CN116323685A - Curable composition - Google Patents

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CN116323685A
CN116323685A CN202180065817.5A CN202180065817A CN116323685A CN 116323685 A CN116323685 A CN 116323685A CN 202180065817 A CN202180065817 A CN 202180065817A CN 116323685 A CN116323685 A CN 116323685A
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meth
mass
group
curable composition
carbon atoms
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松山绫花
井上胜治
河西裕
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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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
    • C08F22/00—Homopolymers and 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
    • C08F22/10—Esters
    • C08F22/1006—Esters of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate
    • 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
    • C08F122/00—Homopolymers 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
    • C08F122/10—Esters
    • C08F122/1006—Esters of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate
    • 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
    • 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
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/20—Esters of polyhydric alcohols or polyhydric phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • 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
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • 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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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Materials For Photolithography (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

The curable composition of the present invention comprises inorganic fine particles (A), a polymerizable compound (B) and a polymerization initiator (C), wherein the polymerizable compound (B) comprises a compound represented by the formula (B1), and the average transmittance at a wavelength of 400 to 700nm at the time of film formation is 90% or more per 1.0 μm film thickness, and the conditions are that the curable composition is applied to a glass substrate such that the average thickness of a cured film is within a range of 1.0.+ -. 0.2. Mu.m, and an LED lamp is used at 2000J/m 2 UV with a wavelength of 385 nm. R is R 1 R is R 2 Hydrogen atom, alkyl group having 1 to 20 carbon atoms, etc. R is R 3 Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a (meth) acrylic group, or the like. [ chemical formula 1 ]]

Description

Curable composition
Technical Field
The present invention relates to a curable composition and a cured film.
Background
Organic electroluminescent devices are used in display devices, lighting devices, and the like, and studies have been made to control refractive index to improve efficiency of extracting light from a light emitting layer. The curable composition disclosed in patent document 1 is intended to provide a cured film having a high refractive index, and for example, the composition contains 45 mass% of zirconia nanoparticles, 25 mass% of tricyclodecane dimethanol dimethacrylate as a ring-structured polyfunctional compound, 14 mass% of 1, 9-nonanediol dimethacrylate as an acyclic polyfunctional compound, and 10 mass% of isobutyl methacrylate as a monofunctional compound together with a polymerization initiator and a surfactant.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2017-61606
Disclosure of Invention
Problems to be solved by the invention
However, when the ring structure polyfunctional compound is combined with the acyclic structure polyfunctional compound, the curable composition may not be sufficiently cured.
The purpose of the present invention is to provide a curable composition having excellent curability.
Means for solving the problems
The present invention capable of solving the above-described problems has the following configuration.
[1] A curable composition comprising inorganic fine particles (A), a polymerizable compound (B) and a polymerization initiator (C),
the polymerizable compound (B) contains a compound represented by the formula (B1),
[ chemical formula 1]
Figure BDA0004144317250000021
(wherein R is 1 R is R 2 Each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a substituent. R is R 3 The above-mentioned alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, or (meth) acrylic group may have a substituent. )
The average transmittance at a wavelength of 400 to 700nm at the time of film formation under the following conditions is 90% or more per 1.0 μm film thickness.
[ film Forming conditions ]
The curable composition was applied to a glass substrate so that the average thickness of the cured film was within the range of 1.0.+ -. 0.2. Mu.m, and an LED lamp was used at 2000J/m 2 UV with a wavelength of 385 nm.
[2] The curable composition according to [1], wherein the content of the inorganic fine particles (A) in the curable composition is 10% by mass or more.
[3] A cured film formed from the curable composition of [1] or [2 ].
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, the curability of the curable composition can be improved.
Detailed Description
The present invention provides a curable composition containing inorganic fine particles (A), a polymerizable compound (B), and a polymerization initiator (C), characterized by containing a specific monomer as the polymerizable compound (B).
Inorganic particles (A) >)
The inorganic fine particles (a) are preferably particles having no wavelength conversion ability to the visible light region, and preferably particles having a refractive index of 1.6 or more. The higher the refractive index of the inorganic fine particles (a), the higher the refractive index of the film obtained from the curable composition, and the higher the efficiency of extracting light from the light-emitting layer. The refractive index is preferably 1.8 or more, more preferably 2.0 or more. The refractive index may be 3.5 or less, or 3.0 or less, for example. The refractive index is a value at the D line of sodium.
The inorganic fine particles (a) include oxides, nitrides, and the like, and specifically, tiO 2 (titanium oxide; refractive index 2.3-2.7), nb 2 O 5 (niobium oxide; refractive index 2.3), ta 2 O 5 (tantalum oxide; refractive index 2.3), BN (boron nitride; refractive index 2.2), zrO 2 (zirconia; refractive index 2.1), snO 2 (tin oxide; refractive index 2.0), ITO (tin doped indium oxide; refractive index 2.0), si 3 N 4 (silicon nitride; refractive index 2.0), ceO 2 (cerium oxide; refractive index 1.9-2.0), znO (zinc oxide; refractive index 1.9), Y 2 O 3 (yttrium oxide; refractive index 1.9), ATO (antimony doped tin oxide; refractive index 1.7-1.9), sbO 5 (antimony oxide; refractive index 1.8), al 2 O 3 (alumina; refractive index 1.8), tiN (titanium nitride; refractive index 1.6), etc., preferably oxides of elements of groups 3 to 5 or 12 to 15 of the periodic Table, or nitrides of elements of group 4 of the periodic Table, more preferably titanium oxide, zirconium oxide, aluminum oxide, niobium oxide, and silicon nitride, still more preferably titanium oxide and zirconium oxide. The inorganic fine particles (A) may be 1 or 2 or more kinds thereof may be combined.
The volume average particle diameter of the inorganic fine particles (A) is, for example, 100nm or less, preferably 50nm or less, and more preferably 30nm or less. The smaller the particle diameter, the more visible light transmittance of the resulting film can be improved. The lower limit of the volume average particle diameter of the inorganic fine particles (A) is not particularly limited, and is, for example, 0.1nm or more, preferably 0.5nm or more, and more preferably 1.0nm or more.
The content of the inorganic fine particles (a) in the curable composition is, for example, 10 mass% or more, preferably 15 mass% or more, more preferably 20 mass% or more, and particularly preferably 30 mass% or more. The higher the content of the inorganic fine particles (a), the higher the refractive index of the film obtained from the curable composition becomes, and the efficiency of extracting light from the light-emitting layer improves. The content of the inorganic fine particles (a) is, for example, 80 mass% or less, preferably 70 mass% or less, more preferably 60 mass% or less, and still more preferably 50 mass% or less.
The inorganic fine particles (a) may be surface-treated with a coupling agent. The coupling agent may be a silane coupling agent, a zirconium coupling agent, a titanate coupling agent, an aluminate coupling agent, or the like, and may be 1 kind or 2 or more kinds.
Examples of the silane coupling agent include γ - (meth) acryloxypropyl dimethylmethoxysilane, γ - (meth) acryloxypropyl methyldimethoxysilane, γ - (meth) acryloxypropyl trimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyldimethylmethoxysilane, phenylmethyldimethoxysilane, phenyldiethylmethoxysilane, phenylethyldimethoxysilane, phenyltrimethoxysilane, and diphenyldimethoxysilane.
Examples of the zirconium-based coupling agent include tetrapropyl zirconate, tetrabutyl zirconate, tetra (triethanolamine) zirconate, tetraisopropyl zirconate, zirconium acetylacetonate butyrate, zirconium stearate butyrate, monoalkoxy zirconium aluminate, trialkoxy zirconium aluminate, and tetraalkoxy zirconium aluminate.
Examples of the titanate coupling agent include isopropyl triisostearoyl titanate, isopropyl tristearoyl titanate, isopropyl trioctanoyl titanate, isopropyl dimethacrylate isostearoyl titanate, isopropyl tris (dodecyl) benzenesulfonyl titanate, isopropyl isostearoyl diacryloyl titanate, isopropyl tris (dioctyl phosphate) titanate, triisohard titanate isopropyl, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tris (N-aminoethyl) titanate, tetraoctyl bis (ditridecyl) phosphite, tetra (2, 2-dialloxymethyl-1-butyl) bis (ditridecyl) phosphite, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, and the like.
Examples of the aluminate coupling agent include diisobutyl (oleyl) acetoacetylaluminate and acetoacetylaluminum diisopropylate.
The inorganic fine particles (a) may be contained in the curable composition together with the dispersant. As the dispersant, any type of dispersant such as nonionic, anionic, and cationic dispersants may be used, and anionic dispersants are preferable. As the anionic dispersant, a phosphate dispersant can be preferably used.
As the dispersant, commercially available ones may be used, and examples thereof include DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, DISPEYK-166, DISPEYK-170, DISPERBYK-171, DISPEYK-182, DISPEYK-2000, DISPEYK-2001 (BYK Chemie, GMBH), solsperse 32000, solsperse 36000, solsperse 28000, solsperse 20000, solsperse 45000 (Lubrizol, wickliffe, OH, USA).
The amount of the dispersant is, for example, 1 part by mass or more, preferably 5 parts by mass or more, and more preferably 10 parts by mass or more, based on 100 parts by mass of the inorganic fine particles (a). The larger the amount of the dispersant, the more the dispersibility of the inorganic fine particles (a) can be improved. The amount of the dispersant is, for example, 100 parts by mass or less, preferably 60 parts by mass or less, and more preferably 40 parts by mass or less, based on 100 parts by mass of the inorganic fine particles (a). The smaller the amount of the dispersant, the more the refractive index of the curable composition can be increased.
< polymerizable Compound (B) >)
The polymerizable compound (B) contains a compound represented by the formula (B1) (hereinafter, sometimes referred to as a compound (B1)). The curable composition containing the compound (B1) in the polymerizable compound (B) is excellent in visible light transmittance and curability of the obtained cured film.
[ chemical formula 2]
Figure BDA0004144317250000051
(wherein R is 1 R is R 2 Each independently isA hydrogen atom, or an alkyl group having 1 to 20 carbon atoms which may have a substituent. R is R 3 The above-mentioned alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, or (meth) acrylic group may have a substituent. )
The alkyl group having 1 to 20 carbon atoms may be any of straight-chain and branched-chain ones. Specific examples of the linear or branched alkyl group include methyl, ethyl, propyl, isobutyl, butyl, tert-butyl, hexyl, heptyl, octyl, nonyl, decyl, heptadecyl, undecyl and the like. The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 8, and still more preferably 1 to 4.
The alkenyl group having 2 to 20 carbon atoms may be any of straight-chain and branched-chain ones. Specific examples of the straight-chain or branched alkenyl group include a vinyl group, an allyl group, a methallyl group, a propenyl group, a butenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a heptadecenyl group, and an undecenyl group. The number of carbon atoms of the alkenyl group is preferably 2 to 12, more preferably 2 to 8, and even more preferably 2 to 4.
Examples of the aryl group having 6 to 20 carbon atoms include phenyl, tolyl, xylyl, trimethylphenyl, and naphthyl. The number of carbon atoms of the aryl group is preferably 6 to 15, more preferably 6 to 12, and even more preferably 6 to 9.
Examples of the substituent include: halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; a hydroxyl group; -NR a R b (R a R is R b Each independently is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms); a nitro group; alkoxy groups having 1 to 10 carbon atoms such as methoxy and ethoxy; alkoxycarbonyl groups having 2 to 10 carbon atoms such as methoxycarbonyl and ethoxycarbonyl; etc.
As R 1 R is R 2 Preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
As R 3 Preferably hydrogenAn atom or a (meth) acrylic group.
The following compounds are preferred as the compound (B1).
[ chemical formula 3]
Figure BDA0004144317250000071
The polymerizable compound (B) may contain a compound having an ethylenic double bond other than the compound (B1) (hereinafter, may be referred to as another polymerizable compound). The proportion of the compound (B1) in the polymerizable compound (B) is, for example, 30 mass% or more, preferably 50 mass% or more, more preferably 70 mass% or more, still more preferably 90 mass% or more, particularly preferably 95 mass% or more, and may be 100 mass% or more.
Examples of the other polymerizable compound include a polyfunctional compound (B2) having an acyclic structure, a polyfunctional compound (B3) having a ring structure, a monofunctional compound (B4), and the like. These other polymerizable compounds may be 1 or 2 or more kinds may be combined.
Examples of the polyfunctional compound (B2) having a non-cyclic structure include compounds having 2 or more polymerizable groups of the same (meth) acryloyl group, and examples of the 2-functional compound having a non-cyclic structure include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 8-octanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and other di (meth) acrylates in which a methylene group of the alkylene glycol having 1 to 40 carbon atoms may be replaced with-O-.
Examples of the compound having a non-cyclic structure and having 3 or more functions include esters of a diol having 4 to 40 carbon atoms and 3 to 6 (meth) acrylic acids, which have 3 or more hydroxyl groups and may have an ether bond, such as trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
Examples of the polyfunctional compound (B3) having a ring structure include compounds having 2 or more (meth) acryloyl groups as a polymerizable group, and examples of the 2-functional compound having a ring structure include di (meth) acrylates of cycloalkanediols having about 4 to 8 carbon atoms such as tricyclodecane dimethanol di (meth) acrylate, cyclohexane dimethanol di (meth) acrylate, cyclopentane dimethanol di (meth) acrylate and the like; di (meth) acrylates of diols obtained by hydroxy alkylene etherification of the OH groups of bisphenols, such as propoxylated bisphenol a di (meth) acrylate and ethoxylated bisphenol a di (meth) acrylate; 9, 9-bis [4- (2-acryloyloxyethoxy) phenyl ] fluorene, and the like.
Examples of the compound having a ring structure and having 3 or more functions include ethoxylated isocyanuric acid tri (meth) acrylate, epsilon-caprolactone-modified tris- (2-acryloyloxyethyl) isocyanurate, and the like.
Examples of the monofunctional compound (B4) include (meth) acrylic esters of alkanols having 1 to 12 carbon atoms such as ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and lauryl (meth) acrylate; (meth) acrylic acid esters of alkylene glycol monoethers such as ethyl diethylene glycol (meth) acrylate; monofunctional compounds having a ring structure, such as dicyclopentadiene (meth) acrylate, isobornyloxy ethyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentadienyloxy ethyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate; monofunctional compounds having a nitrogen atom such as (meth) acryloylmorpholine and 7-amino-3, 7-dimethyloctyl (meth) acrylate.
In the curable composition, the polymerizable compound (B) is, for example, 80 mass% or less, preferably 70 mass% or less, and more preferably 60 mass% or less. The lower the content of the polymerizable compound (B), the higher the refractive index of the film obtained from the curable composition becomes, and the efficiency of extracting light from the light-emitting layer improves. The content of the polymerizable compound (B) is, for example, 20 mass% or more, preferably 30 mass% or more, and more preferably 40 mass% or more.
Polymerization initiator (C) >, and process for producing the same
The polymerization initiator (C) is not particularly limited as long as it is a compound capable of generating a living radical, an acid, or the like under the action of light or heat to initiate polymerization, and a known polymerization initiator, preferably a photopolymerization initiator, may be used. Examples of the polymerization initiator generating active radicals include O-acyl oxime compounds, alkyl phenone compounds, triazine compounds, acyl phosphine oxide compounds, phosphonate compounds, and bisimidazole compounds. These polymerization initiators may be used alone or in combination of 2 or more.
The O-acyl oxime compound is a compound having a partial structure represented by the formula (c 1). Hereinafter, the term "connection" means a bond.
[ chemical formula 4]
Figure BDA0004144317250000091
Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethane-1-imine, N-acetoxy-1- [ 9-ethyl-6- { 2-methyl-4- (3, 3-dimethyl-2, 4-dioxacyclopentylmethoxy) benzoyl } -9H-carbazol-3-yl ] ethane-1-imine, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-one-2-imine and the like. Commercially available products such as Irgacure OXE01, OXE02 (BASF corporation) and N-1919 (ADEKA corporation) can be used.
The alkyl benzene ketone compound is a compound having a partial structure represented by formula (c 2) or a partial structure represented by formula (c 3). In these partial structures, the benzene ring may have a substituent.
[ chemical formula 5]
Figure BDA0004144317250000101
Examples of the compound having a partial structure represented by the formula (c 2) include 2-methyl-2-morpholino-1- (4-methylsulfanyl phenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] butan-1-one, and the like. Commercially available products such as Irgacure369, 907 and 379 (the above are manufactured by BASF corporation) can be used.
Examples of the compound having a partial structure represented by the formula (c 3) include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] propan-1-one, 1-hydroxycyclohexylphenyl ketone, an oligomer of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α -diethoxyacetophenone, and benzyl dimethyl ketal.
Examples of the triazine compound include 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6-piperonyl-1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (5-methylfuran-2-yl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (furan-2-yl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (4-diethylamino-2-methylphenyl) vinyl ] -1,3, 5-triazine, and 2, 4-bis (trichloromethyl) -6- [ 2- (3, 4-dimethoxyphenyl) vinyl ] -1,3, 5-triazine.
Examples of the acylphosphine oxide compound include 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide and bis (2, 4, 6-trimethylbenzoyl) -phenyl phosphine oxide. Commercial products such as Irgacure 819 (registered trademark) manufactured by BASF corporation can be used.
Examples of the phosphonate compound include ethyl (2, 4, 6-trimethylbenzoyl) phenylphosphonate and the like. A commercially available product such as Omnirad TPO-L (manufactured by IGM Resins B.V.) can be used.
Examples of the biimidazole compound include 2,2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenylbiimidazole, 2' -bis (2, 3-dichlorophenyl) -4,4', 5' -tetraphenylbiimidazole, 2' -bis (2-chlorophenyl) -4,4', and 5,5' -tetrakis (alkoxyphenyl) biimidazole, 2' -bis (2-chlorophenyl) -4,4', 5' -tetrakis (dialkoxyphenyl) biimidazole, 2' -bis (2-chlorophenyl) -4,4', 5' -tetrakis (trialkoxyphenyl) biimidazole, biimidazole compounds in which the phenyl group at the 4,4', 5' -position is substituted with a carboalkoxy group (for example, see Japanese patent application laid-open No. 7-10913 and the like), and the like.
Further, as the polymerization initiator (C), there may be mentioned: benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, 3', 4' -tetrakis (t-butylperoxycarbonyl) benzophenone, and 2,4, 6-trimethylbenzophenone; quinone compounds such as 9, 10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone, and the like; 10-butyl-2-chloroacridone, benzil, methyl benzoylformate, titanocene compound, and the like. These are preferably used in combination with a polymerization initiator auxiliary (C1) (particularly an amine) described later.
As the polymerization initiator (C), an acid generator is also included. Examples of the acid generator include onium salts such as 4-hydroxyphenyldimethyl sulfonium p-toluenesulfonate, 4-hydroxyphenyldimethyl sulfonium hexafluoroantimonate, 4-acetoxyphenyl dimethyl sulfonium p-toluenesulfonate, 4-acetoxyphenyl methyl benzyl sulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate and diphenyliodonium hexafluoroantimonate, nitrobenzyl toluenesulfonate and benzoin toluenesulfonate.
The polymerization initiator (C) is preferably a polymerization initiator containing at least 1 selected from the group consisting of an O-acyl oxime compound, an alkyl phenone compound, a triazine compound, an acyl phosphine oxide compound, a phosphonate compound, and a biimidazole compound, and preferably a polymerization initiator containing at least 1 selected from the group consisting of an acyl phosphine oxide compound and a phosphonate compound.
When at least 1 selected from the group consisting of an acylphosphine oxide compound and a phosphonate compound is contained, the total content of the acylphosphine oxide compound and the phosphonate compound in the polymerization initiator (C) is, for example, 50 mass% or more, preferably 70 mass% or more, more preferably 90 mass% or more, and may be 100 mass%.
The content of the polymerization initiator (C) is, for example, 0.1 mass% or more, preferably 1 mass% or more, more preferably 10 mass% or more, for example, 40 mass% or less, preferably 30 mass% or less, more preferably 25 mass% or less, based on 100 parts by mass of the polymerizable compound (B).
Polymerization initiation aid (C1)
The polymerization initiator aid (C1) is a compound used for accelerating the polymerization of a polymerizable compound to be polymerized by a polymerization initiator, or a sensitizer. When the polymerization initiator auxiliary (C1) is contained, it is usually used in combination with the polymerization initiator (C).
Examples of the polymerization initiator aid (C1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.
Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N-dimethyl-p-toluidine, 4 '-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4 '-bis (diethylamino) benzophenone, and 4,4' -bis (ethylmethylamino) benzophenone. Commercial products such as EAB-F (manufactured by Baogu chemical industries, ltd.) can be used.
Examples of the alkoxyanthracene compound include 9, 10-dimethoxy anthracene, 2-ethyl-9, 10-dimethoxy anthracene, 9, 10-diethoxy anthracene, 2-ethyl-9, 10-diethoxy anthracene, 9, 10-dibutoxyanthracene, and 2-ethyl-9, 10-dibutoxyanthracene.
Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.
Examples of the carboxylic acid compound include phenylthioalkyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylthioalkyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylthioalkyl acetic acid, dimethoxyphenylthioalkyl acetic acid, chlorophenyl thioalkyl acetic acid, dichlorophenylthioalkyl acetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, and the like.
When the polymerization initiator aid (C1) is used, the content thereof is, for example, 0.1 mass% or more, preferably 1 mass% or more, more preferably 10 mass% or more, for example, 40 mass% or less, preferably 30 mass% or less, more preferably 25 mass% or less, based on 100 parts by mass of the polymerizable compound (B).
The curable composition may contain a resin (D), a solvent (E), and the like as necessary.
< resin (D) >)
The resin (D) is not particularly limited, but is preferably an alkali-soluble resin. The resin (D) includes the following resins [ K1] to [ K6 ].
Resin [ K1]: a copolymer having a structural unit derived from at least 1 (a) (hereinafter, sometimes referred to as "(a)") selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and a structural unit derived from a monomer (b) (hereinafter, sometimes referred to as "(b)") having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond;
resin [ K2]: a copolymer having a structural unit derived from (a), a structural unit derived from (b), and a structural unit derived from a monomer (c) copolymerizable with (a) (hereinafter, sometimes referred to as "(c)") which is different from (a) and (b);
resin [ K3]: a copolymer having structural units derived from (a) and structural units derived from (c);
resin [ K4]: a copolymer having a structural unit obtained by adding (b) to a structural unit derived from (a) and a structural unit derived from (c);
resin [ K5]: a copolymer having a structural unit obtained by adding (a) to a structural unit derived from (b) and a structural unit derived from (c);
Resin [ K6]: a copolymer comprising a structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a carboxylic anhydride, and a structural unit derived from (c).
Specific examples of (a) include:
unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, ortho-, meta-, and para-vinylbenzoic acid;
unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5, 6-tetrahydrophthalic acid, 1,2,3, 6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1, 4-cyclohexene dicarboxylic acid;
carboxyl group-containing bicyclic unsaturated compounds such as methyl-5-norbornene-2, 3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5, 6-dicarboxyibicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
unsaturated dicarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5, 6-tetrahydrophthalic anhydride, 1,2,3, 6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5, 6-dicarboxyibicyclo [2.2.1] hept-2-ene anhydride;
Unsaturated mono- [ (meth) acryloyloxyalkyl ] esters of polycarboxylic acids having 2 or more members such as mono [ 2- (meth) acryloyloxyethyl ] succinate and mono [ 2- (meth) acryloyloxyethyl ] phthalate;
unsaturated acrylates containing hydroxyl groups and carboxyl groups in the same molecule, such as α - (hydroxymethyl) acrylic acid.
Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and solubility of the obtained resin in an alkaline aqueous solution.
(b) For example, the polymerizable compound is a compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least 1 selected from the group consisting of an ethylene oxide ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. (b) Preferred are monomers having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.
In the present specification, "(meth) acrylic acid" means at least 1 selected from the group consisting of acrylic acid and methacrylic acid. The expression "(meth) acryl" and "(meth) acrylate" have the same meaning.
Examples of (b) include a monomer (b 1) having an oxirane group and an ethylenic unsaturated bond (hereinafter, sometimes referred to as "(b 1)"), a monomer (b 2) having an oxetanyl group and an ethylenic unsaturated bond (hereinafter, sometimes referred to as "(b 2)"), a monomer (b 3) having a tetrahydrofuranyl group and an ethylenic unsaturated bond (hereinafter, sometimes referred to as "(b 3)"), and the like.
Examples of the (b 1) include a monomer (b 1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter, sometimes referred to as "(b 1-1)") and a monomer (b 1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter, sometimes referred to as "(b 1-2)").
Examples of (b 1-1) include glycidyl (meth) acrylate, β -methyl glycidyl (meth) acrylate, β -ethyl glycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α -methyl o-vinylbenzyl glycidyl ether, α -methyl m-vinylbenzyl glycidyl ether, α -methyl p-vinylbenzyl glycidyl ether, 2, 3-bis (glycidoxymethyl) styrene, 2, 4-bis (glycidoxymethyl) styrene, 2, 5-bis (glycidoxymethyl) styrene, 2, 6-bis (glycidoxymethyl) styrene, 2,3, 4-tris (glycidoxymethyl) styrene, 2,3, 5-tris (glycidoxymethyl) styrene, 2,3, 6-tris (glycidoxymethyl) styrene, 3,4, 5-tris (glycidoxymethyl) styrene, 2, 4-tris (glycidoxymethyl) styrene, and the like.
Examples of the (b 1-2) include vinylcyclohexene monoxide, 1, 2-epoxy-4-vinylcyclohexane (for example, celloxide 2000; manufactured by Daicel), 3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, cyclomer A400; manufactured by Daicel), 3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, cyclomer M100; manufactured by Daicel), a compound represented by the formula (I) and a compound represented by the formula (II).
[ chemical formula 6]
Figure BDA0004144317250000151
[ in the formula (I) and the formula (II), R a R is R b Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.
X a X is X b Represents a single bond, O-R c -、＊-R c -O-、＊-R c -S-or O-R c -NH-。
R c Represents an alkanediyl group having 1 to 6 carbon atoms.
And represents a bond to O. ]
Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl and the like.
Examples of the alkyl group having a hydrogen atom substituted with a hydroxyl group include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, and 4-hydroxybutyl group.
As R a R is R b Preferably, the hydrogen atom, methyl group, hydroxymethyl group, 1-hydroxyethyl group, and 2-hydroxyethyl group are exemplified, and more preferably, the hydrogen atom and methyl group are exemplified.
Examples of the alkanediyl group include methylene, ethylene, propane-1, 2-diyl, propane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5-diyl and hexane-1, 6-diyl.
As X a X is X b Preferred examples include single bond, methylene, vinyl, and O-CH 2 -O-and-CH 2 CH 2 O-, more preferably, it may be a single bond or O-CH 2 CH 2 -O- (. Times. Represents a bond to O).
The compound represented by the formula (I) may be a compound represented by any one of the formulas (I-1) to (I-15), or the like. Among them, the compounds represented by the formula (I-1), the formula (I-3), the formula (I-5), the formula (I-7), the formula (I-9) or the formula (I-11) to the formula (I-15) are preferable, and the compounds represented by the formula (I-1), the formula (I-7), the formula (I-9) or the formula (I-15) are more preferable.
[ chemical formula 7]
Figure BDA0004144317250000171
[ chemical formula 8]
Figure BDA0004144317250000172
The compound represented by the formula (II) includes compounds represented by any one of the formulas (II-1) to (II-15), and the like. Among them, the compounds represented by the formula (II-1), the formula (II-3), the formula (II-5), the formula (II-7), the formula (II-9) or the formulas (II-11) to (II-15) are preferable, and the compounds represented by the formula (II-1), the formula (II-7), the formula (II-9) or the formula (II-15) are more preferable.
[ chemical formula 9]
Figure BDA0004144317250000181
[ chemical formula 10]
Figure BDA0004144317250000182
The compound represented by the formula (I) and the compound represented by the formula (II) may be used singly or in combination of 2 or more. When the compound represented by the formula (I) and the compound represented by the formula (II) are used in combination, the ratio of the compounds [ the compound represented by the formula (I) ]: the compound represented by the formula (II) is preferably 5 on a molar basis: 95-95: 5, more preferably 20: 80-80: 20.
as (b 2), monomers having an oxetanyl group and a (meth) acryloyloxy group are more preferable. Examples of (b 2) include 3-methyl-3-methacryloyloxymethyl oxetane, 3-methyl-3-acryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl oxetane, 3-ethyl-3-acryloyloxymethyl oxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, and 3-ethyl-3-acryloyloxyethyl oxetane.
The monomer (b 3) is more preferably a monomer having a tetrahydrofuranyl group and a (meth) acryloyloxy group. Specific examples of (b 3) include tetrahydrofurfuryl acrylate (for example, viscoat v#150, manufactured by osaka organic chemical industry (ltd)), and tetrahydrofurfuryl methacrylate.
The (b) is preferably (b 1) from the viewpoint of further improving the reliability of the obtained cured film such as heat resistance and chemical resistance. Further, from the viewpoint of excellent storage stability of the curable composition, it is more preferable that (b 1-2).
Examples of (c) include:
methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, twelve (meth) acrylateAlkyl esters, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo (meth) acrylate [5.2.1.0 2,6 ]Decane-8-yl ester (which is also known as dicyclohexyl (meth) acrylate ". Additionally, sometimes referred to as tricyclodecyl (meth) acrylate". In this technical field), tricyclo (meth) acrylate [ 5.2.1.0) 2,6 ](meth) acrylic esters such as decen-8-yl ester (which is known as dicyclopentenyl (meth) acrylate ". In this technical field), dicyclopentyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthalene (meth) acrylate, benzyl (meth) acrylate, and the like;
Hydroxy group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate;
bicyclo [2.2.1] hept-2-ene, 5-methylcyclobicyclo [2.2.1] hept-2-ene, 5-ethylcyclo [2.2.1] hept-2-ene, 5-hydroxycyclo [2.2.1] hept-2-ene, 5-hydroxymethylcyclo [2.2.1] hept-2-ene, 5- (2 '-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5, 6-dihydroxybicyclo [2.2.1] hept-2-ene, 5, 6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-di (2' -hydroxyethyl) bicyclo [2.2.1] hept-2-ene 5, 6-dimethoxy-bicyclo [2.2.1] hept-2-ene, 5, 6-diethoxy-bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methyl-bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethyl-bicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methyl-bicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5, 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, bicyclic unsaturated compounds such as 5, 6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene;
Dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, and N- (9-acridinyl) maleimide;
styrene, alpha-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1, 3-butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene, and the like.
Among these, styrene, vinyl toluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable from the viewpoints of copolymerization reactivity and heat resistance.
In the resin [ K1], the ratio of the structural units derived from each of the structural units constituting the resin [ K1] is preferably:
structural units from (a): 2 to 60 mol%
Structural units from (b): 40 to 98 mol%,
More preferably:
structural units from (a): 10 to 50 mol percent
Structural units from (b): 50 to 90 mol%.
When the ratio of the structural units of the resin [ K1] is within the above range, the storage stability of the curable composition, the developability upon forming a pattern, and the solvent resistance of the resulting developed product tend to be excellent.
The resin [ K1] can be produced, for example, by a method described in "experimental method of polymer synthesis" (experimental method of polymer synthesis) (published by Dain Kagaku Kogyo Co., ltd., chemical Co., ltd., 1 st edition, 1 brush 1972, 3 months, 1 st.), and a cited document described in the above document.
Specifically, the following methods are mentioned: the predetermined amounts of (a) and (b), the polymerization initiator, the solvent, and the like are added to a reaction vessel, and oxygen is replaced with nitrogen, for example, to prepare a deoxidized atmosphere, and heating and heat preservation are performed while stirring. The polymerization initiator, solvent, and the like used herein are not particularly limited, and those commonly used in the art can be used. For example, as the polymerization initiator, azo compounds (2, 2 '-azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile) and the like), organic peroxides (benzoyl peroxide and the like) may be mentioned, and as the solvent, the respective monomers may be dissolved, and a solvent (E) of the curable composition, a solvent described later, and the like may be mentioned.
The copolymer obtained may be a solution after the reaction, a concentrated or diluted solution, or a substance extracted as a solid (powder) by a method such as reprecipitation. In particular, by using the solvent (E) contained in the curable composition as the solvent for the polymerization, the solution after the reaction can be directly used for the preparation of the curable composition, and thus the process for producing the curable composition can be simplified.
In the resin [ K2], the ratio of the structural units derived from each of the structural units constituting the resin [ K2] is preferably:
structural units from (a): 2 to 45 mol percent
Structural units from (b): 2 to 95 mol percent
Structural units from (c): 1 to 65 mol%,
more preferably:
structural units from (a): 5 to 40 mol percent
Structural units from (b): 5 to 80 mol%
Structural units from (c): 5 to 60 mol%.
When the ratio of the structural units of the resin [ K2] is within the above-mentioned range, the storage stability of the curable composition, the developability upon pattern formation, and the solvent resistance, heat resistance and mechanical strength of the resulting developed product tend to be excellent.
The resin [ K2] can be produced, for example, in the same manner as described for the production method of the resin [ K1 ].
In the resin [ K3], the ratio of the structural units derived from each of the structural units constituting the resin [ K3] is preferably:
structural units from (a): 2 to 60 mol%
Structural units from (c): 40 to 98 mol%,
more preferably:
structural units from (a): 10 to 50 mol percent
Structural units from (c): 50 to 90 mol%.
The resin [ K3] can be produced, for example, in the same manner as described for the production method of the resin [ K1 ].
The resin [ K4] can be produced by: to obtain a copolymer of (a) and (c), and adding a cyclic ether having 2 to 4 carbon atoms of (b) to a carboxylic acid and/or carboxylic anhydride of (a).
First, copolymers of (a) and (c) are produced in the same manner as described for the production method of the resin [ K1 ]. In this case, the ratio of the structural units derived from each is preferably the same ratio as the ratio exemplified in the resin [ K3 ].
Then, the cyclic ether having 2 to 4 carbon atoms of (b) is reacted with a part of the carboxylic acid and/or carboxylic anhydride derived from (a) in the copolymer.
After the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced with air from nitrogen, and a catalyst for the reaction of (b), carboxylic acid or carboxylic anhydride with cyclic ether (e.g., tris (dimethylaminomethyl) phenol, etc.), a polymerization inhibitor (e.g., hydroquinone, etc.), etc. are added to the flask and reacted at 60 to 130℃for 1 to 10 hours, for example, to produce the resin [ K4].
The amount of (b) used is preferably 5 to 80 moles, more preferably 10 to 75 moles, per 100 moles of (a). By setting in this range, there is a tendency that: the curable composition is excellent in storage stability, developability upon patterning, and balance among solvent resistance, heat resistance, mechanical strength and sensitivity of the resulting developed product. The (b) used in the resin [ K4] is preferably (b 1), more preferably (b 1-1), in view of the high reactivity of the cyclic ether and the difficulty of leaving unreacted (b).
The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor to be used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b) and (c).
The reaction conditions such as the charging method, the reaction temperature and the reaction time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by polymerization, and the like. The charging method and the reaction temperature may be appropriately adjusted in consideration of production equipment, the amount of heat generated by polymerization, and the like, similarly to the polymerization conditions.
As the first stage, the copolymer of (b) and (c) was obtained in the same manner as the above-mentioned method for producing the resin [ K1 ]. As in the above, the copolymer obtained may be used as it is, or may be concentrated or diluted, or may be taken out as a solid (powder) by a method such as reprecipitation.
The ratio of the structural units derived from (b) and (c) relative to the total number of moles of all the structural units constituting the copolymer is preferably:
structural units from (b): 5 to 95 mol percent
Structural units from (c): 5 to 95 mol%,
more preferably:
structural units from (b): 10 to 90 mol%
Structural units from (c): 10 to 90 mol%.
Further, the resin [ K5] can be obtained by reacting the carboxylic acid or carboxylic anhydride of (a) with the cyclic ether of (b) of the copolymer of (b) and (c) under the same conditions as those of the process for producing the resin [ K4 ].
The amount of (a) to be reacted with the copolymer is preferably 5 to 80 moles per 100 moles of (b). The (b) used in the resin [ K5] is preferably (b 1), more preferably (b 1-1), in view of the high reactivity of the cyclic ether and the difficulty of leaving unreacted (b).
The resin [ K6] is a resin obtained by further reacting a carboxylic anhydride with the resin [ K5]. The carboxylic anhydride is reacted with a hydroxyl group (which is generated by the reaction of a cyclic ether with a carboxylic acid or carboxylic anhydride).
Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5, 6-tetrahydrophthalic anhydride, 1,2,3, 6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5, 6-dicarboxyibicyclo [2.2.1] hept-2-ene anhydride. The amount of carboxylic anhydride used is preferably 0.5 to 1 mole relative to 1 mole of (a).
Specific examples of the resin (D) include: 3, 4-epoxycyclohexylmethyl (meth) acrylate/(meth) acrylic acid copolymer, 3, 4-epoxytricyclo [5.2.1.0 2,6 ]Decyl ester/(meth) acrylic acid copolymer and other resins [ K1 ]]The method comprises the steps of carrying out a first treatment on the surface of the Glycidyl (meth) acrylate/(meth) acrylic acid benzyl/(meth) acrylic acid copolymer, glycidyl (meth) acrylate/styrene/(meth) acrylic acid copolymer, acrylic acid 3, 4-epoxytricyclo [5.2.1.0 2,6 ]Decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide copolymer, 3-methyl-3- (meth) acryloyloxymethyl oxetane/(meth) acrylic acid/styrene copolymer and other resins [ K2 ]]The method comprises the steps of carrying out a first treatment on the surface of the Resins [ K3 ] such as benzyl (meth) acrylate/(meth) acrylic acid copolymer and styrene/(meth) acrylic acid copolymer]The method comprises the steps of carrying out a first treatment on the surface of the Resins such as resins obtained by adding glycidyl (meth) acrylate to benzyl (meth) acrylate/(meth) acrylic acid copolymer, resins obtained by adding glycidyl (meth) acrylate to tricyclodecyl (meth) acrylate/styrene/(meth) acrylic acid copolymer, and resins obtained by adding glycidyl (meth) acrylate to tricyclodecyl (meth) acrylate/(meth) acrylic acid benzyl/(meth) acrylic acid copolymer [ K4 ]The method comprises the steps of carrying out a first treatment on the surface of the Resins such as resins obtained by reacting a copolymer of tricyclodecyl (meth) acrylate/(meth) glycidyl acrylate with (meth) acrylic acid, and resins obtained by reacting a copolymer of tricyclodecyl (meth) acrylate/styrene/(meth) glycidyl acrylate with (meth) acrylic acid[K5]The method comprises the steps of carrying out a first treatment on the surface of the Resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate/(meth) glycidyl acrylate with (meth) acrylic acid, and resin obtained by further reacting the resin with tetrahydrophthalic anhydride [ K6 ]]Etc.
Among them, the resin (D) is preferably the resin [ K1] or the resin [ K2], and particularly preferably the resin [ K2].
The weight average molecular weight of the resin (D) in terms of polystyrene is preferably 3,000 ～ 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 30,000. When the molecular weight is within the above range, the hardness of the cured film tends to be high.
The dispersity [ weight average molecular weight (Mw)/number average molecular weight (Mn) ] of the resin (D) is preferably 1.1 to 6, more preferably 1.2 to 4.
The acid value of the resin (D) is preferably 50 to 170mg-KOH/g, more preferably 60 to 150mg-KOH/g, still more preferably 70 to 135mg-KOH/g, in terms of solid content. The acid value is a value measured as the amount (mg) of potassium hydroxide required for neutralizing 1g of the resin (D), and can be obtained by, for example, titration using an aqueous potassium hydroxide solution.
The solid content of the resin (D) in the curable composition is, for example, 500 parts by mass or less, preferably 200 parts by mass or less, more preferably 50 parts by mass or less, still more preferably 30 parts by mass or less, particularly preferably 10 parts by mass or less, and may be 0 parts by mass, based on 100 parts by mass of the polymerizable compound (B).
Solvent (E) >, solvent (E)
The solvent (E) is not particularly limited, and solvents commonly used in the art can be used. For example, the number of the cells to be processed, examples thereof include ester solvents (solvents containing-COO-and not containing-O-in the molecule), ether solvents (solvents containing-O-in the molecule) and a solvent containing no-COO-, an ether ester solvent (a solvent containing-COO-and-O-in the molecule), a ketone solvent (a solvent containing-CO-; and a solvent containing no-COO-, an ether ester solvent (a solvent containing-COO-and-O-in the molecule), a solvent containing a solvent and a solvent containing a solvent and a solvent Ketone solvents (containing-CO-, in the molecule)
Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and gamma-butyrolactone.
Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1, 4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methylethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, and methylanisole.
Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like.
Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, methyl ethyl ketone, 2-heptanone, 3-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, isophorone, and the like.
Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerol.
Examples of the alcohol ketone solvent include dimers of ketones selected from the ketone solvents such as diacetone alcohol.
Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.
Examples of the amide solvent include N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone.
Among the above solvents, from the viewpoint of handleability and drying, an organic solvent having a boiling point of 120 ℃ to 180 ℃ at 1atm is preferable. The solvent is preferably propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, methyl ethyl ketone, butyl acetate, 2-heptanone, diacetone alcohol, or N, N-dimethylformamide, more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate methyl ethyl ketone, or ethyl 3-ethoxypropionate.
When the curable composition contains the solvent (E), the content of the solvent (E) in the curable composition is, for example, 40 mass% or less, preferably 30 mass% or less, more preferably 20 mass% or less, still more preferably 15 mass% or less, particularly preferably 10 mass% or less, most preferably 5 mass% or less, and may be 0 mass% or less. The curable composition of the present invention has high fluidity and excellent handleability even when it contains no solvent.
Surfactant (F) >)
The curable composition may contain a surfactant (F). The surfactant (F) may be used as a leveling agent, and examples thereof include silicone surfactants, fluorine surfactants, and silicone surfactants having fluorine atoms. They may have a polymerizable group in a side chain.
Examples of the silicone surfactant include surfactants having a siloxane bond in the molecule. Examples of the surfactant having a siloxane bond in the molecule include octamethyl cyclotetrasiloxane. The silicone surfactant may be TORAY SILICONE DC PA, TORAY SILICONE SH PA, TORAY SILICONE DC PA, TORAY SILICONE SH PA, TORAY SILICONE SH PA, TORAY SILICONE SH PA, TORAY SILICONE SH PA, TORAY SILICONE SH8400 (trade name: manufactured by Touretcorning Co., ltd.), KF994, KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Xinyue chemical Co., ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Michao Japanese new materials contract Co., ltd.).
The fluorine-based surfactant includes surfactants having a fluorocarbon chain in the molecule. Specifically, there may be mentioned FLOURAD FC430, FLOURAD FC431 (manufactured by Sumitomo 3M (registered trademark)), MEGAFAC F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC F554, MEGAFAC R30, MEGAFAC RS-718-K (manufactured by DIC (registered trademark)), EFTOP EF301, EFTOP EF303, EFTOP EF351, EFTOP EF352 (manufactured by Mitsubishi comprehensive materials), SURFLON S381, SURFLON S382, SURFLON SC101, SURFLON SC105 (manufactured by Succinum (manufactured by Asahi) and E5844 (manufactured by Dain-gold-fine chemical institute).
Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, there are exemplified MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477, MEGAFAC F443 (manufactured by DIC corporation), and the like.
When the surfactant (F) is contained, the content thereof may be, for example, 0.001 mass% or more and 2 mass% or less, or may be 0.001 mass% or more and 1.5 mass% or less, relative to the total amount of the curable composition. The content is preferably 0.001 mass% or more and 0.2 mass% or less, more preferably 0.002 mass% or more and 0.1 mass% or less, and still more preferably 0.005 mass% or more and 0.07 mass% or less.
< other Components >)
The curable composition of the present invention may contain additives known in the art, such as fillers, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, and the like, as needed.
< Properties of curable composition >
The curable composition of the present invention has a viscosity of, for example, 300 mPas or less, preferably 260 mPas or less, and more preferably 210 mPas or less at a temperature of 23 ℃. The viscosity is, for example, 1 mPas or more. When the viscosity is within the above range, clogging of the ink and bending in flight are less likely to occur when coating by the inkjet method. The viscosity can be measured, for example, by optimizing the rotational speed of the rotor (preferably, 1 rpm) using an E-type viscometer.
The curable composition of the present invention is excellent in visible light transmittance. Specifically, the average transmittance of the cured film obtained by the film forming method 1 described below at a wavelength of 400 to 700nm is 90% or more, preferably 93% or more, more preferably 95% or more, per 1.0 μm film thickness. The cured film obtained by the film forming method 1 described below preferably has a total transmittance of 90% or more, more preferably 93% or more, and still more preferably 95% or more per 1.0 μm film thickness in the wavelength range of 400 to 700 nm.
[ film Forming method 1]
The curable composition was applied to a glass substrate so that the average thickness of the cured film was in the range of 1.0.+ -. 0.2. Mu.m, and an LED lamp was used at 2000J/m 2 UV with a wavelength of 385 nm.
When the average thickness of the obtained cured film was 1.0 μm, the transmittance T (film thickness was 1.0 μm) was directly set to the transmittance per 1.0 μm film thickness, and when the average thickness of the obtained cured film was x μm (x was a value within the range of 1.0±0.2 and was not 1.0), the transmittance was based on a' = -log 10 T ', the transmittance T ' (at a film thickness of x μm) is converted into absorbance A ' (at a film thickness of x μm), the absorbance A ' (at a film thickness of x μm) is obtained by multiplying the reciprocal of the film thickness of x (μm) by the absorbance A ' (at a film thickness of x μm), and then the absorbance A (at a film thickness of 1.0 μm) is obtained based on A= -log 10 T the transmittance T (at a film thickness of 1.0 μm) was calculated, and the transmittance T per film thickness of 1.0 μm was obtained. Then, the average value of the wavelengths in the range of 400 to 700nm was calculated for the transmittance per 1.0 μm film thickness.
The cured film obtained from the curable composition of the present invention has a high refractive index. Specifically, the refractive index of the cured film obtained by the film forming method 2 described below, measured by a spectroscopic ellipsometer, at a wavelength of 550nm is, for example, 1.5 or more, preferably 1.6 or more, more preferably 1.65 or more, for example, 3.0 or less, preferably 2.5 or less, more preferably 2.0 or less.
[ film Forming method 2]
The obtained curable composition was applied to a 4-inch Si wafer substrate using a spin coater so that the average film thickness of the cured film became 0.5 μm. Using LED lamps at 2000J/m 2 UV with a wavelength of 385 nm.
< cured film >)
The curable composition may be applied to a substrate by spin coating, casting, micro gravure coating, bar coating, roll coating, bar coating, dip coating, spray coating, screen printing, flexographic printing, offset printing, ink jet printing, capillary coating, nozzle coating, or the like, and irradiated with radiation such as UV to produce a cured film. In addition, a patterned cured film (i.e., a cured film formed only on a part of the substrate) may be produced by photolithography, inkjet printing, or the like.
The thickness of the cured film is usually about 1nm to 50. Mu.m, preferably 1 μm to 50. Mu.m.
The cured film can be used as a microlens, a sealing material, or the like, and is particularly preferably used as a microlens, a sealing material, or the like of a light-emitting element.
Examples
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples at all, and it is needless to say that the present invention can be implemented with appropriate modifications within the scope of the gist of the present invention described above and below, and these modifications are included in the technical scope of the present invention.
Example 1
[ production of inorganic microparticle Dispersion ]
To a zirconium oxide dispersion (zirconium oxide/dispersant/methyl ethyl ketone=55/15/30, mass ratio, volume average particle diameter of zirconium oxide, 10 nm), glycerol triacrylate (MT 3547, manufactured by east asia synthesis (ltd)) as a polymerizable compound was added, and the methyl ethyl ketone was removed by distillation under reduced pressure, to obtain a glycerol triacrylate dispersion of zirconium oxide particles (hereinafter referred to as an inorganic fine particle dispersion). The residual amount of methyl ethyl ketone was confirmed by Gas Chromatography (GC) analysis.
[ preparation of curable composition ]
The component ratio of the inorganic fine particle dispersion was adjusted so that 37 parts by mass of zirconia particles, 9 parts by mass of a dispersant and 46 parts by mass of glycerol triacrylate were mixed, and 8 parts by mass of ethyl (2, 4, 6-trimethylbenzoyl) phenylphosphonate (Omnirad TPO-L, manufactured by IGM Resins b.v. company, hereinafter referred to as TPO-L) was dissolved, and then filtered through a membrane filter made of Polytetrafluoroethylene (PTFE) to obtain a curable composition 1.
Example 2
An inorganic fine particle dispersion was produced in the same manner as in example 1.
The composition ratio of the inorganic fine particle dispersion was adjusted so that 37 parts by mass of zirconia particles, 9 parts by mass of a dispersant, and 45 parts by mass of glycerol triacrylate were mixed, and 8 parts by mass of bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide (IRGACURE (registered trademark) 819, manufactured by basf corporation, hereinafter referred to as IRG 819) and 1 part by mass of octamethyl cyclotetrasiloxane (manufactured by tokyo chemical industry co., ltd.) as a surfactant were further blended, dissolved, and then filtered through a membrane filter made of Polytetrafluoroethylene (PTFE), to obtain a curable composition 2.
Example 3
An inorganic fine particle dispersion was produced in the same manner as in example 1.
The component ratio of the inorganic fine particle dispersion was adjusted so that 33 parts by mass of zirconia particles, 8 parts by mass of dispersant, 41 parts by mass of glycerol triacrylate, and 10 parts by mass of tricyclodecane dimethanol diacrylate (a-DCP, manufactured by new middle-aged chemical industries, co., hereinafter sometimes referred to as a-DCP) were mixed with 8 parts by mass of IRG819 as a polymerization initiator, dissolved, and filtered through a membrane filter made of Polytetrafluoroethylene (PTFE), to obtain a curable composition 3.
Comparative example 1
Comparative curable composition 1 was obtained in the same manner as in example 1 except that tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Xinzhou chemical Co., ltd.), 1, 10-decane diol diacrylate (A-DOD-N, manufactured by Xinzhou chemical Co., ltd.), and a mixture of isobutyl methacrylate (manufactured by Tokyo chemical Co., ltd.) were used as the polymerizable compound instead of glycerol triacrylate, octamethyl cyclotetrasiloxane (manufactured by Tokyo chemical Co., ltd.) was used as the surfactant, and that 5 parts by mass of IRG819 was used as the polymerization initiator instead of 8 parts by mass of TPO-L.
Comparative curable composition 1 contained 37 parts by mass of zirconia particles, 9 parts by mass of a dispersant, 24 parts by mass of a-DCP, 14 parts by mass of a-DOD-N, 10 parts by mass of isobutyl methacrylate, 5 parts by mass of IRG819, 1 part by mass of octamethyl cyclotetrasiloxane.
[ evaluation of curable composition ]
The viscosity of the obtained curable composition at a temperature of 23℃was measured using an E-type viscometer under the condition that the rotation speed of a rotor was 1 rpm.
[ production of cured film and evaluation 1 and 2]
The obtained curable composition was applied to a 2-inch square glass substrate (EAGLE XG; manufactured by Corning) using a spin coater so that the average thickness of the cured film became 10 μm. Next, using an LED lamp, a wavelength of 385nm and an accumulated light quantity of 2000J/m were carried out 2 UV irradiation of (c) to obtain a cured film.
The following evaluations were performed on the obtained cured film and curable composition. The evaluation results are shown in Table 1.
1. Curability (tackiness)
When an ethylene glove with an embossed surface was put on, the cured film surface was lightly touched, and the cured film was marked with "o" when no trace of the glove was left, and "x" when no trace of the glove was left.
2. Coatability of coating
The thickness of the cured film at 2 was measured, and the difference between the film thicknesses at 2 was defined as "o" when the difference was within 5% of the average value of the film thicknesses at 2, and as "x" when the difference was greater than 5%.
[ production of cured film and evaluation 3]
3. Transmittance of light
The obtained curable composition was applied to a 2-inch square glass substrate using a spin coater so that the average thickness of the cured film became 1.0 μm. Next, using an LED lamp, a wavelength of 385nm and an accumulated light quantity of 2000J/m were carried out 2 UV irradiation of (c) to obtain a cured film. The transmittance of the cured film was measured using a micro-spectrophotometer at 400nm to 700nm, and the average transmittance was taken as the transmittance of the cured film.
[ production of cured film and evaluation 4]
4. Refractive index
The curable composition was applied to a 4-inch Si wafer substrate using a spin coater so that the average film thickness of the cured film became 0.5 μm. Next, an LED lamp was used at 2000J/m 2 UV with a wavelength of 385 nm. The refractive index of the cured film was obtained by irradiating the cured product with light having a wavelength in the range of 400nm to 1600nm at angles of 60 °, 70 °, 75 ° using a spectroscopic ellipsometer, and the refractive index was obtained as the refractive index of the cured film.
The results are shown in Table 1.
TABLE 1
Figure BDA0004144317250000331
a-1: zirconia nanoparticles
b-1: glycerol triacrylate
b-2：A-DCP
b-3：A-DOD-N
b-4: isobutyl methacrylate
c-1：TPO-L
c-2：IRG819
e-1: methyl ethyl ketone
f-1: octamethyl cyclotetrasiloxane

Claims (3)

1. A curable composition comprising inorganic fine particles (A), a polymerizable compound (B) and a polymerization initiator (C),
the polymerizable compound (B) contains a compound represented by the formula (B1),
[ chemical formula 1]
Figure FDA0004144317240000011
In the formula (B1), R 1 R is R 2 Each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a substituent; r is R 3 Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a (meth) acrylic group, wherein the alkyl group having 1 to 20 carbon atoms, the alkenyl group having 2 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, and the (meth) acrylic group may have a substituent,
the average transmittance of 400 to 700nm at the film formation under the following conditions is 90% or more per 1.0 μm film thickness,
[ film Forming conditions ]
The curable composition was applied to a glass substrate so that the average thickness of the cured film was within the range of 1.0.+ -. 0.2. Mu.m, and an LED lamp was used at 2000J/m 2 UV with a wavelength of 385 nm.
2. The curable composition according to claim 1, wherein the inorganic fine particles (A) are contained in the curable composition in an amount of 10% by mass or more.
3. A cured film formed from the curable composition according to claim 1 or 2.
CN202180065817.5A 2020-10-29 2021-10-20 Curable composition Pending CN116323685A (en)

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