WO2017170668A1 - 高屈折率硬化膜形成用樹脂組成物 - Google Patents
高屈折率硬化膜形成用樹脂組成物 Download PDFInfo
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- 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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/026—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising acrylic acid, methacrylic acid or derivatives thereof
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- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- 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
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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- 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
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
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- 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
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
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- 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
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
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- 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
- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
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- 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
- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate
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- 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
- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/12—Esters of phenols or saturated alcohols
- C08F222/20—Esters containing oxygen in addition to the carboxy oxygen
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- 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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/023—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type using a coupling agent
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
Definitions
- the present invention relates to a resin composition for forming a high refractive index cured film.
- 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.
- pattern processing by the photolithography method has a problem that not only the process is complicated but also the cost is high.
- a composition that can form a protective film, an insulating film, and the like at a necessary site has been proposed by a simpler method and at a lower cost (see, for example, Patent Document 1).
- the transmittance and visibility are often improved by suppressing the reflection of light by providing a coating film having a high refractive index (see, for example, Patent Document 2).
- the present invention has been made in view of the above circumstances, and can provide a composition that not only can be formed at a necessary site by a simple method such as a printing method but also provides a cured film having a high refractive index. Objective.
- a composition containing a predetermined fluorene compound and a predetermined aromatic ring-containing polymer can provide a cured film having a high refractive index.
- the present invention has been completed.
- the present invention provides the following resin composition for forming a high refractive index cured film.
- a fluorene compound represented by the formula [1] and
- a resin composition for forming a high refractive index cured film comprising an aromatic ring-containing polymer containing a repeating unit derived from an aromatic ring-containing compound containing a polymerizable double bond.
- R 1 and R 2 each independently represent a hydrogen atom or a methyl group
- L 1 and L 2 each independently include a phenylene group or a substituent which may contain a substituent.
- An optionally substituted naphthalenediyl group, L 3 and L 4 each independently represents an alkylene group having 1 to 6 carbon atoms, and m and n are 0 ⁇ m ⁇ 40, 0 ⁇ n ⁇ 40 and 0 ⁇ . represents an integer satisfying m + n ⁇ 40.
- (c) 1 high refractive index cured film forming resin composition containing a solvent. 3.
- the polyfunctional (meth) acrylate compound includes 4 containing at least one selected from the group consisting of a compound containing three (meth) acryloyl groups and a compound containing four (meth) acryloyl groups in one molecule.
- G The resin composition for high refractive index cured film formation of 8 in which a silane coupling agent contains the silane compound represented by Formula [4].
- R 6 represents a methyl group or an ethyl group
- X represents a hydrolyzable group
- Y represents a reactive functional group
- L 7 represents a single bond or an alkylene having 1 to 10 carbon atoms.
- A represents an integer of 0 to 2.
- the resin composition for forming a high refractive index cured film according to any one of 1 to 10 which is used for a screen printing method.
- a high refractive index cured film obtained from the high refractive index cured film forming resin composition of any one of 12.1 to 11.
- a conductive member comprising a base material on which a metal electrode and / or metal wiring is formed, and 12 high refractive index cured films formed on the base material so as to be in contact with the electrode and / or wiring.
- the cured film obtained using the composition of the present invention can be easily formed by a simple method such as a printing method, has a high refractive index, and is excellent in light transmittance. Therefore, the composition of the present invention can form a cured film such as a protective film, a planarizing film, or an insulating film in various displays such as an organic electroluminescence (EL) element, or a protective film or an insulating film in a touch panel.
- EL organic electroluminescence
- the resin composition for forming a high refractive index cured film of the present invention includes (a) a fluorene compound represented by the formula [1] described later, and (b) (meth) acrylic acid and / or an aliphatic (meth) acrylate compound. And an aromatic ring-containing polymer containing a repeating unit derived from an aromatic ring-containing compound containing a polymerizable double bond (excluding those having a silane structure in the side chain).
- R 1 and R 2 each independently represents a hydrogen atom or a methyl group.
- L 1 and L 2 each independently represent a phenylene group which may contain a substituent or a naphthalenediyl group which may contain a substituent.
- L 3 and L 4 each independently represents an alkylene group having 1 to 6 carbon atoms.
- naphthalenediyl group which may contain the substituent include 1,2-naphthalenediyl group, 1,4-naphthalenediyl group, 1,5-naphthalenediyl group, 1,8-naphthalenediyl group, and 2,3. -Naphthalenediyl group, 2,6-naphthalenediyl group and the like.
- L 1 and L 2 are preferably a 1,4-phenylene group or the like.
- alkylene group examples include a methylene group, an ethylene group, a trimethylene group, a methylethylene group, a tetramethylene group, a 1-methyltrimethylene group, a 1,1-dimethylethylene group, a pentamethylene group, and a 1-methyltetramethylene group.
- 2-methyltetramethylene group 1,1-dimethyltrimethylene group, 1,2-dimethyltrimethylene group, 2,2-dimethyltrimethylene group, 1-ethyltrimethylene group, hexamethylene group, 1-methylpenta Methylene group, 2-methylpentamethylene group, 3-methylpentamethylene group, 1,1-dimethyltetramethylene group, 1,2-dimethyltetramethylene group, 2,2-dimethyltetramethylene group, 1-ethyltetramethylene group 1,1,2-trimethyltrimethylene group, 1,2,2-trimethyltrimethylene group, 1-ethyl- - methyltrimethylene group, a 1-ethyl-2-methyltrimethylene group.
- an alkylene group having 2 to 4 carbon atoms is preferable.
- an ethylene group, a trimethylene group, a methylethylene group, a tetramethylene group, a 1-methyltrimethylene group, 1 1,1-dimethylethylene group and the like are preferable.
- m and n represent integers satisfying 0 ⁇ m ⁇ 40, 0 ⁇ n ⁇ 40 and 0 ⁇ m + n ⁇ 40.
- m and n are preferably integers that satisfy 0 ⁇ m ⁇ 30, 0 ⁇ n ⁇ 30, and 0 ⁇ m + n ⁇ 30, and satisfy 0 ⁇ m ⁇ 20, 0 ⁇ n ⁇ 20, and 2 ⁇ m + n ⁇ 20.
- the compound represented by the formula [1] include, for example, 9,9-bis (4-((meth) acryloyloxy) phenyl) -9H-fluorene, 9,9-bis (4- (2- (Meth) acryloyloxyethoxy) phenyl) -9H-fluorene, 9,9-bis (4- (2- (2- (meth) acryloyloxyethoxy) ethoxy) phenyl) -9H-fluorene, Ogsol® EA -0200, EA-0300, EA-F5003, EA-F5503, EA-F5510, EA-F5710, GA-5000 (above, manufactured by Osaka Gas Chemical Co., Ltd.), NK ester A-BPEF (Shin Nakamura Chemical Co., Ltd.) But not limited to these).
- the content of the fluorene compound as the component (a) is preferably 1 to 200 parts by mass, more preferably 5 to 150 parts by mass with respect to 100 parts by mass of the aromatic ring-containing polymer as the component (b). 10 to 100 parts by mass is even more preferable. If content of the fluorene compound of (a) component is the said range, a refractive index is high and the cured film of sufficient hardness is obtained.
- the aromatic ring-containing polymer (b) is a repeating unit derived from (meth) acrylic acid and / or an aliphatic (meth) acrylate compound (excluding those having a silane structure in the side chain), and polymerizability. It includes a repeating unit derived from an aromatic ring-containing compound containing a double bond.
- Examples of the aliphatic (meth) acrylate compound include those represented by the formula [2].
- R 3 represents a hydrogen atom or a methyl group.
- R 4 represents an alkyl group having 1 to 20 carbon atoms which may be substituted with a hydroxy group, an epoxy group, a (meth) acryloyl group or an isocyanato group.
- the alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic.
- Examples of the aliphatic (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and 2,2,2 (meth) acrylic acid.
- Examples include 4-hydroxybutyl acid.
- the aliphatic (meth) acrylate compound preferably contains one kind selected from methyl (meth) acrylate and ethyl (meth) acrylate, and more preferably. , Including methyl (meth) acrylate.
- the aromatic ring-containing compound containing a polymerizable double bond is not particularly limited as long as it can be copolymerized with (meth) acrylic acid or an aliphatic (meth) acrylate compound.
- aromatic ring-containing compounds include those represented by the following formula [3].
- R 5 represents a hydrogen atom or a methyl group.
- L 5 represents a single bond or —C ( ⁇ O) —OL 6 —
- L 6 represents a single bond or an alkylene group having 1 to 6 carbon atoms which may contain an ether bond.
- Ar represents an aromatic ring-containing group having 6 to 20 carbon atoms, and part or all of the hydrogen atoms of the aromatic ring-containing group are halogen atoms such as chlorine atom, bromine atom, iodine atom; methyl group, ethyl group, etc. May be substituted with a substituent such as an alkyl group having 1 to 6 carbon atoms.
- L 6 includes a single bond, a methylene group, an ethylene group, a trimethylene group, a methylethylene group, a tetramethylene group, an ethyleneoxyethylene group, a 3,6-dioxaoctane-1,8-diyl group (—CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 —), (methylethylene) oxy (methylethylene) group and the like are preferable.
- aromatic ring-containing group examples include a phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3- Aryl groups such as phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, 9H-carbazol-9-yl group; phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 1-anthryloxy group, 2-anthryloxy group, 9-anthryloxy group, 1-phenanthryloxy group, 2-phenanthryloxy group, 3-phenanthryloxy group 4-phenanthryloxy group, 9-phenanthryloxy group, 2-biphenylyloxy group, 3-biphenylyloxy group Groups, aryloxy groups such as
- the aromatic ring-containing group includes phenyl group, 1-naphthyl group, 2-naphthyl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, 9H-carbazol-9-yl group, phenoxy group 1-naphthyloxy group, 2-naphthyloxy group, 2-biphenylyloxy group, 3-biphenylyloxy group, 4-biphenylyloxy group, 2-phenoxyphenyl group, 3-phenoxyphenyl group, 4-phenoxyphenyl Groups are preferred.
- Examples of the aromatic ring-containing compound represented by the formula [3] include an aromatic ring-containing vinyl compound and an aromatic ring-containing (meth) acrylate compound.
- aromatic ring-containing vinyl compound examples include styrenes such as styrene, ⁇ -methylstyrene, chlorostyrene, bromostyrene, 4-tert-butylstyrene; 1-vinylnaphthalene, 2-vinylnaphthalene, 2-vinylanthracene, 9- Aromatic vinyl compounds such as vinylanthracene, 2-vinylbiphenyl, 3-vinylbiphenyl, 4-vinylbiphenyl, N-vinylcarbazole and the like can be mentioned.
- styrenes such as styrene, ⁇ -methylstyrene, chlorostyrene, bromostyrene, 4-tert-butylstyrene
- 1-vinylnaphthalene 2-vinylnaphthalene
- 2-vinylanthracene 2-vinylanthracene
- 9- Aromatic vinyl compounds such as vinylanthracene
- aromatic ring-containing (meth) acrylate compound examples include phenyl (meth) acrylate, benzyl (meth) acrylate, 1-phenylethyl (meth) acrylate, 2-phenylethyl (meth) acrylate, and (meth) acrylic.
- 1-naphthyl acid 1-naphthylmethyl (meth) acrylate, 2-naphthyl (meth) acrylate, 2-naphthylmethyl (meth) acrylate, 9-anthryl (meth) acrylate, (meth) acrylic acid 9- Anthrylmethyl, 9-phenanthrylmethyl (meth) acrylate, 1-phenoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 2-phenoxybenzyl (meth) acrylate, (meth) acryl 3-phenoxybenzyl acid, 4-phenoxybenzyl (meth) acrylate, 2- (2-biphenylyloxy) ethyl (meth) acrylate, (meth) acrylic Examples include 2- (3-biphenylyloxy) ethyl acid, 2- (4-biphenylyloxy) ethyl (meth) acrylate, and the like.
- aromatic ring-containing compound represented by the formula [3] styrene, 2-phenoxybenzyl (meth) acrylate, 3-phenoxybenzyl (meth) acrylate, 4-phenoxybenzyl (meth) acrylate , 2- (2-biphenylyloxy) ethyl (meth) acrylate, 2- (3-biphenylyloxy) ethyl (meth) acrylate, 2- (4-biphenylyloxy) ethyl (meth) acrylate, etc.
- Styrene, 3-phenoxybenzyl (meth) acrylate, 2- (2-biphenylyloxy) ethyl (meth) acrylate, and the like are more preferable.
- aromatic ring-containing compounds can be used singly or in combination of two or more.
- the aromatic ring-containing polymer of the component may contain other repeating units other than the repeating unit as long as the effects of the present invention are not impaired.
- Typical examples of the monomer that gives other repeating units include vinyl compounds, maleimides, acrylonitrile, and maleic anhydride.
- Examples of the vinyl compound include methyl vinyl ether, 2-hydroxyethyl vinyl ether, propyl vinyl ether, benzyl vinyl ether, and phenyl vinyl ether.
- maleimides examples include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like.
- the repeating unit derived from the aromatic ring-containing compound containing a polymerizable double bond is (meth) acrylic acid and / or ( It is preferably contained in an amount of 0.3 to 20 mol, more preferably 0.5 to 10 mol, and even more preferably 1 to 5 mol with respect to 1 mol of the repeating unit derived from the (meth) acrylate compound. .
- the inclusion of repeating units derived from (meth) acrylic acid and / or (meth) acrylate compounds and repeating units derived from aromatic ring-containing compounds containing a polymerizable double bond is preferably 50 to 100 mol%, more preferably 75 to 100 mol%, and even more preferably 100 mol%.
- the aromatic ring-containing polymer of component (b) can be synthesized by polymerizing the monomer that gives the repeating unit described above.
- radical polymerization anionic polymerization, cationic polymerization, and the like can be adopted.
- radical polymerization is preferable because a polymer having a weight average molecular weight (Mw) necessary in the present invention can be produced relatively easily.
- the initiator examples include peroxides such as benzoyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide; persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate; azobisisobutyronitrile, azobis (2 -Methylbutyronitrile), azobisisovaleronitrile, azo compounds such as 2,2′-azobis (isobutyric acid) dimethyl, and the like.
- the amount of such an initiator used varies depending on the type and amount of the monomer and the reaction temperature, and thus cannot be specified unconditionally, but is usually about 0.005 to 0.05 mol per 1 mol of the monomer.
- the reaction temperature during the polymerization may be appropriately set from 0 ° C. to the boiling point of the solvent used, but is usually about 20 to 100 ° C.
- the reaction time is about 0.1 to 30 hours.
- Polymerization is preferably performed in a solvent, and a solvent generally used in this kind of reaction can be used as a solvent for the polymerization reaction.
- a solvent generally used in this kind of reaction can be used as a solvent for the polymerization reaction.
- water methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2- Pentanol, 3-pentanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 1-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-octanol, 2-ethyl-1- Alcohols such as hexanol, benzyl alcohol, cyclohexanol; ethers such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopen
- Dialkylene glycol monoalkyl ether acetates such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; esters such as ethyl acetate, butyl acetate, ethyl propionate, cellosolve acetate; n-pentane, n-hexane, n -Heptane, n-octane, n-nonane, n-decane, cyclopentane, methylcyclope Aliphatic or aromatic hydrocarbons such as tan, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene and anisole; acetals such as methylal and diethyl acetal; fatty acids such as formic acid, acetic acid and propionic acid; nitropropane,
- the weight average molecular weight (Mw) of the aromatic ring-containing polymer of component (b) is preferably 5,000 to 500,000 from the viewpoint of preparing a composition that ensures the solubility of the polymer and gives a suitable cured film. is there.
- the upper limit value of the Mw of the polymer is preferably 200,000, more preferably 150,000, still more preferably 100,000, still more preferably.
- the lower limit is preferably 10,000, more preferably 15,000, still more preferably 30,000, Preferably it is 40,000.
- Mw is a measured value in terms of polystyrene by gel permeation chromatography (GPC).
- the aromatic ring-containing polymer may be a random copolymer, an alternating copolymer, or a block copolymer.
- the composition of the present invention may contain (c) a solvent.
- the solvent can dissolve the components (a) and (b) described above, and (d) a monofunctional (meth) acrylate compound, (e) a polyfunctional (meth) acrylate compound, and (f) an ion trap described later.
- an agent (g) a silane coupling agent, (h) a radical polymerization initiator, a polymerization inhibitor, other additives and the like, there is no particular limitation as long as these can be dissolved.
- the solvent include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, 1,2-ethanediol (ethylene glycol), 1,2-propanediol (propylene glycol), 1,2-butanediol, 2,3-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol (hexylene glycol), 1,3-octylene Glycols such as glycol and 3,6-octylene glycol; Triols such as glycerin; Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutylene
- Alkyl aryl ethers Alkyl aralkyl ethers such as ethyl benzyl ether; Cyclic alkyl monoethers such as 2-methylfuran, tetrahydrofuran, tetrahydropyran; Cyclic alkyl diethers such as 1,4-dioxane; Cyclic alkyl triethers such as trioxane; Diepoxyalkyl ethers such as diglycidyl ether; Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate, n-pentyl acetate, (3-methylbutyl) acetate, n-hexyl acetate, (2-ethylbutyl ) Alkyl acetates such as linear or branched alkyl acetate
- Alkyl butyrates such as cycloalkyl butyrate and cyclic alkyl butyrate such as 2-methylcyclohexyl butyrate; ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, sec-butyl lactate, tert Linear or branched alkyl lactates such as butyl lactate, n-pentyl lactate, (3-methylbutyl) lactate, n-hexyl lactate, (2-ethylbutyl) lactate, (2-ethylhexyl) lactate, cyclohexyl lactate, 2 Alkyl esters such as alkyl lactates such as cyclic alkyl lactates such as methylcyclohexyl lactate; Aralkyl acetates such as aralkyl acetates such as benzyl acetate, aralkyl
- the composition of the present invention is preferably 150 ° C. or higher, more preferably 180 ° C. or higher, and still more preferably 200 ° C. or higher, from the viewpoint of obtaining a suitable film with good reproducibility when the composition is applied by a printing method.
- the composition of the present invention is a solvent having a characteristic of dissolving the aromatic ring-containing polymer as the component (b), specifically, glycols. , Alkylene glycol diacetates, dialkylene glycol monoalkyl ethers, dialkylene glycol monoaralkyl ethers, dialkylene glycol monoaryl ethers, alkylene glycol monoalkyl ether acetates and alkylene glycol monoaralkyl ethers Preferably it contains seeds.
- solvents include propylene glycol diacetate, 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, diethylene glycol benzyl ether, and the like, without limitation.
- the solvent of component (c) is preferably in an amount such that the solid content concentration in the composition of the present invention is 1 to 95% by mass, more preferably in an amount such that the solid content concentration is 5 to 90% by mass, An amount such that the solid content concentration is 10 to 85% by mass is even more preferable.
- solid content means what remove
- composition of the present invention is for the purpose of adjusting the adhesion and hardness of the cured film, and further, monofunctional (meth) acrylate compound, polyfunctional (meth) acrylate compound, radical polymerization initiator, silane coupling agent, polymerization Inhibitors may be included.
- the composition of the present invention may contain (d) a monofunctional (meth) acrylate compound.
- the monofunctional (meth) acrylate compound is a compound containing one (meth) acryloyl group in the molecule.
- the aliphatic component exemplified as the monomer component of the aromatic ring-containing polymer (b) component examples thereof include (meth) acrylate compounds and aromatic ring-containing (meth) acrylate compounds.
- an aromatic ring-containing (meth) acrylate compound is preferable, and in particular, those exemplified as the aromatic ring-containing (meth) acrylate compound represented by the formula [3] preferable.
- a monofunctional (meth) acrylate compound can be used individually by 1 type or in combination of 2 or more types.
- aromatic ring-containing (meth) acrylate compounds include benzyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 2-phenoxybenzyl (meth) acrylate, and 3-phenoxy (meth) acrylate.
- benzyl (meth) acrylate, 3-phenoxybenzyl (meth) acrylate, and 2- (2-biphenylyloxy) ethyl (meth) acrylate are more preferred, and 3-phenoxybenzyl (meth) acrylate is more preferred. Even more preferred.
- the content of the monofunctional (meth) acrylate compound as the component (d) is preferably 0 to 100 parts by mass with respect to 100 parts by mass of the aromatic ring-containing polymer as the component (b) from the viewpoint of the refractive index of the resulting cured film. 0 to 50 parts by mass is more preferable, and 0 to 30 parts by mass is even more preferable.
- the composition of the present invention may contain (e) a polyfunctional (meth) acrylate compound from the viewpoint of adjusting the physical properties of the cured film.
- the polyfunctional (meth) acrylate compound is a compound containing at least two (meth) acryloyl groups in the molecule. Specifically, an ester of a polyhydric alcohol and (meth) acrylic acid is used. Can be mentioned. Further, particularly from the viewpoint of improving the hardness, the number of (meth) acryloyl groups in one molecule of the polyfunctional (meth) acrylate compound is preferably 3 to 6, more preferably 3 or 4.
- polyhydric alcohols examples include glycerol, erythritol, pentaerythritol, trimethylolethane, trimethylolpropane, dipentaerythritol, ditrimethylolpropane, and the like.
- polyfunctional (meth) acrylate compound examples include two (meth) acryloyl groups such as neopentyl glycol di (meth) acrylate, bisphenol A di (meth) acrylate, and ethylene oxide-modified bisphenol A di (meth) acrylate.
- a bifunctional (meth) acrylate compound having three (meth) acryloyl groups such as pentaerythritol tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, etc.
- Acrylate compound tetrafunctional (meth) acrylate compound having four (meth) acryloyl groups such as pentaerythritol tetra (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate; dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) 5 or 6 (meth) 5-6 functional having an acryloyl group (meth) acrylate compounds such as acrylate and the like, but not limited thereto.
- a polyfunctional (meth) acrylate compound can be used individually by 1 type or in combination of 2 or more types.
- the polyfunctional (meth) acrylate compound can be easily obtained as a commercial product.
- Specific examples thereof include, for example, KAYARAD (registered trademark) NPGDA, R-551, T-1420 manufactured by Nippon Kayaku Co., Ltd. , DPHA, DPHA-2C, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, R-526, MANDA, GPO-303, TMPTA , THE-330, TPA-320, TPA-330, PET-30, RP-1040; Aronix (registered trademark) M-211B, M-6200, M-309, M-400, M- manufactured by Toagosei Co., Ltd.
- the polyfunctional (meth) acrylate compound contained in the composition of the present invention contains at least one polyfunctional (meth) acrylate compound having 3 or 4 (meth) acryloyl groups. .
- the content thereof is preferably 10 to 300 parts by mass, and 20 to 200 parts by mass with respect to 100 parts by mass of the aromatic ring-containing polymer as the component (b). More preferred is 50 to 150 parts by mass. If content is the said range, the hardness improvement effect of a cured film will be acquired and a crack will not generate
- the composition of the present invention may contain (f) an ion trapping agent.
- the ion trapping agent prevents migration due to contact of the metal wiring, etc. with water, especially when the substrate is made of metal or when metal wiring is formed on the substrate. It has the function to do.
- a preferred example of the ion trapping agent includes a compound having a nitrogen-based heterocyclic ring in the structure.
- the nitrogen-based heterocyclic ring has a cyclic structure having a 3-membered ring or more having a saturated or unsaturated bond, and one or more nitrogen atoms in the cyclic structure.
- nitrogen-based heterocycle examples include those having a saturated bond, such as aziridine (ethyleneimine), azetidine (azacyclobutane), azolidine (pyrrolidine), azinan (piperidine), azepane (hexamethyleneimine), and the like.
- azirine (1H-azirine, 2H-azirine), azeto (azacyclobutadiene), azole (1H-pyrrole, 2H-pyrrole, imidazole, pyrazole, 1,2,3-triazole, 1,2 , 4-triazole, 1H-tetrazole), pyridine, azepine (azatropylidene), imidazoline, pyrazine, triazine (1,2,3-triazine, 1,2,4-triazine, 1,3,5-triazine), etc.
- porphyrins and choline with multiple nitrogen-based heterocycles And phthalocyanine are examples of the alpha-1, 1,2,3-triazine, 1,2,4-triazine, 1,3,5-triazine.
- the nitrogen-based heterocycle may be condensed with nitrogen-based heterocycles or aromatic hydrocarbon compounds (benzene ring, naphthalene ring, etc.), for example, benzotriazole, indole, isoindole, benzimidazole, quinoline. , Isoquinoline, quinoxaline, cinnoline, purine, pteridine, acridine, carbazole and the like.
- aromatic hydrocarbon compounds benzene ring, naphthalene ring, etc.
- the nitrogen-based heterocycle may contain other heteroatoms other than nitrogen atoms, such as thiazole containing sulfur atoms, isothiazole, thiazine, etc., oxazole containing oxygen atoms, isoxazole, Examples include furazane, morpholine, 3-pyrazolone, 5-pyrazolone, and benzoxazole.
- an addition compound of a nitrogen-based heterocyclic ring in which another nitrogen-based heterocyclic ring such as isocyanuric acid is added to these nitrogen-based heterocyclic rings may be used.
- these nitrogen-based heterocycles can be used alone or in combination.
- the compound having a nitrogen-based heterocycle in the structure include 2,4-diamino-6-vinyl-1,3,5-triazine, 2,4-diamino-6-vinyl-1,3,5- Triazine isocyanuric acid adduct salt, 2,4-diamino-6- (2- (meth) acryloyloxyethyl) -1,3,5-triazine, 2- [2-hydroxy-4- (hexyloxy) phenyl]- 4,6-diphenyl-1,3,5-triazine, 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- [2-hydroxy-4- [3- (2-ethylhexyl-1-oxy)- 2-hydroxypropyl
- the ion trapping agent preferably includes a 1H-benzotriazole compound, more preferably includes 1H-benzotriazole optionally substituted with an alkyl group having 1 to 3 carbon atoms, and 5-methyl-1H— Even more preferably, it contains benzotriazole.
- the compound having a nitrogen-based heterocycle in the structure can be synthesized by a known method, or can be obtained as a commercial product.
- Specific examples of commercially available products include Tinuvin (registered trademark) 234, 326, 328, 329, 400, 405, 460, 571, 928, 1577, P, PS, UVITEX (registered trademark) OB, IRGAGUARD (registered trademark) D.
- ion trapping agents include hydrazide derivatives and sulfur-containing phosphites.
- Specific examples thereof include decamethylene dicarboxylic acid disalicyloyl hydrazide, N, N′-bis [3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyl] hydrazine, 2,2′- Oxamidobis [ethyl 3- (3,5-tert-butyl-4-hydroxyphenyl) propionate], bisbenzylidene hydrazide oxalate, bis (2-phenoxypropionylhydrazide) isophthalate, tris [2-tert-butyl-4- ( And 2'-methyl-4'-hydroxy-5'-tert-butylphenylthio) -5-methylphenyl] phosphite. These may be used alone or in combination of two or more.
- the hydrazide derivative and sulfur-containing phosphites can be synthesized by a known method or can be obtained as a commercial product.
- Specific examples of commercially available products include Inhibitor OABH (manufactured by Eastman), Adekastab (registered trademark) CDA-6 (manufactured by ADEKA), Irganox (registered trademark) MD 1024 (manufactured by BASF), and the like.
- the content is preferably from the viewpoint of obtaining a thin film excellent in hardness, adhesion, etc. with good reproducibility with respect to 100 parts by mass of the aromatic ring-containing polymer of component (b). It is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, and still more preferably 0.01 from the viewpoint of excellent migration suppressing ability. More than part by mass.
- the composition of the present invention may contain (g) a silane coupling agent from the viewpoint of improving the adhesion of the resulting cured film to a substrate or the like.
- the silane coupling agent has the formula The silane compound represented by [4] is included.
- R 6 represents a methyl group or an ethyl group.
- X represents a hydrolyzable group.
- Y represents a reactive functional group.
- L 7 represents a single bond or an alkylene group having 1 to 10 carbon atoms.
- a represents an integer of 0 to 2.
- Examples of the alkylene group having 1 to 10 carbon atoms represented by L 7 include a methylene group, an ethylene group, a trimethylene group, a methylethylene group, a tetramethylene group, a 1-methyltrimethylene group, a pentamethylene group, and 2,2-dimethyl.
- a trimethylene group, a hexamethylene group, an octamethylene group, a decamethylene group, etc. are mentioned. Among these, a trimethylene group is preferable.
- 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 isopropoxy 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.
- Examples of the reactive functional group represented by Y include an amino group, a ureido group, a (meth) acryloyloxy group, a vinyl group, an epoxy group, and a mercapto group.
- an amino group, a ureido group, and a (meth) acryloyloxy group are preferable, and an amino group or a ureido group is more preferable.
- silane coupling agent examples include 3-aminopropyltrichlorosilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyl (methyl) (dimethoxy) silane, 3-aminopropyl ( Methyl) (diethoxy) silane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, vinyltrichlorosilane , Vinyltrimethoxysilane, vinyltriethoxysilane, allyltrichlorosilane, allyltrimethoxysilane, allyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltri
- 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meta ) Acrylyloxypropyltriethoxysilane and the like are preferable.
- the silane coupling agent can be synthesized by a known method or can be obtained as a commercial product. Moreover, a silane coupling agent can be used 1 type or in combination of 2 or more types.
- the content is preferably 0.001 to 10 parts by mass, and 0.01 to 5 parts by mass with respect to 100 parts by mass of the aromatic ring-containing polymer as component (b). Is more preferable, and 0.05 to 1 part by mass is even more preferable. If content is the said range, the adhesive improvement effect will be acquired and hardness will not fall.
- the composition of the present invention may contain (h) a radical polymerization initiator in order to promote polymerization of the polymerizable component contained in the composition.
- a radical polymerization initiator in order to promote polymerization of the polymerizable component contained in the composition.
- a low-temperature curing treatment or a photo-curing treatment can be performed by the radical polymerization initiator.
- the radical polymerization initiator may be any substance that can release a substance that initiates radical polymerization by light irradiation and / or heating.
- photo radical polymerization initiators include benzophenone derivatives, imidazole derivatives, bisimidazole derivatives, N-aryl glycine derivatives, organic azide compounds, titanocene compounds, aluminate complexes, organic peroxides, N-alkoxypyridinium salts, thioxanthone derivatives. Etc.
- IRGACURE registered trademark 651, 184, 369, 784 manufactured by BASF.
- commercially available products other than those described above can also be used. Specifically, IRGACURE 500, 907, 379, 819, 127, 754, 250, 1800, 1870, OXE01, TPO, DAROCUR (registered trademark) 1173 manufactured by BASF; Lambson Speedcure (registered trademark) MBB, PBZ, ITX, CTX, EDB; Esacure (registered trademark) ONE, KIP150, KTO46 manufactured by Lamberti; Kayacure (registered trademark) DETX-S, CTX, BMS manufactured by Nippon Kayaku Co., Ltd. DMBI and the like.
- thermal radical polymerization initiator examples include acetyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, Peroxides such as lauroyl peroxide, tert-butylperoxyacetate, tert-butylperoxypivalate, tert-butylperoxy-2-ethylhexanoate (tert-butyl-2-ethylhexaneperoxoate); 2,2′-azo Bisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), (1-phenylethyl) azodiphenylmethane, 2,2′-azobis (4-methoxy-2,4- Dimethyl valeronitrile), di
- 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, grabbe (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
- the content thereof is preferably 1 to 20 parts by mass and more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the aromatic ring-containing polymer of the (b) component.
- the composition of the present invention may contain a polymerization inhibitor, if necessary.
- a polymerization inhibitor examples include 2,6-diisobutylphenol, 3,5-di-tert-butylphenol, 3,5-di-tert-butylcresol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, 4-methoxy-1-naphthol and the like can be mentioned.
- a polymerization inhibitor is included, the content thereof is preferably 1% by mass or less, more preferably 0.5% by mass or less, based on the total solid content.
- composition of the present invention may further comprise a surfactant, a crosslinking agent, an antifoaming agent, a rheology modifier, a pigment, a dye, a storage stabilizer, a polyhydric phenol, A dissolution accelerator such as a polyvalent carboxylic acid can 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.
- crosslinking agent examples include a polyfunctional epoxy compound, a polyfunctional isocyanate compound, a polyfunctional thiol compound, a melamine-based crosslinking agent, and the like.
- a polyfunctional (meth) acrylate compound When included, a trifunctional or higher functional thiol compound is preferable.
- 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 (2- (3-mercaptopropionyloxy) ethyl) isocyanurate, 1,3,5-tris (2- (3-mercaptobutyryloxy) ethyl) isocyanate.
- Trifunctional thiol compounds such as Nurate (Showa Denko KK, Karenz MT (registered trademark) NR1), trimethylolpropane tris (3-mercaptopropionate); pentaerythritol tetrakis (3-mercaptopropionate), penta Tetrafunctional thiol compounds such as erythritol tetrakis (3-mercaptobutyrate) (produced by Showa Denko KK, Karenz MT ⁇ PEI); hexafunctional thiol compounds such as dipentaerythritol hexakis (3-mercaptopropionate) It is done.
- 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. s. If a viscosity is the said range, applicability
- 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 10,000 from the viewpoint of printability. 100,000 mPa ⁇ s. If the viscosity is within the above range, the discharge property is good, there is no load on the process, the composition does not diffuse after coating, and the transfer property of the composition to the substrate does not decrease. .
- the viscosity of the composition of the present invention at 25 ° C. 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. -S. If the viscosity is within the above range, the discharge property is good, there is no load on the process, the composition does not diffuse after coating, and the transfer property of the composition to the substrate does not decrease. . In the present invention, 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 aromatic ring-containing polymer of component (b) is dissolved in a solvent, and other components are mixed in this solution at a predetermined ratio to obtain a uniform solution.
- the aromatic ring-containing polymer-containing solution obtained by the polymerization reaction in a solvent can be used as it is. In this case, what is necessary is just to put another component in an aromatic ring containing polymer containing solution and to make it a uniform solution. Further, a solvent may be further added for the purpose of adjusting the concentration.
- composition thus prepared is preferably used after being filtered using a filter having a pore diameter of about 0.2 ⁇ m from the viewpoint of obtaining a more uniform cured film.
- the composition of the present invention is applied to a substrate having electrodes and / or wiring (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; Metal nanoparticles such as silver nanoparticles and copper nanoparticles, poly (3,4-ethylenedioxythiophene) / poly (styrenesulfonate) (PEDOT / PSS), conductive polymers such as graphene and carbon nanotubes are coated On glass substrate; quartz substrate; indium tin oxide (ITO) substrate; ITO film substrate; resin film substrate such as triacetyl cellulose (TAC) film, polyester film, acrylic film, cycloolefin (COP) film)
- TAC triacetyl cellulose
- COC triacetyl cellulose
- the pre-baking is generally preferably performed at 60 to 150 ° C., more preferably 80 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 is taken.
- post-baking for thermosetting is performed. Specifically, heating is performed using a hot plate, an oven, or the like. Post bake is generally performed at 150 to 300 ° C., more preferably 200 to 250 ° C., for 1 to 30 minutes when using a hot plate, and 1 to 90 minutes when using an oven. It is done.
- the composition of the present invention contains a thermal radical polymerization initiator, curing at a low temperature is possible.
- the pre-bake conditions are the same as described above, but the post-bake temperature is preferably 60 to 200 ° C., more preferably 80 to 150 ° C. Other conditions are the same as described above.
- photocuring can be performed by irradiating light, such as an ultraviolet-ray (UV), to the said coating film after prebaking.
- the light preferably has a wavelength in the range of 200 to 500 nm and an exposure amount of 100 to 5,000 mJ / cm 2 .
- post-baking for thermosetting may be performed. Specifically, heating is performed using a hot plate, an oven, or the like. In general, post-baking is preferably performed at 60 to 150 ° C., more preferably 80 to 120 ° C., for 1 to 30 minutes when using a hot plate, and 1 to 90 minutes when using an oven. It is done.
- the step of the substrate can be sufficiently flattened, and a cured film having a high refractive index can be formed.
- the cured film of the present invention can be easily formed by a simple method such as a printing method and has a high refractive index, a protective film, a planarizing film, an insulating film, etc. in various displays such as an organic EL element, touch panel, etc. It is expected as a material for forming a cured film such as a protective film or an insulating film.
- the conductive member having the cured film of the present invention formed so as to be in contact with the electrode and / or the wiring on the substrate on which the metal electrode and / or the metal wiring is formed has the corrosion of the electrode and / or the wiring. Therefore, an increase in resistance in the electrodes and wiring, separation between the electrodes and metal and other members, and the like are suppressed, and as a result, durability is excellent.
- Nertaro Awatori (registered trademark) ARE-310 (2) Spin coater: Cee (registered trademark) 100 manufactured by Brewer Science (3) UV exposure apparatus: Heraeus belt conveyor type UV lamp system (H bulb) (4) Thermostatic chamber: Small environmental tester SH-222 manufactured by ESPEC Corporation (5) Gel permeation chromatography (GPC) Equipment: Shodex (registered trademark) GPC-101 manufactured by Showa Denko KK Column: Shodex GPC KF-803L + KF-804L manufactured by Showa Denko K.K.
- GPC Gel permeation chromatography
- EPPA Ethoxylated o-phenylphenol acrylate (NK ester A-LEN-10 manufactured by Shin-Nakamura Chemical Co., Ltd.)
- MAA Methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
- MMA Methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
- POBA 3-phenoxybenzyl acrylate (Kyoeisha Chemical Co., Ltd.
- Examples 2 to 4 Comparative Examples 1 and 2
- Each varnish was prepared in the same manner as in Example 1 except that the composition of each component was changed as shown in Table 1.
- the cured film obtained from the composition of the present invention had a high refractive index of 1.56 or more at a wavelength of 633 nm (Examples 1 to 4).
- a cured film using a polymer having no aromatic group (Comparative Example 1) and a cured film not containing a fluorene compound (Comparative Example 2) have low refractive indexes of 1.557 and 1.540, respectively. It was.
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Abstract
Description
1.(a)式[1]で表されるフルオレン化合物、並びに
(b)(メタ)アクリル酸及び/又は脂肪族(メタ)アクリレート化合物に由来する繰り返し単位(ただし、側鎖にシラン構造を有するものを除く。)、及び重合性二重結合を含む芳香環含有化合物に由来する繰り返し単位を含む芳香環含有ポリマー
を含む高屈折率硬化膜形成用樹脂組成物。
2.更に、(c)溶媒を含む1の高屈折率硬化膜形成用樹脂組成物。
3.更に、(d)単官能(メタ)アクリレート化合物を含む1又は2の高屈折率硬化膜形成用樹脂組成物。
4.更に、(e)多官能(メタ)アクリレート化合物を含む1~3のいずれかの高屈折率硬化膜形成用樹脂組成物。
5.(e)多官能(メタ)アクリレート化合物が、1分子中に3つの(メタ)アクリロイル基を含む化合物及び4つの(メタ)アクリロイル基を含む化合物からなる群から選ばれる少なくとも1種を含む4の高屈折率硬化膜形成用樹脂組成物。
6.更に、(f)イオントラップ剤を含む1~5のいずれかの高屈折率硬化膜形成用樹脂組成物。
7.(f)イオントラップ剤が、ベンゾ-1H-トリアゾール化合物を含む6の高屈折率硬化膜形成用樹脂組成物。
8.更に、(g)シランカップリング剤を含む1~7のいずれかの高屈折率硬化膜形成用樹脂組成物。
9.(g)シランカップリング剤が、式[4]で表されるシラン化合物を含む8の高屈折率硬化膜形成用樹脂組成物。
10.更に、(h)ラジカル重合開始剤を含む1~9のいずれかの高屈折率硬化膜形成用樹脂組成物。
11.スクリーン印刷法用である、1~10のいずれかの高屈折率硬化膜形成用樹脂組成物。
12.1~11のいずれかの高屈折率硬化膜形成用樹脂組成物から得られる高屈折率硬化膜。
13.金属の電極及び/又は金属の配線が形成された基材と、この基材上に前記電極及び/又は配線と接するように形成された12の高屈折率硬化膜とを備える導電性部材。
(b)成分の芳香環含有ポリマーは、(メタ)アクリル酸及び/又は脂肪族(メタ)アクリレート化合物に由来する繰り返し単位(ただし、側鎖にシラン構造を有するものを除く。)、及び重合性二重結合を含む芳香環含有化合物に由来する繰り返し単位を含む。
本発明の組成物は、(c)溶媒を含んでもよい。(c)溶媒は、前述した(a)及び(b)成分を溶解でき、更に後述する(d)単官能(メタ)アクリレート化合物、(e)多官能(メタ)アクリレート化合物、(f)イオントラップ剤、(g)シランカップリング剤、(h)ラジカル重合開始剤、重合禁止剤、その他の添加剤等を含む場合においては、これらをも溶解できるものであれば、特に限定されない。
グリセリン等のトリオール類;
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モノプロピルエーテル、エチレングリコールモノ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モノイソブチルエーテル、エチレングリコールモノヘキシルエーテルなどのエチレングリコールモノアルキルエーテル類、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プロピルエーテル、プロピレングリコールモノイソプロピルエーテル、プロピ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イソブチルエーテル、プロピレングリコールモノヘキシルエーテルなどのプロピレングリコールモノアルキルエーテル類等のアルキレングリコールモノアルキルエーテル類;
エチレングリコールモノフェニルエーテルなどのエチレングリコールモノアリールエーテル類、プロピレングリコールモノフェニルエーテルなどのプロピレングリコールモノアリールエーテル類等のアルキレングリコールモノアリールエーテル類;
エチレングリコールモノベンジルエーテルなどのエチレングリコールモノアラルキルエーテル類、プロピレングリコールモノベンジルエーテルなどのプロピレングリコールモノアラルキルエーテル類等のアルキレングリコールモノアラルキルエーテル類;
エチレングリコールブトキシエチルエーテルなどのエチレングリコールアルコキシアルキルエーテル類、プロピレングリコールブトキシエチルエーテルなどのプロピレングリコールアルコキシアルキルエーテル類等のアルキレングリコールアルコキシアルキルエーテル類;
エチレングリコールジメチルエーテル、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ジプロピルエーテル、エチレングリコールジイソプロピルエーテル、エチレングリコールジブチルエーテルなどのエチレングリコールジアルキルエーテル類、プロピレングリコールジメチルエーテル、プロピレングリコールジエチルエーテル、プロピレングリコールジプロピルエーテル、プロピレングリコールジイソプロピルエーテル、プロピレングリコールジブチルエーテルなどのプロピレングリコールジアルキルエーテル類等のアルキレングリコールジアルキルエーテル類;
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プロピルエーテルアセテート、エチレングリコールモノイソプロピ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などのエチレングリコールモノアルキルエーテルアセテート類、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、プロピレングリコールモノイソプロピルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテートなどのプロピレングリコールモノアルキルエーテルアセテート類等のアルキレングリコールモノアルキルエーテルアセテート類;
エチレングリコールモノアセテートなどのエチレングリコールモノアセテート類、プロピレングリコールモノアセテートなどのプロピレングリコールモノアセテート類等のアルキレングリコールモノアセテート類;
エチレングリコールジアセテートなどのエチレングリコールジアセテート類、プロピレングリコールジアセテートなどのプロピレングリコールジアセテート類等のアルキレングリコールジアセテート類;
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プロピルエーテル、ジエチレングリコールモノイソプロピルエーテル、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モノイソブチルエーテル、ジエチレングリコールモノヘキシルエーテルなどのジエチレングリコールモノアルキルエーテル類、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プロピルエーテル、ジプロピレングリコールモノイソプロピルエーテル、ジプロピレングリコールモノブチルエーテル、ジプロピレングリコールモノイソブチルエーテル、ジプロピレングリコールモノヘキシルエーテルなどのジプロピレングリコールモノアルキルエーテル類等のジアルキレングリコールモノアルキルエーテル類;
ジエチレングリコールモノベンジルエーテル等のジアルキレングリコールモノアラルキルエーテル類;
ジエチレングリコールモノフェニルエーテルなどのジエチレングリコールモノアリールエーテル類、ジプロピレングリコールモノフェニルエーテルなどのジプロピレングリコールモノアリールエーテル類等のジアルキレングリコールモノアリールエーテル類;
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プロピルエーテル、ジエチレングリコールジイソプロピルエーテル、ジエチレングリコールジブチルエーテルなどのジエチレングリコールジアルキルエーテル類、ジプロピレングリコールジメチルエーテル、ジプロピレングリコールジエチルエーテル、ジプロピレングリコールジプロピルエーテル、ジプロピレングリコールジイソプロピルエーテル、ジプロピレングリコールジブチルエーテルなどのジプロピレングリコールジアルキルエーテル類等のジアルキレングリコールジアルキルエーテル類;
ジエチレングリコールモノメチルエーテルアセテート、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プロピルエーテルアセテート、ジエチレングリコールモノイソプロピ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、ジエチレングリコールモノイソブチルエーテルアセテート、ジエチレングリコールモノヘキシルエーテルアセテートなどのジエチレングリコールモノアルキルエーテルアセテート類、ジプロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノエチルエーテルアセテート、ジプロピレングリコールモノプロピルエーテルアセテート、ジプロピレングリコールモノイソプロピルエーテルアセテート、ジプロピレングリコールモノブチルエーテルアセテート、ジプロピレングリコールモノイソブチルエーテルアセテート、ジプロピレングリコールモノヘキシルエーテルアセテートなどのジプロピレングリコールモノアルキルエーテルアセテート類等のジアルキレングリコールモノアルキルエーテルアセテート類;
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エチルエーテルなどのトリエチレングリコールモノアルキルエーテル類、トリプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノエチルエーテルなどのトリプロピレングリコールモノアルキルエーテル類等のトリアルキレングリコールモノアルキルエーテル類;
トリエチレングリコールジメチルエーテル、トリエチレングリコールジエチルエーテルなどのトリエチレングリコールジアルキルエーテル類、トリプロピレングリコールジメチルエーテル、トリプロピレングリコールジエチルエーテルなどのトリプロピレングリコールジアルキルエーテル類等のトリアルキレングリコールジアルキルエーテル類;
1-プロパノール、2-プロパノール、1-ブタノール、2-ブタノール、1-ペンタノール、1-ヘキサノール、1-ヘプタノール、1-ノナノール、1-デカノール、1-ウンデカノール、1-ドデカノール、1-テトラデカノールなどの直鎖脂肪族アルコール類、シクロヘキサノール、2-メチルシクロヘキサノールなどの環状脂肪族アルコール類等の脂肪族アルコール類;
フェノール等のフェノール類;
ベンジルアルコール等の芳香族アルコール類;
フルフリルアルコール等の複素環含有アルコール類;
テトラヒドロフルフリルアルコール等の水素化複素環含有アルコール類;
ジイソプロピルエーテル、ジ-n-ブチルエーテル、ジ-n-ヘキシルエーテル等のジアルキルエーテル類;
メチルフェニルエーテル、エチルフェニルエーテル、n-ブチルフェニルエーテル、ベンジル(3-メチルブチル)エーテル、(2-メチルフェニル)メチルエーテル、(3-メチルフェニル)メチルエーテル、(4-メチルフェニル)メチルエーテル等のアルキルアリールエーテル類;
エチルベンジルエーテル等のアルキルアラルキルエーテル類;
2-メチルフラン、テトラヒドロフラン、テトラヒドロピラン等の環状アルキルモノエーテル類;
1,4-ジオキサン等の環状アルキルジエーテル類;
トリオキサン等の環状アルキルトリエーテル類;
ジグリシジルエーテル等のジエポキシアルキルエーテル類;
エチルアセテート、n-プロピルアセテート、イソプロピルアセテート、n-ブチルアセテート、イソブチルアセテート、sec-ブチルアセテート、tert-ブチルアセテート、n-ペンチルアセテート、(3-メチルブチル)アセテート、n-ヘキシルアセテート、(2-エチルブチル)アセテート、(2-エチルヘキシル)アセテートなどの直鎖状又は分岐状アルキルアセテート類、シクロヘキシルアセテート、2-メチルシクロヘキシルアセテートなどの環状アルキルアセテート類等のアルキルアセテート類;エチルプロピオネート、n-プロピルプロピオネート、イソプロピルプロピオネート、n-ブチルプロピオネート、イソブチルプロピオネート、sec-ブチルプロピオネート、tert-ブチルプロピオネート、n-ペンチルプロピオネート、(3-メチルブチル)プロピオネート、n-ヘキシルプロピオネート、(2-エチルブチル)プロピオネート、(2-エチルヘキシル)プロピオネートなどの直鎖状又は分岐状アルキルプロピオネート類、シクロヘキシルプロピオネート、2-メチルシクロヘキシルプロピオネートなどの環状アルキルプロピオネート類等のアルキルプロピオネート類;エチルブチレート、n-プロピルブチレート、イソプロピルブチレート、n-ブチルブチレート、イソブチルブチレート、sec-ブチルブチレート、tert-ブチルブチレート、n-ペンチルブチレート、(3-メチルブチル)ブチレート、n-ヘキシルブチレート、(2-エチルブチル)ブチレート、(2-エチルヘキシル)ブチレートなどの直鎖状又は分岐状アルキルブチレート類、シクロヘキシルブチレート、2-メチルシクロヘキシルブチレート等の環状アルキルブチレート類などのアルキルブチレート類;エチルラクテート、n-プロピルラクテート、イソプロピルラクテート、n-ブチルラクテート、イソブチルラクテート、sec-ブチルラクテート、tert-ブチルラクテート、n-ペンチルラクテート、(3-メチルブチル)ラクテート、n-ヘキシルラクテート、(2-エチルブチル)ラクテート、(2-エチルヘキシル)ラクテートなどの直鎖状又は分岐状アルキルラクテート類、シクロヘキシルラクテート、2-メチルシクロヘキシルラクテートなどの環状アルキルラクテート類等のアルキルラクテート類等のアルキルエステル類;
ベンジルアセテートなどのアラルキルアセテート類、ベンジルプロピオネートなどのアラルキルプロピオネート類、ベンジルブチレートなどのアラルキルブチレート類、ベンジルラクテートなどのアラルキルラクテート類等のアラルキルアルキルエステル類;
ジエチルケトン、ジイソブチルケトン、メチルエチルケトン、メチルn-プロピルケトン、メチルn-ブチルケトン、メチルイソブチルケトン、メチルn-プロピルケトン、メチルn-ヘキシルケトン、エチルn-ブチルケトン、ジ-n-プロピルケトン等のジアルキルケトン類;
イソホロン等の環状アルケニルケトン類;
シクロヘキサノン等の環状アルキルケトン類;
4-ヒドロキシ-4-メチル-2-ペンタノン(ジアセトンアルコール)等のヒドロキシジアルキルケトン類;
フルフラール等の複素環含有アルデヒド類;
ヘプタン、オクタン、2,2,3-トリメチルヘキサン、デカン、ドデカン等の直鎖状又は分岐状アルカン類;
トルエン、キシレン、o-キシレン、m-キシレン、p-キシレン、メシチレン、テトラリン、シクロヘキシルベンゼン等のアルキルベンゼン類;
シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン等の環状アルカン類
等が挙げられるが、これらに限定されない。これらの溶媒は、1種単独で又は2種以上混合して用いることができる。
本発明の組成物は、(d)単官能(メタ)アクリレート化合物を含んでもよい。本発明において単官能(メタ)アクリレート化合物とは、分子中に1つの(メタ)アクリロイル基を含む化合物のことであり、例えば、(b)成分の芳香環含有ポリマーのモノマー成分として例示した脂肪族(メタ)アクリレート化合物や芳香環含有(メタ)アクリレート化合物が挙げられる。これらのうち、(d)単官能(メタ)アクリレート化合物としては、芳香環含有(メタ)アクリレート化合物が好ましく、特に式[3]で表される芳香環含有(メタ)アクリレート化合物として例示したものが好ましい。単官能(メタ)アクリレート化合物は、1種単独で又は2種以上を組み合わせて用いることができる。
本発明の組成物は、硬化膜の物性を調整する点から、(e)多官能(メタ)アクリレート化合物を含んでもよい。本発明において多官能(メタ)アクリレート化合物とは、分子中に少なくとも2つの(メタ)アクリロイル基を含む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、特に硬度を改善する点から、当該多官能(メタ)アクリレート化合物の1分子中の(メタ)アクリロイル基の数は、好ましくは3~6であるが、より好ましくは3又は4である。このような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。
本発明の組成物は、(f)イオントラップ剤を含んでもよい。(f)イオントラップ剤は、特に、基板が金属製である場合や基板上に金属配線が形成されている場合等においては、当該金属配線等が水と接触することでマイグレーションを起こすことを防止する機能を有する。
本発明の組成物は、得られる硬化膜の基板等への密着性を向上させる点から、(g)シランカップリング剤を含んでもよく、好ましい態様によれば、当該シランカップリング剤は、式[4]で表されるシラン化合物を含む。
本発明の組成物は、当該組成物に含まれる重合性成分の重合を促進させるため、(h)ラジカル重合開始剤を含んでもよい。例えば、高温で処理することによって自発的に重合するが、基板が変性する等高温硬化処理ができない事情があるときは、ラジカル重合開始剤によって低温硬化処理又は光硬化処理が可能となる。
本発明の組成物を、電極及び/又は配線を有する基板(例えば、シリコン/二酸化シリコン被覆基板;シリコンニトリド基板;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;酸化インジウムスズ(ITO)基板;ITOフィルム基板;トリアセチルセルロース(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。
(1)攪拌脱泡
装置:(株)シンキー製自転・公転ミキサー あわとり練太郎(登録商標)ARE-310
(2)スピンコート
装置:Brewer Science社製Cee(登録商標)100
(3)UV露光
装置:ヘレウス社製ベルトコンベアー式UVランプシステム(Hバルブ)
(4)恒温槽
装置:エスペック(株)製小型環境試験器SH-222
(5)ゲル浸透クロマトグラフィー(GPC)
装置:昭和電工(株)製Shodex(登録商標)GPC-101
カラム:昭和電工(株)製Shodex GPC KF-803L+KF-804L
カラム温度:40℃
溶媒:THF
流量:1mL/分
検出器:RI
検量線:標準ポリスチレン
(6)屈折率測定
装置:Metricon社製モデル2010/M プリズムカプラ
測定温度:25℃
(7)全光線透過率測定
装置:日本電色工業(株)製ヘーズメーターNDH 5000
波長範囲:380~780nm
EPPA:エトキシ化o-フェニルフェノールアクリレート(新中村化学工業(株)製NKエステルA-LEN-10)
MAA:メタクリル酸(東京化成工業(株)製)
MMA:メタクリル酸メチル(東京化成工業(株)製)
POBA:3-フェノキシベンジルアクリレート(共栄社化学(株)製ライトアクリレートPOB-A)
St:スチレン(東京化成工業(株)製)
MAIB:2,2'-アゾビス(イソ酪酸)ジメチル(東京化成工業(株)製)
BPFDA:ビスフェノールフルオレンジアクリレート(大阪ガスケミカル(株)製オグソールEA-F5710)
TMPTA:トリメチロールプロパントリアクリレート(新中村化学工業(株)製NKエステルA-TMPT)
A771:ポリシロキサン系消泡剤(MUNZING社製AGITAN771)
APTES:(3-アミノプロピル)トリエトキシシラン(信越化学工業(株)製LS-3150)
MBT:5-メチル-1H-ベンゾトリアゾール(東京化成工業(株)製)
I184:1-ヒドロキシシクロヘキシル=フェニル=ケトン(BASF社製IRGACURE(登録商標)184)
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(東京化成工業(株)製)
PGDA:プロピレングリコールジアセテート(和光純薬工業(株)製)
[製造例1]芳香環含有ポリマーの製造1
1Lの四つ口フラスコに、溶媒としてPGDA324.5gを仕込んだ。このPGDA中に、窒素雰囲気下、70℃(内温)で攪拌しながら、MMA61.6g(0.62mol)、St150.0g(1.44mol)及びMAIB4.72g(0.02mol)の混合液を、2時間かけて滴下した。滴下後、更に70℃で20時間反応させ、ポリマー濃度40質量%のポリマー溶液P1を得た。P1中のポリマーのMwは、65,000であった。
1Lの四つ口フラスコに、溶媒としてPGDA315.1gを仕込んだ。このPGDA中に、窒素雰囲気下、70℃(内温)で攪拌しながら、MMA30.0g(0.30mol)、POBA177.8g(0.70mol)及びMAIB2.30g(0.01mol)の混合液を、2時間かけて滴下した。滴下後、更に70℃で20時間反応させ、ポリマー濃度40質量%のポリマー溶液P2を得た。P2中のポリマーのMwは、125,000であった。
1Lの四つ口フラスコに、溶媒としてPGDA329.5gを仕込んだ。このPGDA中に、窒素雰囲気下、70℃(内温)で攪拌しながら、MMA30.0g(0.30mol)、EPPA187.4g(0.70mol)及びMAIB2.30g(0.01mol)の混合液を、2時間かけて滴下した。滴下後、更に70℃で20時間反応させ、ポリマー濃度40質量%のポリマー溶液P3を得た。P3中のポリマーのMwは、56,000であった。
1Lの四つ口フラスコに、溶媒としてPGDA345.0gを仕込んだ。このPGDA中に、窒素雰囲気下、70℃(内温)で攪拌しながら、MAA27.5g(0.32mol)、EPPA200.0g(0.75mol)及びMAIB2.45g(0.01mol)の混合液を、2時間かけて滴下した。滴下後、更に70℃で20時間反応させ、ポリマー濃度40質量%のポリマー溶液P4を得た。P4中のポリマーのMwは、70,000であった。
1Lの四つ口フラスコに、溶媒としてDEGEEA303.5gを仕込んだ。このDEGEEA中に、窒素雰囲気下、70℃(内温)で攪拌しながら、MMA200.0g(2.00mol)及びMAIB2.30g(0.01mol)の混合液を、2時間かけて滴下した。滴下後、更に70℃で20時間反応させ、ポリマー濃度40質量%のポリマー溶液P5を得た。P5中のポリマーのMwは、95,000であった。
[実施例1]
製造例1で得られたポリマー溶液P1 250質量部(ポリマーとして100質量部)、フルオレン化合物としてBPFDA55質量部、多官能(メタ)アクリレートとしてTMPTA55質量部、イオントラップ剤としてMBT6質量部、シランカップリング剤としてAPTES0.1質量部、消泡剤としてA771 0.65質量部、ラジカル重合開始剤としてI184 6.4質量部、及び溶媒としてPGDA70質量部を混合した。この混合物を、2,000rpmで10分間攪拌脱泡し、固形分濃度50質量%のワニスを調製した。なお、ここで固形分とは、溶媒を除く全成分を指す。
各成分の配合を表1に記載のように変更した以外は、実施例1と同様にして各ワニスを調製した。
[屈折率評価]
実施例1~4及び比較例1~2のワニスを、それぞれガラス基板上にスピンコートにより塗布し、110℃のオーブンで10分間プリベークした。得られた塗膜をUV露光(露光量800mJ/cm2)し、更に110℃のオーブンで30分間ポストベークすることで、厚さ約5μmの硬化膜を作製した。
得られた硬化膜の波長633nmにおける屈折率及び全光線透過率を測定した。結果を表2に併せて示す。
Claims (13)
- (a)式[1]で表されるフルオレン化合物、並びに
(b)(メタ)アクリル酸及び/又は脂肪族(メタ)アクリレート化合物に由来する繰り返し単位(ただし、側鎖にシラン構造を有するものを除く。)、及び重合性二重結合を含む芳香環含有化合物に由来する繰り返し単位を含む芳香環含有ポリマー
を含む高屈折率硬化膜形成用樹脂組成物。
- 更に、(c)溶媒を含む請求項1記載の高屈折率硬化膜形成用樹脂組成物。
- 更に、(d)単官能(メタ)アクリレート化合物を含む請求項1又は2記載の高屈折率硬化膜形成用樹脂組成物。
- 更に、(e)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項記載の高屈折率硬化膜形成用樹脂組成物。
- (e)多官能(メタ)アクリレート化合物が、1分子中に3つの(メタ)アクリロイル基を含む化合物及び4つの(メタ)アクリロイル基を含む化合物からなる群から選ばれる少なくとも1種を含む請求項4記載の高屈折率硬化膜形成用樹脂組成物。
- 更に、(f)イオントラップ剤を含む請求項1~5のいずれか1項記載の高屈折率硬化膜形成用樹脂組成物。
- (f)イオントラップ剤が、ベンゾ-1H-トリアゾール化合物を含む請求項6記載の高屈折率硬化膜形成用樹脂組成物。
- 更に、(g)シランカップリング剤を含む請求項1~7のいずれか1項記載の高屈折率硬化膜形成用樹脂組成物。
- 更に、(h)ラジカル重合開始剤を含む請求項1~9のいずれか1項記載の高屈折率硬化膜形成用樹脂組成物。
- スクリーン印刷法用である、請求項1~10のいずれか1項記載の高屈折率硬化膜形成用樹脂組成物。
- 請求項1~11のいずれか1項記載の高屈折率硬化膜形成用樹脂組成物から得られる高屈折率硬化膜。
- 金属の電極及び/又は金属の配線が形成された基材と、この基材上に前記電極及び/又は配線と接するように形成された請求項12記載の高屈折率硬化膜とを備える導電性部材。
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