WO2016017497A1 - Resin composition for forming cured film - Google Patents

Resin composition for forming cured film Download PDF

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Publication number
WO2016017497A1
WO2016017497A1 PCT/JP2015/070810 JP2015070810W WO2016017497A1 WO 2016017497 A1 WO2016017497 A1 WO 2016017497A1 JP 2015070810 W JP2015070810 W JP 2015070810W WO 2016017497 A1 WO2016017497 A1 WO 2016017497A1
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WIPO (PCT)
Prior art keywords
cured film
resin composition
group
forming
ether
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PCT/JP2015/070810
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French (fr)
Japanese (ja)
Inventor
隼人 服部
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日産化学工業株式会社
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Publication date
Application filed by 日産化学工業株式会社 filed Critical 日産化学工業株式会社
Priority to KR1020167034453A priority Critical patent/KR102149165B1/en
Priority to JP2016538289A priority patent/JP6555266B2/en
Priority to CN201580039405.9A priority patent/CN106536647B/en
Publication of WO2016017497A1 publication Critical patent/WO2016017497A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/14—Esterification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34922—Melamine; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic

Definitions

  • the present invention relates to a resin composition for forming a cured film.
  • Patent Document 1 a protective film, an insulating film, and the like necessary for a touch panel and the like have been formed in a necessary portion by pattern processing by a photolithography method using a photosensitive resin composition.
  • the present inventor can solve the above problems with a composition containing a specific copolymer, a melamine-based crosslinking agent, a thermal radical polymerization initiator, and a solvent.
  • the present invention was completed.
  • this invention provides the following resin composition for cured film formation.
  • A a copolymer containing monomer units represented by formulas (1) and (2), (In the formula, each R 1 independently represents a hydrogen atom or a methyl group.
  • R 2 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • R 3 represents a hydrogen atom or a methyl group.
  • B Melamine-based crosslinking agent, A cured film-forming resin composition comprising (C) a thermal radical polymerization initiator and (D) a solvent.
  • A The cured film forming resin composition of 1, wherein the copolymer is a copolymer containing monomer units represented by formulas (1), (2-1), and (2-2).
  • the cured film obtained by using the resin composition for forming a cured film of the present invention has high hardness, excellent adhesion, transparency and resistance to ITO sputtering, and also has resistance to a resist stripper. Therefore, it is useful as a material for forming a cured film such as a protective film, an insulating film, or the like in a touch panel such as a protective film, a planarizing film, or an insulating film in various displays such as an organic electroluminescence (EL) element. Moreover, since it is excellent also in a softness
  • R ⁇ 1 > represents a hydrogen atom or a methyl group each independently, and a methyl group is preferable.
  • R 2 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • R 3 represents a hydrogen atom or a methyl group, and preferably a hydrogen atom.
  • the alkyl group may be linear, branched or cyclic, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, i -Butyl group, s-butyl group, t-butyl group, cyclobutyl group, n-pentyl group and the like.
  • part or all of the hydrogen atoms of the alkyl group may be substituted with a substituent, and examples of the substituent include a halogen atom, a hydroxy group, and an amino group.
  • the copolymer preferably contains a monomer unit represented by the formulas (1), (2-1) and (2-2) from the viewpoint of improving adhesion.
  • R 1 and R 3 are the same as described above.
  • R 4 represents an alkyl group having 1 to 5 carbon atoms. Examples of the alkyl group having 1 to 5 carbon atoms are the same as those described above.
  • the weight average molecular weight (Mw) of the copolymer is preferably 5,000 to 200,000, more preferably 10,000 to 100,000, and still more preferably 15,000 in consideration of handling properties and adhesion. ⁇ 80,000.
  • Mw exceeds 200,000, solubility in a solvent may be reduced and handling properties may be reduced.
  • Mw is less than 5,000, adhesion may be reduced.
  • Mw is a polystyrene conversion measured value by gel permeation chromatography (GPC).
  • the copolymer of component (A) is prepared by synthesizing poly (meth) acrylic acid, poly (meth) acrylic acid ester or (meth) acrylic acid- (meth) acrylic acid ester copolymer by a conventionally known method.
  • the copolymer can be synthesized by ring-opening addition of 3,4-epoxycyclohexylmethyl (meth) acrylate to the copolymer. Specifically, the ring-opening addition reaction can be carried out according to the method described in JP-A-10-087725 and the like.
  • the upper limit of the content of the component (B) is preferably 200 parts by mass, more preferably 100 parts by mass, with respect to 100 parts by mass of the component (A), from the viewpoint of suppressing a decrease in storage stability.
  • the lower limit is preferably 30 parts by mass, more preferably 50 parts by mass with respect to 100 parts by mass of the component (A), from the viewpoint of obtaining a cured film having excellent solvent resistance with good reproducibility.
  • the solvent examples include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono Benzyl ether, ethylene glycol monophenyl ether, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, die Lenglycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, diethylene glycol
  • Solvents can be used singly or in combination of two or more. Moreover, the solvent used when superposing
  • the solvent preferably has a boiling point of 150 ° C. or higher, more preferably 180 ° C. or higher, and even more preferably 200 ° C. or higher.
  • solvents include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol monohexyl ether, triethylene glycol Monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol monophenyl ether, ethylene glycol monobenzyl ether Le, diethylene glycol benzyl ether or the like are particularly preferable.
  • the amount of the solvent is preferably such that the solid content concentration in the composition of the present invention is 1 to 95% by mass, more preferably the solid content concentration is 5 to 90% by mass, and the solid content concentration Is more preferably 10 to 85% by mass.
  • solid content removes (D) solvent from all the components of the composition of this invention.
  • the composition of the present invention preferably contains a silane coupling agent as the component (E).
  • a silane coupling agent is a silane compound represented by the formula (3).
  • R 5 represents a methyl group or an ethyl group.
  • X represents a hydrolyzable group.
  • Y represents a reactive functional group.
  • m is an integer of 0 to 3.
  • n is an integer of 0 to 3, preferably an integer of 0 to 2.
  • silane coupling agent examples include 3-aminopropyltrichlorosilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, and 3-aminopropylmethyldiethoxysilane.
  • 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyl Triethoxysilane and the like are particularly preferable.
  • a commercial item can be used as said silane coupling agent.
  • the content thereof is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the component (A). More preferably, the amount is 0.05 to 1 part by mass. If the content is less than 0.001 part by mass, the effect of improving the adhesion may not be obtained, and if it exceeds 10 parts by mass, the hardness may decrease.
  • the composition of the present invention preferably contains a polyfunctional (meth) acrylate compound as the component (F).
  • the polyfunctional (meth) acrylate compound is a compound having at least three (meth) acryloxy groups in the molecule, and specifically includes an ester of a polyhydric alcohol and (meth) acrylic acid.
  • the number of (meth) acryloxy groups in one molecule is 3 to 6, preferably 3 or 4.
  • polyhydric alcohol examples include glycerol, erythritol, pentaerythritol, trimethylolethane, trimethylolpropane, dipentaerythritol, ditrimethylolpropane, and the like.
  • polyfunctional (meth) acrylate compound examples include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentane.
  • Examples include acrylate, dipentaerythritol pentamethacrylate, trimethylolethane triacrylate, trimethylolethane trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetramethacrylate, and the like.
  • the polyfunctional (meth) acrylate compound can be easily obtained as a commercial product.
  • Specific examples thereof include, for example, KAYARAD (registered trademark) T-1420, DPHA, DPHA-2C, manufactured by Nippon Kayaku Co., Ltd.
  • Aronix (registered trademark) M-210, M-240, M-6200, M-309, M-400, M-402, M-405, M-450, M-7100, M-8030, M-8060, M -1310, M-1600, M-1960, M-8100, M-8530, M-8560, M-9050; Biscoat 295, 300, 360, GPT, 3PA, 400, 260, manufactured by Osaka Organic Chemical Industry Co., Ltd. 312, 335HP; NK ester A-9300, A-9300-1CL, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A- from Shin-Nakamura Chemical Co., Ltd. TMM-3LM-N, A-TMPT, AD-TMP, ATM-35E, A-TMMT, A-9550, A-DPH, TMPT, and the like.
  • the content thereof is preferably 10 to 300 parts by weight, more preferably 20 to 200 parts by weight, even more preferably 100 parts by weight of the component (A). Is 50 to 150 parts by mass.
  • the content is less than 10 parts by mass, the effect of improving the hardness of the cured film may not be obtained.
  • the content exceeds 300 parts by mass the adhesion and flexibility characteristics are degraded and cracks are generated. May be easier to do.
  • a polyfunctional (meth) acrylate compound can be used 1 type or in combination of 2 or more types.
  • the composition of the present invention preferably contains an ion trap agent from the viewpoint of suppressing migration of a metal wiring or the like in contact with the cured film.
  • an ion trapping agent a compound having a chelating ability having an unpaired electron in the structure is preferable.
  • N, N′-bis [3- (3,5-di-t-butyl-4- Hydroxyphenyl) propionyl] hydrazine Irganox MD1024, manufactured by BASF
  • bis (benzylidene hydrazide) oxalate Eastman Inhibitor OABH, manufactured by Eastman Chemical
  • benzotriazole 5-methylbenzotriazole and the like.
  • ADK STAB CDA-1 manufactured by ADEKA
  • ADK STAB CDA-6 manufactured by ADEKA
  • Qunox manufactured by Mitsui Toatsu Fine Co., Ltd.
  • Naugard XL-1 uniroyal Etc.
  • 5-methylbenzotriazole is particularly preferable.
  • the content thereof is preferably 0.0001 to 20 parts by mass, more preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the component (A). It is. If the amount is less than 0.0001 parts by mass, the effect of protecting the metal wiring may not be obtained. If the amount exceeds 20 parts by mass, characteristics such as hardness and adhesion as a cured film may be reduced, and the cost may be reduced. May also be disadvantageous.
  • the composition of this invention contains a polyfunctional thiol compound as needed.
  • the polyfunctional thiol compound used in the composition of the present invention is preferably a trifunctional or higher functional thiol compound.
  • the polyfunctional thiol compound can be obtained as an addition reaction product of a polyhydric alcohol and a monofunctional and / or polyfunctional thiol compound.
  • Specific compounds include 1,3,5-tris (3-mercaptopropionyloxyethyl) isocyanurate and 1,3,5-tris (3-mercaptobutyryloxyethyl) isocyanurate (manufactured by Showa Denko KK).
  • the content thereof is preferably 0.1 to 8% by mass, more preferably 0.8 to 5% by mass in the total solid content. If the content is too large, the stability, odor, adhesion and the like of the composition may deteriorate.
  • composition of this invention contains a polymerization inhibitor as needed.
  • the polymerization inhibitor include 2,6-diisobutylphenol, 3,5-di-t-butylphenol, 3,5-di-t-butylcresol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and t-butylcatechol. 4-methoxy-1-naphthol and the like.
  • the content thereof is preferably 1% by mass or less, more preferably 0.5% by mass or less, based on the total solid content.
  • the content exceeds 1% by mass, poor curing may occur and the reaction may become insufficient.
  • composition of the present invention may further comprise a surfactant, an antifoaming agent, a rheology modifier, a pigment, a dye, a storage stabilizer, a polyhydric phenol or a polycarboxylic acid as long as the effects of the present invention are not impaired.
  • a dissolution accelerator such as an acid may be included.
  • the surfactant is not particularly limited, and examples thereof include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surfactant.
  • this type of surfactant include, for example, F-top (registered trademark) EF301, EF303, EF352 manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd .; Mega-Fac® (registered trademark) F171, F173 manufactured by DIC Corporation; FLUORAD manufactured by 3M (Registered trademark) FC430, FC431; Asahi Guard Co., Ltd. Asahi Guard (registered trademark) AG710, AGC Seimi Chemical Co., Ltd. Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 etc. Can be mentioned.
  • Antifoaming agents include, but are not limited to, acetylene glycol, silicone fluids and emulsions, ethoxylated or propoxylated silicones, hydrocarbons, fatty acid ester derivatives, acetylated polyamides, poly (alkylene oxide) polymers and copolymers, and the like. .
  • the composition of the present invention preferably contains an antifoaming agent.
  • the viscosity at 25 ° C. of the composition of the present invention is preferably 1 to 10,000 mPa ⁇ s, more preferably 1 to 5,000 mPa ⁇ s, and still more preferably 1 to 1,000 mPa ⁇ s from the viewpoint of applicability. It is. If the viscosity is too low, the desired film thickness may not be obtained, and if the viscosity is too high, the coatability may deteriorate.
  • the viscosity at 25 ° C. of the composition of the present invention is preferably 10 to 100,000 mPa ⁇ s, more preferably 500 to 100,000 mPa ⁇ s, and still more preferably 1,000 to 100 from the viewpoint of printability. 1,000 mPa ⁇ s. If the viscosity is too low, the composition may diffuse after application, and a desired pattern may not be formed. If the viscosity is too high, the discharge performance may be reduced, and a load on the process may occur. Transferability to the surface may be reduced.
  • the viscosity at 25 ° C. of the composition is preferably 10 to 100,000 mPa ⁇ s, more preferably 5,000 to 100,000 mPa ⁇ s, and even more preferably 20,000 to 100,000 mPa ⁇ s. If the viscosity is too low, the composition may diffuse after application, and a desired pattern may not be formed. If the viscosity is too high, the discharge performance may be reduced, and a load on the process may occur. Transferability to the surface may be reduced.
  • the viscosity is a value measured with an E-type viscometer.
  • the method for preparing the composition of the present invention is not particularly limited. As an example, there may be mentioned a method in which the component (A) is dissolved in the solvent (D) and the components (B) and (C) are mixed in this solution at a predetermined ratio in an arbitrary order to obtain a uniform solution. In addition, in an appropriate stage of this preparation method, there may be mentioned a preparation method in which components (E) to (I) and other components are further added and mixed as necessary.
  • the resin composition for forming a cured film in a solution state thus prepared is preferably used after being filtered using a filter having a pore size of about 0.2 ⁇ m.
  • the resin composition for forming a cured film of the present invention is a substrate (for example, a silicon / silicon dioxide-coated substrate; a silicon nitride substrate; a metal such as aluminum, molybdenum, chromium, copper, or silver; a metal nanowire such as a silver nanowire; or a silver nanoparticle.
  • a substrate for example, a silicon / silicon dioxide-coated substrate; a silicon nitride substrate; a metal such as aluminum, molybdenum, chromium, copper, or silver; a metal nanowire such as a silver nanowire; or a silver nanoparticle.
  • the coating film can be formed by coating by a printing method such as ink printing, flexographic printing, gravure printing, offset printing, gravure offset printing, etc., and then pre-drying (prebaking) with a hot plate or oven.
  • the composition of the present invention is particularly suitable for printing methods such as inkjet coating, screen printing, flexographic printing, and gravure offset printing.
  • the pre-bake is generally preferably performed at 60 ° C. to 150 ° C., more preferably at 80 ° C. to 120 ° C., for 0.5 to 30 minutes when using a hot plate, and 0.5 to 90 minutes when using an oven. The method of doing is taken.
  • post-baking for thermosetting is performed. Specifically, heating is performed using a hot plate, an oven, or the like.
  • the post-baking is generally performed at a temperature of preferably 150 ° C. to 300 ° C., more preferably 200 ° C. to 250 ° C. for 1 to 30 minutes when using a hot plate, and 1 to 90 minutes when using an oven. Is taken.
  • the step of the substrate can be sufficiently flattened, and a cured film having high transparency can be formed.
  • the cured film of the present invention has at least the necessary level of flatness, hardness and adhesion, the protective film, flattening film, and insulating film in various displays such as thin film transistor (TFT) type liquid crystal display elements and organic EL elements. It is also useful as a material for forming a cured film such as a protective film or an insulating film in a touch panel. Moreover, since it is excellent also in a softness
  • TFT thin film transistor
  • the reagents and devices used in the examples are as follows. ⁇ Reagent> ⁇ DEGEEA (diethylene glycol monoethyl ether acetate), DEGME (diethylene glycol monomethyl ether): manufactured by Tokyo Chemical Industry Co., Ltd. ⁇ MEA (2-aminoethanol): manufactured by Kanto Chemical Co., Ltd. ⁇ PET-30: pentaerythritol (tri / tetra) ) Acrylate, Nippon Kayaku Co., Ltd. UPS: 3-ureidopropyltriethoxysilane, Toray Dow Corning AY43-031 ⁇ CYCLOMER-P: Cyclomer P (ACA) Z250 manufactured by Daicel Ornex Co., Ltd.
  • CYMEL303 Melamine-based crosslinking agent, manufactured by Nippon Cytec Industries, Ltd.
  • Perbutyl L Thermal radical polymerization initiator, manufactured by NOF Corporation ⁇ Device>
  • Stirrer Shintaro Awatori Nertaro ARE-310 ⁇
  • Ultraviolet visible near infrared spectrophotometer ultraviolet-3100PC manufactured by Shimadzu Corporation
  • composition [Example 1] In a 200 mL container, 41.5 g of CYCLOMER-P, 9.8 g of PET-30, 9.8 g of CYMEL 303, 0.6 g of perbutyl L, 0.2 g of UPS, and 37.5 g of DEGEA were placed. This was put into a stirrer and stirred at 2,000 rpm for 10 minutes to prepare a composition (varnish).
  • Example 2 In a 200 mL container, 33.5 g of CYCLOMER-P, 11.8 g of PET-30, 11.8 g of CYMEL 303, 0.5 g of perbutyl L, 0.2 g of UPS, and 42.2 g of DEGEA were placed. This was put into a stirrer and stirred at 2,000 rpm for 10 minutes to prepare a composition (varnish).
  • the cured film obtained from the composition (varnish) of the present invention is excellent in hardness and adhesion, has a high light transmittance of 92% or more, and also has good solvent resistance and ITO sputtering resistance. It was excellent.

Abstract

　Provided is a resin composition for forming a cured film, the resin composition including (A) a copolymer containing monomer units represented by formulas (1) and (2), (B) a melamine crosslinking agent, (C) a thermal radical polymerization initiator, and (D) a solvent. (In the formulas, R1 each independently represent a hydrogen atom or methyl group. R2 represents a hydrogen atom or C1-5 alkyl group. R3 represents a hydrogen atom or methyl group.)

Description

硬化膜形成用樹脂組成物Resin composition for forming cured film
　本発明は、硬化膜形成用樹脂組成物に関する。 The present invention relates to a resin composition for forming a cured film.
　従来、タッチパネル等に必要な保護膜、絶縁膜等は、感光性樹脂組成物を用いたフォトリソグラフィー法によるパターン加工によって必要とする部位に形成されてきた（特許文献１）。 Conventionally, a protective film, an insulating film, and the like necessary for a touch panel and the like have been formed in a necessary portion by pattern processing by a photolithography method using a photosensitive resin composition (Patent Document 1).
　しかし、フォトリソグラフィー法によるパターン加工は、工程が複雑であるだけでなく、コストもかかるという問題があった。そのため、より簡便な方法で、かつ低コストで、必要な部位に保護膜、絶縁膜等を形成できる組成物が望まれていた。 However, pattern processing by the photolithography method has a problem that not only the process is complicated but also costly. Therefore, there has been a demand for a composition that can form a protective film, an insulating film, and the like at a necessary site by a simpler method and at a lower cost.
　また、特許文献２に示すように絶縁膜上にＩＴＯ膜をスパッタで形成する場合、絶縁膜とＩＴＯ膜の応力差によってクラック等が入る場合があり、この種の保護膜、絶縁膜については、ＩＴＯのスパッタに対する耐性も必要となる。 Further, as shown in Patent Document 2, when an ITO film is formed on an insulating film by sputtering, cracks or the like may occur due to a stress difference between the insulating film and the ITO film. For this type of protective film and insulating film, Resistance to sputtering of ITO is also required.
特開２０１３－０６４９７３号公報JP 2013-064973 A 特開２０１１－０７６３８６号公報Japanese Unexamined Patent Publication No. 2011-076386
　本発明は、前記事情に鑑みなされたものであり、印刷法等による簡便な方法で必要な部位に膜を形成することができ、しかも高光透過率、高密着性、高硬度を有し、更にはＩＴＯスパッタに対する耐性をも有する硬化膜を形成可能な組成物を提供することを目的とする。 The present invention has been made in view of the above circumstances, and can form a film at a necessary site by a simple method such as a printing method, and has high light transmittance, high adhesion, and high hardness, Is intended to provide a composition capable of forming a cured film having resistance to ITO sputtering.
　本発明者は、前記課題を解決すべく鋭意検討を重ねた結果、特定の共重合体、メラミン系架橋剤、熱ラジカル重合開始剤、及び溶剤を含む組成物によって、前記課題を解決し得ることを見出し、本発明を完成させた。 As a result of intensive studies to solve the above problems, the present inventor can solve the above problems with a composition containing a specific copolymer, a melamine-based crosslinking agent, a thermal radical polymerization initiator, and a solvent. The present invention was completed.
　すなわち、本発明は、下記硬化膜形成用樹脂組成物を提供する。
１．（Ａ）式（１）及び（２）で表されるモノマー単位を含有する共重合体、
Figure JPOXMLDOC01-appb-C000003
 （式中、Ｒ1は、それぞれ独立に、水素原子又はメチル基を表す。Ｒ2は、水素原子又は炭素数１～５のアルキル基を表す。Ｒ3は、水素原子又はメチル基を表す。）
（Ｂ）メラミン系架橋剤、
（Ｃ）熱ラジカル重合開始剤、及び
（Ｄ）溶剤
を含むことを特徴とする硬化膜形成用樹脂組成物。
２．（Ａ）共重合体が、式（１）、（２－１）及び（２－２）で表されるモノマー単位を含有する共重合体である１の硬化膜形成用樹脂組成物。
Figure JPOXMLDOC01-appb-C000004
 （式中、Ｒ1及びＲ3は、前記と同じ。Ｒ4は、炭素数１～５のアルキル基を表す。）
３．更に、（Ｅ）シランカップリング剤を含む１又は２の硬化膜形成用樹脂組成物。
４．更に、（Ｆ）多官能(メタ)アクリレート化合物を含む１～３のいずれかの硬化膜形成用樹脂組成物。
５．（Ｄ）溶剤が、沸点が１５０℃以上である１～４のいずれかの硬化膜形成用樹脂組成物。
６．１～５のいずれかの硬化膜形成用樹脂組成物を用いて得られる硬化膜。
７．６の硬化膜を基板上に積層してなる積層体。
８．６の硬化膜を含むタッチパネル。 That is, this invention provides the following resin composition for cured film formation.
1. (A) a copolymer containing monomer units represented by formulas (1) and (2),
Figure JPOXMLDOC01-appb-C000003
 (In the formula, each R 1 independently represents a hydrogen atom or a methyl group. R 2 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R 3 represents a hydrogen atom or a methyl group. )
(B) Melamine-based crosslinking agent,
A cured film-forming resin composition comprising (C) a thermal radical polymerization initiator and (D) a solvent.
2. (A) The cured film forming resin composition of 1, wherein the copolymer is a copolymer containing monomer units represented by formulas (1), (2-1), and (2-2).
Figure JPOXMLDOC01-appb-C000004
 (In the formula, R 1 and R 3 are the same as described above. R 4 represents an alkyl group having 1 to 5 carbon atoms.)
3. Furthermore, (E) 1 or 2 resin composition for cured film formation containing a silane coupling agent.
4). And (F) a resin composition for forming a cured film according to any one of 1 to 3, comprising a polyfunctional (meth) acrylate compound.
5. (D) The resin composition for forming a cured film according to any one of 1 to 4, wherein the solvent has a boiling point of 150 ° C. or higher.
6. A cured film obtained using the cured resin composition for forming a cured film according to any one of 1 to 5.
A laminate formed by laminating a cured film of 7.6 on a substrate.
A touch panel including a cured film of 8.6.
　本発明の硬化膜形成用樹脂組成物を用いて得られる硬化膜は、硬度が高く、密着性、透明性及びＩＴＯスパッタに対する耐性に優れ、更にはレジスト剥離剤に対する耐性をも備える。そのため、有機エレクトロルミネッセンス（ＥＬ）素子等の各種ディスプレイにおける保護膜、平坦化膜、絶縁膜等、タッチパネルにおける保護膜、絶縁膜等の硬化膜を形成する材料として有用である。また、柔軟性にも優れることから、ＩＴＯフィルム用のオーバーコート材としても好適である。 The cured film obtained by using the resin composition for forming a cured film of the present invention has high hardness, excellent adhesion, transparency and resistance to ITO sputtering, and also has resistance to a resist stripper. Therefore, it is useful as a material for forming a cured film such as a protective film, an insulating film, or the like in a touch panel such as a protective film, a planarizing film, or an insulating film in various displays such as an organic electroluminescence (EL) element. Moreover, since it is excellent also in a softness | flexibility, it is suitable also as an overcoat material for ITO films.
［硬化膜形成用樹脂組成物］
　本発明の組成物は、（Ａ）下記共重合体、（Ｂ）メラミン系架橋剤、（Ｃ）熱ラジカル重合開始剤、及び（Ｄ）溶剤を含む。 [Resin composition for forming cured film]
The composition of the present invention comprises (A) the following copolymer, (B) a melamine-based crosslinking agent, (C) a thermal radical polymerization initiator, and (D) a solvent.
［（Ａ）共重合体］
　（Ａ）成分は、式（１）及び（２）で表されるモノマー単位を含有する共重合体である。
Figure JPOXMLDOC01-appb-C000005
 [(A) Copolymer]
(A) A component is a copolymer containing the monomer unit represented by Formula (1) and (2).
Figure JPOXMLDOC01-appb-C000005
　式中、Ｒ1は、それぞれ独立に、水素原子又はメチル基を表し、メチル基が好ましい。Ｒ2は、水素原子又は炭素数１～５のアルキル基を表す。Ｒ3は、水素原子又はメチル基を表し、水素原子が好ましい。 In formula, R < 1 > represents a hydrogen atom or a methyl group each independently, and a methyl group is preferable. R 2 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R 3 represents a hydrogen atom or a methyl group, and preferably a hydrogen atom.
　前記アルキル基は、直鎖状、分岐状、環状のいずれでもよく、その具体例としては、メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、シクロプロピル基、ｎ－ブチル基、ｉ－ブチル基、ｓ－ブチル基、ｔ－ブチル基、シクロブチル基、ｎ－ペンチル基等が挙げられる。また、前記アルキル基の水素原子の一部又は全部が置換基で置換されていてもよく、前記置換基としては、ハロゲン原子、ヒドロキシ基、アミノ基等が挙げられる。 The alkyl group may be linear, branched or cyclic, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, i -Butyl group, s-butyl group, t-butyl group, cyclobutyl group, n-pentyl group and the like. Moreover, part or all of the hydrogen atoms of the alkyl group may be substituted with a substituent, and examples of the substituent include a halogen atom, a hydroxy group, and an amino group.
　前記共重合体は、密着性の向上の観点から、式（１）、（２－１）及び（２－２）で表されるモノマー単位を含むものが好ましい。
Figure JPOXMLDOC01-appb-C000006
 The copolymer preferably contains a monomer unit represented by the formulas (1), (2-1) and (2-2) from the viewpoint of improving adhesion.
Figure JPOXMLDOC01-appb-C000006
　式中、Ｒ1及びＲ3は、前記と同じである。Ｒ4は、炭素数１～５のアルキル基を表す。炭素数１～５のアルキル基としては、前述したものと同じものが挙げられる。 In the formula, R 1 and R 3 are the same as described above. R 4 represents an alkyl group having 1 to 5 carbon atoms. Examples of the alkyl group having 1 to 5 carbon atoms are the same as those described above.
　（Ａ）成分の共重合体は、耐溶剤性と硬度とに優れる硬化膜を再現性よく得る観点から全モノマー単位中、式（１）で表されるモノマー単位を、好ましくは５モル％以上、より好ましくは１０モル％以上含有する。 The copolymer of the component (A) is preferably a monomer unit represented by the formula (1), preferably 5 mol% or more in all monomer units from the viewpoint of obtaining a cured film excellent in solvent resistance and hardness with good reproducibility. More preferably, it contains 10 mol% or more.
　前記共重合体の重量平均分子量（Ｍｗ）は、ハンドリング性、密着性を考慮すると、好ましくは５,０００～２００,０００、より好ましくは１０,０００～１００,０００、より一層好ましくは１５,０００～８０,０００である。Ｍｗが２００,０００を超えると、溶剤に対する溶解性が低下しハンドリング性が低下することがあり、Ｍｗが５,０００未満であると、密着性が低下することがある。 The weight average molecular weight (Mw) of the copolymer is preferably 5,000 to 200,000, more preferably 10,000 to 100,000, and still more preferably 15,000 in consideration of handling properties and adhesion. ~ 80,000. When Mw exceeds 200,000, solubility in a solvent may be reduced and handling properties may be reduced. When Mw is less than 5,000, adhesion may be reduced.
　また、印刷性を考慮すると、前記共重合体のＭｗは、好ましくは１０,０００～２００,０００、より好ましくは３０,０００～１８０,０００、より一層好ましくは４０,０００～１７０,０００である。Ｍｗが２００,０００を超えると、溶剤に対する溶解性が低下しハンドリング性が低下することがあり、Ｍｗが１０,０００未満であると、印刷性が低下することがある。 In consideration of printability, the Mw of the copolymer is preferably 10,000 to 200,000, more preferably 30,000 to 180,000, and still more preferably 40,000 to 170,000. . When Mw exceeds 200,000, solubility in a solvent may be reduced and handling properties may be reduced. When Mw is less than 10,000, printability may be reduced.
　なお、Ｍｗは、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）によるポリスチレン換算測定値である。 In addition, Mw is a polystyrene conversion measured value by gel permeation chromatography (GPC).
　前記共重合体は、ランダム共重合体、交互共重合体、ブロック共重合体のいずれでもよい。 The copolymer may be a random copolymer, an alternating copolymer, or a block copolymer.
　（Ａ）成分の共重合体は、従来公知の方法で、ポリ(メタ)アクリル酸、ポリ(メタ)アクリル酸エステル又は(メタ)アクリル酸－(メタ)アクリル酸エステル共重合体を合成した後、該共重合体に３,４－エポキシシクロヘキシルメチル(メタ)アクリレートを開環付加させることで合成することができる。開環付加反応は、具体的には、特開平１０－０８７７２５号公報等に記載の方法に従って行うことができる。 The copolymer of component (A) is prepared by synthesizing poly (meth) acrylic acid, poly (meth) acrylic acid ester or (meth) acrylic acid- (meth) acrylic acid ester copolymer by a conventionally known method. The copolymer can be synthesized by ring-opening addition of 3,4-epoxycyclohexylmethyl (meth) acrylate to the copolymer. Specifically, the ring-opening addition reaction can be carried out according to the method described in JP-A-10-087725 and the like.
　（Ａ）成分の共重合体は、市販品として入手可能であり、例えば、サイクロマーP(ACA)Z200M、サイクロマーP(ACA)Z230AA、サイクロマーP(ACA)Z250、サイクロマーP(ACA)Z251、サイクロマーP(ACA)Z300、サイクロマーP(ACA)Z320、サイクロマーP(ACA)Z254F（以上、ダイセル・オルネクス(株)製）等が挙げられる。 The copolymer of component (A) is available as a commercial product, for example, cyclomer P (ACA) Z200M, cyclomer P (ACA) Z230AA, cyclomer P (ACA) Z250, cyclomer P (ACA) Z251, Cyclomer P (ACA) Z300, Cyclomer P (ACA) Z320, Cyclomer P (ACA) Z254F (above, manufactured by Daicel Ornex Co., Ltd.) and the like.
［（Ｂ）メラミン系架橋剤］
　（Ｂ）成分はメラミン系架橋剤であり、（Ａ）成分の架橋に寄与するものである。メラミン系架橋剤としては、メチロール基、メトキシメチル基等の架橋形成置換基を有するメラミン系化合物が挙げられる。メラミン系架橋剤としては、例えば、日本サイテックインダストリーズ(株)製CYMEL（登録商標）303（ヘキサメトキシメチルメラミン）、1170（テトラブトキシメチルグリコールウリル）、1123（テトラメトキシメチルベンゾグアナミン）等のサイメルシリーズ；(株)三和ケミカル製のメチル化メラミン樹脂であるニカラック（登録商標）MW-30HM、MW-390、MW-100LM、MX-750LM、メチル化尿素樹脂であるMX-270、MX-280、MX-290等のニカラックシリーズ等が挙げられる。 [(B) Melamine crosslinking agent]
The component (B) is a melamine-based crosslinking agent and contributes to the crosslinking of the component (A). Examples of the melamine-based crosslinking agent include melamine-based compounds having a crosslinking-forming substituent such as a methylol group or a methoxymethyl group. Examples of melamine-based crosslinking agents include Cymel series such as CYMEL (registered trademark) 303 (hexamethoxymethylmelamine), 1170 (tetrabutoxymethylglycoluril), 1123 (tetramethoxymethylbenzoguanamine) manufactured by Nippon Cytec Industries, Ltd. Nicalac (registered trademark) MW-30HM, MW-390, MW-100LM, MX-750LM, which is a methylated melamine resin manufactured by Sanwa Chemical Co., Ltd., MX-270, MX-280, which are methylated urea resins Nicarak series such as MX-290.
　（Ｂ）成分の含有量の上限値は、保存安定性の低下を抑制する観点から、（Ａ）成分１００質量部に対して、好ましくは２００質量部、より好ましくは１００質量部であり、その下限値は、耐溶剤性に優れる硬化膜を再現性よく得る観点から、（Ａ）成分１００質量部に対し、好ましくは３０質量部、より好ましくは５０質量部である。 The upper limit of the content of the component (B) is preferably 200 parts by mass, more preferably 100 parts by mass, with respect to 100 parts by mass of the component (A), from the viewpoint of suppressing a decrease in storage stability. The lower limit is preferably 30 parts by mass, more preferably 50 parts by mass with respect to 100 parts by mass of the component (A), from the viewpoint of obtaining a cured film having excellent solvent resistance with good reproducibility.
［（Ｃ）熱ラジカル重合開始剤］
　（Ｃ）成分は熱ラジカル重合開始剤であり、（Ａ）成分の重合の開始又は促進に寄与するものである。熱ラジカル重合開始剤としては、例えば、アセチルペルオキシド、ベンゾイルペルオキシド、メチルエチルケトンペルオキシド、シクロヘキサノンペルオキシド、過酸化水素、ｔ－ブチルヒドロペルオキシド、クメンヒドロペルオキシド、ジ－ｔ－ブチルペルオキシド、ジクミルペルオキシド、ジラウロイルペルオキシド、ｔ－ブチルペルオキシアセテート、ｔ－ブチルペルオキシピバレート、ｔ－ブチルペルオキシ－２－エチルヘキサノエート（ｔ－ブチル２－エチルヘキサンペルオキソエート）等の過酸化物；２,２'－アゾビスイソブチロニトリル、２,２'－アゾビス(２,４－ジメチルバレロニトリル)、(１－フェニルエチル)アゾジフェニルメタン、２,２'－アゾビス(４－メトキシ－２,４－ジメチルバレロニトリル)、ジメチル２,２'－アゾビスイソブチレート、２,２'－アゾビス(２－メチルブチロニトリル)、１,１'－アゾビス(１－シクロヘキサンカルボニトリル)、２－(カルバモイルアゾ)イソブチロニトリル、２,２'－アゾビス(２,４,４－トリメチルペンタン)、２－フェニルアゾ－２,４－ジメチル－４－メトキシバレロニトリル、２,２'－アゾビス(２－メチルプロパン)等のアゾ系化合物；過硫酸アンモニウム、過硫酸ナトリウム、過硫酸カリウム等の過硫酸塩等が挙げられるが、これらに限定されない。 [(C) Thermal radical polymerization initiator]
The component (C) is a thermal radical polymerization initiator and contributes to the initiation or acceleration of the polymerization of the component (A). Examples of the thermal radical polymerization initiator include acetyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, dilauroyl peroxide. , Peroxides such as t-butyl peroxyacetate, t-butyl peroxypivalate, t-butyl peroxy-2-ethylhexanoate (t-butyl 2-ethylhexane peroxoate); 2,2′-azobisiso Butyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), (1-phenylethyl) azodiphenylmethane, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azo Bisisobutyrate, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) isobutyronitrile, 2,2'- Azo compounds such as azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2′-azobis (2-methylpropane); ammonium persulfate, Examples thereof include, but are not limited to, persulfates such as sodium sulfate and potassium persulfate.
　市販の熱ラジカル重合開始剤としては、例えば、日油(株)製パーロイル（登録商標）IB、NPP、IPP、SBP、TCP、OPP、SA、355、L、パーブチル（登録商標）ND、NHP、MA、PV、355、A、C、D、E、L、I、O、P、Z、パーヘキシル（登録商標）ND、PV、D、I、O、Z、パーオクタ（登録商標）ND、ナイパー（登録商標）PMB、BMT、BW、パーテトラ（登録商標）A、パーヘキサ（登録商標）MC、TMH、HC、250、25B、C、25Z、22、V、パーオクタ（登録商標）O、パークミル（登録商標）ND、D、パーメンタ（登録商標）H、ノフマー（登録商標）BC；和光純薬工業(株)製V-70、V-65、V-59、V-40、V-30、VA-044、VA-046B、VA-061、V-50、VA-057、VA-086、VF-096、VAm-110、V-601、V-501；BASF社製IRGACURE（登録商標）184、369、651、500、819、907、784、2959、CGI1700、CGI1750、CGI1850、CG24-61、TPO、DAROCUR（登録商標）1116、1173；サイテックサーフェイススペシャルティーズ社製UVECRYL（登録商標）P36；Lamberti社製Esacure（登録商標）KIP150、KIP65LT、KIP100F、KT37、KT55、KTO46、KIP75/B等が挙げられるが、これらに限定されない。 Examples of commercially available thermal radical polymerization initiators include, for example, NOF Corporation Parroyl (registered trademark) IB, NPP, IPP, SBP, TCP, OPP, SA, 355, L, perbutyl (registered trademark) ND, NHP, MA, PV, 355, A, C, D, E, L, I, O, P, Z, Perhexyl (registered trademark) ND, PV, D, I, O, Z, Perocta (registered trademark) ND, Nyper ( (Registered trademark) PMB, BMT, BW, pertetra (registered trademark) A, perhexa (registered trademark) MC, TMH, HC, 250, 25B, C, 25Z, 22, V, perocta (registered trademark) O, park mill (registered trademark) ) ND, D, Permenta (registered trademark) H, NOFMER (registered trademark) BC; V-70, V-65, V-59, V-40, V-30, VA-044 manufactured by Wako Pure Chemical Industries, Ltd. , VA-046B, VA-061, V-50, VA-057, VA-086, VF-096, VAm-110, V-601, V-501; IRGACURE (registered trademark) 184, 369, 651 manufactured by BASF , 500, 819, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, TPO, DAROCUR (registered trademark) 1116, 1173; Tech Surface Specialties Inc. UVECRYL (registered trademark) P36; Lamberti Co. Esacure (TM) KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / but B, and the like, without limitation.
　（Ｃ）成分の含有量の上限値は、保存安定性の低下を抑制する観点から、（Ａ）成分１００質量部に対して、好ましくは２０質量部、より好ましくは１０質量部であり、その下限値は、耐溶剤性と硬度に優れる硬化膜を再現性よく得る観点から、（Ａ）成分１００質量部に対し、好ましくは０.０１質量部、より好ましく０.１質量部である。 The upper limit of the content of the component (C) is preferably 20 parts by mass, more preferably 10 parts by mass with respect to 100 parts by mass of the component (A), from the viewpoint of suppressing a decrease in storage stability. The lower limit is preferably 0.01 parts by mass, more preferably 0.1 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of obtaining a cured film having excellent solvent resistance and hardness with good reproducibility.
［（Ｄ）溶剤］
　（Ｄ）成分は、溶剤であり、前記（Ａ）～（Ｃ）成分を溶解でき、本発明の組成物が後述の（Ｅ）～（Ｉ）成分及びその他の添加剤を含む場合はこれらも溶解できるものであれば、特に限定されない。つまり、本発明の組成物は、（Ｄ）成分以外の成分が（Ｄ）成分に溶解した溶液である。 [(D) Solvent]
The component (D) is a solvent, can dissolve the components (A) to (C), and if the composition of the present invention contains the components (E) to (I) described below and other additives, these are also included. If it can melt | dissolve, it will not specifically limit. That is, the composition of the present invention is a solution in which components other than the component (D) are dissolved in the component (D).
　溶剤の具体例としては、エチレングリコール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールジエチルエーテル、エチレングリコールイソプロピルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールジブチルエーテル、エチレングリコールモノヘキシルエーテル、エチレングリコールモノベンジルエーテル、エチレングリコールモノフェニルエーテル、エチレングリコールモノアセテート、エチレングリコールジアセテート、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノブチルエーテルアセテート、ジエチレングリコール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールメチルエチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールジブチルエーテル、ジエチレングリコールモノヘキシルエーテル、ジエチレングリコールモノベンジルエーテル、ジエチレングリコールモノフェニルエーテル、ジエチレングリコールアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノブチルエーテル、プロピレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノブチルエーテル、ジプロピレングリコール、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノブチルエーテル、トリプロピレングリコールモノメチルエーテル、トリメチレングリコール、ヘキシレングリコール、オクチレングリコール、メトキシメトキシエタノール、１－ブトキシエトキシプロパノール、酢酸イソブチル、酢酸メトキシブチル、酢酸２－エチルへキシル、酢酸シクロヘキシル、酢酸メチルシクロヘキシル、酢酸ベンジル、酢酸イソアミル、プロピオン酸ｎ－ブチル、乳酸イソブチル、乳酸ｎ－ブチル、乳酸ｎ－アミル、乳酸イソアミル、イソ吉草酸イソアミル、アセト酪酸エチル、ステアリン酸ブチル、シュウ酸ジブチル、マロン酸ジエチル、安息香酸メチル、安息香酸エチル、安息香酸プロピル、サリチル酸メチル、メチルフェニルエーテル、エチルベンジルエーテル、エチルフェニルエーテル、ジクロロエチルエーテル、ジイソアミルエーテル、ｎ－ヘキシルエーテル、１,４－ジオキサン、ジエチルアセタール、シネオール、メチルエチルケトン、メチルプロピルケトン、メチルブチルケトン、メチルイソブチルケトン、ジエチルケトン、エチルｎ－ブチルケトン、ジ－ｎ－プロピルケトン、アセトニルアセトン、ホロン、イソホロン、アセトフェノン、グリセリン、ブタノール、２－ブタノール、１,３－ブタンジオール、２,３－ブタンジオール、イソアミルアルコール、１,５－ペンタンジオール、２－メチルシクロヘキサノール、２－エチルヘキサノール、３,５,５－トリメチルヘキサノール、１－オクタノール、２－オクタノール、ノナノール、ｎ－デカノール、トリメチルノニルアルコール、ベンジルアルコール、α－テルピネオール、テトラヒドロフルフリルアルコール、フルフリルアルコール、アビエチノール、トリグリコールジクロリド、トリクロロ酢酸、乳酸、吉草酸、イソ吉草酸、カプロン酸、２－エチルへキサン酸、カプリル酸、無水酪酸、デカン、ジペンテン、ｐ－メンタン、ドデカン、１,１,２－トリクロロエタン、１,１,１,２－テトラクロロエタン、１,１,２,２－テトラクロロエタン、ヘキサクロロエタン、トルエン、キシレン、ｏ－ジクロロベンゼン、ｍ－ジクロロベンゼン、ｐ－ジクロロベンゼン、１,２,４－トリクロロベンゼン、ｏ－ジブロモベンゼン、ベンゾニトリル、ニトロベンゼン、α－トルニトリル（フェニルアセトニトリル）、Ｎ－メチルホルムアミド、Ｎ－メチルアセトアミド、２－ピロリドン等が挙げられる。 Specific examples of the solvent include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono Benzyl ether, ethylene glycol monophenyl ether, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, die Lenglycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, diethylene glycol monohexyl ether, diethylene glycol monobenzyl ether, diethylene glycol monophenyl ether, diethylene glycol acetate, diethylene glycol monoethyl ether acetate, Diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl Ether, propylene glycol monobutyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, trimethylene glycol, hexylene glycol, octylene glycol, methoxymethoxy Ethanol, 1-butoxyethoxypropanol, isobutyl acetate, methoxybutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, benzyl acetate, isoamyl acetate, n-butyl propionate, isobutyl lactate, n-butyl lactate, lactic acid n-amyl, isoamyl lactate, isoamyl isovalerate, ethyl acetobutyrate, butyl stearate, dioxalate Butyl, diethyl malonate, methyl benzoate, ethyl benzoate, propyl benzoate, methyl salicylate, methyl phenyl ether, ethyl benzyl ether, ethyl phenyl ether, dichloroethyl ether, diisoamyl ether, n-hexyl ether, 1,4- Dioxane, diethyl acetal, cineol, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, ethyl n-butyl ketone, di-n-propyl ketone, acetonyl acetone, holon, isophorone, acetophenone, glycerin, butanol, 2-butanol, 1,3-butanediol, 2,3-butanediol, isoamyl alcohol, 1,5-pentanediol, 2-methylcyclohexanol, 2-ethylhexene Sanol, 3,5,5-trimethylhexanol, 1-octanol, 2-octanol, nonanol, n-decanol, trimethylnonyl alcohol, benzyl alcohol, α-terpineol, tetrahydrofurfuryl alcohol, furfuryl alcohol, abiethinol, triglycol dichloride , Trichloroacetic acid, lactic acid, valeric acid, isovaleric acid, caproic acid, 2-ethylhexanoic acid, caprylic acid, butyric anhydride, decane, dipentene, p-menthane, dodecane, 1,1,2-trichloroethane, 1,1 , 1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, hexachloroethane, toluene, xylene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, 1,2,4-trichlorobenzene, o-Dibromobenzene, Zonitoriru, nitrobenzene, alpha-tolunitrile (phenylacetonitrile), N- methylformamide, N- methylacetamide, 2-pyrrolidone, and the like.
　溶剤は、１種単独で又は２種以上を混合して使用することができる。また、（Ａ）成分を重合する際に用いた溶剤をそのまま用いることもできる。 Solvents can be used singly or in combination of two or more. Moreover, the solvent used when superposing | polymerizing (A) component can also be used as it is.
　溶剤は、印刷性の観点からは、沸点が１５０℃以上であることが好ましく、１８０℃以上であることがより好ましく、２００℃以上であることがより一層好ましい。このような溶剤としては、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノブチルエーテルアセテート、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル、ジエチレングリコールモノヘキシルエーテル、トリエチレングリコールモノブチルエーテル、プロピレングリコールモノブチルエーテル、ジプロピレングリコール、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジエチレングリコールモノフェニルエーテル、エチレングリコールモノベンジルエーテル、ジエチレングリコールモノベンジルエーテル等が特に好ましい。 From the viewpoint of printability, the solvent preferably has a boiling point of 150 ° C. or higher, more preferably 180 ° C. or higher, and even more preferably 200 ° C. or higher. Such solvents include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol monohexyl ether, triethylene glycol Monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol monophenyl ether, ethylene glycol monobenzyl ether Le, diethylene glycol benzyl ether or the like are particularly preferable.
　溶剤を２種以上混合して使用する場合は、少なくとも１種の沸点が１５０℃以上であることが好ましく、１８０℃以上であることがより好ましく、２００℃以上であることがより一層好ましい。 When two or more solvents are used in combination, at least one boiling point is preferably 150 ° C. or higher, more preferably 180 ° C. or higher, and even more preferably 200 ° C. or higher.
　溶剤の量は、本発明の組成物中の固形分濃度が１～９５質量％となるような量が好ましく、固形分濃度が５～９０質量％となるような量がより好ましく、固形分濃度が１０～８５質量％となるような量がより一層好ましい。ここで、固形分とは、本発明の組成物の全成分から（Ｄ）溶剤を除いたものである。 The amount of the solvent is preferably such that the solid content concentration in the composition of the present invention is 1 to 95% by mass, more preferably the solid content concentration is 5 to 90% by mass, and the solid content concentration Is more preferably 10 to 85% by mass. Here, solid content removes (D) solvent from all the components of the composition of this invention.
　本発明の組成物は、更に
（Ｅ）シランカップリング剤、
（Ｆ）多官能(メタ)アクリレート化合物、
（Ｇ）イオントラップ剤、
（Ｈ）多官能チオール化合物、
（Ｉ）重合禁止剤
等を含んでもよい。 The composition of the present invention further comprises (E) a silane coupling agent,
(F) a polyfunctional (meth) acrylate compound,
(G) an ion trap agent,
(H) a polyfunctional thiol compound,
(I) A polymerization inhibitor may be included.
［（Ｅ）シランカップリング剤］
　本発明の組成物は、密着性を向上させる観点から、好ましくは、（Ｅ）成分としてシランカップリング剤を含む。シランカップリング剤の好ましい一例としては、式（３）で表されるシラン化合物が挙げられる。 [(E) Silane coupling agent]
From the viewpoint of improving adhesion, the composition of the present invention preferably contains a silane coupling agent as the component (E). A preferred example of the silane coupling agent is a silane compound represented by the formula (3).
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　式（３）中、Ｒ5は、メチル基又はエチル基を表す。Ｘは、加水分解性基を表す。Ｙは、反応性官能基を表す。ｍは、０～３の整数である。ｎは、０～３の整数であり、０～２の整数が好ましい。 In formula (3), R 5 represents a methyl group or an ethyl group. X represents a hydrolyzable group. Y represents a reactive functional group. m is an integer of 0 to 3. n is an integer of 0 to 3, preferably an integer of 0 to 2.
　Ｘで表される加水分解性基としては、ハロゲン原子、炭素数１～３のアルコキシ基、炭素数２～４のアルコキシアルコキシ基等が挙げられる。前記ハロゲン原子としては、塩素原子、臭素原子等が挙げられる。炭素数１～３のアルコキシ基としては、直鎖状又は分岐状のものが好ましく、具体的には、メトキシ基、エトキシ基、ｎ－プロポキシ基及びｉ－プロポキシ基である。また、炭素数２～４のアルコキシアルコキシ基として具体的には、メトキシメトキシ基、２－メトキシエトキシ基、エトキシメトキシ基及び２－エトキシエトキシ基である。 Examples of the hydrolyzable group represented by X include a halogen atom, an alkoxy group having 1 to 3 carbon atoms, and an alkoxyalkoxy group having 2 to 4 carbon atoms. Examples of the halogen atom include a chlorine atom and a bromine atom. The alkoxy group having 1 to 3 carbon atoms is preferably linear or branched, and specifically includes a methoxy group, an ethoxy group, an n-propoxy group, and an i-propoxy group. Specific examples of the alkoxyalkoxy group having 2 to 4 carbon atoms include a methoxymethoxy group, a 2-methoxyethoxy group, an ethoxymethoxy group, and a 2-ethoxyethoxy group.
　Ｙで表される反応性官能基としては、アミノ基、ウレイド基、(メタ)アクリロキシ基、ビニル基、エポキシ基、メルカプト基等が挙げられ、アミノ基、ウレイド基、(メタ)アクリロキシ基等が好ましい。特に好ましくはアミノ基又はウレイド基である。 Examples of the reactive functional group represented by Y include an amino group, a ureido group, a (meth) acryloxy group, a vinyl group, an epoxy group, a mercapto group, and the like, such as an amino group, a ureido group, and a (meth) acryloxy group. preferable. Particularly preferred is an amino group or a ureido group.
　前記シランカップリング剤の具体例としては、３－アミノプロピルトリクロロシラン、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、３－アミノプロピルメチルジメトキシシラン、３－アミノプロピルメチルジエトキシシラン、３－ウレイドプロピルトリメトキシシラン、３－ウレイドプロピルトリエトキシシラン、３－アクリロキシプロピルトリメトキシシラン、３－アクリロキシプロピルトリエトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルトリエトキシシラン、ビニルトリクロロシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、アリルトリクロロシラン、アリルトリメトキシシラン、アリルトリエトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、３－グリシドキシプロピルトリエトキシシラン、３－メルカプトプロピルトリメトキシシラン、３－メルカプトプロピルトリエトキシシラン、３－メルカプトプロピルメチルジメトキシシラン、３－メルカプトプロピルメチルジエトキシシラン等が挙げられる。 Specific examples of the silane coupling agent include 3-aminopropyltrichlorosilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, and 3-aminopropylmethyldiethoxysilane. 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltri Ethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrichlorosilane, allyltrimethoxysilane, allyltriethoxysilane, 3-glycidoxy Propyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, Examples include 3-mercaptopropylmethyldiethoxysilane.
　これらのうち、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、３－ウレイドプロピルトリメトキシシラン、３－ウレイドプロピルトリエトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルトリエトキシシラン等が特に好ましい。前記シランカップリング剤としては、市販品を使用し得る。 Of these, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyl Triethoxysilane and the like are particularly preferable. A commercial item can be used as said silane coupling agent.
　本発明の組成物が（Ｅ）成分を含む場合、その含有量は、（Ａ）成分１００質量部に対して、好ましくは０.００１～１０質量部、より好ましくは０.０１～５質量部、より一層好ましくは０.０５～１質量部である。含有量が０.００１質量部未満だと密着性の向上効果が得られないことがあり、１０質量部を超えると硬度が低下することがある。 When the composition of the present invention contains the component (E), the content thereof is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the component (A). More preferably, the amount is 0.05 to 1 part by mass. If the content is less than 0.001 part by mass, the effect of improving the adhesion may not be obtained, and if it exceeds 10 parts by mass, the hardness may decrease.
［（Ｆ）多官能(メタ)アクリレート化合物］
　本発明の組成物は、硬度を改善する観点から、好ましくは、（Ｆ）成分として多官能(メタ)アクリレート化合物を含む。多官能(メタ)アクリレート化合物とは、分子中に少なくとも３つの(メタ)アクリロキシ基を有する化合物のことであり、具体的には、多価アルコールと(メタ)アクリル酸とのエステルが挙げられる。また、１分子中の(メタ)アクリロキシ基の数は３～６であり、好ましくは３又は４である。 [(F) Polyfunctional (meth) acrylate compound]
From the viewpoint of improving hardness, the composition of the present invention preferably contains a polyfunctional (meth) acrylate compound as the component (F). The polyfunctional (meth) acrylate compound is a compound having at least three (meth) acryloxy groups in the molecule, and specifically includes an ester of a polyhydric alcohol and (meth) acrylic acid. The number of (meth) acryloxy groups in one molecule is 3 to 6, preferably 3 or 4.
　前記多価アルコールとしては、グリセロール、エリスリトール、ペンタエリスリトール、トリメチロールエタン、トリメチロールプロパン、ジペンタエリスリトール、ジトリメチロールプロパン等が挙げられる。 Examples of the polyhydric alcohol include glycerol, erythritol, pentaerythritol, trimethylolethane, trimethylolpropane, dipentaerythritol, ditrimethylolpropane, and the like.
　前記多官能(メタ)アクリレート化合物の具体例としては、ペンタエリスリトールテトラアクリレート、ペンタエリスリトールテトラメタクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールトリメタクリレート、ジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールヘキサメタクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールペンタメタクリレート、トリメチロールエタントリアクリレート、トリメチロールエタントリメタクリレート、トリメチロールプロパントリアクリレート、トリメチロールプロパントリメタクリレート、ジトリメチロールプロパンテトラアクリレート、ジトリメチロールプロパンテトラメタクリレート等が挙げられる。 Specific examples of the polyfunctional (meth) acrylate compound include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentane. Examples include acrylate, dipentaerythritol pentamethacrylate, trimethylolethane triacrylate, trimethylolethane trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetramethacrylate, and the like.
　前記多官能(メタ)アクリレート化合物は、市販品として容易に入手が可能であり、その具体例としては、例えば日本化薬(株)製KAYARAD（登録商標）T-1420、DPHA、DPHA-2C、D-310、D-330、DPCA-20、DPCA-30、DPCA-60、DPCA-120、DN-0075、DN-2475、R-526、NPGDA、PEG400DA、MANDA、R-167、HX-220、HX620、R-551、R-712、R-604、R-684、GPO-303、TMPTA、THE-330、TPA-320、TPA-330、PET-30、RP-1040；東亞合成(株)製アロニックス（登録商標）M-210、M-240、M-6200、M-309、M-400、M-402、M-405、M-450、M-7100、M-8030、M-8060、M-1310、M-1600、M-1960、M-8100、M-8530、M-8560、M-9050；大阪有機化学工業(株)製ビスコート295、300、360、GPT、3PA、400、260、312、335HP；新中村化学工業(株)製NKエステルA-9300、A-9300-1CL、A-GLY-9E、A-GLY-20E、A-TMM-3、A-TMM-3L、A-TMM-3LM-N、A-TMPT、AD-TMP、ATM-35E、A-TMMT、A-9550、A-DPH、TMPT等が挙げられる。 The polyfunctional (meth) acrylate compound can be easily obtained as a commercial product. Specific examples thereof include, for example, KAYARAD (registered trademark) T-1420, DPHA, DPHA-2C, manufactured by Nippon Kayaku Co., Ltd. D-310, D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, R-526, NPGDA, PEG400DA, MANDA, R-167, HX-220, HX620, R-551, R-712, R-604, R-684, GPO-303, TMPTA, THE-330, TPA-320, TPA-330, PET-30, RP-1040; manufactured by Toagosei Co., Ltd. Aronix (registered trademark) M-210, M-240, M-6200, M-309, M-400, M-402, M-405, M-450, M-7100, M-8030, M-8060, M -1310, M-1600, M-1960, M-8100, M-8530, M-8560, M-9050; Biscoat 295, 300, 360, GPT, 3PA, 400, 260, manufactured by Osaka Organic Chemical Industry Co., Ltd. 312, 335HP; NK ester A-9300, A-9300-1CL, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A- from Shin-Nakamura Chemical Co., Ltd. TMM-3LM-N, A-TMPT, AD-TMP, ATM-35E, A-TMMT, A-9550, A-DPH, TMPT, and the like.
　本発明の組成物が（Ｆ）成分を含む場合、その含有量は、（Ａ）成分１００質量部に対して、好ましくは１０～３００質量部、より好ましくは２０～２００質量部、より一層好ましくは５０～１５０質量部である。含有量が１０質量部未満である場合には、硬化膜の硬度改善効果が得られないことがあり、３００質量部を超える場合には、密着性と柔軟性の特性が低下し、クラックが発生し易くなることがある。多官能(メタ)アクリレート化合物は、１種又は２種以上を組み合わせて用いることができる。 When the composition of the present invention contains the component (F), the content thereof is preferably 10 to 300 parts by weight, more preferably 20 to 200 parts by weight, even more preferably 100 parts by weight of the component (A). Is 50 to 150 parts by mass. When the content is less than 10 parts by mass, the effect of improving the hardness of the cured film may not be obtained. When the content exceeds 300 parts by mass, the adhesion and flexibility characteristics are degraded and cracks are generated. May be easier to do. A polyfunctional (meth) acrylate compound can be used 1 type or in combination of 2 or more types.
［（Ｇ）イオントラップ剤］
　本発明の組成物は、硬化膜に接する金属配線等のマイグレーションを抑制する観点から、好ましくは、イオントラップ剤を含む。このようなイオントラップ剤としては、構造中に不対電子を持つキレート形成能を有する化合物が好ましく、例えば、Ｎ,Ｎ'－ビス[３－(３,５－ジ－ｔ－ブチル－４－ヒドロキシフェニル)プロピオニル]ヒドラジン（Irganox MD1024、BASF社製）、シュウ酸ビス(ベンジリデンヒドラジド)（Eastman Inhibitor OABH、イーストマンケミカル社製）、ベンゾトリアゾール、５－メチルベンゾトリアゾール等が挙げられる。これらは市販品として入手できる。また、その他の市販品として、アデカスタブCDA-1（(株)ADEKA製）、アデカスタブCDA-6（(株)ADEKA製）、Qunox（三井東圧ファイン(株)製）、Naugard XL-1（ユニロイアル(株)製）等が挙げられる。これらのうち、特に５－メチルベンゾトリアゾールが好ましい。 [(G) Ion trap agent]
The composition of the present invention preferably contains an ion trap agent from the viewpoint of suppressing migration of a metal wiring or the like in contact with the cured film. As such an ion trapping agent, a compound having a chelating ability having an unpaired electron in the structure is preferable. For example, N, N′-bis [3- (3,5-di-t-butyl-4- Hydroxyphenyl) propionyl] hydrazine (Irganox MD1024, manufactured by BASF), bis (benzylidene hydrazide) oxalate (Eastman Inhibitor OABH, manufactured by Eastman Chemical), benzotriazole, 5-methylbenzotriazole and the like. These are available as commercial products. Other commercially available products include ADK STAB CDA-1 (manufactured by ADEKA), ADK STAB CDA-6 (manufactured by ADEKA), Qunox (manufactured by Mitsui Toatsu Fine Co., Ltd.), Naugard XL-1 (uniroyal) Etc.). Of these, 5-methylbenzotriazole is particularly preferable.
　本発明の組成物が（Ｇ）成分を含む場合、その含有量は、（Ａ）成分１００質量部に対して、好ましくは０.０００１～２０質量部、より好ましくは０.００１～１０質量部である。０.０００１質量部未満であると金属配線保護の効果が得られないことがあり、２０質量部を超えると硬化膜としての硬度、密着性等の特性を低下させることがあり、またコスト的にも不利となることがある。 When the composition of the present invention contains the component (G), the content thereof is preferably 0.0001 to 20 parts by mass, more preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the component (A). It is. If the amount is less than 0.0001 parts by mass, the effect of protecting the metal wiring may not be obtained. If the amount exceeds 20 parts by mass, characteristics such as hardness and adhesion as a cured film may be reduced, and the cost may be reduced. May also be disadvantageous.
［（Ｈ）多官能チオール化合物］
　本発明の組成物は、必要に応じて、多官能チオール化合物を含む。本発明の組成物に用いられる多官能チオール化合物としては、３官能以上のチオール化合物が好ましい。多官能チオール化合物は、多価アルコールと、単官能及び／又は多官能チオール化合物との付加反応物として得ることができる。具体的な化合物としては、１,３,５－トリス(３－メルカプトプロピオニルオキシエチル)イソシアヌレート、１,３,５－トリス(３－メルカプトブチリルオキシエチル)イソシアヌレート（昭和電工(株)製、カレンズMT（登録商標）NR1）、トリメチロールプロパントリス(３－メルカプトプロピオネート)等の３官能チオール化合物；ペンタエリスリトールテトラキス(３－メルカプトプロピオネート)、ペンタエリスリトールテトラキス(３－メルカプトブチレート)（昭和電工(株)製、カレンズMT（登録商標）PEI）等の４官能チオール化合物；ジペンタエリスリトールヘキサキス(３－プロピオネート)等の６官能チオール化合物等が挙げられる。 [(H) Polyfunctional thiol compound]
The composition of this invention contains a polyfunctional thiol compound as needed. The polyfunctional thiol compound used in the composition of the present invention is preferably a trifunctional or higher functional thiol compound. The polyfunctional thiol compound can be obtained as an addition reaction product of a polyhydric alcohol and a monofunctional and / or polyfunctional thiol compound. Specific compounds include 1,3,5-tris (3-mercaptopropionyloxyethyl) isocyanurate and 1,3,5-tris (3-mercaptobutyryloxyethyl) isocyanurate (manufactured by Showa Denko KK). , Karenz MT (registered trademark) NR1), trifunctional thiol compounds such as trimethylolpropane tris (3-mercaptopropionate); pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate) ) (Made by Showa Denko KK, Karenz MT (registered trademark) PEI) and the like; and tetrafunctional thiol compounds such as dipentaerythritol hexakis (3-propionate).
　本発明の組成物が（Ｈ）成分を含む場合、その含有量は、全固形分中０.１～８質量％が好ましく、０.８～５質量％がより好ましい。含有量が多すぎると組成物の安定性、臭気、密着性等が悪化することがある。 When the composition of the present invention contains the component (H), the content thereof is preferably 0.1 to 8% by mass, more preferably 0.8 to 5% by mass in the total solid content. If the content is too large, the stability, odor, adhesion and the like of the composition may deteriorate.
［（Ｉ）重合禁止剤］
　本発明の組成物は、必要に応じて、重合禁止剤を含む。前記重合禁止剤の具体例としては、２,６－ジイソブチルフェノール、３,５－ジ－ｔ－ブチルフェノール、３,５－ジ－ｔ－ブチルクレゾール、ヒドロキノン、ヒドロキノンモノメチルエーテル、ピロガロール、ｔ－ブチルカテコール、４－メトキシ－１－ナフトール等が挙げられる。 [(I) Polymerization inhibitor]
The composition of this invention contains a polymerization inhibitor as needed. Specific examples of the polymerization inhibitor include 2,6-diisobutylphenol, 3,5-di-t-butylphenol, 3,5-di-t-butylcresol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, and t-butylcatechol. 4-methoxy-1-naphthol and the like.
　本発明の組成物が（Ｉ）成分を含む場合、その含有量は、全固形分中１質量％以下が好ましく、０.５質量％以下がより好ましい。含有量が１質量％を超えると、硬化不良を起こし、反応が不十分となることがある。 When the composition of the present invention includes the component (I), the content thereof is preferably 1% by mass or less, more preferably 0.5% by mass or less, based on the total solid content. When the content exceeds 1% by mass, poor curing may occur and the reaction may become insufficient.
［その他の添加剤］
　本発明の組成物は、本発明の効果を損なわない限りにおいて、必要に応じて、更に界面活性剤、消泡剤、レオロジー調整剤、顔料、染料、保存安定剤、多価フェノールや多価カルボン酸等の溶解促進剤等を含んでもよい。 [Other additives]
The composition of the present invention may further comprise a surfactant, an antifoaming agent, a rheology modifier, a pigment, a dye, a storage stabilizer, a polyhydric phenol or a polycarboxylic acid as long as the effects of the present invention are not impaired. A dissolution accelerator such as an acid may be included.
　界面活性剤としては、特に限定されないが、例えば、フッ素系界面活性剤、シリコン系界面活性剤、ノニオン系界面活性剤等が挙げられる。この種の界面活性剤としては、例えば、三菱マテリアル電子化成(株)製エフトップ（登録商標）EF301、EF303、EF352；ＤＩＣ(株)製メガファック（登録商標）F171、F173；スリーエム社製FLUORAD（登録商標）FC430、FC431；旭硝子(株)製アサヒガード（登録商標）AG710、ＡＧＣセイミケミカル(株)製サーフロン（登録商標）S-382、SC101、SC102、SC103、SC104、SC105、SC106等が挙げられる。 The surfactant is not particularly limited, and examples thereof include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surfactant. Examples of this type of surfactant include, for example, F-top (registered trademark) EF301, EF303, EF352 manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd .; Mega-Fac® (registered trademark) F171, F173 manufactured by DIC Corporation; FLUORAD manufactured by 3M (Registered trademark) FC430, FC431; Asahi Guard Co., Ltd. Asahi Guard (registered trademark) AG710, AGC Seimi Chemical Co., Ltd. Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 etc. Can be mentioned.
　消泡剤としては、アセチレングリコール、シリコーン流体及び乳剤、エトキシ化又はプロポキシ化シリコーン、炭化水素、脂肪酸エステル誘導体、アセチル化ポリアミド、ポリ(アルキレンオキシド)ポリマー及びコポリマー等が挙げられるが、これらに限定されない。スクリーン印刷を行う場合は、本発明の組成物は消泡剤を含むことが好ましい。 Antifoaming agents include, but are not limited to, acetylene glycol, silicone fluids and emulsions, ethoxylated or propoxylated silicones, hydrocarbons, fatty acid ester derivatives, acetylated polyamides, poly (alkylene oxide) polymers and copolymers, and the like. . When screen printing is performed, the composition of the present invention preferably contains an antifoaming agent.
　本発明の組成物の２５℃における粘度は、塗布性の観点から、好ましくは１～１０,０００ｍＰａ・ｓ、より好ましくは１～５,０００ｍＰａ・ｓ、より一層好ましくは１～１,０００ｍＰａ・ｓである。粘度が低すぎると、目的の膜厚が得られないことがあり、粘度が高すぎると、塗布性が低下することがある。 The viscosity at 25 ° C. of the composition of the present invention is preferably 1 to 10,000 mPa · s, more preferably 1 to 5,000 mPa · s, and still more preferably 1 to 1,000 mPa · s from the viewpoint of applicability. It is. If the viscosity is too low, the desired film thickness may not be obtained, and if the viscosity is too high, the coatability may deteriorate.
　また、本発明の組成物の２５℃における粘度は、印刷性の観点から、好ましくは１０～１００,０００ｍＰａ・ｓ、より好ましくは５００～１００,０００ｍＰａ・ｓ、より一層好ましくは１,０００～１００,０００ｍＰａ・ｓである。粘度が低すぎると、塗布後に組成物が拡散してしまい、所望のパターンが形成されないことがあり、粘度が高すぎると、吐出性が低くなる等工程への負荷が生じたり、組成物の基板への転写性が低下したりすることがある。 Further, the viscosity at 25 ° C. of the composition of the present invention is preferably 10 to 100,000 mPa · s, more preferably 500 to 100,000 mPa · s, and still more preferably 1,000 to 100 from the viewpoint of printability. 1,000 mPa · s. If the viscosity is too low, the composition may diffuse after application, and a desired pattern may not be formed. If the viscosity is too high, the discharge performance may be reduced, and a load on the process may occur. Transferability to the surface may be reduced.
　タッチパネルにおけるＸ軸電極及びＹ軸電極が直交する部分にブリッジ構造を構成するための絶縁膜のように微細な構造をスクリーン印刷、グラビアオフセット印刷等の印刷法によって形成する場合には、本発明の組成物の２５℃における粘度は、好ましくは１０～１００,０００ｍＰａ・ｓ、より好ましくは５,０００～１００,０００ｍＰａ・ｓ、より一層好ましくは２０,０００～１００,０００ｍＰａ・ｓである。粘度が低すぎると、塗布後に組成物が拡散してしまい、所望のパターンが形成されないことがあり、粘度が高すぎると、吐出性が低くなる等工程への負荷が生じたり、組成物の基板への転写性が低下したりすることがある。 In the case where a fine structure such as an insulating film for forming a bridge structure is formed by a printing method such as screen printing or gravure offset printing in a portion where the X-axis electrode and the Y-axis electrode in the touch panel are orthogonal to each other, The viscosity at 25 ° C. of the composition is preferably 10 to 100,000 mPa · s, more preferably 5,000 to 100,000 mPa · s, and even more preferably 20,000 to 100,000 mPa · s. If the viscosity is too low, the composition may diffuse after application, and a desired pattern may not be formed. If the viscosity is too high, the discharge performance may be reduced, and a load on the process may occur. Transferability to the surface may be reduced.
　なお、本発明において、粘度は、Ｅ型粘度計による測定値である。 In the present invention, the viscosity is a value measured with an E-type viscometer.
［組成物の調製方法］
　本発明の組成物の調製方法は、特に限定されない。一例としては、（Ａ）成分を（Ｄ）溶剤に溶解し、この溶液に（Ｂ）、（Ｃ）成分を任意の順序で所定の割合で混合し、均一な溶液とする方法が挙げられる。また、この調製方法の適当な段階において、必要に応じて（Ｅ）～（Ｉ）成分やその他の成分を更に加えて混合する調製方法が挙げられる。こうして調製された溶液状態の硬化膜形成用樹脂組成物は、孔径が０.２μｍ程度のフィルタ等を用いて濾過した後に使用することが好ましい。 [Method for Preparing Composition]
The method for preparing the composition of the present invention is not particularly limited. As an example, there may be mentioned a method in which the component (A) is dissolved in the solvent (D) and the components (B) and (C) are mixed in this solution at a predetermined ratio in an arbitrary order to obtain a uniform solution. In addition, in an appropriate stage of this preparation method, there may be mentioned a preparation method in which components (E) to (I) and other components are further added and mixed as necessary. The resin composition for forming a cured film in a solution state thus prepared is preferably used after being filtered using a filter having a pore size of about 0.2 μm.
［塗膜及び硬化膜］
　本発明の硬化膜形成用樹脂組成物を基板（例えば、シリコン／二酸化シリコン被覆基板；シリコンナイトライド基板；アルミニウム、モリブデン、クロム、銅、銀等の金属、銀ナノワイヤ等の金属ナノワイヤ、銀ナノ粒子、銅ナノ粒子等の金属ナノ粒子、ポリ（３,４－エチレンジオキシチオフェン）／ポリ（スチレンスルホン酸塩）（ＰＥＤＯＴ／ＰＳＳ）、グラフェン、カーボンナノチューブ等の導電性ポリマーが被覆された基板；ガラス基板；石英基板；ＩＴＯ基板；ＩＴＯフィルム基板；ＴＡＣフィルム、ポリエステルフィルム、アクリルフィルム、シクロオレフィン（ＣＯＰ）フィルム等の樹脂フィルム基板）等の上に、回転塗布、流し塗布、ロール塗布、スリット塗布、スリットに続いた回転塗布、インクジェット塗布、スクリーン印刷、フレキソ印刷、グラビア印刷、オフセット印刷、グラビアオフセット印刷等の印刷法等によって塗布し、その後、ホットプレート又はオーブン等で予備乾燥（プリベーク）することにより、塗膜を形成することができる。本発明の組成物は、特にインクジェット塗布、スクリーン印刷、フレキソ印刷、グラビアオフセット印刷等の印刷法に適している。 [Coating and cured film]
The resin composition for forming a cured film of the present invention is a substrate (for example, a silicon / silicon dioxide-coated substrate; a silicon nitride substrate; a metal such as aluminum, molybdenum, chromium, copper, or silver; a metal nanowire such as a silver nanowire; or a silver nanoparticle. A substrate coated with a conductive polymer such as metal nanoparticles such as copper nanoparticles, poly (3,4-ethylenedioxythiophene) / poly (styrenesulfonate) (PEDOT / PSS), graphene, carbon nanotubes; Glass substrate; quartz substrate; ITO substrate; ITO film substrate; resin film substrate such as TAC film, polyester film, acrylic film, cycloolefin (COP) film), etc., spin coating, flow coating, roll coating, slit coating , Spin coating following slit, ink jet coating, screen The coating film can be formed by coating by a printing method such as ink printing, flexographic printing, gravure printing, offset printing, gravure offset printing, etc., and then pre-drying (prebaking) with a hot plate or oven. The composition of the present invention is particularly suitable for printing methods such as inkjet coating, screen printing, flexographic printing, and gravure offset printing.
　プリベークは、一般に、好ましくは６０℃～１５０℃、より好ましくは８０℃～１２０℃で、ホットプレートを用いる場合には０.５～３０分間、オーブンを用いる場合には０.５～９０分間処理するという方法が採られる。 The pre-bake is generally preferably performed at 60 ° C. to 150 ° C., more preferably at 80 ° C. to 120 ° C., for 0.5 to 30 minutes when using a hot plate, and 0.5 to 90 minutes when using an oven. The method of doing is taken.
　次いで、熱硬化のためのポストベークを行う。具体的には、ホットプレート、オーブン等を用いて加熱する。ポストベークは、一般に、好ましくは１５０℃～３００℃、より好ましくは２００℃～２５０℃で、ホットプレートを用いる場合には１～３０分間、オーブンを用いる場合には１～９０分間処理するという方法が採られる。 Next, post-baking for thermosetting is performed. Specifically, heating is performed using a hot plate, an oven, or the like. The post-baking is generally performed at a temperature of preferably 150 ° C. to 300 ° C., more preferably 200 ° C. to 250 ° C. for 1 to 30 minutes when using a hot plate, and 1 to 90 minutes when using an oven. Is taken.
　前記のような条件のもとで本発明の組成物を硬化させることにより、基板の段差を十分に平坦化でき、高透明性を有する硬化膜を形成することができる。 By curing the composition of the present invention under the above conditions, the step of the substrate can be sufficiently flattened, and a cured film having high transparency can be formed.
　本発明の硬化膜は、少なくとも必要な水準の平坦化性、硬度及び密着性を有するため、薄膜トランジスタ（ＴＦＴ）型液晶表示素子、有機ＥＬ素子等の各種ディスプレイにおける保護膜、平坦化膜、絶縁膜等、タッチパネルにおける保護膜、絶縁膜等の硬化膜を形成する材料としても有用である。また、柔軟性にも優れるため、ＩＴＯフィルム用のオーバーコート材としても好適である。 Since the cured film of the present invention has at least the necessary level of flatness, hardness and adhesion, the protective film, flattening film, and insulating film in various displays such as thin film transistor (TFT) type liquid crystal display elements and organic EL elements. It is also useful as a material for forming a cured film such as a protective film or an insulating film in a touch panel. Moreover, since it is excellent also in a softness | flexibility, it is suitable also as an overcoat material for ITO films.
　以下、実施例を挙げて、本発明を更に詳しく説明するが、本発明は、下記実施例に限定されない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
　また、実施例で用いた試薬及び装置は次のとおりである。
＜試薬＞
・ＤＥＧＥＥＡ（ジエチレングリコールモノエチルエーテルアセテート）、ＤＥＧＭＥ（ジエチレングリコールモノメチルエーテル）：東京化成工業(株)製
・ＭＥＡ（２－アミノエタノール）：関東化学(株)製
・ＰＥＴ－３０：ペンタエリスリトール(トリ／テトラ)アクリレート、日本化薬(株)製
・ＵＰＳ：３－ウレイドプロピルトリエトキシシラン、東レ・ダウコーニング(株)製AY43-031
・ＣＹＣＬＯＭＥＲ－Ｐ：ダイセル・オルネクス(株)製サイクロマーP(ACA)Z250
・ＣＹＭＥＬ３０３：メラミン系架橋剤、日本サイテックインダストリーズ(株)製
・パーブチルＬ：熱ラジカル重合開始剤、日油(株)製
＜装置＞
・攪拌装置：(株)シンキー製あわとり練太郎ARE-310
・紫外可視近赤外分析光度計（紫外可視吸収スペクトル測定）：(株)島津製作所製UV-3100PC The reagents and devices used in the examples are as follows.
<Reagent>
・ DEGEEA (diethylene glycol monoethyl ether acetate), DEGME (diethylene glycol monomethyl ether): manufactured by Tokyo Chemical Industry Co., Ltd. ・ MEA (2-aminoethanol): manufactured by Kanto Chemical Co., Ltd. ・ PET-30: pentaerythritol (tri / tetra) ) Acrylate, Nippon Kayaku Co., Ltd. UPS: 3-ureidopropyltriethoxysilane, Toray Dow Corning AY43-031
・ CYCLOMER-P: Cyclomer P (ACA) Z250 manufactured by Daicel Ornex Co., Ltd.
・ CYMEL303: Melamine-based crosslinking agent, manufactured by Nippon Cytec Industries, Ltd. ・ Perbutyl L: Thermal radical polymerization initiator, manufactured by NOF Corporation <Device>
・ Stirrer: Shintaro Awatori Nertaro ARE-310
・ Ultraviolet visible near infrared spectrophotometer (ultraviolet visible absorption spectrum measurement): UV-3100PC manufactured by Shimadzu Corporation
［１］組成物の作製
［実施例１］
　２００ｍＬの容器に、ＣＹＣＬＯＭＥＲ－Ｐを４１.５ｇ、ＰＥＴ－３０を９.８ｇ、ＣＹＭＥＬ３０３を９.８ｇ、パーブチルＬを０.６ｇ、ＵＰＳを０.２ｇ、及びＤＥＧＥＥＡを３７.５ｇ入れた。これを攪拌装置に入れ、１０分間、２,０００ｒｐｍで攪拌し、組成物（ワニス）を作製した。 [1] Preparation of composition [Example 1]
In a 200 mL container, 41.5 g of CYCLOMER-P, 9.8 g of PET-30, 9.8 g of CYMEL 303, 0.6 g of perbutyl L, 0.2 g of UPS, and 37.5 g of DEGEA were placed. This was put into a stirrer and stirred at 2,000 rpm for 10 minutes to prepare a composition (varnish).
［実施例２］
　２００ｍＬの容器に、ＣＹＣＬＯＭＥＲ－Ｐを３３.５ｇ、ＰＥＴ－３０を１１.８ｇ、ＣＹＭＥＬ３０３を１１.８ｇ、パーブチルＬを０.５ｇ、ＵＰＳを０.２ｇ、及びＤＥＧＥＥＡを４２.２ｇ入れた。これを攪拌装置に入れ、１０分間、２,０００ｒｐｍで攪拌し、組成物（ワニス）を作製した。 [Example 2]
In a 200 mL container, 33.5 g of CYCLOMER-P, 11.8 g of PET-30, 11.8 g of CYMEL 303, 0.5 g of perbutyl L, 0.2 g of UPS, and 42.2 g of DEGEA were placed. This was put into a stirrer and stirred at 2,000 rpm for 10 minutes to prepare a composition (varnish).
［２］硬化膜の作製及びその評価
［２－１］光透過率の測定
　実施例１及び２のワニスを、それぞれ石英ガラス基板上にスピンコートにより塗布し、１１０℃で２分間プリベークした。次いで、２３０℃で３０分間ポストベークし、厚さ２μｍの硬化膜を作製した。
　そして、得られた各硬化膜の波長４００ｎｍにおける光透過率を測定した。なお、用いた石英ガラス基板の光透過率は９３.８％であった。 [2] Production of cured film and evaluation thereof [2-1] Measurement of light transmittance Each of the varnishes of Examples 1 and 2 was applied onto a quartz glass substrate by spin coating, and prebaked at 110 ° C. for 2 minutes. Subsequently, it post-baked for 30 minutes at 230 degreeC, and produced the cured film with a thickness of 2 micrometers.
And the light transmittance in wavelength 400nm of each obtained cured film was measured. The light transmittance of the quartz glass substrate used was 93.8%.
［２－２］鉛筆硬度及び密着性の評価
　実施例１及び２のワニスを、それぞれＩＴＯ付ガラス基板上にバーコーターを用いて塗布し、１１０℃で２分間プリベークした。次いで、２３０℃で３０分間ポストベークし、厚さ約２μｍの硬化膜を作製した。そして、得られた硬化膜について、以下の方法によって、硬度及び密着性の評価をした。 [2-2] Evaluation of pencil hardness and adhesion The varnishes of Examples 1 and 2 were each applied onto a glass substrate with ITO using a bar coater and prebaked at 110 ° C. for 2 minutes. Subsequently, it post-baked for 30 minutes at 230 degreeC, and produced the cured film about 2 micrometers thick. And about the obtained cured film, hardness and adhesiveness were evaluated with the following method.
［鉛筆硬度の評価］
　ＪＩＳ Ｋ ５４００に準拠し、１,０００ｇ荷重で測定した。 [Evaluation of pencil hardness]
Based on JIS K 5400, the measurement was performed under a load of 1,000 g.
［密着性の評価］
　クロスカット試験方法により評価した。まず、カッターガイドを用いて、硬化膜に１００個の碁盤目を作成した。次に、当該碁盤目上にニチバン(株)製のセロハンテープを接着し、上から消しゴムで強く擦り、十分に密着させた。そして、次にセロハンテープをはがし、その際に、１００個の碁盤目のうち、何個が剥離したかで評価を行った。
　　０Ｂ：６６個以上が剥離
　　１Ｂ：３６～６５個が剥離
　　２Ｂ：１６～３５個が剥離
　　３Ｂ：６～１５個が剥離
　　４Ｂ：１～５個が剥離
　　５Ｂ：剥離なし [Evaluation of adhesion]
The cross-cut test method was used for evaluation. First, 100 grids were prepared on the cured film using a cutter guide. Next, a cellophane tape made by Nichiban Co., Ltd. was bonded onto the grid, and rubbed with an eraser from above to make it adhere sufficiently. Then, the cellophane tape was peeled off, and at that time, it was evaluated how many of the 100 grids were peeled off.
0B: 66 or more peeled 1B: 36-65 peeled 2B: 16-35 peeled 3B: 6-15 peeled 4B: 1-5 peeled 5B: No peeling
［２－３］耐溶剤性の評価
　実施例１及び２のワニスを、それぞれシリコンウェハ上にスピンコートにより塗布し、１１０℃で２分間プリベークした。次いで、２３０℃で３０分間ポストベークし、厚さ２μｍの硬化膜を作製した。得られた各硬化膜を、ＭＥＡ：ＤＥＧＭＥ＝３：７の混合溶媒（質量比）に６０℃で２分間浸積し、純水で３０秒間リンスし、１００℃で１分間乾燥した。そして、各薄膜の膜厚を測定し、膜減りを確認することで耐溶剤性を評価した。 [2-3] Evaluation of solvent resistance The varnishes of Examples 1 and 2 were each applied onto a silicon wafer by spin coating and prebaked at 110 ° C. for 2 minutes. Subsequently, it post-baked for 30 minutes at 230 degreeC, and produced the cured film with a thickness of 2 micrometers. The obtained cured films were immersed in a mixed solvent (mass ratio) of MEA: DEGME = 3: 7 at 60 ° C. for 2 minutes, rinsed with pure water for 30 seconds, and dried at 100 ° C. for 1 minute. And the solvent resistance was evaluated by measuring the film thickness of each thin film and confirming the film reduction.
［２－４］ＩＴＯスパッタ耐性の評価
　実施例１及び２のワニスを用いて、それぞれ１０ｃｍ角の無アルカリガラス基板上に４ｃｍ角のベタ膜をスクリーン印刷により印刷し、１１０℃で２分間プリベークを行った。次いで２３０℃で３０分間ポストベークを行い、硬化膜を作製した。得られた硬化膜は５μｍであった。得られた硬化膜付きガラス基板に対し、基板温度２００℃、スパッタリング時間１.９分間でＩＴＯスパッタリングを行い、膜厚約３００ÅのＩＴＯ膜を成膜した。ＩＴＯスパッタ後の状態を目視で観察し、異常の有無を確認した。 [2-4] Evaluation of ITO Sputtering Resistance Using the varnishes of Examples 1 and 2, a 4 cm square solid film was printed on a 10 cm square non-alkali glass substrate by screen printing, and prebaked at 110 ° C. for 2 minutes. went. Next, post-baking was performed at 230 ° C. for 30 minutes to prepare a cured film. The obtained cured film was 5 μm. The obtained glass substrate with a cured film was subjected to ITO sputtering at a substrate temperature of 200 ° C. and a sputtering time of 1.9 minutes to form an ITO film having a thickness of about 300 mm. The state after ITO sputtering was visually observed to confirm the presence or absence of abnormality.
　前記測定及び評価の結果を表１に示す。
Figure JPOXMLDOC01-appb-T000008
 The results of the measurement and evaluation are shown in Table 1.
Figure JPOXMLDOC01-appb-T000008
　表１から明らかなように、本発明の組成物（ワニス）から得られる硬化膜は、硬度と密着性に優れ、光透過率も９２％以上と高く、更に耐溶剤性とＩＴＯスパッタ耐性にも優れるものであった。 As is clear from Table 1, the cured film obtained from the composition (varnish) of the present invention is excellent in hardness and adhesion, has a high light transmittance of 92% or more, and also has good solvent resistance and ITO sputtering resistance. It was excellent.

Claims (8)

  1. 　（Ａ）式（１）及び（２）で表されるモノマー単位を含有する共重合体、
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ1は、それぞれ独立に、水素原子又はメチル基を表す。Ｒ2は、水素原子又は炭素数１～５のアルキル基を表す。Ｒ3は、水素原子又はメチル基を表す。）
    （Ｂ）メラミン系架橋剤、
    （Ｃ）熱ラジカル重合開始剤、及び
    （Ｄ）溶剤
    を含むことを特徴とする硬化膜形成用樹脂組成物。     (A) a copolymer containing monomer units represented by formulas (1) and (2),
    Figure JPOXMLDOC01-appb-C000001
     (In the formula, each R 1 independently represents a hydrogen atom or a methyl group. R 2 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R 3 represents a hydrogen atom or a methyl group. )
    (B) Melamine-based crosslinking agent,
    A cured film-forming resin composition comprising (C) a thermal radical polymerization initiator and (D) a solvent.
  2. 　（Ａ）共重合体が、式（１）、（２－１）及び（２－２）で表されるモノマー単位を含有する共重合体である請求項１記載の硬化膜形成用樹脂組成物。
    Figure JPOXMLDOC01-appb-C000002
     （式中、Ｒ1及びＲ3は、前記と同じ。Ｒ4は、炭素数１～５のアルキル基を表す。）     The resin composition for forming a cured film according to claim 1, wherein the copolymer (A) is a copolymer containing monomer units represented by formulas (1), (2-1) and (2-2). .
    Figure JPOXMLDOC01-appb-C000002
     (In the formula, R 1 and R 3 are the same as described above. R 4 represents an alkyl group having 1 to 5 carbon atoms.)
  3. 　更に、（Ｅ）シランカップリング剤を含む請求項１又は２記載の硬化膜形成用樹脂組成物。 Furthermore, the resin composition for forming a cured film according to claim 1 or 2, further comprising (E) a silane coupling agent.
  4. 　更に、（Ｆ）多官能(メタ)アクリレート化合物を含む請求項１～３のいずれか１項記載の硬化膜形成用樹脂組成物。 The resin composition for forming a cured film according to any one of claims 1 to 3, further comprising (F) a polyfunctional (meth) acrylate compound.
  5. 　（Ｄ）溶剤が、沸点が１５０℃以上である請求項１～４のいずれか１項記載の硬化膜形成用樹脂組成物。 The resin composition for forming a cured film according to any one of claims 1 to 4, wherein the solvent (D) has a boiling point of 150 ° C or higher.
  6. 　請求項１～５のいずれか１項記載の硬化膜形成用樹脂組成物を用いて得られる硬化膜。 A cured film obtained using the cured film forming resin composition according to any one of claims 1 to 5.
  7. 　請求項６記載の硬化膜を基板上に積層してなる積層体。 A laminate formed by laminating the cured film according to claim 6 on a substrate.
  8. 　請求項６記載の硬化膜を含むタッチパネル。 A touch panel including the cured film according to claim 6.
PCT/JP2015/070810 2014-08-01 2015-07-22 Resin composition for forming cured film WO2016017497A1 (en)

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TWI666274B (en) 2019-07-21
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KR20170039082A (en) 2017-04-10

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