; diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane tri Polyoxyalkylene glycol poly(meth)acrylates such as (meth)acrylate; Poly(meth)acrylates such as neopentyl glycol hydroxypivalate di(meth)acrylate; Isocyanurate type poly(meth)acrylates such as [(meth)acryloxyethyl] isocyanurate, etc.

The content of the aforementioned photocurable component per solid content of the etching resist composition is preferably 5 to 38% by mass, more preferably 10 to 20% by mass. When the content of the photocurable component is 5% by mass or more, the photocurability is improved. When less than 38% by mass, the adhesiveness will increase.

(Photopolymerization initiator)

When the etching resist composition of the present invention is a developing type, it is preferable to contain a photopolymerization initiator.

The photopolymerization initiator includes, for example, bis-(2,6-dichlorobenzyl)phenylphosphine oxide, and bis-(2,6-dichlorobenzyl)-2,5-dimethyl Phenyl phosphine oxide, bis-(2,6-dichlorobenzyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzyl)-1-naphthalene Phosphine oxide, bis-(2,6-dimethoxybenzyl) phenylphosphine oxide, bis-(2,6-dimethoxybenzyl)-2,4,4- Trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzyl)-2,5-dimethylphenylphosphine oxide, bis-(2,4,6-trimethyl) Benzyl)-phenylphosphine oxide (manufactured by BASF JAPAN, IRGACURE819), etc.; 2,6-dimethoxybenzyl diphenylphosphine oxide, 2 ,6-Dichlorobenzyldiphenylphosphine oxide, 2,4,6-trimethylbenzylphenylphosphonic acid methyl ester, 2-methylbenzyldiphenylphosphine oxide Monoacetate such as trimethylacetoxyphenylphosphonic acid isopropyl ester, 2,4,6-trimethylbenzyldiphenylphosphine oxide (made by BASF JAPAN, DAROCUR TPO), etc. Phosphine oxides; 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- Hydroxyacetophenones such as propane-1-one and 2-hydroxy-2-methyl-1-phenylpropane-1-one; benzoin, benzyl ester, benzoin methyl ether, benzoin ethyl ether, benzoin n -Benzoins such as propyl ether, benzoin isopropyl ether, and benzoin n-butyl ether; benzoin alkyl ethers; benzophenone, p-methylbenzophenone, Michler’s ketone, methyl diphenyl Benzophenones such as methyl ketone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone; acetophenone, 2,2-dimethoxy -2-Phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl- 1-[4-(Methylthio)phenyl]-2-morpholinyl-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)- Butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl)-1-[4-(4-morpholinyl)phenyl]-1-butanone , N,N-dimethylaminoacetophenone and other acetophenones; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone Thioxanthones such as ketones, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc.; anthraquinone, chloroanthraquinone, 2-methylanthracene Quinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-pentylanthraquinone, 2-aminoanthraquinone and other anthraquinones; acetophenone dimethyl condensation Ketals such as ketones and benzyl dimethyl ketals; ethyl-4-dimethylamino benzoate, 2-(dimethylamino) ethyl benzoate, p-dimethyl Benzoic acid esters such as ethyl benzoic acid; 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzyloxime)], ethyl ketone , 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1-(0-acetoxime) and other oxime esters; double (η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, bis(cyclopentadienyl) -Bis[2,6-difluoro-3-(2-(1-pyrrol-1-yl)ethyl)phenyl]titanium etc. Titanium; phenyl disulfide 2-nitrosulfide, Butyroin, anisidine ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, etc. The photopolymerization initiator can be used singly or in combination of two or more kinds.

The content of the aforementioned photopolymerization initiator per unit solid content of the etching resist composition is preferably 1-8% by mass, more preferably 2-5% by mass. When the content of the photopolymerization initiator is 1% by mass or more, the photocurability is improved. At 8% by mass or less, vignetting is less likely to occur, and the hardening depth becomes appropriate.

(Coupling agent)

The etching resist composition of the present invention may contain a coupling agent. As the coupling agent, silane coupling agent, titanium coupling agent, zirconium coupling agent, aluminum coupling agent, etc. can be used. The coupling agent is preferably a silane coupling agent. The coupling agent can be used alone or in combination of two or more.

Silane coupling agent is composed of organic matter (organic base) and silicon, generally XnR'(n-1)Si-R"-Y(X=hydroxyl, alkoxy, etc., Y=vinyl, epoxy, benzene Vinyl, methacryloxy, acryloxy, amino, ureido, chloropropyl, mercapto, polysulfide, isocyanate, etc.) represented by the compound. Because there are two or more different in the molecule The reactive group is usually used as an intermediary for connecting organic materials and inorganic materials that are very difficult to connect, and is used for strength improvement of composite materials, resin modification, surface modification, etc.

Silane coupling agents, for example, N-γ-(aminoethyl)-γ-aminopropyltriethoxysilane, N-γ-(aminoethyl)-γ-aminopropyltrimethoxy Silane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxy Silane, γ-aminopropylmethyl diethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylphenyl diethoxysilane, 2-amino-1 -Methylethyltriethoxysilane, N-methyl-γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N-butyl- γ-aminopropylmethyl diethoxysilane, N-β-(aminoethyl)-γ-aminopropyl triethoxysilane, N-β-(aminoethyl)-N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-ring Oxypropoxypropylmethyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyl Dimethoxysilane, γ-isocyanate propyltriethoxysilane, vinyl triethoxysilane, vinyl trimethoxysilane, vinyl ginseng (2-methoxyethoxy) silane, methyl Propyleneoxypropyltrimethoxysilane, γ-polyoxyethylene propyltrimethoxysilane, etc.

Commercially available silane coupling agents include, for example, 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, KBM -6123, KBE-585, KBM-703, KBM-802, KBM-803, KBE-846, KBE-9007 (all trade names; made by Shin-Etsu Silicone), etc.

Titanium coupling agents include, for example, tetraethoxy titanate, tetraisopropyl titanate, or tetra-n-butyl titanate and other titanium alcoholates, butyl titanate dimer, tetra (2-Ethylhexyl) titanate, polyhydroxytitanium stearic acid Ester, titanium tetraacetone acetonate, titanium polyacetate acetonate, titanium octyl glycolate, ethyl titanium acetone, titanium lactate, titanium triethanolamine salt, etc. For 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 resistance to hydrogen fluoride, even if it does not contain a coupling agent, the resist is not easily peeled off during the immersion step in the etching solution. Therefore, although the content of the coupling agent is not necessary, the preferred amount when the coupling agent is contained is 0.5-5 mass% per solid content of the etching resist composition. At 0.5% by mass or more, better resistance to etching resist can be obtained. Stability characteristics can be obtained at 5% by mass or less.

(filler)

In the present invention, inorganic fillers and organic fillers conventionally used for etching resists can be used. For example, inorganic fillers include, for example, body colorants such as barium sulfate, barium titanate, talc, clay, alumina, aluminum hydroxide, silicon nitride, and aluminum nitride. These inorganic fillers play a role in appropriately adjusting the viscosity of the resist composition during adjustment, inhibiting the curing shrinkage of the coating film during thermal drying or light curing, and improving the adhesion to the substrate. Among them, talc is particularly preferably used in order to achieve good adhesion to the substrate. The filler can be used alone or in combination of two or more.

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 laser diffraction/scattering method.

The matching amount of the filler, per unit solid content of the etching resist composition, is preferably 0.01 to 70% by mass, more preferably 10 to 40% by mass. When the mixing amount of the filler is more than 0.01% by mass, the adhesion between the resist and the substrate is improved High, at 70% by mass or less, the fluidity of the composition improves.

(Organic solvents)

The etching resist composition of the present invention can be matched with organic solvents. Specific examples of organic solvents include alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. , Ethyl acetate, n-propyl acetate, n-butyl acetate and other esters, dibutyl ether, tetrahydrofuran, 1,4-dioxane and other ethers, n-hexane, n -Aliphatic hydrocarbons such as heptane and n-octane, aromatic hydrocarbons such as benzene, toluene, and 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, more preferably 30 to 80% by mass.

(Other additives)

In addition, the resist composition of the present invention can be combined with other additives conventionally used in the field of etching resists. 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 Class, phthalocyanine. Blue, phthalocyanine. Green, iodine green, bis-azo yellow, crystal violet, titanium oxide, carbon black, naphthalene black and other commonly used coloring agents, silicone-based, fluorine-based, polymer-based defoaming agents and flattening agents, etc. Without compromising the effect of the present invention, such an additive can be used to adjust the appropriate amount to match within the desired effect range of the additive.

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

In addition, the etching resist composition of the present invention can be used after being dried into a thin film as follows. In the case of the development type, the desired pattern can be formed by exposure and development in the same manner as described above. In the case of thermal drying type, the pattern can be formed by laser processing.

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. When forming a dry film, firstly dilute the etching resist composition of the present invention with the above-mentioned organic solvent, adjust it to an appropriate viscosity, and use a chipped wheel coater, knife coater, lip coater, and bar coater. Coating machine, extrusion coating machine, reverse coating machine, reverse coating machine, gravure coating machine, spraying machine, etc., to coat the carrier film to a uniform thickness. After that, the coated composition is usually dried at a temperature of 50 to 130° C. for 1 to 30 minutes to form a resin layer. Although the thickness of the coating film is not particularly limited, it is generally selected appropriately in the range of the film thickness after drying of 10 to 150 μm, preferably 20 to 60 μm.

The carrier film can be a plastic film, such as polyester film such as polyethylene terephthalate (PET), polyimide film, polyimide film, polypropylene film, and polystyrene film. Wait. Although the thickness of the carrier film is not particularly limited, it is generally appropriately selected in the range of 10 to 150 μm.

After the resin layer composed of the etching resist composition of the present invention is formed on the carrier film, for the purpose of preventing dust from adhering to the surface of the film, it is further preferred to laminate a peelable protective film on the surface of the film. As the peelable protective film, for example, polyethylene film, polytetrafluoroethylene film, polypropylene film, surface-treated paper, etc. can be used. As the protective film, when the protective film is peeled off, the adhesive strength between the resin layer and the carrier film may be smaller.

In addition, the dry film of the present invention may be one obtained by coating the etching resist composition of the present invention on the protective film and drying to form a resin layer, and then laminating a carrier film on its surface. That is, when a dry film is produced in the present invention, as the film to which the etching resist composition of the present invention is applied, either a carrier film or a protective film can be used.

In the case of a dry film, the etching resist composition layer of the present invention can be laminated on the substrate with a laminator or the like so that the layer of the etching resist composition of the present invention contacts the glass substrate, and then the carrier film is peeled off to coat the glass substrate with the etching resist.

When the etching resist composition of the present invention is a developing-type liquid composition, after adjusting to a uniform solution or dispersion, a coating method such as screen printing or curtain coater is used on a substrate such as a glass substrate It is only necessary to coat it so that the film thickness after drying is preferably 20-100 μm, more preferably 30-60 μm. After coating, for example, at 70 to 100° C., for 20 to 40 minutes, thermal drying in a drying oven, etc., the etching resist is exposed through the mask to burn the pattern. After that, it is developed with an aqueous alkali solution to form a pattern. For example, if it is thermally dried at 100 to 200°C, preferably 120 to 150°C, for 20 to 60 minutes, in a drying oven, etc., the desired pattern can be obtained. Dry etch resist coated substrate.

When it is in the form of a developed dry film, it is bonded to the substrate by a laminator or the like so that the layer of the etching resist composition of the present invention is in contact with the substrate After the substrate is placed, the 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 heat-drying liquid composition, after adjusting it to a uniform solution or dispersion, apply screen printing to a substrate such as a glass substrate to form a desired pattern after drying. It is preferable to apply the coating film of the film to a film thickness of 20 to 100 μm, more preferably 30 to 60 μm. After printing, for example, at 100 to 200°C, preferably 120 to 150°C, for 20 to 60 minutes, thermal drying in a drying oven, etc., a substrate coated with a dry etching resist in a desired pattern can be obtained.

When the dried state of the resist coating film after thermal drying is tested in accordance with the test method of JIS C 5400, it is better to adhere to the substrate as a film having a pencil hardness of F or higher and then thermally dry it.

In the form of a heat-drying dry film, the layer of the etching resist composition of the present invention is bonded to the base material by a laminator or the like so that the layer of the etching resist composition of the present invention is in contact with the base material, and then laser processing is used to form the desired Graphic type is sufficient.

By subjecting the glass substrate covered with the etching resist to an etching process with an etching solution, the part of the substrate not covered with the resist can be etched.

The etching solution is not particularly limited, and conventionally used etching solutions containing hydrogen fluoride may be used (for example, a mixture of hydrogen fluoride and inorganic acids (nitric acid, phosphoric acid, etc.), or any one or more of weak acids such as water, acetic acid, etc.). Because the etching resist film formed with the etching resist composition of the present invention has excellent hydrogen fluoride resistance, an etching solution with a higher concentration of hydrogen fluoride can be used.

Furthermore, the etching resist film formed with the etching resist composition of the present invention can be peeled off with a dilute alkali aqueous solution, for example, it can be soluble in sodium hydroxide. Conventional peeling liquids such as liquid, potassium hydroxide aqueous solution, etc. are easy to remove. The concentration of alkali substances such as sodium hydroxide is, for example, 1 to 5% by mass.

In addition to screen printing, the etching resist composition of the present invention can also be applied to printing methods such as gravure printing and offset printing. In addition, the etching resist composition may be applied several times. The coating method at that time can be wet-on-wet coating such as two-coat-one-bake or dry-on-wet coating such as two-coat-two-bake.

The etching resist composition of the present invention is suitable for forming an etching resist film on a glass substrate. For example, in addition to glass processing of tempered glass (OGC) used in tablets or smartphones or electronic parts such as loudspeakers, earphones, silicon wafers, etc., it can also be used in the processing of lenses, medical devices, and optical sensors. It can also be used as an etching resist for silicon wafers. The processing of glass etching is not particularly limited, and it can be used, for example, for surface processing or formation of through-holes.

[Example]

Hereinafter, the present invention will be specifically explained with examples and comparative examples, but the present invention is not limited to the following examples. In addition, "parts" and "%" in the following are quality standards without particular limitation.

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

The epoxy resin represented by the above general formula (1) (NC-3000P manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 286, softening point 67° C., n is 2.24) is added. 2860g (10 equivalents), 720.6g (10 equivalents) of acrylic acid, methyl hydroquinone 5.5 g, 1349.6 g of carbitol acetate and 578.4 g of coal-dissolved petroleum spirit were heated and stirred at 90°C to dissolve the reaction mixture. Next, the reaction solution was cooled to 60°C, 16.5g of triphenylphosphine was added, heated to 98°C, and reacted for about 32 hours. The acid value (mgKOH/g) was 3.0 or less, and then cooled to obtain epoxy acrylate resin. (a-1). Add 5530.6 g of epoxy acrylate resin (a-1), 1338.5 g of tetrahydro anhydrous phthalic acid, 504.5 g of carbitol acetate, and 216.2 g of coal soluble petroleum spirit, and react at 95°C for 10 hours to obtain a base Soluble resin (A-1). The solid content of the product is 65.0%, the solid acid value (mgKOH/g) is 100, and the viscosity (25°C, dPa·s) is 375.

(Alkali-soluble resin with bisphenol F structure: Resin A-2)

In the above general formula (2), X is CH ₂ and the average degree of polymerization n is 6.2 bisphenol F type epoxy resin (epoxy equivalent 950g/eq, softening point 85°C) 380 parts and epichlorohydrin 925 parts After dissolving 462.5 parts of dimethyl sulfoxide, add 60.9 parts of 98.5% NaOH at 70°C for 100 minutes while stirring. After the addition, the reaction was carried out at 70°C for 3 hours. After the reaction is completed, 250 parts of water are added for washing. After the oil and water are separated, most of the dimethyl sulfide and excess unreacted epichlorohydrin are recovered by distillation under reduced pressure from the oil layer, so that the reaction product containing the residual by-product salt and dimethyl sulfide is dissolved in the formaldehyde 750 parts of isobutyl ketone, 10 parts of 30% NaOH were added, and the reaction was carried out at 70°C for 1 hour. After the completion of the reaction, it was washed twice with 200 parts of water. After oil-water separation, methyl isobutyl ketone was distilled and recovered from the oil layer to obtain epoxy resin (a) having an epoxy equivalent of 310 g/eq and a softening point of 69°C. The obtained epoxy resin (a) is calculated based on the epoxy equivalent, and is epoxidized about 5 of the 6.2 alcoholic hydroxyl groups in the bisphenol F epoxy resin of the starting material. Put 310 parts of the epoxy resin (a) and 282 parts of carbitol acetate into the flask and heat at 90°C. Stir and dissolve. Once the obtained solution is 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, and reacted for about 60 hours to obtain an acid value of 0.2mgKOH/g reactant. 140 parts (0.92 mol) of tetrahydro anhydrous phthalic acid was added to this, and it heated to 90 degreeC, and reacted, and alkali-soluble resin (A-2) was obtained. The solid content concentration of the product was 65.0%, and the solid content acid value (mgKOH/g) was 100.

(Alkali-soluble resin with bisphenol A structure: resin A-3)

In the above general formula (2), X is C(CH ₃ ) ₂ and the average degree of polymerization n is 3.3 bisphenol A epoxy resin (epoxy equivalent 650g/eq, softening point 81.1℃) 371 parts and table After 925 parts of chlorohydrin was dissolved in 462.5 parts of dimethyl sulfoxide, 52.8 parts of 98.5% NaOH was added at 70°C with stirring in 100 minutes. After the addition, the reaction was carried out at 70°C for 3 hours. After the reaction is completed, 250 parts of water are added for washing. After the oil and water are separated, most of the dimethyl sulfide and excess unreacted epichlorohydrin are distilled and recovered from the oil layer under reduced pressure, so that the reaction product containing the residual by-product salt and dimethyl sulfide is dissolved in the formaldehyde 750 parts of isobutyl ketone, 10 parts of 30% NaOH were added, and the reaction was carried out at 70°C for 1 hour. After the completion of the reaction, it was washed twice with 200 parts of water. After oil-water separation, methyl isobutyl ketone was distilled and recovered from the oil layer to obtain epoxy resin (a) having an epoxy equivalent of 287 g/eq and a softening point of 64.2°C. The obtained epoxy resin (a) is calculated from the epoxy equivalent, and is about 3.1 of the 3.3 alcoholic hydroxyl groups in the bisphenol A epoxy resin of the starting material being epoxidized. Put 310 parts of the epoxy resin (a) and 282 parts of carbitol acetate into the flask and heat at 90°C. Stir and dissolve. Once the obtained solution is 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, and reacted for about 60 hours to obtain an acid value of 0.2mgKOH/g reactant. 140 parts (0.92 mol) of tetrahydroanhydrous phthalic acid was added to this, and it heated to 90 degreeC, and reacted, and the alkali-soluble resin (A-3) was obtained. The solid content concentration of the product was 64.0%, and the solid content acid value (mgKOH/g) was 100.

(Alkali-soluble resin that has neither biphenyl structure nor bisphenol structure: resin R-1)

A styrene-acrylic copolymer resin having a carboxyl group (Joncryl 67 manufactured by BASF JAPAN (solid content 100%, solid content acid value 200 mgKOH/g)) was used. Hereinafter referred to as resin R-1).

(Alkali-soluble resin without biphenyl structure and bisphenol structure: Resin R-2)

A phenolic novolak resin (BRG-557 (solid content 100%, softening point 85°C) manufactured by Showa Denko Corporation) was used. Hereinafter, it is referred to as resin R-2.

(Alkali-soluble resin without biphenyl structure and bisphenol structure: Resin R-3)

Put 210 parts of cresol novolac type epoxy resin (EPICLON N-680 manufactured by DIC Corporation, epoxy equivalent: 210) into a four-necked flask with a stirrer and reflux cooler, add 96.4 parts of carbitol acetate, and Heat to dissolve. Next, 0.46 parts 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° C., 72 parts of acrylic acid was slowly dropped until the acid value became 3.0 mgKOH/g or less, and the reaction was performed for about 16 hours. The reaction product was cooled to 80 to 90°C. 76 parts of tetrahydrophthalic anhydride were added and reacted for 8 hours, and after cooling, it took out and obtained alkali-soluble resin (R-3). The solids concentration of the product was 65%, and the acid value of the solids was 85 mgKOH/g.

(Alkali-soluble resin without biphenyl structure and bisphenol structure: Resin R-4)

In a 2 liter separable flask equipped with a stirrer, a thermometer, a reflux cooler, a dropping funnel, and a nitrogen introduction tube, 900 g of diethylene glycol dimethyl ether as a solvent and t-butylperoxy as a polymerization initiator are added 21.4 g of 2-ethylhexanoate (PERBUTYL O manufactured by NOF Corporation) was heated to 90°C. 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 (PLACCELFM1 manufactured by Daicel) were polymerized in it. Together with 21.4 g of bis(4-t-butylcyclohexyl)peroxydicarbonate (PEROYL TCP manufactured by NOF Corporation) as the starting agent, it was added dropwise over 3 hours, and then matured for 6 hours to obtain a carboxyl group-containing copolymer. Polymeric resin. In addition, the reaction system is carried out in a nitrogen environment.

Next, 363.9 g of 3,4-epoxycyclohexyl methacrylate (Cyclomer M100 manufactured by Daicel) and dimethylbenzylamine as a ring-opening catalyst: 3.6 g were added to the obtained carboxyl group-containing copolymer resin. Hydroquinone monomethyl ether of polymerization inhibitor: 1.80g, by heating to 100°C, Stirring was performed to carry out the ring-opening addition reaction of the epoxy group for 16 hours to obtain alkali-soluble resin (R-4). The solid content 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.

According to the combination shown in the table below, the ingredients are matched and mixed with a mixer, and then dispersed and kneaded with 3 roller grinders to prepare their respective compositions. The matching amount in the table is parts by mass. In addition, the blending amount of resin in the table is the solid content. In addition, 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 resist compositions .

The obtained etching resist composition of each Example and Comparative Example was evaluated based on the following. The results are shown in the table below.

(Development type etching resist film formation, hydrogen fluoride etching test and peeling test)

The development type etching resist compositions of Examples 1 to 5 and Comparative Examples 1 to 4 were screen-printed on a 1.8mm lime soda glass with a size of 100mm×150mm, and the film thickness after drying became 30 It can be printed with a thickness of ~40μm. After printing, dry at 80°C for 20 minutes to evaporate the organic solvent to form a non-stick coating. Afterwards, it was selectively exposed with active energy rays through the photomask, and the unexposed area was developed with 1% sodium carbonate aqueous solution to form a resist pattern, and thermally cured at 120°C for 30 minutes to obtain a test substrate.

The test substrate prepared by the above method was immersed in a 10% hydrogen fluoride etching solution, the state of the coating film was observed every 10 minutes, and the time during which the penetration of the solution was observed was measured as the etching resistance time.

In addition, the test substrate prepared by the above method was thermally cured and then immersed in a stripping solution heated to a liquid temperature of 60°C with a 5% caustic soda aqueous solution. The etching resist film formed from the developing type etching resist composition was swollen For the peeling type, the time from the swelling of the coating film of the test substrate to the peeling is measured as the peeling time.

(Formation of thermal drying type etching resist film, hydrogen fluoride etching test and peeling test)

The thermal drying type etching resist compositions of Example 6 and Comparative Examples 5 to 8 were each formed on a 1.8mm lime soda glass by screen printing method, and the film thickness after drying became a thickness of 40-50μm. type. After printing, drying was performed at 120°C for 30 minutes to evaporate the organic solvent to form a non-stick coating film to obtain a test substrate.

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

In addition, the test substrate prepared by the above method was thermally cured and then immersed in a stripping liquid heated to a liquid temperature of 60°C with a 5% caustic soda aqueous solution, and the etching resist film formed by the thermal drying type etching resist composition was For the dissolution peeling type, the time when the coating film on the test substrate starts to dissolve is measured as the peeling time.

As shown in the above table, it can be seen that an etching resist film formed using an etching resist composition containing an alkali-soluble resin having a biphenyl structure is excellent in hydrogen fluoride resistance, and particularly in the case of a development type, the resistance time is greatly improved. Furthermore, it was confirmed that the releasability was also improved by using the alkali-soluble resin having a bisphenol epoxy structure in combination. In addition, generally compared to the development type etching resist (for example, Examples 1 to 5, Comparative Examples 1 to 4), the alkali-removing type thermal drying type etching resist (for example, Example 6, Comparative Examples 5 to 8) The resistance to hydrogen fluoride tends to be poor. However, as shown in Table 4, it can be seen that by using the alkali-soluble resin with a biphenyl structure alone or in combination with an alkali-soluble resin with a bisphenol structure, the etching resist film formed even if it is an alkali-removable type Thermal drying type etching resist, the hydrogen fluoride resistance is still improved.

Claims (4)

An etching resist composition characterized by containing (A) an alkali-soluble resin having a biphenyl structure and (B) an alkali-soluble resin having a bisphenol structure. The aforementioned (A) an alkali-soluble resin having a biphenyl structure is selected At least one alkali-soluble resin from the following (A1) to (A2): (A1) among the reactants of a bifunctional or higher polyfunctional epoxy resin with a biphenyl structure and an unsaturated group-containing monocarboxylic acid A carboxyl group-containing resin formed by the addition of a dibasic acid anhydride to the hydroxyl group present in the side chain, (A2) is added to the aforementioned (A1) resin and then added to one molecule with one epoxy group and one or more (methyl ) A (meth)acrylate modified resin having a carboxyl group composed of an acrylic compound, the aforementioned (B) alkali-soluble resin having a bisphenol structure, at least one selected from the following (B1) to (B4) Alkali-soluble resin: (B1) Dibasic acid anhydride is added to the hydroxyl group in the side chain of the reactant of a bifunctional or more multifunctional epoxy resin with a bisphenol type structure and a monocarboxylic acid containing an unsaturated group The resulting carboxyl group-containing resin, (B2) is added to the aforementioned (B1) resin and then a compound with 1 epoxy group and 1 or more (meth)acrylic groups in one molecule is formed with a carboxyl group (Meth)acrylate modified resin, (B3) epoxy resin and unsaturated group-containing epoxy resin after adding epoxy group to the hydroxyl group of bifunctional or more multifunctional bisphenol epoxy resin having hydroxyl group The carboxyl group-containing resin that is the reactant of the monocarboxylic acid and the dibasic acid anhydride, (B4) is added to the resin of the aforementioned (B3) and has 1 epoxy group and more than 1 (meth)propylene in 1 molecule A (meth)acrylate modified resin having a carboxyl group composed of a compound of an acyl group. The etching resist composition of claim 1, which further contains a photocurable component. Such as the etching resist composition of claim 1 or 2, which further contains a coupling agent. A dry film characterized by having a resin layer obtained by coating the etching resist composition of any one of claims 1 to 3 on the film and drying it.