JP2016222889A - Etching resist composition and dry film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an etching resist composition from which an etching resist film excellent in adhesion with an ITO film and in strong acid resistance can be formed, and a dry film having a resin layer obtained from the composition.SOLUTION: An etching resist composition comprises an alkali-soluble resin having at least one structure of a urethane structure and a bisphenol structure. A dry film has a resin layer obtained from the above composition.SELECTED DRAWING: None

Description

  The present invention relates to an etching resist composition and a dry film, and more specifically, has an etching resist composition capable of forming an etching resist film excellent in adhesion to an ITO film and strong acid resistance, and a resin layer obtained from the composition. It relates to dry film.

  An ITO (indium tin oxide) electrode is used as a transparent electrode of an image display device such as a flat panel display. Etching using strong acid is known as a processing technique for forming ITO electrodes, and the ITO film on the substrate is coated with a patterned etching resist film as a mask and uncoated with an etching solution such as concentrated hydrochloric acid. By dissolving the portion, a desired patterned ITO electrode can be formed (for example, Patent Documents 1 and 2).

Japanese Patent Laid-Open No. 10-198032 International Publication No. 2010/134549

  The etching resist film used in the above-mentioned ITO electrode forming method is required to be able to be in close contact with the ITO film in order to prevent the coating portion from coming into contact with the etching solution. Further, it is required that the film can be in close contact with the ITO film without being peeled off even when exposed to a strong acid used as an etching solution. When the etching resist film has insufficient adhesion to the ITO film or peels off with a strong acid, the coating part also comes into contact with the etching solution, so that an ITO electrode having a desired pattern cannot be obtained. The problem arises.

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

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

  That is, the etching resist composition of the present invention contains an alkali-soluble resin having at least one of a urethane structure and a bisphenol structure.

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

  ADVANTAGE OF THE INVENTION According to this invention, the dry resist film which has the resin layer obtained from the etching resist composition which can form the etching resist film excellent in the adhesiveness with an ITO film | membrane and strong acid tolerance, and this composition can be provided.

  The etching resist composition of the present invention comprises an alkali-soluble resin having at least one of a urethane structure and a bisphenol structure. Since the etching resist film formed from the etching resist composition of the present invention is excellent in adhesion to the ITO film and strong acid resistance, peeling from the ITO film hardly occurs during the etching process. As a result, the substrate can be etched with high accuracy. Further, since a stronger acid can be used as an etchant in the etching process, 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 strong 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 any of a development type, a heat drying type, a photo-curing type, and a thermosetting type. The heat drying type is preferable in that it has excellent peelability.

  Moreover, the etching resist composition of this invention can improve line | wire width reproducibility by adjusting TI value (thixotropic index) to 2.5 or more.

  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 at least one of a urethane structure and a bisphenol structure. As the alkali-soluble resin, a carboxyl group-containing resin or a phenolic hydroxyl group-containing resin can be used, and a carboxyl group-containing resin is preferable. When the etching resist composition of the present invention is a development type, the alkali-soluble resin preferably has an ethylenically unsaturated bond. Alkali-soluble resins may be used alone or in combination of two or more. From the balance between excellent etching resistance and peelability, alkali-soluble resins having a urethane structure and bisphenol structures are used. It is preferable to use a combination of the alkali-soluble resins.

Specific examples of the carboxyl group-containing resin having a urethane structure include compounds (any of oligomers and polymers) listed as the following (1) to (4).
(1) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers A carboxyl group-containing urethane resin by a polyaddition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
(2) Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( Photosensitive carboxyl group-containing urethane resin by polyaddition reaction of (meth) acrylate or its modified partial anhydride, carboxyl group-containing dialcohol compound and diol compound.
(3) During the synthesis of the resin of the above (1) or (2), a compound having one hydroxyl group and one or more (meth) acryl groups in a molecule such as hydroxyalkyl (meth) acrylate is added, and the terminal ( Photosensitive carboxyl group-containing urethane resin that has been meta-acrylated.
(4) During the synthesis of the resin of (1) or (2) above, one isocyanate group and one or more (meth) acrylic groups in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate The photosensitive carboxyl group-containing urethane resin which added the compound which has and was terminally (meth) acrylated.

  In addition, in this specification, (meth) acrylate is a term which generically refers to acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.

  Specific examples of the carboxyl group-containing resin having a bisphenol structure include an unsaturated group after adding an epoxy group to the hydroxyl group of a bifunctional or higher polyfunctional bisphenol type epoxy resin having a hydroxyl group as shown below with epichlorohydrin or the like. A carboxyl group-containing resin obtained by further reacting a monocarboxylic acid and a dibasic acid anhydride, and a compound having one epoxy group and one or more (meth) acryloyl groups in one molecule are further added to the resin. And a (meth) acrylate-modified resin having a carboxyl group. 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 (1).

（式中、ＸはＣＨ_２またはＣ（ＣＨ_３）_２を表し、ｎは１〜１２である。）

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

  The carboxyl group-containing resin having at least one of a urethane structure and a bisphenol structure preferably has an acid value of 30 to 300 mgKOH / g, and more preferably 50 to 150 mgKOH / g. When the acid value is 30 mgKOH / g or more, developability is improved. When the acid value is 300 mgKOH / g or less, the etching resistance is improved.

  Examples of the phenolic hydroxyl group-containing resin having at least one of a urethane structure and a bisphenol structure include a phenol novolak resin, an alkylphenol volac resin, and a bisphenol A novolac resin having at least one of a urethane structure and a bisphenol structure. , Dicyclopentadiene type phenolic resin, Xylok type phenolic resin, terpene modified phenolic resin, polyvinylphenols, bisphenol F, bisphenol S type phenolic resin, poly-p-hydroxystyrene, condensate of naphthol and aldehydes, dihydroxynaphthalene and aldehyde A phenolic hydroxyl group-containing resin such as a condensate with the above can be used.

  The weight average molecular weight of the alkali-soluble resin having at least one of a urethane structure and a bisphenol structure varies depending on the resin skeleton, but is preferably 1,000 to 150,000, and preferably 5,000 to 100,000. More preferably. When the weight average molecular weight is 1,000 or more, etching resistance is improved. When the weight average molecular weight is 150,000 or less, the developability is good.

  When an alkali-soluble resin having a urethane structure and an alkali-soluble resin having a bisphenol structure are used in combination, the ratio of the alkali-soluble resin having a urethane structure and the alkali-soluble resin having a bisphenol structure is preferably a ratio of 9: 1 to 1: 9. More preferably, when blended at a ratio of 8: 2 to 3: 7, adhesion and etching resistance are improved.

  The blending amount of the alkali-soluble resin having at least one of the urethane structure and the bisphenol structure is preferably 10 to 80% by mass, and 30 to 75% by mass, based on the solid content of the etching resist composition. More preferably. When the amount is 10% by mass or more, the adhesion is improved. When the blending amount is 80% by mass or less, the viscosity is stable. The etching resist composition of the present invention may contain other alkali-soluble resins as long as the effects of the present invention are not impaired.

(Photocurable component)
The etching resist composition of the present invention can have etching resist resistance and adhesion equivalent to those of heat drying even in the case of a development type or a photo-curing type. In that case, it is preferable to contain a photocurable component. The photocurable component may be any resin that can be cured by irradiation with active energy rays, and particularly in the present invention, a compound having one or more ethylenically unsaturated bonds in the molecule is preferably used. A photocurable component may be used individually by 1 type, and may be used in combination of 2 or more type.

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

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

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

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

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

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

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

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

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

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

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

The etching resist composition of the present invention preferably has a TI value in the range of 2.5 to 5.0. More preferably, it is 3.0-4.0.
Viscosity is measured using a rotary viscometer with the number of rotations being continuously changed to 1, 2.5, 5, 10, 20, 50 rotations. Among these, a numerical value obtained by dividing the value of 5 rotation values by the value of 50 rotation values is used as a TI value, which is used as an indicator of fluidity. When the TI value is 2.5 or more, the fluidity of the composition is low and difficult to flow, that is, the reproducibility of the printed line width is good. On the other hand, when the TI value is 5.0 or less, the leveling property of the composition becomes good. In order to adjust the TI value, it is preferable to blend a flow regulator in terms of ease of adjustment. Examples of the flow modifier include waxes such as amide, polyethylene, polypropylene and modified products thereof, modified urea, polyurethane, polyhydroxycarboxylic acid amide, fine powder silica, organic bentonite, and the like. More preferably, at least one of them is blended. 5-20 mass parts is preferable with respect to 100 mass parts of alkali-soluble resin, and 8-18 mass parts is more preferable.

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

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

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

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

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

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

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

  In the case of a dry film, after laminating the layer of the etching resist composition of the present invention so as to contact the ITO film on the substrate, the carrier film is peeled off to cover the ITO film with the etching resist. be able to.

  When the etching resist composition of the present invention is a development-type liquid composition, after adjusting it as a uniform solution or dispersion, for the ITO film on the substrate, using a coating method such as screen printing or curtain coater, The film thickness after drying is preferably 5 to 50 μm, more preferably 10 to 30 μm. After the application, for example, heat drying is performed in a drying furnace at 70 to 100 ° C. for 10 to 30 minutes, and then the etching resist is exposed through a mask to print a pattern. Thereafter, development is performed with an alkaline aqueous solution to form a pattern, and a substrate coated with an etching resist can be obtained. Reheating after development is not necessarily required, but the resistance can be further improved by performing reheating.

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

  When the etching resist composition of the present invention is a heat-drying liquid composition, it is prepared as a uniform solution or dispersion, and then dried in a desired pattern by screen printing or the like on the ITO film on the substrate. The coating film is preferably 5 to 50 μm, more preferably 10 to 30 μm. After printing, for example, at 70 to 150 ° C., preferably at 80 to 120 ° C., for 10 to 30 minutes, by drying in a drying furnace or the like, a substrate coated with an etching resist dried in a desired pattern can be obtained. it can.

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

  In the case of a heat drying type dry film, a desired pattern may be formed by laser processing or the like after laminating or the like so that the layer of the etching resist composition of the present invention is in contact with the ITO film. .

  By etching the ITO film covered with the etching resist with an etching solution, a portion not covered with the resist can be etched.

  The etching solution is not particularly limited, and a well-known and commonly used etching solution for ITO film may be used (for example, strong acid such as hydrochloric acid, cupric chloride-hydrochloric acid aqueous solution, ferric chloride-hydrochloric acid aqueous solution, oxalic acid aqueous solution). Including any one or more). Since the etching resist film formed with the etching resist composition of the present invention is excellent in strong acid resistance, a stronger strong acid than usual may be used as an etching solution.

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

  The etching resist composition of the present invention can be applied to printing methods such as a spray coating method, a curtain coating method, a gravure method, and a gravure offset method in addition to a screen printing method. In addition, the etching resist composition can be applied in a plurality of times.

  The etching resist composition of the present invention can be suitably used for forming an etching resist film on an ITO film, and is used to form an ITO electrode, particularly an ITO electrode used for a flat panel display such as a liquid crystal display or a plasma display. Can be suitably used.

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

(Synthesis of alkali-soluble resin A-1 having urethane structure)
A polycarbonate diol derived from 1,5-pentanediol and 1,6-hexanediol as a compound having two or more alcoholic hydroxyl groups in a reaction vessel equipped with a stirrer, a thermometer and a condenser (manufactured by Asahi Kasei Chemicals Corporation) 2400 g (3.0 mol) of T5650J, number average molecular weight 800), 603 g (4.5 mol) of dimethylolbutanoic acid, and 238 g (2.6 mol) of 2-hydroxyethyl acrylate as a monohydroxyl compound were charged. Next, 1887 g (8.5 mol) of isophorone diisocyanate is added as a compound having an isocyanate group which is not aromatic, and the mixture is heated to 60 ° C. with stirring and stopped, and when the temperature in the reaction vessel starts to decrease. It heated again and stirring was continued at 80 degreeC, it confirmed that the absorption spectrum (2280cm < ^-1 >) of the isocyanate group disappeared in the infrared absorption spectrum, and reaction was complete | finished. Subsequently, carbitol acetate was added so that solid content might be 50 wt%, and the resin solution of alkali-soluble resin (A-1) was obtained. The acid value of the solid content of the obtained resin solution was 51.0 mgKOH / g.

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

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

(Synthesis of alkali-soluble resin A-4 having urethane structure)
A polycarbonate diol derived from 1,5-pentanediol and 1,6-hexanediol as a compound having two or more alcoholic hydroxyl groups in a reaction vessel equipped with a stirrer, a thermometer and a condenser (manufactured by Asahi Kasei Chemicals Corporation) 3600 g (4.5 mol) of TJ5650J, number average molecular weight 800), 814 g (5.5 mol) of dimethylolbutanoic acid, and 118 g (1.6 mol) of n-butanol as a molecular weight modifier (reaction terminator) I put it in. Next, 2009 g (10.8 mol) of trimethylhexamethylene diisocyanate was added as an isocyanate compound having no aromatic ring, and the mixture was heated to 60 ° C. with stirring and stopped, and when the temperature in the reaction vessel began to decrease. It heated again and stirring was continued at 80 degreeC, it confirmed that the absorption spectrum (2280cm < ^-1 >) of the isocyanate group disappeared in the infrared absorption spectrum, and reaction was complete | finished. Subsequently, carbitol acetate was added so that a solid content might be 60 wt%, and the resin solution of alkali-soluble resin (A-4) was obtained. The acid value of the solid content of the obtained resin solution was 49.8 mgKOH / g.

(Alkali-soluble resin having neither urethane structure nor bisphenol structure: Resin R-1)
Put 210 parts of cresol novolac type epoxy resin (DIC Epiklon N-680, epoxy equivalent: 210) into a four-necked flask equipped with a stirrer and reflux condenser, add 96.4 parts of carbitol acetate, and dissolve by heating. did. Next, 0.46 part of hydroquinone as a polymerization inhibitor and 1.38 parts of triphenylphosphine as a reaction catalyst were added. This mixture was heated to 95 to 105 ° C., 72 parts of acrylic acid was gradually added dropwise, and the mixture was allowed to react for about 16 hours until the acid value became 3.0 mgKOH / g or less. The reaction product was cooled to 80 to 90 ° C., 76 parts of tetrahydrophthalic anhydride was added, allowed to react for 8 hours, cooled, and then taken out to obtain a resin solution of an alkali-soluble resin (R-1). The resin solution obtained had a solid content concentration of 65% and a solid acid value of 85 mgKOH / g.

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

(Alkali-soluble resin having neither urethane structure nor bisphenol structure: Resin R-3)
A styrene-acrylic copolymer resin having a carboxyl group (Jonkrill 67 (solid content: 100%, solid content acid value: 200 mgKOH / g) manufactured by BASF Japan Ltd.) was used. Hereinafter, it is referred to as Resin R-3.

(Alkali-soluble resin having neither urethane structure nor bisphenol structure: Resin R-4)
In a flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, 325.0 parts by mass of dipropylene glycol monomethyl ether as a solvent was heated to 110 ° C., 174.0 parts by mass of methacrylic acid, and ε-caprolactone modified Methacrylic acid (average molecular weight 314) 174.0 parts by mass, methyl methacrylate 77.0 parts by mass, dipropylene glycol monomethyl ether 222.0 parts by mass, and t-butylperoxy 2-ethylhexanoate as a polymerization catalyst A mixture of 12.0 parts by mass (Perbutyl O manufactured by NOF Corporation) was added dropwise over 3 hours, and further stirred at 110 ° C. for 3 hours to deactivate the polymerization catalyst to obtain a resin solution.
After cooling the resin solution, add 289.0 parts by mass of Daicel Cyclomer M100, 3.0 parts by mass of triphenylphosphine, and 1.3 parts by mass of hydroquinone monomethyl ether, and heat the mixture to 100 ° C. and stir. An epoxy group ring-opening addition reaction was carried out to obtain a resin solution of an alkali-soluble resin (R-4). The solid content concentration of the obtained resin solution was 45.5% by mass, and the acid value of the solid was 79.8 mgKOH / g. Moreover, the weight average molecular weight (Mw) was 15,000.

  In accordance with the composition shown in the following table, each component was blended, premixed with a stirrer, dispersed with a three-roll mill, and kneaded to prepare compositions. The compounding quantity in a table | surface shows a mass part. Moreover, the compounding quantity of the resin in a table | surface shows solid content. Examples 1 to 6 and Comparative Examples 1 to 3 in Table 1 are heat-drying type etching resist compositions, and Examples 7 and 8 and Comparative Examples 4 and 5 in Table 2 are development type. It is an etching resist composition.

＊１：ウレタン構造を有するアルカリ可溶性樹脂
＊２：ビスフェノールＦ構造を有するアルカリ可溶性樹脂
＊３：ビスフェノールＡ構造を有するアルカリ可溶性樹脂
＊４：ウレタン構造を有するアルカリ可溶性樹脂
＊５：ウレタン構造およびビスフェノール構造の何れも有しないアルカリ可溶性樹脂
（クレゾールノボラック構造を有するアルカリ可溶性樹脂）
＊６：ウレタン構造およびビスフェノール構造の何れも有しないアルカリ可溶性樹脂
（カルボキシル基含有共重合樹脂）
＊７：ウレタン構造およびビスフェノール構造の何れも有しないアルカリ可溶性樹脂
（スチレン、アクリル共重合樹脂（ＢＡＳＦジャパン社製ジョンクリル６７））
＊９：シリコーン系消泡剤（信越化学社製）
＊１０：タルク（富士タルク社製）
＊１１：フタロシアニンブルー
＊１２：ジエチレングリコールモノエチルエーテルアセテート
※ 表１中の樹脂の配合量はいずれも固形分の値。

* 1: Alkali-soluble resin having urethane structure * 2: Alkali-soluble resin having bisphenol F structure * 3: Alkali-soluble resin having bisphenol A structure * 4: Alkali-soluble resin having urethane structure * 5: Urethane structure and bisphenol structure None of these alkali-soluble resins (alkali-soluble resins having a cresol novolak structure)
* 6: Alkali-soluble resin (carboxyl group-containing copolymer resin) that has neither urethane structure nor bisphenol structure
* 7: Alkali-soluble resin (styrene, acrylic copolymer resin (John Kuryl 67 manufactured by BASF Japan)) that has neither urethane structure nor bisphenol structure
* 9: Silicone defoaming agent (Shin-Etsu Chemical Co., Ltd.)
* 10: Talc (manufactured by Fuji Talc)
* 11: Phthalocyanine blue * 12: Diethylene glycol monoethyl ether acetate * The amount of resin in Table 1 is the solid content.

＊１３：微粉末シリカ（日本アエロジル社製）
＊１４：有機ベントナイト（白石カルシウム社製）
※表２中の樹脂の配合量はいずれも固形分の値。

* 13: Fine powder silica (Nippon Aerosil Co., Ltd.)
* 14: Organic bentonite (manufactured by Shiroishi Calcium)
* The resin content in Table 2 is the solid content.

＊８：ウレタン構造およびビスフェノール構造の何れも有しないアルカリ可溶性樹脂
（カルボキシル基含有共重合樹脂）
＊１５：多官能アクリルモノマー（東亜合成社製）
＊１６：α−アミノアルキルフェノン系光重合開始剤（ＢＡＳＦジャパン社製）
※表３中の樹脂の配合量はいずれも固形分の値。

* 8: Alkali-soluble resin (carboxyl group-containing copolymer resin) that has neither urethane structure nor bisphenol structure
* 15: Multifunctional acrylic monomer (Toa Gosei Co., Ltd.)
* 16: α-aminoalkylphenone photopolymerization initiator (manufactured by BASF Japan)
* The resin content in Table 3 is the solid content.

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

(Formation of heat-drying etching resist film, adhesion test, strong acid resistance test and peelability test)
Each of the heat-drying etching resist compositions of Examples 1 to 8 and Comparative Examples 1 to 3 has a thickness of 7 to 15 μm after drying by screen printing on a PET film on which an ITO film is deposited. Was printed as follows. After printing, it was dried at 80 ° C. for 20 minutes to evaporate the organic solvent, thereby forming a tack-free coating film (hereinafter referred to as a coating film after drying).
In accordance with JIS K5600-5-6: 1999, a peeling test was performed in which a cross cut was applied to the coating film after drying, a cellophane tape was applied, and the cellophane tape was peeled off. The state of peeling of the coating film was visually observed, and the adhesion with the ITO film was evaluated according to the following criteria.
○: No peeling.
Δ: Slight peeling.
X: There is peeling.
After drying, the coating film was immersed in 35% concentrated hydrochloric acid heated to 50 ° C. for 15 minutes for etching treatment. After the etching treatment, washed with water and dried at 80 ° C. for 10 minutes, and then, in accordance with JIS K5600-5-6: 1999, a peeling test was performed in which a cross cut was made, a cellophane tape was applied, and this was peeled off. . The state of peeling of the coating film was visually observed, and the strong acid resistance was evaluated according to the following criteria.
○: No peeling.
Δ: Slight peeling.
X: There is peeling.
Further, after drying, the coating film was immersed in 35% concentrated hydrochloric acid heated to 50 ° C. for 15 minutes for etching treatment (hereinafter referred to as “dried and etched film after coating”). After the etching treatment, the film was immersed in a 3% aqueous solution of caustic soda heated to 50 ° C., and after drying and etching, the peeling time of the coating film was measured and evaluated according to the following criteria. In addition, it was confirmed whether the peeled form was dissolved or swollen.
A: 20 seconds or less.
○: More than 20 seconds and less than 40 seconds.
Δ: More than 40 seconds and less than 60 seconds.

Further, each of the heat drying type etching resist compositions of Examples 7 and 8 was set to a temperature of 25 ° C. using a rotary viscometer (TV type rotary viscometer manufactured by Toki Sangyo Co., Ltd.), Measurements were made by continuously changing 2.5, 5, 10, 20, and 50 rotations, and a value obtained by dividing the value of 5 rotations by the value of 50 rotations was taken as the TI value.
In addition, each of the heat-drying etching resist compositions of Examples 7 and 8 was line / spaced by screen printing using a plate made of SUS 400 mesh and emulsion of 10 μm on a PET film on which an ITO film was deposited. = 100/100 μm pattern was printed. After printing, it was dried at 80 ° C. for 20 minutes to evaporate the organic solvent and form a tack-free coating film. The line width of the pattern formed by the above method was measured using an optical microscope, and the measured line width was evaluated according to the following criteria.
○: The line width spread with respect to the design value is less than 20%.
X: The spread of the line width with respect to the design value is 20% or more.

(Development-type etching resist film formation, adhesion test and strong acid resistance test)
Each of the development-type etching resist compositions of Examples 9 to 12 and Comparative Examples 4 and 5 has a thickness of 7 to 15 μm after drying by screen printing on a PET film on which an ITO film is deposited. Was printed. After printing, it was dried at 80 ° C. for 20 minutes to evaporate the organic solvent, thereby forming a tack-free coating film. Then, it exposed selectively with an active energy ray through the photomask, and developed the unexposed part with alkaline aqueous solution, and formed the resist pattern (henceforth a coating film after image development).
In accordance with JIS K5600-5-6: 1999, a peeling test was performed in which a cross-cut was applied to the coated film after development, a cellophane tape was applied, and the cellophane tape was peeled off. The state of peeling of the coating film was visually observed, and the adhesion with the ITO film was evaluated according to the following criteria.
○: No peeling.
Δ: Slight peeling.
X: There is peeling.
After the development, the coating film was immersed in 35% concentrated hydrochloric acid heated to 50 ° C. for 15 minutes for etching treatment. After the etching treatment, washed with water and dried at 80 ° C. for 10 minutes, and then, in accordance with JIS K5600-5-6: 1999, a peeling test was performed in which a cross cut was made, a cellophane tape was applied, and this was peeled off. . The state of peeling of the coating film was visually observed, and the strong acid resistance was evaluated according to the following criteria.
○: No peeling.
Δ: Slight peeling.
X: There is peeling.
The developed coating film was immersed in 35% concentrated hydrochloric acid heated to 50 ° C. for 15 minutes for etching treatment (hereinafter referred to as a developed and etched coating film). After the etching treatment, the film was immersed in a 3% aqueous solution of caustic soda heated to 50 ° C., and after the development and etching, the peeling time of the coating film was measured and evaluated according to the following criteria. In addition, it was confirmed whether the peeled form was dissolved or swollen.
A: 20 seconds or less.
○: More than 20 seconds and less than 40 seconds.
Δ: More than 40 seconds and less than 60 seconds.
X: Over 60 seconds.

  As shown in the above table, an etching resist film formed using an etching resist composition containing an alkali-soluble resin having at least one of a urethane structure and a bisphenol structure has an adhesive property with a ITO film and a strong acid. It turns out that it is excellent in tolerance.

Claims (2)

  An etching resist composition comprising an alkali-soluble resin having at least one of a urethane structure and a bisphenol structure. A dry film comprising a resin layer obtained by applying and drying the etching resist composition according to claim 1 on a film.