WO2007010865A1 - Curable composition, cured film and multilayer body - Google Patents

Curable composition, cured film and multilayer body Download PDF

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Publication number
WO2007010865A1
WO2007010865A1 PCT/JP2006/314087 JP2006314087W WO2007010865A1 WO 2007010865 A1 WO2007010865 A1 WO 2007010865A1 JP 2006314087 W JP2006314087 W JP 2006314087W WO 2007010865 A1 WO2007010865 A1 WO 2007010865A1
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WO
WIPO (PCT)
Prior art keywords
compound
meth
cured film
curable composition
group
Prior art date
Application number
PCT/JP2006/314087
Other languages
French (fr)
Japanese (ja)
Inventor
Jun Kaneda
Hayato Takahashi
Shinsuke Tsurutani
Kazunori Shigemori
Hiroshi Tominaga
Original Assignee
Toyo Ink Mfg. Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyo Ink Mfg. Co., Ltd. filed Critical Toyo Ink Mfg. Co., Ltd.
Priority to KR1020087003658A priority Critical patent/KR101276736B1/en
Priority to JP2007525998A priority patent/JP4924425B2/en
Priority to CN2006800259024A priority patent/CN101223198B/en
Publication of WO2007010865A1 publication Critical patent/WO2007010865A1/en

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Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter

Definitions

  • the present invention relates to a curable composition having hard coat properties, a cured film using the same, and a laminate thereof.
  • Patent Document 1 discloses a method of preparing a conductive paint by mixing conductive powder such as tin oxide and a plurality of monomer components in an organic solvent using a ball mill or the like.
  • Patent Document 2 discloses a method of preparing a dispersion for conductive paint by mixing antimony-doped tin oxide and an ultraviolet curable silane coupling agent in an organic solvent using a ball mill.
  • Patent Document 3 discloses a method for producing a conductive coating material by dispersing a conductive oxide fine powder in a mixed solvent of an easily dispersible low boiling solvent and a hardly dispersible high boiling solvent.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 04-172634
  • Patent Document 2 Japanese Patent Laid-Open No. 06-2644009
  • Patent Document 3 JP 2001-131485 A
  • the present invention has excellent physical properties in all of high refractive index property, antistatic property, hard coat property, transparency and light resistance while containing a metal oxide having an average primary particle size of lOOnm or less. It is an object of the present invention to provide a curable composition that can form a coating film and is stable over time, a cured film using the same, and a laminate thereof.
  • the present invention provides a metal oxide having an average primary particle size of 5 to: LOOnm,
  • the ethylenically unsaturated double bond of the amino group-containing photocurable compound is preferably derived from an acrylate or metatalylate group. Further, the amino group-containing photocurable compound reacts with an atorato toy compound or a metatarate compound having a pencil hardness after photocuring of H or more and a primary or secondary amine. It is preferable that it is a compound formed.
  • Another aspect of the present invention relates to a cured film obtained by curing the above curable composition.
  • Another aspect of the present invention relates to a laminate including a base material and the cured film.
  • Another aspect of the present invention relates to an optical semiconductor element sealing material containing the curable composition.
  • Yet another aspect of the invention relates to a method for producing a cured film, comprising: applying the curable composition to a substrate; and irradiating an active energy line to cure the curable composition.
  • the curable composition of the present invention comprises a functional group obtained by reacting an ethylenically unsaturated double bond with a primary amine or a secondary amine, and an unreacted ethylenically unsaturated double bond. Since it contains an amino group-containing photocurable compound and functions well as a dispersant, the dispersibility of a metal oxide having an average primary particle diameter of 5 to LOONm can be enhanced. As a result, the curable composition of the present invention is excellent in curability, antistatic property, hard coat property, transparent property. It is possible to form a cured film excellent in lightness, light resistance and high refractive index and a laminate thereof. Therefore, it can be suitably used particularly for plastic optical parts, optical disks, antireflection films, touch panels, film-type liquid crystal elements, and can also be suitably used as a hard coating agent for various plastic laminates.
  • This curable composition can form a cured film having a high refractive index, and when this is applied to a base material having the same refractive index, the resulting laminate does not produce reflection interference fringes, and is used for optical applications. Is preferably used. Furthermore, since the refractive index of the cured product containing a metal oxide can be controlled to be high, it is also suitable as an optical semiconductor element sealing material.
  • This curable composition has a functional group obtained by reacting at least an average primary particle diameter of 5 to: a metal oxide of LOOnm, an ethylenically unsaturated double bond, and a primary or secondary amine. And an amino group-containing photocurable compound having an unreacted ethylenically unsaturated double bond, and containing two or more kinds of metal acid compounds and two or more kinds of amino groups containing photocurable. Each compound may be included.
  • the metal oxide is a metal oxide having an average primary particle size of 5 to: LOOnm.
  • the average primary particle diameter of the metal oxide can be measured by directly observing the particles themselves using, for example, a transmission electron microscope (TEM) or a scanning electron microscope (SEM).
  • the metal oxide is preferably one containing at least one element selected from the group force of titanium, zinc, zirconium, antimony, indium, tin, aluminum, and silicon power.
  • those containing any one element of antimony, indium, tin and zinc are more preferable because of their good conductivity.
  • antimony pentoxide titanium oxide, zinc oxide, zirconium oxide, silicon oxide, antimony-doped tin oxide (ATO), tin-doped indium oxide (ITO), fluorine Elementally doped tin oxide (FTO), phosphorus doped tin oxide (PTO), zinc antimonate (AZO), indium doped oxide and zinc (IZO), tin oxide, ATO coated oxide and titanium oxide, aluminum doped zinc oxide, gallium Examples include doped acid zinc. Two or more of these metal oxides can be used in combination.
  • TL-20 ATO
  • TL-30 ATO
  • TL-30S PTO
  • T L-120 ITO
  • TL 130 ITO
  • PazetCK aluminum-doped zinc oxide
  • PazetGK gallium-doped zinc oxide
  • the amino group-containing photocurable compound functions as a dispersant for the above metal oxide compound, and comprises an ethylenically unsaturated double bond and a primary or secondary amine. It contains a reacted functional group (amino group) and an unreacted ethylenically unsaturated double bond.
  • the ethylenically unsaturated double bond of the amino group-containing photocurable compound is preferably derived from an acrylate or metatalylate group.
  • the “primary amine or secondary amine” is a concept that includes or includes both the primary amine and the secondary amine.
  • “atallylate group or metatalylate group” is a concept that includes or includes the use of both an acrylate group and a metatalylate group.
  • the attalate and the metatarrate may be collectively referred to as “(meth) arylate”.
  • this amino group-containing photocurable compound comprises an attalitoy toy compound or a methacrylate compound having a pencil hardness after photocuring of H or more, and a primary or secondary amine.
  • a compound obtained by reaction is preferable.
  • This (meta) ata relay toy compound is It is more preferable that the pencil hardness is 2H or more, and it is more preferable that the pencil hardness is 3H or more.
  • the pencil hardness is based on JIS-K5600 (base material: easy-adhesive PET film with a thickness of 100 m, load: 500 g), and the concentration of the pencil that does not damage the cured film with a film thickness of 10 / zm. The symbol.
  • the pencil hardness after photocuring is less than H.
  • a (meth) acrylate compound and an amino group-containing photocurable compound obtained by reacting a primary or secondary amine are contained, a metal Since there is no major problem with the dispersibility of oxides, the transparency of the cured film after photocuring is good, but it may cause problems with hard coat properties, and it can be used for hard coat applications. However, it may cause problems.
  • talato toy compounds include polyfunctional attalylate compounds containing three or more attalyloyl groups, or three or more methacryloyl groups.
  • the polyfunctional methacrylate compound contained is preferred because of good photocurability.
  • dipentaerythritol hexaatalylate dipentaerythritol is a monomer.
  • examples include ruhydroxypentaacrylate and dipentaerythritol tetraacrylate (PETTA).
  • PETTA dipentaerythritol tetraacrylate
  • examples of the oligomer or polymer include a polyester (meth) atelate compound, an epoxy (meth) talate toy compound, and a urethane (meth) ate tale toy compound.
  • a compound having a molecular weight of 1000 to 20000 it is preferable to use a compound having a molecular weight of 1000 to 20000.
  • a polyester acrylate compound having a molecular weight of 1000 to 20000, an epoxy atelar toy compound, Or urethane ata relay toy compound is more preferable.
  • a commercially available compound can be used as a (meth) talate toy compound in which the pencil hardness of the cured film after photocuring is H or higher.
  • Specific examples include the following products. Toa Gosei Co., Ltd .: Alonix M-400, Aguchi-X M-402, Aguchi-X M-408, Aguchi-X M-450, Aguchi-X M-7100, Aronix M-8030, ⁇ ⁇ -tuss M—8060, Osaka Organic Chemical Industry Co., Ltd .: Biscote # 400,
  • NK Ester A-TMMT NK Oligo EA-1020
  • NK Origo EMA-1020 NK ⁇ -y ⁇ EA-6310
  • NK-year-old Rigo MA 6, NK-year-old Rigo U—4HA, NK-year-old Rigo U—6HA, NK-year-old Rigo U—32 4A,
  • Purple light UV—7600B Purple light UV—7610B, Purple light UV—7 620EA, Purple light UV—7630B, Purple light UV—1400B, Purple light UV—1700B, Purple light UV—6 300B,
  • KAYARAD DPHA Nippon Kayaku Co., Ltd .: KAYARAD DPHA, KAYARAD DPHA—40H, KAYA RAD D—310, KAYARAD D—330.
  • examples of the (meth) attareito toy compound in which the pencil hardness of the cured film after photocuring is H or more include a compound represented by the following general formula (1).
  • I ⁇ to R 4 each independently represents a hydrogen atom or a methyl group
  • R 5 to R 8 each independently represents an unsubstituted or substituted linear or branched alkylene group.
  • R 9 represents a tetravalent aliphatic group or an aromatic group.
  • examples of the tetravalent aliphatic skeleton of R 9 include a tetravalent aliphatic group that is an alkyl skeleton having a carbon chain number of 4 to LO, specifically a butane skeleton, a cyclobutane skeleton, and a hexane skeleton. , Cyclohexane skeleton, decalin skeleton and the like.
  • tetravalent aromatic group of R 9 specifically, a phenyl skeleton, a benzophenone skeleton, a biphenyl skeleton, a phenol skeleton, a diphenylsulfone skeleton, a diphenylsulfide skeleton.
  • Examples include perylene skeleton, fluorene skeleton, tetrahydronaphthalene skeleton and naphthalene skeleton.
  • the (meth) acrylate compound represented by the general formula (1) includes, for example, an aliphatic skeleton or an aromatic skeleton, and a compound (xl) having two or more carboxylic anhydride groups, and a carboxylic acid
  • a compound (X) having a carboxyl group obtained by reacting a compound (x2) having a functional group capable of reacting with an anhydrous group is reacted with a compound (Y) having a functional group capable of reacting with a carboxyl group. Obtained.
  • examples of the “functional group capable of reacting with a carboxylic acid anhydride group” in the compound (x2) include a hydroxyl group, an amino group, a glycidyl group, and the like. Is particularly preferred.
  • examples of the “functional group capable of reacting with a carboxyl group” in the compound (Y) include an epoxy group, an oxazoline group, a hydroxy group, an amino group, a carpoimide group, an isocyanate group, an isothiocyanate group, and a vinyl ether group.
  • Examples of the aliphatic tetracarboxylic dianhydride represented by the general formula (2) include butanetetracarboxylic dianhydride.
  • aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride having a biphenyl skeleton, and oxydiphthalic dianhydride.
  • Fluorene skeletons such as diphenylsulfone tetracarboxylic dianhydride, diphenylsulfide tetracarboxylic dianhydride, perylenetetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride having naphthalene skeleton 9,9-bis (3,4-dicarboxyphenol) fluorene dianhydride or having 9,9-bis [4- (3,4-dicarboxyphenoxy) phenol] fluorene dianhydride Tetrahydronaphthalene carboxylic dianhydride having a tetrahydronaphthalene skeleton, ethylene glycolenobis (anhydrotrimellitate), Examples include reserine bis (anhydrotrimellitate) monoacetate. Commercially available products include “Ricacid TMT A—C”, “Ricacid MTA-10”, “Ricacid MTA-15”, “Ricacid TM
  • biphenyl tetracarboxylic dianhydride has a biphenyl skeleton, and the biphenyl skeleton is efficiently introduced into the molecule of the compound represented by the formula (1). It is particularly preferred because it can have both hard coat properties of the cured film and good dispersibility of the metal oxide.
  • the first and second hydroxyl group-containing (meth) ataretoy compound may be the same or different! /! /.
  • examples of such hydroxyl group-containing (meth) atalytoi compounds and salts 4-hydroxybutyl (meth) atarylate, 2-hydroxybutyl (meth) atalylate, 2-hydroxy-3-phenoxypropyl (Meth) Atalylate, 2-Atalyloylochetiru 2-Hydroxyethyl phthalic acid, Glycerol mono (meth) atarylate, 2-Hydroxy —3-Ataliloyloxypropyl (meth) Atalylate, Dihydroxy Atari Rate, Glycerol (Meth) Atalylate, Isocyanuric Acid EO-modified Diatalylate, Pentaerythritol Mono (Meth) Atylate, Dipentaerythritol Mono (Meth) Atylate, Pentaerythri
  • pentaerythritol tri (meth) acrylate dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. are preferred. .
  • Specific commercial products include Biscoat # 300 (Osaka Organic Chemical Co., Ltd.), KA YARAD PET30 (Nippon Kayaku Co., Ltd.), PETIA (Daicel UCB Co., Ltd.), Aronix M305 (Toagosei) Co., Ltd.), NK Ester A— TMM— 3LMN (Shin Nakamura Chemical Co., Ltd.), Light Atarilate PE— 3A (Kyoeisha Co., Ltd.), SR—444 (Cartoma Co., Ltd.), Light Examples include Atarilate DPE-6A (manufactured by Kyoeisha Co., Ltd.), KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), and Aronix M402 (manufactured by Toagosei Co., Ltd.).
  • KAYARAD PET30 (manufactured by Nippon Kayaku Co., Ltd.) mainly composed of pentaerythritol tri (meth) acrylate is more preferable because of good dispersibility of the metal oxide.
  • polyfunctional (meth) ataretoy compound an amino group-containing photocurable compound obtained by containing about 5 to 15% of polyfunctional (meth) atalylate having two hydroxyl groups as accessory components This is preferable because the weight average molecular weight after curing tends to be high, and the dispersibility of the metal oxide is also improved.
  • the reaction between the aliphatic or aromatic tetracarboxylic dianhydride and the first and second hydroxyl group-containing (meth) acrylate compounds is carried out by reaction of an aliphatic or aromatic tetracarboxylic dianhydride.
  • This is a reaction between the two carboxylic anhydride groups possessed by the hydroxyl groups possessed by the first and second hydroxyl group-containing (meth) acrylate compounds, and is well known in the art.
  • an aromatic tetracarboxylic dianhydride and a first and second hydroxyl group-containing (meth) atalytoi compound are mixed in an organic solvent such as cyclohexanone with 1,8-diazabicyclo [5. 4.
  • the reaction can be carried out at a temperature of 50 to 120 ° C in the presence of a catalyst such as 0] -7-undecene.
  • a polymerization inhibitor such as methoquinone can be added to the reaction system.
  • the compound represented by the general formula (1) can be obtained by adding an epoxy group-containing compound which is: (in this case, R 7 and R 8 are —CH 2 CH 2 (OH) 2 CH— groups ;).
  • Examples of the compound represented by the formula (6) include epoxy group-containing (meth) acrylate, such as glycidyl methacrylate and glycidyl acrylate; o-phenol phenol glycidyl ether, p-phenol Flavors such as phenol glycidyl ether, monostyrenated phenol glycidyl ether, 4-ciano 4-hydroxybiphenol glycidyl ether, 4, 4'-biphenol monoglycidyl ether, 4, 4'-biphenol diglycidyl ether Group glycidyl ether compounds and the like.
  • epoxy group-containing (meth) acrylate such as glycidyl methacrylate and glycidyl acrylate
  • o-phenol phenol glycidyl ether p-phenol Flavors such as phenol glycidyl ether, monostyrenated phenol glycidyl ether, 4-ciano 4-hydroxybi
  • the reaction between the compound represented by formula (5) and the compound represented by formula (6) is carried out by reacting the carboxyl group possessed by the compound represented by formula (5) with the epoxy group possessed by the compound represented by formula (6). It is well known in the art. For example, this reaction can be carried out at a temperature of 50 to 120 ° C. in the presence of an amine catalyst such as dimethylbenzylamine.
  • These reactions may be carried out without solvent or in a solvent inert to the reaction.
  • powerful solvents include hydrocarbon solvents such as n-hexane, benzene, and toluene; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate.
  • Solvents such as jetyl, tetrahydrofuran, dioxane, etc .; halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, or parkrene; acetonitrile, N, N-dimethylformamide, N, N Dimethylacetamide, N, N— Examples include polar solvents such as dimethylimidazolidinone. These solvents may be used in combination of two or more.
  • the primary or secondary amine constituting the amino group-containing photocurable compound is an amine compound having at least one primary amino group or secondary amino group in one molecule, An aliphatic amine having low rigidity is more preferable. Furthermore, when an amine compound having two or more primary or secondary amino groups in the molecule is used, a plurality of talaritoy compounds or methacrylate compounds are complex per molecule of the amine compound.
  • the reaction product has a high molecular weight and has a gely problem. Therefore, it is possible to reduce the amount of amine compound added to the (meth) atalytoi compound, or to control the reaction conditions, etc., so that the versatile amino group-containing photocuring compound can be used. I prefer to get things.
  • the amine compound may have a polar functional group other than the amino group that does not react with the (meth) acrylate compound.
  • a polar functional group include a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a cyano group, and a nitroxyl group.
  • monoamines include aminomethane, aminoethane, 1-aminopropane, 2-aminopropane, 1-aminobutane, 2-aminobutane, 1-aminopentane, 2-aminopentane, 3 Amaminopentane, Isoamylamine, 1-Aminohexane, 1-Aminoheptane, 2-Aminoheptane, 2-Otatinoleamine, 1-Aminononane, 1-Aminodecane, 1-Aminododecane, 1-Aminotridecane, 1-Aminohexadecane, Stearinoreamine, aminocyclopropane, aminocyclobutane, aminocyclopentane, aminocyclohexane, aminocyclododecane, 1-amino-2-ethylhexyl, 1-amino-2-methylpropane, 2-
  • monoamines include dimethylamine, jetylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine.
  • examples of amine compounds having a plurality of amino groups in the molecule include 3-aminopyrrolidine, dimethyl Aminoethylamine, Ethylaminoethylamine, Jetylaminoethylamine, N, N Diisopropylaminoethylamine, 1,2-Diaminopropane, 1,3 Diaminopropane, Methylaminopropylamine, Dimethylamino Propylamine, Jetylaminopropylpyramine, Dibutylaminopropylamine, 2-Hydroxyethylaminopropylamine, Bis (3-aminopropyl) ether, Dimethylaminoethoxypropylamine, 1,2-bis (3-amino Propoxy) ethane, 1,3 bis (3-aminopropoxy) -2,2 dimethylpropane, 1 , 2 Diaminobutane,
  • the amine compounds shown above may be used alone or in combination of two or more.
  • an aliphatic monoamine having only a secondary amino group is preferable because the dispersibility of the metal oxide is good, the Michael addition reaction is completed in one step, and coloring due to the reaction is small.
  • Aliphatic monoamines having only secondary amino groups include dimethylamine, jetylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine, di-n-propylamine, di-n- Butyramine, Disec Butyramine, N-ethyl-1,2 Dimethylpropylamine, Piperidine, 2-Pipecoline, 3-Pipecoline, 4-Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, Examples include 2-methylaminoethanol, 3-methylamino-1,2-propanediol, 1-piperazine ethanol, 3-piperidinemethanol, 2-piperidineethanol, 4-piperidineethanol, 4-piperidinol, pyrrolidine, 3-aminopyrrolidine, and 3-pyrrolidinol.
  • dimethylamine, jetylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine, di-n-pylamine, di-n-ptyramine are metal oxide dispersions. From the viewpoint of better properties and dispersion stability.
  • the (meth) atareto toy compound and the primary or secondary ammine having a pencil hardness after photocuring of not less than H are an ethylenic defect in the (meth) atareto toy compound. 100 double saturated bonds It is preferable to react with the base at a ratio of primary or secondary amine of 0.5 to 50 mol, more preferably 1.0 to 30 mol.
  • amino groups that is, ethylenically unsaturated double bonds and primary or A functional group reacted with a secondary amine
  • amino groups that is, ethylenically unsaturated double bonds and primary or A functional group reacted with a secondary amine
  • 50 to 95.5 moles more preferably 70 to 99 moles
  • reaction ratio of primary or secondary amine When the reaction ratio of primary or secondary amine is less than 0.5 mol, the ratio of amino groups in the resulting amino group-containing photocurable compound is small, so that the metal acid compound is good. Therefore, the dispersibility of the cured film becomes low, and the transparency of the cured film tends to deteriorate.
  • reaction ratio exceeds 50 mol, the ratio of amino groups in the resulting amino group-containing photocurable composite is very large, so that good metal oxide dispersibility can be obtained. Since the ratio of ethylenically unsaturated double bonds is low, the photocurability at the time of preparing the coating film becomes poor, and the hard coat property of the cured film tends to deteriorate.
  • the amino group-containing photocurable compound is obtained by reacting the (meth) acrylate compound and the primary or secondary amine in a solvent in which two components can be dissolved. It is This introduces an amino group at the end of the molecule by Michael addition of the amino group in the primary or secondary amine to the ethylenically unsaturated double bond in the (meth) atalytoi compound. It is a reaction.
  • reaction temperature 10 to 110 ° C is preferable, and 20 to 80 ° C is more preferable because the reaction proceeds promptly even at room temperature.
  • the reaction temperature is less than 10 ° C, the solubility of the raw material (meth) acrylate compound or the reaction product amino group-containing photo-curing compound decreases, and the reaction rate decreases immediately and the reaction time decreases. The problem is likely to occur such as a drop in productivity due to the longer time required.
  • the reaction temperature exceeds 110 ° C, the reaction product is colored. Therefore, the curable composition using the colored amino group-containing photocurable compound and the color of the cured film are affected. It will be.
  • the solvent used in the reaction of the (meth) ataretoy compound with the primary or secondary amine is a raw material of the (meth) ateretoy compound and primary or There is no particular limitation as long as it does not have reactivity with the secondary amine.
  • solvents examples include cyclohexanone, methyl isobutyl ketone, methyl ethyl ketone, acetone, toluene, xylene, butanol, isopropanol, propylene glycol monomonomethylolate, dimethyl adipate, dimethyl succinate, and dimethyl glutarate. It is done. Of these, a plurality of solvents may be used in combination.
  • the addition amount of the metal oxide in the curable composition is not particularly limited! However, it is preferable in 100 parts by weight of the total solid content of the metal oxide and the amino group-containing photocurable compound. Is 1 to 80 parts by weight, more preferably 10 to 70 parts by weight. If the addition amount of the metal oxide is less than 1 part by weight, the antistatic property derived from the metal oxide may be inferior, and if it exceeds 80 parts by weight, the film forming property may be inferior due to the small amount of the organic component. is there.
  • the curable composition includes, for example, as described above, a (meth) atalytoy compound and a primary or secondary ammine, and ethylene in the (meth) atalytoy compound. Reacting at 100 to 50 mol of primary or secondary amine with respect to 100 mol of the unsaturated double bond to produce an amino group-containing photocurable compound; and The amino group-containing photocurable compound and an average primary particle size of 5 to: a metal oxide having LOOnm can be mixed.
  • the curable composition of the present invention is prepared by simply mixing the metal oxide powder and the amino group-containing photocurable compound, the intended effect can be obtained sufficiently.
  • mechanically mixed with a kneader, roll, attritor, super mill, dry pulverizer, etc., or a solution containing an amino group-containing photocurable compound is added to a suspension system using a metal oxide powder and an organic solvent. If a close mixing system such as deposition of an amino group-containing photocurable compound on the surface of the metal oxide is performed, even better results can be obtained.
  • a paint conditioner (red devil) is used for dispersing or dissolving a metal oxide, an amino group-containing photocurable compound or curable composition in a non-aqueous vehicle such as an organic solvent, and mixing thereof.
  • Ball mill sand mill (such as “Dyno mill” manufactured by Shinmaru Enterprises), attritor, pearl mill (such as “DCP mill” manufactured by Eiritsuhi), coball mill, homomixer, homogenizer (“EM Technique”) CLEAMIX ”, etc.), wet jet mills (Genus PY, Genas PY, Nanomizer I, Nanomizer 1), microbead mills (Superapec Mill, Kotobuki Co., Ltd., Ultraapec Mill) Etc.) A disperser can be used.
  • disperser When using media in the disperser, it is preferable to use glass beads, zirco beads, alumina beads, magnetic beads, styrene beads, or the like. Regarding dispersion, two or more types of dispersers or two or more types of media of different sizes may be used and used in stages.
  • the curable composition of the present invention contains at least a metal oxide and an amino group-containing photocurable compound, and further, a solvent and various additives may impair the purpose and effect of the present invention. It can be included in a range that is not.
  • solvents, photopolymerization initiators, photocurable compounds, polymerization inhibitors, photosensitizers, leveling agents, surfactants, antibacterial agents, anti-blocking agents, plasticizers, UV absorbers examples include infrared absorbers, antioxidants, silane coupling agents, conductive polymers, conductive surfactants, inorganic fillers, pigments and dyes.
  • the production method of the curable composition containing components other than the metal oxide and the amino group-containing photocurable compound is not particularly limited, but there are several methods. Specifically, first, a metal oxide and an amino group-containing photocurable compound are mixed and dispersed in an organic solvent to obtain a stable metal oxide dispersion, and then various other additives are added and adjusted. From the beginning, a method of dispersing and manufacturing a metal oxide, an amino group-containing photocurable compound, an organic solvent and other additives are mixed.
  • the solvent various known organic solvents that are not particularly limited can be used. Specifically, for example, cyclohexanone, methyl isobutyl ketone, methyl ethyl ketone, acetone, acetyl acetate, toluene, xylene, n-butanol, isobutanol, tert-butanol, n-propanol, isopropanol, ethanol, methanol, 3-methoxy 1-butanol, 3-methoxy-2-butanol, ethylene glycol monomethyl ether, ethylene glycol mono n -butyl ether, 2-ethoxyethanol, 1-methoxy 2-propanol, diacetone alcohol, lactyl acetate, butyl lactate, Propylene glycol monomono chinenoate ethere, ethylene glycol mono
  • a hydroxyl group-containing solvent has good wettability with respect to a metal oxide having a highly hydrophilic particle surface property. Therefore, when it is contained in the solvent composition, the dispersibility of the metal oxide and This is preferable because it is very effective in improving the temporal stability of the coating material (curable composition) and also improves the leveling property of the coating process.
  • the hydroxyl group-containing solvent content in the total solvent composition is preferably 10 to: LOO% by weight.
  • hydroxyl group-containing solvent examples include n-butanol, isobutanol, tert-butanol, n-propanol, isopropanol, ethanol, methanol, 3-methoxy 1-butanol, 3-methoxy 2-butanol, and ethylene glycolol.
  • examples thereof include monomethylol ether, ethylene glycol-no-mono n-butyl ether, 2-ethoxyethanol, 1-methoxy 2-propanol, diacetone alcohol, ethyl acetate, butyl lactate and propylene glycol monomethyl ether.
  • 3-methoxy-1-butanol, propylene glycol monomethylenotenole, ethyleneglycololemonomethenoatenore, and ethyleneglycololemononole n-butyl ether have better dispersibility and dispersion stability of metal oxides. This is preferable.
  • the photopolymerization initiator is not particularly limited as long as it has a function capable of initiating vinyl polymerization by photoexcitation, for example, a monocarbonyl compound, a dicarbonyl compound, a acetophenone compound, a benzoin ether compound, a acylphosphine.
  • a monocarbonyl compound for example, a monocarbonyl compound, a dicarbonyl compound, a acetophenone compound, a benzoin ether compound, a acylphosphine.
  • Xoxide compounds and aminocarbo-Louis compounds can be used.
  • monocarbon compounds include benzophenone, 4-methyl-benzophenone, 2,4,6 trimethylbenzophenone, methyl-o benzoylbenzoate, 4-phenylbenzophenone, 4- (4 —Methylphenol-thiophene-luethanone, 3,3′-dimethyl 4-methoxybenzophenone, 4- (1, 3--ataryloyl 1, 3, 3 ′ dimethyl 4--methoxybenzophenone, 4-— 1,3—Atarylloyl 1,4,7, 10, 13 pentaxotridecyl) benzophenone, 3, 3 ′, 4,4′-tetra (t-butylperoxycarbol) benzophenone, 4-benzoyl-N, N , N Trimethyl-1-propanamine hydrochloride, 4-benzoyl N, N dimethyl N— 2— (1-oxo-2-pro-loxychetyl) Methaammuum oxalate, 2—Z4—Isopropyl thi
  • Dicarbol compounds include 1, 2, 2 trimethyl monobicyclo [2.1.1] heptane 1, 2, 3 dione, benzyl, 2 ethyl anthraquinone, 9, 10 phenanthrenequinone, methyl (X o Examples include xenobenzene acetate, 4-phenol penzyl, etc.
  • acetophenone compound examples include 2-hydroxy-1-2-methyl-1-phenolpropane-1-one, 1- (4-isopropylphenol) 2-hydroxy-2- Methyl 1-phenol Propanone 1-one, 1— (4-Isopropylphenol) 2 Hydroxy di-2-methyl —1-phenol propane mono-1-one, 1-hydroxy monocyclohexyl phenol ketone , 2-Hydroxy-2-methyl-1-styrylpropane 1-one polymer, methoxyacetophenone, dibutoxyacetophenone, 2,2-dimethoxy 1,2-diphenylethane-1 1,2-diethoxy 1,2-diphenylethane 1-on, 2-methyl-1 [4 (methylthio) phenol] 2-morpholinopropane 1-on, 2-benzyl 2-dimethylaminoamino 1- (4-morpholinophenol ) Butane 1-one, 1-Ferro 1, 2—Puffed Pandione 2— (o Ethoxycarbol) oxime, 3, 6 Bis (2-methyl—
  • benzoin ether compound examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin normal butyl ether.
  • acyl phosphine oxide compounds examples include 2,4,6 trimethyl benzoyl diphosphine phosphoxide, 4-n-propyl phenoyl (2, 6 dichlorobenzoyl) phosphine oxide, and the like.
  • aminocarbole compounds include methyl-4- (dimethoxyamino) benzoate, ethyl 4- (dimethylamino) benzoate, 2-n-butoxetyl-4- (dimethylamino) benzoate, isoamiru 4 (dimethylamino) benzoate, 2 (dimethylamino) Ye
  • examples thereof include tilbenzoate, 4,4′-bis-4-dimethylaminobenzophenone, 4,4′-bis-4-jetylaminobenzophenone, 2,5′bis (4-jetylaminobenzal) cyclopentanone, and the like.
  • photopolymerization initiators include Ciba Specialty Chemicals Co., Ltd. Irgacure 184, 651, 500, 907, 127, 369, 784, 2959, BASF's Lucirin TPO, Japan Siebel Hegner Co., Ltd. ) Made Esacure One.
  • the photopolymerization initiator is not limited to the above compound, and any photopolymerization initiator may be used as long as it has the ability to initiate polymerization by ultraviolet rays. These photopolymerization initiators may be used alone or in combination of two or more.
  • the amount of the photopolymerization initiator used is not particularly limited, but it is preferably used within the range of 1 to 20 parts by weight with respect to 100 parts by weight of the total amount of the photocurable compound.
  • a known organic amine or the like can be added as a sensitizer.
  • a cationic polymerization initiator may be used in combination.
  • the curable composition may contain other binder resin or photocurable compound in addition to the amino group-containing photocurable compound.
  • noinder resin examples include polyurethane resin, polyurethane resin, polyurethane urea resin, polyester resin, polyether resin, polycarbonate resin, epoxy resin, amino resin, styrene resin, acrylic resin, and melamine resin.
  • examples thereof include fat, polyamide resin, phenol resin, bull resin and the like. These coffins may be used alone or in combination of two or more.
  • noisyder rosin is preferably used within a range of 20 parts by weight or less based on the total amount (100 parts by weight) of the solid content of the curable composition (components other than the solvent; hereinafter the same).
  • Examples of the photocurable compound include polymerizable unsaturated double bond groups such as (meth) acrylic compounds, fatty acid vinyl compounds, alkyl butyl ether compounds, a-olefin compounds, bur compounds, and echul compounds.
  • a compound having can be used.
  • These compounds having a polymerizable unsaturated double bond group may further have a functional group such as a hydroxyl group, an alkoxy group, a carboxyl group, an amide group, or a silanol group.
  • Amino group-containing light Photocurable compounds other than curable compounds are used in a range of less than 50 parts by weight, particularly in a range of 5 to 40 parts by weight, based on the total amount of solid content of the curable composition (100 parts by weight). It is preferable.
  • (Meth) acrylic compounds include benzyl (meth) acrylate, alkyl (meth) acrylate, alkylene glycol (meth) acrylate, carboxyl group and polymerizable unsaturated double bond. Compounds, (meth) acrylic compounds having a hydroxyl group, and nitrogen-containing (meth) acrylic compounds. Monofunctional and polyfunctional compounds can be used as appropriate. From the viewpoint of photocurability and hard coat properties of the coating film, polyfunctional ones are preferred.
  • monofunctional (meth) acrylic compounds include methyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate. , Butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, no- (Meth) acrylate, Decyl (Meth) acrylate, Undecyl (Meth) acrylate, Dodecyl (Meth) atelate, Tridecyl (Meth) acrylate, Tetradecyl (meth) atelate, Pentadecyl (Meth) atelate Xadecyl (meth) atarylate, heptadecyl (
  • alkyl group-containing (meth) acrylate having an alkyl group having 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms.
  • alkylene glycol-based (meth) acrylate examples include diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meta) ) Atalylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, polytetramethylene glycol Polio having a hydroxyl group at the end, such as (meth) acrylate Mono (meth) acrylate with a xyalkylene chain; methoxy ethylene glycol (meth) acrylate, methoxy diethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, methoxy tetraethylene glycol (meth) acrylate
  • Mono (meth) acrylate with polyoxyalkylene chain phenoxyethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxytriethylene Recall (Meth) Atalylate, Phenoxytetraethylene Glycol (Meth) Atalylate, Phenoxyhexaethylene Glycol (Meth) Atalylate, Phenoxypolyethylene Glycol (Meth) Atalylate, Phenoxytetrapropylene Ethylene Glycol Polyoxyalkylene-based (meth) acrylates having a phenoxy or aryloxy group at the terminal, such as (meth) acrylate.
  • Examples of the compound having a carboxyl group and a polymerizable unsaturated double bond include maleic acid, fumaric acid, itaconic acid, citraconic acid, or alkyl or alkyl monoesters thereof, phthalic acid j8- (meth) atalyst.
  • phthalic acid j8- (meth) atalyst Loxochetyl monoester, isophthalic acid j8-(metha) atalylochechetyl monoester, succinic acid j8-(meth) atalylochechetyl monoester, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, etc.
  • maleic acid fumaric acid, itaconic acid, citraconic acid, or alkyl or alkyl monoesters thereof
  • phthalic acid j8- (meth) atalyst Loxochetyl monoester, isophthalic acid j8-(
  • Examples of the hydroxyl group-containing (meth) acrylic compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meta) ) Atalylate, 4-hydroxybutyrene, 2-hydroxyl 3- Examples include phenoxypropyl (meth) acrylate.
  • Nitrogen-containing (meth) acrylic compounds include (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, N —Propoxymethyl— (meth) acrylamide, N-butoxymethyl— (meth) acrylamide, N-pentoxymethyl- (meth) acrylamide, and other monoalkylol (meth) acrylamides, N, N—di (methylol) acrylamide, N-methylol — N— Methoxymethyl (meth) acrylamide, N, N-di (methylol) acrylamide, N-ethoxymethyl-N-methoxymethylmethacrylamide, N, N-di (ethoxymethyl) acrylamide, N-ethoxymethyl-N-propoxymethyl Methacrylamide, N, N—di Propoxymethyl) acrylamide, N-butoxymethyl—N— (propoxymethyl)
  • Other unsaturated compounds include perfluoromethylmethyl (meth) acrylate, monofluoroethyl methyl (meth) acrylate, 2-perfluorobutyl cetyl (meth) alkyl. Relate, 2-perfluohexyl hexyl (meth) acrylate, 2-perfluoro ota tilethyl (meth) acrylate, 2-perfluoro isono-ruethyl (meth) acrylate, 2-perfluorono-ruethyl (meth) acrylate, 2-Perfluorodecylethyl (meth) acrylate, perfluoropropylpropyl (meth) acrylate, perfluoro octyl propyl (meth) acrylate, perfluorooctylamyl (meth) acrylate, perfluoro Perfluoroalkyl having 1 to 20 carbon atoms, such as fluorooc
  • perfluoroalkyl groups such as perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, perfluorodecylethylene, and perfluoroalkyl groups such as alkylenes Bull monomer; Bull trichlorosilane, Buturis (methoxyethoxy) silane, Vinyl triethoxysilane, y- (meth) Atyloxypropyl trimethoxysilane, and other alkoxysilyl group-containing Bury compounds and derivatives thereof; Glycidyl acrylate, 3, 4 Examples include glycidyl group-containing acrylate, such as epoxycyclohexyl acrylate.
  • Examples of the fatty acid beryl compound include vinyl acetate, vinyl butyrate, vinyl crotonate, butyrate caprylate, laurate, chloroacetate, oleate and stearate.
  • alkyl butyl ether compound examples include butyl benzene ether and ethyl benzene ether.
  • Examples of the a-olefin compound include 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, and 1-hexadecene.
  • Examples of the bur compound include allylic compounds such as allylic acetic acid, allylic alcohol, allylic benzene, and cyano cyanide, cyano cyanide, biscyclohexane, butyl methyl ketone, styrene, ⁇ -methyl styrene, 2-methyl styrene, chlorostyrene, and the like.
  • Examples of the ethul compound include acetylene, eth benzene, ethul toluene, 1 ethynyl-1-cyclohexanol, and the like.
  • Photocurable compounds other than amino group-containing photocurable compounds include polyurethane poly (meth) acrylate and polyepoxy poly (meta) having at least three functional groups from the viewpoint of coating film strength and scratch resistance.
  • Poly (meth) acrylates such as acrylate and polyfunctional acrylates having 3 or more acryloyl groups in the molecule can be preferably used.
  • Polyepoxy poly (meth) acrylate is an epoxy resin whose epoxy group is esterified with (meth) acrylic acid and the functional group is a (meth) taroloyl group.
  • (meth) a to novolac epoxy resin there are adducts such as crylic acid.
  • Polyurethane poly (meth) acrylate is obtained, for example, by reacting diisocyanate and (meth) acrylate having a hydroxyl group, under the condition that polyol and polyisocyanate are excessive in isocyanate group.
  • diisocyanate and (meth) acrylate having a hydroxyl group under the condition that polyol and polyisocyanate are excessive in isocyanate group.
  • an isocyanate group-containing urethane preform made by reacting with (meth) acrylates having a hydroxyl group.
  • it may be obtained by reacting a hydroxyl group-containing urethane prepolymer obtained by reacting a polyol and a polyisocyanate under a hydroxyl group-excess condition with a (meth) acrylate having an isocyanate group.
  • polyols examples include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentandalol, neopentyl glycol, hexane.
  • examples include triol, trimellyl propane, polytetramethylene glycol, and a polycondensation product of adipic acid and ethylene glycol.
  • polyisocyanate examples include tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and the like.
  • Examples of (meth) atalylates having a hydroxyl group include 2-hydroxyethyl (meth) atalyl pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate. Etc.
  • Examples of (meth) acrylates having an isocyanate group include 2- (meth) attalylooxyethylisocyanate, (meth) attalyloyl isocyanate, and the like.
  • Examples of commercially available photocurable composites include the following.
  • Purple light UV—7600B Purple light UV—7610B, Purple light UV—7 620EA, Purple light UV—7630B, Purple light UV—1400B, Purple light UV—1700B, Purple light UV—6 300B,
  • KAYARAD DPHA Nippon Kayaku Co., Ltd .: KAYARAD DPHA, KAYARAD DPHA2C, KAYARA D DPHA-40H, KAYARAD D-310, KAYARAD D-330.
  • the cured film of the present invention is a film formed by curing the curable composition of the present invention.
  • the manufacturing method includes, for example, applying the curable composition to an arbitrary substrate, and irradiating an active energy line to cure the curable composition on the substrate.
  • the curable composition is deposited on an arbitrary substrate so that the film thickness after drying is preferably 0.1 to 30 111, more preferably 0.1 to 20 / ⁇ ⁇ . It can be formed by applying a curing treatment after coating.
  • the cured film may be applied directly to the substrate, or between the cured film and the substrate. There may be one or more lower layers.
  • the substrate examples include metals, ceramics, glass, plastics, wood, slate and the like, and are not particularly limited. Specific plastic types include polyester, polyolefin, polycarbonate, polystyrene, polymethylmetatalylate, triacetyl cellulose resin, ABS resin, AS resin, polyamide, epoxy resin, and melamine resin. It is done.
  • the shape of the substrate is not particularly limited, and includes a film sheet, a plate-like panel, a lens shape, a disk shape, and a fiber-like material.
  • a coating method a known method can be used, for example, a method using a lot or wire bar, or various coatings such as microgravure, gravure, die, curtain, lip, slot or spin. The method can be used.
  • the curing treatment can be performed by irradiating active energy rays such as ultraviolet rays, electron beams, visible rays having a wavelength of 400 to 500 nm, using a known technique.
  • active energy rays such as ultraviolet rays, electron beams, visible rays having a wavelength of 400 to 500 nm
  • a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon lamp clamp, or the like can be used as a source of ultraviolet light and visible light having a wavelength of 400 to 500 nm.
  • a thermionic emission gun, an electrolytic emission gun, or the like can be used as the electron beam source.
  • the active energy dose to be irradiated is preferably within the range of 5 to 2000 miZcm 2 , and more preferably within the range of 50 to: LOOOmjZcm 2 from the viewpoint of easy management in the process.
  • active energy rays can be used in combination with heat treatment by infrared rays, far infrared rays, hot air, high frequency heating or the like.
  • the cured film may be formed by applying a curable composition to a substrate and naturally or forcedly drying it, followed by a curing process. After coating and curing, Forced drying may be used, but it is more preferable to perform curing after natural or forced drying.
  • the curing treatment in the case of curing with an electron beam, it is more preferable to perform the curing treatment after natural or forced drying in order to prevent the curing inhibition by water or the decrease in the strength of the coating film due to the remaining organic solvent.
  • the timing of the curing treatment may be simultaneous with coating or after coating.
  • the obtained cured film is excellent in hard coat property, transparency, light resistance, high refractive index property and antistatic property, and therefore can be suitably used as an optical material. Therefore, the cured film of the present invention is a laminated body, such as a cathode ray tube, a front panel of various display devices such as a flat display panel (liquid crystal display, plasma display, electoric chromic display, light emitting diode display, etc.) or an input thereof. It can also be used as a device.
  • this cured film can be widely used for optical lenses, eyeglass lenses, optical recording disks (compact disks, DVD disks, Blu-ray disks, etc.), light cases, and the like.
  • the surface resistance value of the cured film is preferably 1 ⁇ 10 12 ⁇ or less.
  • the thickness of the cured film is preferably 0.1-30 / ⁇ .
  • the refractive index of the cured film is preferably in the range of 1.5 to 1.8.
  • the laminate of the present invention includes the cured film of the present invention and a substrate.
  • the substrate those exemplified above can be arbitrarily used, and a plastic substrate is particularly preferable.
  • the shape of the substrate is preferably a film shape, a lens shape, or a disk shape.
  • the laminate preferably includes one or more films having different refractive indexes, an adhesive layer or an information recording layer.
  • a laminate including a film ( ⁇ ), an adhesive layer ( ⁇ ) or an information recording layer ( ⁇ ) having different refractive indexes can have a layer structure such as the following (I) to (IX).
  • Films or information recording layers having different refractive indexes have functions other than the functions of the cured product of the present invention.
  • the formation method is not particularly limited, and it is formed by a known method. For example, dry coating methods such as vapor deposition and sputtering, methods using lots and wire bars, and wet coating methods such as microgravure, gravure, die, curtain, lip, slot, and spin can be used.
  • wet coating methods such as microgravure, gravure, die, curtain, lip, slot, and spin can be used.
  • one or more functions such as information recording function, anti-glare function, Newton ring prevention function, adhesive function, blocking of specific wavelength, adhesion improvement, color correction, etc. are given to the laminate as necessary. Any material that can be used can be used.
  • the information recording layer is not particularly limited as long as it is capable of causing some chemical change by laser light or the like and recording information by the change.
  • organic materials include polymethine dyes, naphthalocyanine-based, phthalocyanine-based, squarylium-based, anthraquinone-based, xanthene-based, triphenylmethane-based metal complexes, and one or more of the above dyes. Two or more types can be used in combination.
  • metals such as Te, Ge, Se, In, Sb, Sn, Zn, Au, Al, Cu, and Pt, and semimetals can be used alone or in combination of two or more.
  • the information recording layer may be a laminate or the like.
  • the mode of photochemical change may be any of phase change, bubble, and punching type. Further, it may be a magneto-optical recording layer mainly composed of Fe, Tb, and Co, or may be a spiropyran or fluorinated photochromic material.
  • the high refractive index cured film is also preferably used as a laminate provided with a low refractive index coating cured film on the surface layer to provide an antireflection function. That is, it is preferable to use a laminate obtained by forming a cured film on a substrate such as a film, and more preferably forming a coated cured film, as the antireflection film.
  • the blending amount of the metal oxide in the curable composition of the present invention is adjusted, and the difference in the refractive index between the cured film and the substrate or the cured film and When an arbitrary layer is present between the base material and the base material, the difference in refractive index between the cured film and the lower layer in contact with the cured film is preferably within ⁇ 0.02.
  • the curable composition of the present invention can produce a cured product having a high refractive index by controlling the type and addition amount of the metal oxide. Therefore, the light extraction of the optical semiconductor element
  • the resin layer can be preferably used as an optical semiconductor element sealing material that is required to sequentially reduce the refractive index of the resin layer from the optical semiconductor element side toward the outermost layer.
  • optical semiconductor elements include gallium nitride (GaN: refractive index 2.5), gallium phosphide (GaP: refractive index 2.9), and gallium arsenide (GaAs: refractive index 3.5). Is a high material. Therefore, the refractive index of the cured product that becomes the optical semiconductor element sealing material is preferably 1.5 or more, more preferably 1.5 to 2.1, and more preferably from the viewpoint of increasing the light extraction efficiency. Preferably it is 1.7-7.
  • the metal oxides used include titanium oxide (refractive index 2.5 to 2.7), zirconium oxide (refractive index 2.4), and zinc oxide. Since a dispersant having a refractive index of 1.95 is also required to have a high refractive index, an amino group-containing photocurable compound having an aromatic skeleton is preferred.
  • parts and% represent parts by weight and% by weight, respectively.
  • Ataleletoy compound with a pencil hardness of 3H after photocuring (“UA-306T” manufactured by Kyoeisha Chemical Co., Ltd.) ")
  • U-306T manufactured by Kyoeisha Chemical Co., Ltd.
  • the mixture was cooled to room temperature to obtain a methylisobutyl ketone solution (solid content: 40%) of the amino group-containing photocurable compound (3).
  • Cyclohexanone solution (solid content 50%) containing the above polyfunctional (meth) acrylate compound (b) with a pencil hardness of 3H after photocuring 30.0 parts diluted with 9.1 parts of cyclohexanone
  • Cyclohexanone solution (solid content 60%) containing the above polyfunctional (meth) acrylate compound (c) having a pencil hardness of 3H after photocuring 20.
  • a cyclohexanone solution (solid content 40%) of the amino group-containing photocurable compound (9) was obtained.
  • biphenyl tetracarboxylic dianhydride Mitsubishi Chemical Co., Ltd. 80.0 parts, pentaerythritol triatari Rate (Nippon Kayaku Co., Ltd .: KAYARAD PET—30) 124.8 parts, dipentaerythritol pentaatalylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) 222.8 parts, Hydroquinone 0.21 part, Cyclohexanone 430 0 parts were charged and the temperature was raised to 85 ° C. Next, 1, 8—diazabicyclo [5. 4.
  • This reaction solution was light yellow and transparent with a solid content of 50%, a number average molecular weight (MN) of 1,050, and a weight average molecular weight (MW) of 3,830.
  • metal oxide dispersion was performed by the combination shown in Table 1 to prepare a metal oxide dispersion paste.
  • Dispersion methods include temporary dispersion (using zirca beads (1.25 mm) as media and dispersion with paint shaker for 1 hour) and main dispersion (zirco beads (0.1 mm) as media). The dispersion was carried out in two stages using a dispersion machine UAM-015.
  • ATO “SN-100PJ (average primary particle size: 20nm) manufactured by Ishihara Sangyo Co., Ltd.
  • ITO “Nanotech ITO” manufactured by Shi Kasei Co., Ltd. (average primary particle size: 30 nm)
  • A1 doped ZnO “PazetCK” (average primary particle size: 30 nm) manufactured by Hux Tech Co., Ltd.
  • TiO “TTO-51 (A)] manufactured by Ishihara Sangyo Co., Ltd. (average primary particle size: 20nm)
  • ZnO “FINEX-50” manufactured by Sakai Chemical Industry Co., Ltd. (average primary particle size: 20 nm)
  • Al O Nippon Aerosil Co., Ltd. “Aluminium Oxide C” (average primary particle size: 13
  • a curable composition having the composition shown in Table 2 was prepared using the metal oxide dispersion paste prepared above.
  • the obtained curable composition was applied to a 100 / zm thick easy-to-adhesive PET film ("Cosmo Shine A-4100" manufactured by Toyobo Co., Ltd.) with a bar coater to a film thickness after drying of 5 ⁇ m.
  • an antistatic hard coat layer (cured film) was formed by irradiating 400 miZcm 2 ultraviolet rays with a metal halide lamp.
  • the obtained antistatic hard coat layer was evaluated for surface resistance, scratch resistance, pencil hardness, transparency (haze) and light resistance by the following methods. The results are shown in Table 2.
  • Photo-curable compound (1) “UA-306TJ” manufactured by Kyoeisha Chemical Co., Ltd.
  • Photo-curing compound (2) “KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.
  • Photopolymerization initiator Ciba Specialty Chemicals "Irgacure 184"
  • Solvent PGME (propylene glycol monomethyl ether)
  • each curable composition having the composition shown in Table 3 was prepared.
  • the obtained coating layer was dried at 100 ° C. for 1 minute, and then irradiated with 400 miZcm 2 ultraviolet rays with a metal halide lamp.
  • the low refractive coating liquid was applied on the obtained cured film with a spin coater while adjusting the layer thickness so that the wavelength of light having a dry film thickness of ⁇ / 4 was about 550 ⁇ m. .
  • the obtained coating layer was dried at 100 ° C. for 1 minute, and then irradiated with 400 miZcm 2 ultraviolet rays with a metal halide lamp to obtain a laminate.
  • the refractive index of the cured film was measured by the following method, and the scratch resistance, pencil hardness, transparency (haze), refractive index, and reflection interference fringes of the cured film were evaluated. The results are shown in Table 3.
  • Photocurable compound (1) “UA-306TJ” manufactured by Kyoeisha Chemical Co., Ltd.
  • Photopolymerization initiator “Irgacure 184” manufactured by Chipa's Specialty Chemicals Co., Ltd.
  • Base material 100 m thick easily treated PET film (“Cosmo Shine A-4100” manufactured by Toyobo Co., Ltd.) (Coating to refractive index 1.60)
  • the surface resistance ( ⁇ Z port) of the cured film was evaluated according to the following criteria.
  • the coated product was set on a Gakushin Tester and shook 10 times with a load of 250g using steel wool No.0000.
  • the removed coating was judged for scratching according to the following five-step visual evaluation. The larger the value, the better the scratch resistance of the cured film.
  • a pencil hardness tester (Scratching Tester HEIDON-14 manufactured by HEIDON) was used, and the test was performed five times at a load of 500 g with various changes in pencil core hardness.
  • the pencil hardness of the hardened film was defined as the hardness of the core when the scratch was not scratched once or was scratched only once. In consideration of practical required physical properties, the pencil hardness of the cured film is 2H or more:
  • Turbidity (Haze value) in the obtained coated product was measured using a Haze meter.
  • the coated material was exposed for 24 hours with a light resistance tester (light source: xenon lamp, illuminance: 100 WZcm 2 , black panel temperature: 60 ° C, 60% RH). Thereafter, the coated material was placed on white paper, and the color was measured using a colorimeter (Minolta CR-300). The colorimetric value was displayed as L * a * b *, and the guideline for yellowing of the cured film was judged from the b * value. The smaller the b * value, the smaller the degree of yellowing and the better the light resistance. Considering the practical properties required, the b * value of the cured film is
  • the refractive index of the obtained cured film was measured using an Abbe refractometer manufactured by Atago Co., Ltd. (7) Reflective interference fringes
  • the reflection interference fringes of the obtained cured film were visually evaluated according to the following criteria.

Abstract

Disclosed is a curable composition containing a metal oxide having an average primary particle diameter of 5-100 nm, and an amino group-containing photocurable compound. The amino group-containing photocurable compound has a functional group obtained by reacting an ethylenically unsaturated double bond with a primary or secondary amine, and an unreacted ethylenically unsaturated double bond.

Description

明 細 書  Specification
硬化性組成物、硬化膜及び積層体  Curable composition, cured film and laminate
技術分野  Technical field
[0001] 本発明は、ハードコート性を持った硬化性組成物、及びそれを用いた硬化膜とその 積層体に関する。  The present invention relates to a curable composition having hard coat properties, a cured film using the same, and a laminate thereof.
背景技術  Background art
[0002] 従来、情報通信機器の性能確保と安全対策の面から、機器の表面に、光硬化性組 成物を用いて、耐擦傷性、密着性、高屈折率性などを有するハードコート性塗膜や、 帯電防止性塗膜を形成することが行われて!/ヽる。  [0002] Conventionally, from the viewpoint of ensuring the performance of information communication equipment and safety measures, a hard-coating property having a scratch resistance, adhesion, high refractive index, etc., using a photocurable composition on the surface of the equipment. Forming a coating or antistatic coating is done!
近年、情報通信機器の発達と汎用化には目覚しいものがあり、ハードコート性塗膜 、帯電防止性塗膜等の更なる性能向上及び生産性の向上が求められており、光硬 化性材料を用いた様々な提案がされて 、る。  In recent years, there has been remarkable progress in the development and generalization of information and communication equipment, and there has been a demand for further improvements in performance and productivity of hard coat coatings and antistatic coatings. Various proposals have been made using
[0003] 例えば、以下のような技術提案を挙げることができる（特許文献 1〜3参照)。特許文 献 1では、酸化スズなどの導電性粉末と複数のモノマー成分とを有機溶剤中、ボール ミルなどを用いて混合し、導電性塗料を作成する方法が開示されている。特許文献 2 では、アンチモンドープ酸化スズと紫外線硬化性のあるシランカップリング剤とを有機 溶剤中、ボールミルを用いて混合し、導電性塗料用の分散体を作成する方法が開示 されている。さらに特許文献 3では、導電性酸化物微粉末を易分散性低沸点溶剤と 難分散性高沸点溶剤の混合溶剤中に分散し、導電性塗料を作成する方法が開示さ れている。  [0003] For example, the following technical proposals can be cited (see Patent Documents 1 to 3). Patent Document 1 discloses a method of preparing a conductive paint by mixing conductive powder such as tin oxide and a plurality of monomer components in an organic solvent using a ball mill or the like. Patent Document 2 discloses a method of preparing a dispersion for conductive paint by mixing antimony-doped tin oxide and an ultraviolet curable silane coupling agent in an organic solvent using a ball mill. Further, Patent Document 3 discloses a method for producing a conductive coating material by dispersing a conductive oxide fine powder in a mixed solvent of an easily dispersible low boiling solvent and a hardly dispersible high boiling solvent.
(特許文献 1)特開平 04 - 172634号公報  (Patent Document 1) Japanese Patent Application Laid-Open No. 04-172634
(特許文献 2)特開平 06— 264009号公報  (Patent Document 2) Japanese Patent Laid-Open No. 06-2644009
(特許文献 3)特開 2001— 131485号公報  (Patent Document 3) JP 2001-131485 A
発明の開示  Disclosure of the invention
[0004] しかし、上記方法により、高屈折率性、ハードコート性、帯電防止性、耐光性などに ぉ ヽて良好な物性を併せ持つ硬化性組成物を作成することが可能となっても、有機 溶剤など疎水性の高い媒体に対して、平均一次粒子径が lOOnm以下の金属酸ィ匕 物を安定に、一次粒子レベルで分散および安定化させることはできないため、塗膜 の透明性や光硬化性塗料の経時安定性等の観点で問題を生じやすい。 [0004] However, even if it becomes possible to create a curable composition having both high refractive index properties, hard coat properties, antistatic properties, light resistance, and other good physical properties by the above method, Metal oxides with an average primary particle size of lOOnm or less for highly hydrophobic media such as solvents Since it is impossible to stably disperse and stabilize the product at the primary particle level, problems are likely to occur in terms of the transparency of the coating film and the temporal stability of the photocurable coating.
そこで、本発明は、平均一次粒子径が lOOnm以下の金属酸ィ匕物を含有しながら、 高屈折率性、帯電防止性、ハードコート性、透明性及び耐光性の全てにおいて優れ た物性を併せ持つ塗膜を形成可能な、経時安定性のある硬化性組成物、及びそれ を用いた硬化膜とその積層体を提供することを目的とする。  Therefore, the present invention has excellent physical properties in all of high refractive index property, antistatic property, hard coat property, transparency and light resistance while containing a metal oxide having an average primary particle size of lOOnm or less. It is an object of the present invention to provide a curable composition that can form a coating film and is stable over time, a cured film using the same, and a laminate thereof.
[0005] 本発明は、平均一次粒子径が 5〜： LOOnmの金属酸化物と、 [0005] The present invention provides a metal oxide having an average primary particle size of 5 to: LOOnm,
エチレン性不飽和二重結合と第一級ァミンまたは第二級ァミンとを反応させた官能 基、および、未反応のエチレン性不飽和二重結合を有するアミノ基含有光硬化性ィ匕 合物と、  A functional group obtained by reacting an ethylenically unsaturated double bond with a primary amine or a secondary amine, and an amino group-containing photocurable compound having an unreacted ethylenically unsaturated double bond; ,
を含有する硬化性組成物に関する。  It relates to the curable composition containing this.
前記アミノ基含有光硬化性ィヒ合物のエチレン性不飽和二重結合は、アタリレート基 またはメタタリレート基由来のものであることが好ましい。さらに、前記アミノ基含有光 硬化性ィ匕合物は、光硬化後の鉛筆硬度が H以上になるアタリレートイ匕合物またはメタ タリレート化合物と、第一級ァミンまたは第二級ァミンとを反応させてなる化合物であ ることが好ましい。  The ethylenically unsaturated double bond of the amino group-containing photocurable compound is preferably derived from an acrylate or metatalylate group. Further, the amino group-containing photocurable compound reacts with an atorato toy compound or a metatarate compound having a pencil hardness after photocuring of H or more and a primary or secondary amine. It is preferable that it is a compound formed.
[0006] 別の本発明は、上記硬化性組成物を硬化してなる硬化膜に関する。  [0006] Another aspect of the present invention relates to a cured film obtained by curing the above curable composition.
別の本発明は、基材と、上記硬化膜とを含む積層体に関する。  Another aspect of the present invention relates to a laminate including a base material and the cured film.
別の本発明は、上記硬化性組成物を含む光半導体素子封止材に関する。 さらに別の本発明は、上記硬化性組成物を基材に塗布すること；および活性ェネル ギ一線を照射して硬化性組成物を硬化させること；を含む硬化膜の製造方法に関す る。  Another aspect of the present invention relates to an optical semiconductor element sealing material containing the curable composition. Yet another aspect of the invention relates to a method for producing a cured film, comprising: applying the curable composition to a substrate; and irradiating an active energy line to cure the curable composition.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0007] 本発明の硬化性組成物は、エチレン性不飽和二重結合と第一級ァミンまたは第二 級ァミンとを反応させた官能基、および、未反応のエチレン性不飽和二重結合を有 するアミノ基含有光硬化性化合物を含有し、これが分散剤として良好に機能するため 、平均一次粒子径が 5〜： LOOnmの金属酸化物の分散性を高めることができる。その 結果、本発明の硬化性組成物は、硬化性に優れ、帯電防止性、ハードコート性、透 明性、耐光性、高屈折率性に優れた硬化膜及びその積層体を形成することが可能 である。したがって、特にプラスチック光学部品、光ディスク、反射防止膜、タツチパネ ル、フィルム型液晶素子に好適に使用できるほか、各種プラスチック積層体のハード コート剤としても好適に使用できる。 [0007] The curable composition of the present invention comprises a functional group obtained by reacting an ethylenically unsaturated double bond with a primary amine or a secondary amine, and an unreacted ethylenically unsaturated double bond. Since it contains an amino group-containing photocurable compound and functions well as a dispersant, the dispersibility of a metal oxide having an average primary particle diameter of 5 to LOONm can be enhanced. As a result, the curable composition of the present invention is excellent in curability, antistatic property, hard coat property, transparent property. It is possible to form a cured film excellent in lightness, light resistance and high refractive index and a laminate thereof. Therefore, it can be suitably used particularly for plastic optical parts, optical disks, antireflection films, touch panels, film-type liquid crystal elements, and can also be suitably used as a hard coating agent for various plastic laminates.
この硬化性組成物は、屈折率の高い硬化膜を形成することができ、これを屈折率が 同程度の基材に塗布した場合、得られた積層体は反射干渉縞が生じず、光学用途 に好適に用いられる。さらに、金属酸化物を含んだ硬化物の屈折率を高く制御可能 であることから、光半導体素子封止材としても好適である。  This curable composition can form a cured film having a high refractive index, and when this is applied to a base material having the same refractive index, the resulting laminate does not produce reflection interference fringes, and is used for optical applications. Is preferably used. Furthermore, since the refractive index of the cured product containing a metal oxide can be controlled to be high, it is also suitable as an optical semiconductor element sealing material.
[0008] まず、本発明の硬化性組成物について説明する。  [0008] First, the curable composition of the present invention will be described.
この硬化性組成物は、少なくとも平均一次粒子径が 5〜： LOOnmの金属酸ィ匕物と、 エチレン性不飽和二重結合と第一級ァミンまたは第二級ァミンとを反応させた官能基 、および、未反応のエチレン性不飽和二重結合を有するアミノ基含有光硬化性化合 物とを含有するものであり、二種類以上の金属酸ィヒ物と二種類以上のアミノ基含有 光硬化性化合物をそれぞれ含んでも良 ヽ。  This curable composition has a functional group obtained by reacting at least an average primary particle diameter of 5 to: a metal oxide of LOOnm, an ethylenically unsaturated double bond, and a primary or secondary amine. And an amino group-containing photocurable compound having an unreacted ethylenically unsaturated double bond, and containing two or more kinds of metal acid compounds and two or more kinds of amino groups containing photocurable. Each compound may be included.
[0009] 金属酸化物は、平均一次粒子径が 5〜： LOOnmの金属酸化物である。金属酸化物 の平均一次粒子径は、例えば、透過型電子顕微鏡 (TEM)または走査型電子顕微 鏡 (SEM)などを用いて、粒子自身を直接観察することによって測定できる。  [0009] The metal oxide is a metal oxide having an average primary particle size of 5 to: LOOnm. The average primary particle diameter of the metal oxide can be measured by directly observing the particles themselves using, for example, a transmission electron microscope (TEM) or a scanning electron microscope (SEM).
平均一次粒子径が 5nm未満の金属酸化物の場合、微粒子同士の凝集力が非常 に大き ヽことから、透明性の高 、一次粒子レベルの分散をさせることが非常に困難で ある。一方、平均一次粒子径が lOOnmを超える金属酸ィ匕物の場合、一次粒子レべ ルで分散させることは容易になる力 粒子径が大きいことから可視光などの光に対し て散乱が生じ易ぐ硬化膜の透明性を悪化させる問題が生じる。  In the case of a metal oxide having an average primary particle diameter of less than 5 nm, the cohesive force between the fine particles is very large, so that it is very difficult to disperse at the primary particle level with high transparency. On the other hand, in the case of metal oxides having an average primary particle size exceeding lOOnm, it is easy to disperse at the primary particle level. Because of the large particle size, scattering is likely to occur for light such as visible light. There arises a problem of deteriorating the transparency of the cured film.
[0010] 金属酸化物としては、チタニウム、亜鉛、ジルコニウム、アンチモン、インジウム、ス ズ、アルミニウム、及び珪素力 なる群力 選ばれる少なくとも一種の元素を含有する ものが好ましい。特に、アンチモン、インジウム、スズおよび亜鉛のいずれか一種の元 素を含有するものは、導電性も良好であることから、より好ましい。  [0010] The metal oxide is preferably one containing at least one element selected from the group force of titanium, zinc, zirconium, antimony, indium, tin, aluminum, and silicon power. In particular, those containing any one element of antimony, indium, tin and zinc are more preferable because of their good conductivity.
具体的には、五酸化アンチモン、酸化チタン、酸化亜鉛、酸化ジルコニウム、酸ィ匕 ケィ素、アンチモンドープ酸化スズ (ATO)、スズドープ酸化インジウム（ITO)、フッ 素ドープ酸化スズ (FTO)、リンドープ酸化スズ（PTO)、アンチモン酸亜鉛 (AZO)、 インジウムドープ酸ィ匕亜鉛 (IZO)、酸化スズ、 ATO被覆酸ィ匕チタン、アルミニウムド ープ酸化亜鉛、ガリウムドープ酸ィ匕亜鉛等が挙げられる。これらの金属酸化物は、 2 種類以上を併用しても差し支えない。 Specifically, antimony pentoxide, titanium oxide, zinc oxide, zirconium oxide, silicon oxide, antimony-doped tin oxide (ATO), tin-doped indium oxide (ITO), fluorine Elementally doped tin oxide (FTO), phosphorus doped tin oxide (PTO), zinc antimonate (AZO), indium doped oxide and zinc (IZO), tin oxide, ATO coated oxide and titanium oxide, aluminum doped zinc oxide, gallium Examples include doped acid zinc. Two or more of these metal oxides can be used in combination.
金属酸化物の市販品としては、  As a commercial product of metal oxide,
日産化学工業 (株）製：サンエポック EFR— 6N、サンエポック EFR— 6NP (五酸ィ匕 アンチモン）、  NISSAN CHEMICAL INDUSTRY CO., LTD .: Sanepoch EFR—6N, Sanepoch EFR—6NP (pentanoic acid antimony),
石原産業 (株）製： SN—100P (ATO)、 FS— 10P (ATO)、 SN—102P (ATO)、 FS— 12P (ATO)、 ET—300W(ATO被覆酸化チタン）、 TTO— 55 (A) (酸化チタ ン）、 TTO— 55 (B) (酸化チタン）、 TTO— 55 (C) (酸化チタン）、 TTO— 55 (D) (酸 化チタン）、 TTO— 55 (S) (酸化チタン）、 TTO— 55 (N) (酸化チタン）、 TTO— 51 ( A) (酸化チタン）、 TTO - 51 (C) (酸化チタン）、 TTO— S— 1 (酸化チタン）、 TTO — S— 2 (酸化チタン）、 TTO— S— 3 (酸化チタン）、 TTO— S— 4 (酸化チタン）、 TT O-F- l (鉄含有酸化チタン）、 TTO F— 2 (鉄含有酸化チタン）、 TTO F— 3 ( 鉄含有酸化チタン）、 TTO— F— 11 (鉄含有酸化チタン）、 ST— 01 (酸化チタン）、 S T 21 (酸化チタン）、 ST— 30L (酸化チタン）、 ST— 31 (酸化チタン）、  Ishihara Sangyo Co., Ltd .: SN—100P (ATO), FS—10P (ATO), SN—102P (ATO), FS—12P (ATO), ET—300W (ATO coated titanium oxide), TTO—55 (A ) (Titanium oxide), TTO—55 (B) (Titanium oxide), TTO—55 (C) (Titanium oxide), TTO—55 (D) (Titanium oxide), TTO—55 (S) (Titanium oxide) ), TTO—55 (N) (titanium oxide), TTO—51 (A) (titanium oxide), TTO-51 (C) (titanium oxide), TTO—S—1 (titanium oxide), TTO—S—2 (Titanium oxide), TTO—S—3 (titanium oxide), TTO—S—4 (titanium oxide), TT OF-l (iron-containing titanium oxide), TTO F—2 (iron-containing titanium oxide), TTO F— 3 (iron-containing titanium oxide), TTO—F—11 (iron-containing titanium oxide), ST—01 (titanium oxide), ST 21 (titanium oxide), ST—30L (titanium oxide), ST—31 (titanium oxide) ,
三菱マテリアル (株)製: T— l (ITO)、 S— 1200 (酸化スズ）、  Mitsubishi Materials Corporation: T—l (ITO), S—1200 (tin oxide),
三井金属工業 (株)製:パストラン (ITO、 ATO) ,  Made by Mitsui Kinzoku Kogyo Co., Ltd .: Pastoran (ITO, ATO),
シーアィ化成 (株)製:ナノテック ITO、ナノテック SnO、ナノテック TiO、ナノテック  CY Kasei Co., Ltd .: Nanotech ITO, Nanotech SnO, Nanotech TiO, Nanotech
2 2  twenty two
SiO、ナノテック Al O、ナノテック ZnO、  SiO, Nanotech Al O, Nanotech ZnO,
2 2 3  2 2 3
触媒化成工業 (株）製: TL— 20 (ATO)、 TL— 30 (ATO)、 TL - 30S (PTO)、 T L- 120 (ITO)、 TL 130 (ITO)、  Made by Catalytic Chemical Industry Co., Ltd .: TL-20 (ATO), TL-30 (ATO), TL-30S (PTO), T L-120 (ITO), TL 130 (ITO),
ノヽクスィテック（株）製： PazetCK (アルミニウムドープ酸化亜鉛）、 PazetGK (ガリウ ムドープ酸化亜鉛）、  Made by NOX Sitec: PazetCK (aluminum-doped zinc oxide), PazetGK (gallium-doped zinc oxide),
堺化学工業 (株)製: SC— 18 (アルミニウムドープ酸ィ匕亜鉛）、 FINEX- 25 (酸ィ匕 亜鉛）、 FINEX— 25LP (酸化亜鉛）、 FINEX— 50 (酸化亜鉛）、 FINEX— 50LP ( 酸化亜鉛）、 FINEX— 75 (酸化亜鉛）、 STR— 60C (酸化チタン）、 STR— 60C- LP (酸化チタン）、 STR- 100C (酸化チタン）、 住友大阪セメント（株）製： OZC— 3YC (酸化ジルコニウム）、 OZC— 3 YD (酸化ジ ルコ-ゥム）、 OZC— 3YFA (酸化ジルコニウム）、 OZC— 8YC (酸化ジルコニウム）、 OZC-0S100 (酸化ジルコニウム）、 Manufactured by Sakai Chemical Industry Co., Ltd .: SC-18 (aluminum-doped acid zinc), FINEX-25 (acid zinc), FINEX-25LP (zinc oxide), FINEX-50 (zinc oxide), FINEX-50LP ( Zinc oxide), FINEX—75 (Zinc oxide), STR—60C (Titanium oxide), STR—60C-LP (Titanium oxide), STR-100C (Titanium oxide), Made by Sumitomo Osaka Cement Co., Ltd .: OZC-3YC (zirconium oxide), OZC-3 YD (zirconium oxide), OZC-3YFA (zirconium oxide), OZC-8YC (zirconium oxide), OZC-0S100 (oxidation) zirconium),
日本電工 (株)製： PCS (酸ィ匕ジルコニウム）、 T— 01 (酸ィ匕ジルコニウム）、 日本ァエロジル (株）製： Aluminium Oxide C (酸化アルミニウム）、 AEROSIL 130 (酸化ケィ素）、 AEROSIL200 (酸化ケィ素）、 AEROSIL200V (酸化ケィ素）、 AEROSIL200CF (酸化ケィ素）、 AEROSIL200FA (酸化ケィ素）、 AEROSIL30 0 (酸化ケィ素）、 AEROSIL300CF (酸化ケィ素）、 AEROSIL380 (酸化ケィ素）、 AEROSILR972 (酸化ケィ素）、 AEROSILR974 (酸化ケィ素）、 AEROSILR976 (酸化ケィ素）、 AEROSILR202 (酸化ケィ素）、 AEROSILR805 (酸化ケィ素）、 A EROSILR812 (酸化ケィ素）、 AEROSILR812S (酸化ケィ素）、 AEROSILMOX 50 (酸化ケィ素）、 AEROSILTT600 (酸化ケィ素）、 AEROSILMOX80 (酸化ケィ 素/酸化アルミニウム）、 AEROSILMOX170 (酸化ケィ素/酸化アルミニウム）、 AE ROSILCOX84 (酸化ケィ素/酸化アルミニウム）、  Nippon Denko Co., Ltd .: PCS (acid Zirconium), T-01 (acid Zirconium), Nippon Aerosil Co., Ltd .: Aluminum Oxide C (Aluminum oxide), AEROSIL 130 (Cyanide oxide), AEROSIL200 ( (Cyanide oxide), AEROSIL200V (Chemical oxide), AEROSIL200CF (Chemical oxide), AEROSIL200FA (Chemical oxide), AEROSIL30 0 (Chemical oxide), AEROSIL300CF (Chemical oxide), AEROSIL380 (Chemical oxide), AEROSILR972 ( AEROSILR974 (Chemical oxide), AEROSILR976 (Chemical oxide), AEROSILR202 (Chemical oxide), AEROSILR805 (Chemical oxide), A EROSILR812 (Chemical oxide), AEROSILR812S (Chemical oxide), AEROSILMOX 50 (Chemical oxide), AEROSILTT600 (Chemical oxide), AEROSILMOX80 (Chemical oxide / Aluminum oxide), AEROSILMOX170 (Chemical oxide / Aluminum oxide), AE ROSILCOX84 (Chemical oxide / Aluminum oxide),
等が挙げられる。  Etc.
[0012] アミノ基含有光硬化性ィ匕合物は、上記金属酸ィ匕物の分散剤として機能するもので あり、エチレン性不飽和二重結合と第一級ァミンまたは第二級ァミンとを反応させた 官能基 (ァミノ基）と、未反応のエチレン性不飽和二重結合とを含むものである。この アミノ基含有光硬化性ィ匕合物のエチレン性不飽和二重結合は、アタリレート基または メタタリレート基由来のものであることが好ましい。  [0012] The amino group-containing photocurable compound functions as a dispersant for the above metal oxide compound, and comprises an ethylenically unsaturated double bond and a primary or secondary amine. It contains a reacted functional group (amino group) and an unreacted ethylenically unsaturated double bond. The ethylenically unsaturated double bond of the amino group-containing photocurable compound is preferably derived from an acrylate or metatalylate group.
ここで、「第一級ァミンまたは第二級ァミン」は、第一級ァミンおよび第二級ァミンの 双方を含む、または使用する場合を含む概念である。同様に、「アタリレート基または メタタリレート基」は、アタリレート基およびメタタリレート基の双方を含む、または使用 する場合を含む概念である。以下、アタリレートとメタタリレートをまとめて「(メタ）アタリ レート」と記載する場合がある。  Here, the “primary amine or secondary amine” is a concept that includes or includes both the primary amine and the secondary amine. Similarly, “atallylate group or metatalylate group” is a concept that includes or includes the use of both an acrylate group and a metatalylate group. Hereinafter, the attalate and the metatarrate may be collectively referred to as “(meth) arylate”.
[0013] さらに、このアミノ基含有光硬化性化合物は、光硬化後の鉛筆硬度が H以上になる アタリレートイ匕合物またはメタクリレートイ匕合物と、第一級または第二級ァミンとを反応 させてなる化合物であることが好ましい。この (メタ)アタリレートイ匕合物は、光硬化後 の鉛筆硬度が 2H以上になるものであることがより好ましぐ 3H以上になるものである ことがさらに好ましい。 [0013] Further, this amino group-containing photocurable compound comprises an attalitoy toy compound or a methacrylate compound having a pencil hardness after photocuring of H or more, and a primary or secondary amine. A compound obtained by reaction is preferable. This (meta) ata relay toy compound is It is more preferable that the pencil hardness is 2H or more, and it is more preferable that the pencil hardness is 3H or more.
ここで、鉛筆硬度とは、 JIS— K5600に準拠し (基材:厚み 100 mの易接着処理 P ETフィルム、荷重：500g)、膜厚 10 /z mの硬化膜に傷が発生しない鉛筆の濃度記号 をいう。  Here, the pencil hardness is based on JIS-K5600 (base material: easy-adhesive PET film with a thickness of 100 m, load: 500 g), and the concentration of the pencil that does not damage the cured film with a film thickness of 10 / zm. The symbol.
[0014] 光硬化後の鉛筆硬度が H未満になる (メタ)アタリレート化合物と、第一級または第 二級ァミンとを反応させてなるアミノ基含有光硬化性化合物を含有させた場合、金属 酸ィ匕物の分散性には大きな問題がないことから、光硬化後の硬化膜の透明性は良 好であるが、ハードコート性に問題を生じる可能性があり、ハードコート用途への使用 にお 、て不具合を生じる場合がある。  [0014] The pencil hardness after photocuring is less than H. When a (meth) acrylate compound and an amino group-containing photocurable compound obtained by reacting a primary or secondary amine are contained, a metal Since there is no major problem with the dispersibility of oxides, the transparency of the cured film after photocuring is good, but it may cause problems with hard coat properties, and it can be used for hard coat applications. However, it may cause problems.
光硬化後の硬化膜の鉛筆硬度が H以上になる (メタ)アタリレートイ匕合物としては、 3 個以上のアタリロイル基を含有する多官能アタリレートィヒ合物、または 3個以上のメタ クリロイル基を含有する多官能メタクリレートイ匕合物が、光硬化性も良好であり好まし い。  The pencil hardness of the cured film after photocuring is H or higher. (Meth) talato toy compounds include polyfunctional attalylate compounds containing three or more attalyloyl groups, or three or more methacryloyl groups. The polyfunctional methacrylate compound contained is preferred because of good photocurability.
[0015] 光硬化後の硬化膜の鉛筆硬度が H以上になる (メタ)アタリレートイ匕合物のうち、モノ マーとしては、ジペンタエリスリトールへキサアタリレート（DPHA)、ジペンタエリスリト ールヒドロキシペンタアタリレート、ジペンタエリスリトールテトラアタリレート（PETTA) などが挙げられる。オリゴマーまたはポリマーとしては、ポリエステル (メタ）アタリレート 化合物、エポキシ (メタ)アタリレートイ匕合物、ウレタン (メタ)アタリレートイ匕合物等が挙 げられる。特に、金属酸ィ匕物の分散性がより良好になることから、分子量 1000〜200 00の化合物であることが好ましぐ分子量 1000〜20000のポリエステルアタリレート 化合物、エポキシアタリレートイ匕合物、またはウレタンアタリレートイ匕合物がより好まし い。  [0015] Among the (meth) atareto toy compounds whose cured film after photocuring has a hardness of H or higher, dipentaerythritol hexaatalylate (DPHA), dipentaerythritol is a monomer. Examples include ruhydroxypentaacrylate and dipentaerythritol tetraacrylate (PETTA). Examples of the oligomer or polymer include a polyester (meth) atelate compound, an epoxy (meth) talate toy compound, and a urethane (meth) ate tale toy compound. In particular, since the dispersibility of the metal oxide is better, it is preferable to use a compound having a molecular weight of 1000 to 20000. A polyester acrylate compound having a molecular weight of 1000 to 20000, an epoxy atelar toy compound, Or urethane ata relay toy compound is more preferable.
[0016] 光硬化後の硬化膜の鉛筆硬度が H以上になる (メタ)アタリレートイ匕合物として、巿 販の化合物を使用することが可能である。具体的には、以下の製品が挙げられる。 東亜合成（株）製：ァロニックス M— 400、ァ口-ックス M— 402、ァ口-ックス M— 4 08、ァ口-ックス M— 450、ァ口-ックス M— 7100、ァロニックス M— 8030、ァ口-ッ タス M— 8060、 大阪有機化学工業 (株)製：ビスコート # 400、 [0016] A commercially available compound can be used as a (meth) talate toy compound in which the pencil hardness of the cured film after photocuring is H or higher. Specific examples include the following products. Toa Gosei Co., Ltd .: Alonix M-400, Aguchi-X M-402, Aguchi-X M-408, Aguchi-X M-450, Aguchi-X M-7100, Aronix M-8030,口 口 -tuss M—8060, Osaka Organic Chemical Industry Co., Ltd .: Biscote # 400,
化薬サートマ一 (株)製: SR— 295、  Kayaku Satomaichi Co., Ltd .: SR-295,
ダイセル UCB (株）製： DPHA、 Ebecryl 220、 Ebecryl 1290K、 Ebecryl 51 29、 Ebecryl 2220、 Ebecryl 6602、  Daicel UCB Co., Ltd .: DPHA, Ebecryl 220, Ebecryl 1290K, Ebecryl 51 29, Ebecryl 2220, Ebecryl 6602,
新中村化学工業 (株）製： NKエステル A- TMMT、 NKオリゴ EA—1020、 NKオリ ゴ EMA— 1020、 NK^-y^EA-6310, NK才ジゴ — 63 Made by Shin-Nakamura Chemical Co., Ltd .: NK Ester A-TMMT, NK Oligo EA-1020, NK Origo EMA-1020, NK ^ -y ^ EA-6310, NK Age Jigo — 63
40、 NK才リゴ MA— 6、 NK才リゴ U— 4HA、 NK才リゴ U— 6HA、 NK才リゴ U— 32 4A, 40, NK-year-old Rigo MA—6, NK-year-old Rigo U—4HA, NK-year-old Rigo U—6HA, NK-year-old Rigo U—32 4A,
BASF社製： LaromerEA81、  BASF: LaromerEA81,
サンノプコ（株）製：フォトマー 3016、  Made by San Nopco: Photomer 3016,
荒川化学工業 (株）製：ビームセット 371、ビームセット 575、ビームセット 577、ビー ムセット 700、ビームセット 710、  Arakawa Chemical Industries, Ltd .: Beam Set 371, Beam Set 575, Beam Set 577, Beam Set 700, Beam Set 710,
根上工業 (株）製：アートレジン UN— 3320HA、アートレジン UN— 3320HB、ァ 一トレジン UN—3320HC、アートレジン UN— 3320HS、アートレジン UN— 9000 H、アートレジン UN— 901T、  Negami Kogyo Co., Ltd .: Art Resin UN-3320HA, Art Resin UN-3320HB, Art Resin UN-3320HC, Art Resin UN-3320HS, Art Resin UN-9000 H, Art Resin UN-901T,
日本合成化学工業 (株)製:紫光 UV—7600B、紫光 UV—7610B、紫光 UV—7 620EA、紫光 UV— 7630B、紫光 UV— 1400B、紫光 UV— 1700B、紫光 UV— 6 300B、  Nippon Synthetic Chemical Industry Co., Ltd .: Purple light UV—7600B, Purple light UV—7610B, Purple light UV—7 620EA, Purple light UV—7630B, Purple light UV—1400B, Purple light UV—1700B, Purple light UV—6 300B,
共栄社ィ匕学 (株)製:ライトアタリレート PE— 4A、ライトアタリレート DPE— 6A、 UA — 306H、 UA— 306T、 UA— 3061、  Kyoeisha Co., Ltd .: Light Attalate PE-4A, Light Attalate DPE-6A, UA-306H, UA-306T, UA-3061,
日本化薬（株）製： KAYARAD DPHA, KAYARAD DPHA— 40H、 KAYA RAD D— 310、 KAYARAD D— 330。  Nippon Kayaku Co., Ltd .: KAYARAD DPHA, KAYARAD DPHA—40H, KAYA RAD D—310, KAYARAD D—330.
さらに、光硬化後の硬化膜の鉛筆硬度が H以上になる (メタ)アタリレートイ匕合物とし ては、例えば、下記一般式（1)で表される化合物を挙げることができる。  Furthermore, examples of the (meth) attareito toy compound in which the pencil hardness of the cured film after photocuring is H or more include a compound represented by the following general formula (1).
一般式 (1) General formula (1)
[化 1]
Figure imgf000009_0001
[Chemical 1]
Figure imgf000009_0001
(式中、 I^〜R4は、それぞれ独立に水素原子またはメチル基を示し、 R5〜R8は、そ れぞれ独立に非置換もしくは置換の、直鎖もしくは分岐鎖のアルキレン基を示し、 R9 は、 4価の脂肪族基もしくは芳香族基を示す。 ) (In the formula, I ^ to R 4 each independently represents a hydrogen atom or a methyl group, and R 5 to R 8 each independently represents an unsubstituted or substituted linear or branched alkylene group. R 9 represents a tetravalent aliphatic group or an aromatic group.
式中、 R9の 4価の脂肪族骨格としては、炭素鎖数 4〜： LOのアルキル骨格である 4価 の脂肪族基が挙げられ、具体的にはブタン骨格、シクロブタン骨格、へキサン骨格、 シクロへキサン骨格、デカリン骨格などが挙げられる。さらに、 R9の 4価の芳香族基と しては、具体的にはフエ-ル骨格、ベンゾフエノン骨格、ビフエ-ル骨格、フエ-ルェ 一テル骨格、ジフヱ-ルスルホン骨格、ジフヱ-ルスルフイド骨格、ペリレン骨格、フ ルオレン骨格、テトラヒドロナフタレン骨格及びナフタレン骨格などが挙げられる。 In the formula, examples of the tetravalent aliphatic skeleton of R 9 include a tetravalent aliphatic group that is an alkyl skeleton having a carbon chain number of 4 to LO, specifically a butane skeleton, a cyclobutane skeleton, and a hexane skeleton. , Cyclohexane skeleton, decalin skeleton and the like. Further, as the tetravalent aromatic group of R 9 , specifically, a phenyl skeleton, a benzophenone skeleton, a biphenyl skeleton, a phenol skeleton, a diphenylsulfone skeleton, a diphenylsulfide skeleton, Examples include perylene skeleton, fluorene skeleton, tetrahydronaphthalene skeleton and naphthalene skeleton.
[0018] 一般式 (1)で表される (メタ)アタリレート化合物は、例えば、脂肪族骨格または芳香 族骨格、及び 2つ以上のカルボン酸無水物基を有する化合物（xl)と、カルボン酸無 水物基と反応しうる官能基を有する化合物 (x2)とを反応させてなるカルボキシル基 を有する化合物 (X)と、カルボキシル基と反応しうる官能基を有する化合物 (Y)とを 反応させて得られる。 [0018] The (meth) acrylate compound represented by the general formula (1) includes, for example, an aliphatic skeleton or an aromatic skeleton, and a compound (xl) having two or more carboxylic anhydride groups, and a carboxylic acid A compound (X) having a carboxyl group obtained by reacting a compound (x2) having a functional group capable of reacting with an anhydrous group is reacted with a compound (Y) having a functional group capable of reacting with a carboxyl group. Obtained.
ここで、化合物 (x2)における「カルボン酸無水物基と反応しうる官能基」としては、ヒ ドロキシ基、アミノ基、グリシジル基などが挙げられる力 反応の制御のし易さから、ヒ ドロキシ基が特に好ましい。また、化合物 (Y)における「カルボキシル基と反応しうる 官能基」としては、エポキシ基、ォキサゾリン基、ヒドロキシ基、アミノ基、カルポジイミド 基、イソシァネート基、イソチオシァネート基、ビニルエーテル基などが挙げられる。  Here, examples of the “functional group capable of reacting with a carboxylic acid anhydride group” in the compound (x2) include a hydroxyl group, an amino group, a glycidyl group, and the like. Is particularly preferred. Examples of the “functional group capable of reacting with a carboxyl group” in the compound (Y) include an epoxy group, an oxazoline group, a hydroxy group, an amino group, a carpoimide group, an isocyanate group, an isothiocyanate group, and a vinyl ether group. .
[0019] さらに、一例を挙げて説明する。脂肪族骨格または芳香族骨格、及び 2つ以上の力 ルボン酸無水物基を有する化合物 (xl)である下記一般式（2)： 一般式 (2) [0019] Further, an example will be described. The following general formula (2), which is a compound (xl) having an aliphatic skeleton or an aromatic skeleton, and two or more rubonic anhydride groups: General formula (2)
[化 2][Chemical 2]
Figure imgf000010_0001
Figure imgf000010_0001
(ここで、
Figure imgf000010_0002
R6および R9は、式（1)で定義した通り) で示される化合物 (X)を得ることができる。 (here,
Figure imgf000010_0002
R 6 and R 9 are as defined in formula (1)) The compound (X) shown by can be obtained.
[0020] 上記一般式（2)で示される脂肪族テトラカルボン酸二無水物としては、ブタンテトラ カルボン酸二無水物が挙げられる。  [0020] Examples of the aliphatic tetracarboxylic dianhydride represented by the general formula (2) include butanetetracarboxylic dianhydride.
一方、芳香族テトラカルボン酸二無水物としては、ピロメリット酸二無水物、ベンゾフ エノンテトラカルボン酸二無水物、ビフエ-ル骨格を有するビフエ-ルテトラカルボン 酸二無水物、ォキシジフタル酸二無水物、ジフエ-ルスルホンテトラカルボン酸二無 水物、ジフエ-ルスルフイドテトラカルボン酸二無水物、ペリレンテトラカルボン酸二無 水物、ナフタレン骨格を有するナフタレンテトラカルボン酸二無水物等、フルオレン骨 格を有する 9, 9 ビス（3, 4—ジカルボキシフエ-ル）フルオレン二無水物、あるいは 、 9, 9 ビス [4— (3, 4—ジカルボキシフエノキシ）フエ-ル]フルオレン二無水物、テ トロヒドロナフタレン骨格を有するテトラヒドロナフタレンカルボン酸二無水物、ェチレ ングリコーノレビス（アンヒドロトリメリテート）、グリセリンビス（アンヒドロトリメリテート）モノ アセテート等が挙げられる。市販品としては新日本理化株式会社製「リカシッド TMT A—C」、「リカシッド MTA—10」、「リカシッド MTA—15」、「リカシッド TMEGシリー ズ」、「リカシッド TDA」、「リカシッド DSDA」、などが挙げられる。  On the other hand, examples of aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride having a biphenyl skeleton, and oxydiphthalic dianhydride. Fluorene skeletons, such as diphenylsulfone tetracarboxylic dianhydride, diphenylsulfide tetracarboxylic dianhydride, perylenetetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride having naphthalene skeleton 9,9-bis (3,4-dicarboxyphenol) fluorene dianhydride or having 9,9-bis [4- (3,4-dicarboxyphenoxy) phenol] fluorene dianhydride Tetrahydronaphthalene carboxylic dianhydride having a tetrahydronaphthalene skeleton, ethylene glycolenobis (anhydrotrimellitate), Examples include reserine bis (anhydrotrimellitate) monoacetate. Commercially available products include “Ricacid TMT A—C”, “Ricacid MTA-10”, “Ricacid MTA-15”, “Ricacid TMEG Series”, “Ricacid TDA”, “Ricacid DSDA”, etc. Is mentioned.
これら芳香族テトラカルボン酸二無水物のうち、ビフエニルテトラカルボン酸二無水 物は、ビフエニル骨格を有するものであり、ビフエ二ル骨格を式（1)で示される化合物 の分子内に効率よく導入でき、さらに硬化膜のハードコート性と金属酸化物の良好な 分散性を併せ持つことができるため、特に好ま 、。  Of these aromatic tetracarboxylic dianhydrides, biphenyl tetracarboxylic dianhydride has a biphenyl skeleton, and the biphenyl skeleton is efficiently introduced into the molecule of the compound represented by the formula (1). It is particularly preferred because it can have both hard coat properties of the cured film and good dispersibility of the metal oxide.
[0021] 第 1および第 2のヒドロキシル基含有 (メタ)アタリレートイ匕合物、互いに同じであって も異なって!/、てもよ！/、。そのようなヒドロキシル基含有 (メタ)アタリレートイ匕合物の例と ート、 4ーヒドロキシブチル (メタ）アタリレート、 2 ヒドロキシブチル (メタ）アタリレート、 2 -ヒドロキシ - 3—フエノキシプロピル (メタ）アタリレート、 2 -アタリロイルォキシェチ ルー 2—ヒドロキシェチルフタル酸、グリセロールモノ（メタ）アタリレート、 2—ヒドロキシ —3—アタリロイルォキシプロピル (メタ）アタリレート、ジヒドロキシアタリレート、グリセ口 ール (メタ）アタリレート、イソシァヌル酸 EO変性ジアタリレート、ペンタエリスリトールモ ノ（メタ）アタリレート、ジペンタエリスリトールモノ（メタ）アタリレート、ペンタエリスリトー ルジ（メタ）アタリレート、ジペンタエリスリトールジ (メタ）アタリレート、ペンタエリスリトー ルトリ（メタ）アタリレート、ジペンタエリスリトールトリ（メタ）アタリレート、ジペンタエリスリ トールテトラ (メタ）アタリレート、ジペンタエリスリトールペンタ (メタ）アタリレート等が挙 げられる。硬度を上げる用途の場合は、ペンタエリスリトールトリ (メタ)アタリレート、ジ ペンタエリスリトールトリ（メタ）アタリレート、ジペンタエリスリトールテトラ (メタ）アタリレ ート、ジペンタエリスリトールペンタ (メタ）アタリレート等が好ましい。 [0021] The first and second hydroxyl group-containing (meth) ataretoy compound may be the same or different! /! /. Examples of such hydroxyl group-containing (meth) atalytoi compounds and salts, 4-hydroxybutyl (meth) atarylate, 2-hydroxybutyl (meth) atalylate, 2-hydroxy-3-phenoxypropyl (Meth) Atalylate, 2-Atalyloylochetiru 2-Hydroxyethyl phthalic acid, Glycerol mono (meth) atarylate, 2-Hydroxy —3-Ataliloyloxypropyl (meth) Atalylate, Dihydroxy Atari Rate, Glycerol (Meth) Atalylate, Isocyanuric Acid EO-modified Diatalylate, Pentaerythritol Mono (Meth) Atylate, Dipentaerythritol Mono (Meth) Atylate, Pentaerythritol Rudi (meth) acrylate, dipentaerythritol di (meth) acrylate, pentaerythritol Tolutri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (Meta) Atarirate and so on. For the purpose of increasing hardness, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. are preferred. .
具体的な市販品としては、ビスコート # 300 (大阪有機化学工業株式会社製)、 KA YARAD PET30 (日本化薬株式会社製）、 PETIA (ダイセル UCB (株）製）、ァロ ニックス M305 (東亞合成株式会社製）、 NKエステル A— TMM— 3LMN (新中村 化学工業株式会社製)、ライトアタリレート PE— 3A (共栄社ィ匕学株式会社製)、 SR— 444 (サートマ一株式会社製）、ライトアタリレート DPE— 6A (共栄社ィ匕学株式会社製 )、 KAYARAD DPHA (日本化薬株式会社製）、ァロニックス M402 (東亞合成株 式会社製)等が挙げられる。特に、ペンタエリスリトールトリ（メタ)アタリレートを主成分 とする KAYARAD PET30 (日本化薬株式会社製）は、金属酸化物の分散性が良 好であることからより好ましい。多官能 (メタ)アタリレートイ匕合物の場合、副成分として 水酸基を 2個持つ多官能 (メタ)アタリレートを 5〜15%程度含有することにより、得ら れるァミノ基含有光硬化性化合物の硬化後の重量平均分子量が高分子量化する傾 向にあり、金属酸ィ匕物の分散性もより良好になることから好まし 、。  Specific commercial products include Biscoat # 300 (Osaka Organic Chemical Co., Ltd.), KA YARAD PET30 (Nippon Kayaku Co., Ltd.), PETIA (Daicel UCB Co., Ltd.), Aronix M305 (Toagosei) Co., Ltd.), NK Ester A— TMM— 3LMN (Shin Nakamura Chemical Co., Ltd.), Light Atarilate PE— 3A (Kyoeisha Co., Ltd.), SR—444 (Cartoma Co., Ltd.), Light Examples include Atarilate DPE-6A (manufactured by Kyoeisha Co., Ltd.), KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), and Aronix M402 (manufactured by Toagosei Co., Ltd.). In particular, KAYARAD PET30 (manufactured by Nippon Kayaku Co., Ltd.) mainly composed of pentaerythritol tri (meth) acrylate is more preferable because of good dispersibility of the metal oxide. In the case of polyfunctional (meth) ataretoy compound, an amino group-containing photocurable compound obtained by containing about 5 to 15% of polyfunctional (meth) atalylate having two hydroxyl groups as accessory components This is preferable because the weight average molecular weight after curing tends to be high, and the dispersibility of the metal oxide is also improved.
[0022] 上記脂肪族または芳香族テトラカルボン酸二無水物と、第 1および第 2のヒドロキシ ル基含有 (メタ)アタリレート化合物との反応は、脂肪族または芳香族テトラカルボン 酸二無水物の有する 2つのカルボン酸無水物基と、第 1および第 2のヒドロキシル基 含有 (メタ)アタリレート化合物がそれぞれ有するヒドロキシル基との反応であり、それ 自体当該分野においてよく知られている。例えば、芳香族テトラカルボン酸二無水物 と第 1および第 2のヒドロキシル基含有 (メタ)アタリレートイ匕合物とを、シクロへキサノン のような有機溶媒中、 1, 8—ジァザビシクロ [5. 4. 0]—7—ゥンデセンのような触媒 の存在下、 50〜120°Cの温度で反応させることができる。この場合、反応系に、メトキ ノン（methoquinone)のような重合禁止剤を添加することができる。 [0022] The reaction between the aliphatic or aromatic tetracarboxylic dianhydride and the first and second hydroxyl group-containing (meth) acrylate compounds is carried out by reaction of an aliphatic or aromatic tetracarboxylic dianhydride. This is a reaction between the two carboxylic anhydride groups possessed by the hydroxyl groups possessed by the first and second hydroxyl group-containing (meth) acrylate compounds, and is well known in the art. For example, an aromatic tetracarboxylic dianhydride and a first and second hydroxyl group-containing (meth) atalytoi compound are mixed in an organic solvent such as cyclohexanone with 1,8-diazabicyclo [5. 4. The reaction can be carried out at a temperature of 50 to 120 ° C in the presence of a catalyst such as 0] -7-undecene. In this case, a polymerization inhibitor such as methoquinone can be added to the reaction system.
[0023] 上記反応後、反応生成物である式（5)の化合物 (X)を含む反応混合物に、これを 精製することなぐ例えば、化合物 (Y)である下記一般式 (6)： [0023] After the above reaction, this is added to a reaction mixture containing the compound (X) of the formula (5) as a reaction product. Without purification, for example, the following general formula (6), which is compound (Y):
一般式 (6)  General formula (6)
[化 4]  [Chemical 4]
R°— CH2— CH-CH2 R ° — CH 2 — CH-CH 2
\ /  \ /
0  0
(ここで、 R。は、 CH =C (R3)— C (0) 0—基および CH =C (R4)— C (0) 0—基; R (Where R. is CH = C (R 3 ) — C (0) 0— group and CH = C (R 4 ) — C (0) 0— group; R
2 2  twenty two
3および R4は、上記定義の通り） 3 and R 4 are as defined above)
であるエポキシ基含有ィ匕合物を添加し、反応させて一般式（1)で示される化合物を 得ることができる（この場合、 R7および R8は、 -CH CH (OH) CH—基である。；)。 The compound represented by the general formula (1) can be obtained by adding an epoxy group-containing compound which is: (in this case, R 7 and R 8 are —CH 2 CH 2 (OH) 2 CH— groups ;).
2 2  twenty two
[0024] 式（6)で示される化合物の例には、グリシジルメタタリレート、グリシジルアタリレート のようなエポキシ基含有 (メタ）アタリレート； o フエ-ルフエノールグリシジルエーテ ル、 p—フエ-ルフエノールグリシジルエーテル、モノスチレン化フエノールグリシジル エーテル、 4—シァノ 4—ヒドロキシビフエ-ルグリシジルエーテル、 4, 4'—ビフエノ ールモノグリシジルエーテル、 4, 4'ービフエノールジグリシジルエーテルのような芳 香族グリシジルエーテル化合物等が含まれる。  [0024] Examples of the compound represented by the formula (6) include epoxy group-containing (meth) acrylate, such as glycidyl methacrylate and glycidyl acrylate; o-phenol phenol glycidyl ether, p-phenol Flavors such as phenol glycidyl ether, monostyrenated phenol glycidyl ether, 4-ciano 4-hydroxybiphenol glycidyl ether, 4, 4'-biphenol monoglycidyl ether, 4, 4'-biphenol diglycidyl ether Group glycidyl ether compounds and the like.
式（5)で示される化合物と式 (6)で示される化合物との反応は、式（5)で示される化 合物の有するカルボキシル基と式（6)で示される化合物の有するエポキシ基との反 応であり、それ自体当該分野においてよく知られている。例えば、この反応は、ジメチ ルベンジルァミン等のようなァミン触媒の存在下、 50〜120°Cの温度で行なうことが できる。  The reaction between the compound represented by formula (5) and the compound represented by formula (6) is carried out by reacting the carboxyl group possessed by the compound represented by formula (5) with the epoxy group possessed by the compound represented by formula (6). It is well known in the art. For example, this reaction can be carried out at a temperature of 50 to 120 ° C. in the presence of an amine catalyst such as dimethylbenzylamine.
[0025] これらの反応は、無溶媒で行なってもよぐあるいは反応に対して不活性な溶媒中 で行なってもよい。力かる溶媒としては、例えば、 n—へキサン、ベンゼンまたはトルェ ン等の炭化水素系溶媒；アセトン、メチルェチルケトンまたはメチルイソプチルケトン 等のケトン系溶媒；酢酸ェチルまたは酢酸ブチル等のエステル系溶媒；ジェチルェ 一テル、テトラヒドロフランまたはジォキサン等のエーテル系溶媒;ジクロロメタン、クロ 口ホルム、四塩化炭素、 1, 2—ジクロロェタンまたはパークレン等のハロゲン系溶媒； ァセトニトリル、 N, N—ジメチルホルムアミド、 N, N ジメチルァセトアミド、 N, N— ジメチルイミダゾリジノン等の極性溶媒などが挙げられる。これらの溶媒は、 2種類以 上を併用しても差し支えな 、。 [0025] These reactions may be carried out without solvent or in a solvent inert to the reaction. Examples of powerful solvents include hydrocarbon solvents such as n-hexane, benzene, and toluene; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate. Solvents; ether solvents such as jetyl, tetrahydrofuran, dioxane, etc .; halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, or parkrene; acetonitrile, N, N-dimethylformamide, N, N Dimethylacetamide, N, N— Examples include polar solvents such as dimethylimidazolidinone. These solvents may be used in combination of two or more.
[0026] アミノ基含有光硬化性化合物を構成する第一級または第二級ァミンは、一分子中 に第一級ァミノ基または第二級アミノ基を少なくとも 1個有するアミンィ匕合物であり、剛 直性の少ない脂肪族ァミンがより好ましい。さらに、分子内に第一級または第二級ァ ミノ基を 2個以上有するァミン化合物を用いた場合、ァミン化合物 1分子に対して複数 のアタリレートイ匕合物またはメタクリレートイ匕合物が複雑に反応するため、反応物は高 分子量化し、ゲルィ匕しゃすい問題を有する。そのため、（メタ)アタリレートイ匕合物に対 するアミンィ匕合物の添加量を低減させたり、反応条件などを制御したりすることにより 、汎用性のあるアミノ基含有光硬化性ィ匕合物を得ることが好まし 、。  [0026] The primary or secondary amine constituting the amino group-containing photocurable compound is an amine compound having at least one primary amino group or secondary amino group in one molecule, An aliphatic amine having low rigidity is more preferable. Furthermore, when an amine compound having two or more primary or secondary amino groups in the molecule is used, a plurality of talaritoy compounds or methacrylate compounds are complex per molecule of the amine compound. The reaction product has a high molecular weight and has a gely problem. Therefore, it is possible to reduce the amount of amine compound added to the (meth) atalytoi compound, or to control the reaction conditions, etc., so that the versatile amino group-containing photocuring compound can be used. I prefer to get things.
アミンィ匕合物は、（メタ)アタリレート化合物と反応しない、アミノ基以外の他の極性官 能基を有しても良い。このような極性官能基としては、水酸基、カルボキシル基、スル ホン酸基、リン酸基、シァノ基、ニトロキシル基などが挙げられる。  The amine compound may have a polar functional group other than the amino group that does not react with the (meth) acrylate compound. Examples of such a polar functional group include a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a cyano group, and a nitroxyl group.
[0027] アミノ基含有光硬化性化合物を構成する第一級ァミンのうち、モノアミンとしては、ァ ミノメタン、アミノエタン、 1ーァミノプロパン、 2—ァミノプロパン、 1 アミノブタン、 2— アミノブタン、 1—ァミノペンタン、 2 ァミノペンタン、 3 ァミノペンタン、イソアミルアミ ン、 1—ァミノへキサン、 1—ァミノヘプタン、 2—ァミノヘプタン、 2—オタチノレアミン、 1 —アミノノナン、 1—ァミノデカン、 1—アミノドデカン、 1—アミノトリデカン、 1—ァミノへ キサデカン、ステアリノレアミン、アミノシクロプロパン、アミノシクロブタン、アミノシクロべ ンタン、アミノシクロへキサン、アミノシクロドデカン、 1 アミノー 2—ェチルへキサン、 1 アミノー 2 メチルプロパン、 2 アミノー 2 メチルプロパン、 3 アミノー 1 プロ ペン、 3—ァミノメチルヘプタン、 3—イソプロポキシプロピルァミン、 3—ブトキシプロピ ルァミン、 3 イソブトキシプロピルァミン、 2 ェチルへキシロキシプロピルァミン、 3 —デシロキシプロピルァミン、 3—ラウリロキシプロピルァミン、 3—ミリスチロキシプロピ ルァミン、 2—アミノメチルテトラヒドロフラン、ァニリン、 o ァミノトルエン、 m—アミノト ルェン、 p ァミノトルエン、 o ベンジルァ二リン、 p ベンジルァ二リン、 1—ァ-リノ ナフタレン、 1ーァミノアントラキノン、 2—ァミノアントラキノン、 1ーァミノアントラセン、 2 ァミノアントラセン、 5 ァミノイソキノリン、 o アミノジフエニル、 4 アミノジフエ二 ルエーテル、 2 ァミノべンゾフエノン、 4ーァミノべンゾフエノン、 o アミノアセトフエノ ン、 m—アミノアセトフエノン、 p—アミノアセトフエノン、ベンジルァミン、 at フエ二ノレ ェチルァミン、フエネシルァミン、 p—メトキシフエネシルァミン、 p アミノアゾベンゼン 、 m—ァミノフエノール、 p ァミノフエノール、ァリルアミン等が挙げられる。 [0027] Among the primary amines constituting the amino group-containing photocurable compound, monoamines include aminomethane, aminoethane, 1-aminopropane, 2-aminopropane, 1-aminobutane, 2-aminobutane, 1-aminopentane, 2-aminopentane, 3 Amaminopentane, Isoamylamine, 1-Aminohexane, 1-Aminoheptane, 2-Aminoheptane, 2-Otatinoleamine, 1-Aminononane, 1-Aminodecane, 1-Aminododecane, 1-Aminotridecane, 1-Aminohexadecane, Stearinoreamine, aminocyclopropane, aminocyclobutane, aminocyclopentane, aminocyclohexane, aminocyclododecane, 1-amino-2-ethylhexyl, 1-amino-2-methylpropane, 2-amino-2-methylpropane, 3-amino-1-pro , 3-aminomethylheptane, 3-isopropoxypropylamine, 3-butoxypropylamine, 3 isobutoxypropylamine, 2-ethylhexyloxypropylamine, 3-decyloxypropylamine, 3-lauri Loxypropylamine, 3-myristoxypropylamine, 2-aminomethyltetrahydrofuran, aniline, o-aminotoluene, m-aminotoluene, p-aminotoluene, o-benzylaniline, p-benzylaniline, 1-a-linonaphthalene, 1 -Aminoanthraquinone, 2-aminoanthraquinone, 1-aminoanthracene, 2 aminoanthracene, 5 aminoisoquinoline, o aminodiphenyl, 4 aminodiphenyl Luether, 2-aminobenzophenone, 4-aminobenzophenone, o-aminoacetophenone, m-aminoacetophenone, p-aminoacetophenone, benzylamine, at-phenethylamine, penemethoxylamin, p-methoxyphenesyl Min, p-aminoazobenzene, m-aminophenol, p-aminophenol, arylamine and the like.
[0028] アミノ基含有光硬化性化合物を構成する第二級ァミンのうち、モノアミンとしては、ジ メチルァミン、ジェチルァミン、 N—メチルェチルァミン、 N メチルイソプロピルアミン 、 N—メチルへキシルァミン、ジイソプロピルァミン、ジ n—プロピルァミン、ジ n—ブチ ルァミン、ジ sec ブチルァミン、 N ェチルイソアミルァミン、 N ェチル—1 ,2—ジメ チノレプロピノレアミン、ピぺリジン、 2 ピペコリン、 3 ピペコリン、 4ーピペコリン、 2,4 ールペチジン、 2,6—ルペチジン、 3, 5—ルペチジン、 3 ピペリジンメタノール、ピぺ コリニックアシッド、イソ-ペコチックアシッド、メチルイソ-ペコテート、ェチルイソ-ベ コテート、 2 メチルアミノエタノール、 3 メチルアミノー 1 ,2 プロパンジオール、 1 ーピペラジンエタノール、 2 ピペリジンエタノール、 4ーピペリジンエタノール、 4ーピ ペリジンブチリックアシッド塩酸塩、 4ーピベリジノール、ピロリジン、 3—ピロリジノール 、インドリン、 N ブチルァ-リン、 N—メチルベンジルァミン、 3—ベンジルァミノプロ ピオニックアシッドェチルエーテル、 4 ベンジルピペリジン、ジフエ-ルァミン等が挙 げられる。 Among the secondary amines constituting the amino group-containing photocurable compound, monoamines include dimethylamine, jetylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine. Min, di-n-propylamine, di-n-butylamine, disec-butylamine, N-ethylisoamylamine, N-ethyl-1,2,2-dimethylenopropynoleamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline 2,4-Rupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3 Piperidinemethanol, Pipecolic Acid, Iso-Pecotic Acid, Methyl Iso-Pecotate, Ethyl Iso-Becoteate, 2 Methylaminoethanol, 3 Methylamino 1,2 propanediol, 1-piperazine ethanol, 2 piperi Dine ethanol, 4-piperidine ethanol, 4-piperidine butyric acid hydrochloride, 4-piperidinol, pyrrolidine, 3-pyrrolidinol, indoline, N-butylaline, N-methylbenzylamine, 3-benzylaminopropionic Acid ether ether, 4-benzylpiperidine, diphenylamine and the like.
[0029] さらに、アミノ基含有光硬化性化合物を構成する第一級ァミンおよび第二級ァミン のうち、分子内にアミノ基を複数有するアミンィ匕合物の例としては、 3—ァミノピロリジ ン、ジメチルアミノエチルァミン、ェチルアミノエチルァミン、ジェチルアミノエチルアミ ン、 N, N ジイソプロピルアミノエチルァミン、 1 ,2—ジァミノプロパン、 1 ,3 ジァミノ プロパン、メチルァミノプロピルァミン、ジメチルァミノプロピルァミン、ジェチルアミノプ 口ピルァミン、ジブチルァミノプロピルァミン、 2—ヒドロキシェチルァミノプロピルアミン 、ビス一（3 ァミノプロピル）エーテル、ジメチルアミノエトキシプロピルァミン、 1 , 2— ビス一（3 ァミノプロポキシ）ェタン、 1 , 3 ビス一（3 ァミノプロポキシ）ー 2, 2 ジ メチルプロパン、 1 , 2 ジアミノブタン、 1 , 4ージアミノブタン、ラウリルアミノプロピル ァミン、ジエタノールァミノプロピルァミン、 N—アミノエチルピペリジン、 N—アミノエチ ル 4 ピペコリン、 N ァミノプロピルピぺリジン、 N ァミノプロピル一 2 ピペコリン、 N ァミノプロピル一 4—ピペコリン、 N アミノエチルモルフォリン、 N ァミノプロピ ルモルフォリン、イミノビスプロピルァミン、メチルイミノビスプロピルァミン、 4ーピベリジ ンカルボキシアミド、 4 アミノメチルー 1ーブチルビペリジン、 4 アミノメチルビベリジ ン、 1,3 ジー（4ーピペリジル） プロパン、 4ーピペリジノピペリジン、 N ァミノプロ ピルァニリン、 3—ァミノピロリジン、 N—メチルビペラジン、 N ェチルビペラジン、 N ーァリルピぺラジン、 N—イソブチルビペラジン、 N ァミノプロピルピぺラジン、 1ーシ クロペンチルピペラジン、 N—フエ-ルビペラジン、 1— (2—ピリジル）ピぺラジン、 1 一（4一ピリジル）ピぺラジン、ホモピぺラジン、 N メチルホモピぺラジン等が挙げら れる。 [0029] Further, among the primary and secondary amines constituting the amino group-containing photocurable compound, examples of amine compounds having a plurality of amino groups in the molecule include 3-aminopyrrolidine, dimethyl Aminoethylamine, Ethylaminoethylamine, Jetylaminoethylamine, N, N Diisopropylaminoethylamine, 1,2-Diaminopropane, 1,3 Diaminopropane, Methylaminopropylamine, Dimethylamino Propylamine, Jetylaminopropylpyramine, Dibutylaminopropylamine, 2-Hydroxyethylaminopropylamine, Bis (3-aminopropyl) ether, Dimethylaminoethoxypropylamine, 1,2-bis (3-amino Propoxy) ethane, 1,3 bis (3-aminopropoxy) -2,2 dimethylpropane, 1 , 2 Diaminobutane, 1,4-diaminobutane, laurylaminopropylamine, diethanolaminopropylamine, N-aminoethylpiperidine, N-aminoethyl 4-pipecoline, N-aminopropylpiperidine, N-aminopropyl1-2 pipecoline, N-aminopropyl-4-pipecoline, N-aminoethylmorpholine, N-aminopropylmorpholine, iminobispropylamine, methyliminobispropylamine, 4-piveridinecarboxamide, 4-aminomethyl-1-butylbiperidine, 4-aminomethylbiverine Gin, 1,3 G (4-piperidyl) propane, 4-piperidinopiperidine, N-aminopropyranylline, 3-aminopyrrolidine, N-methylbiperazine, N-ethylbiperazine, N-arylpiperazine, N-isobutylbiperazine, N Aminopropylpiperazine, 1-Cyclopentylpiperazine, N-Ferrubiperazine, 1- (2-Pyridyl) piperazine, 1- (4-Pyridyl) piperazine, Homopiperazine, N-methylhomopiperazine, etc. It is
上記に示すアミンィ匕合物は、単独で用いられるほ力、二種類以上を併用して用い てもよい。  The amine compounds shown above may be used alone or in combination of two or more.
[0030] なかでも、第二級ァミノ基のみを有する脂肪族モノアミンは、金属酸化物の分散性 も良好であり、かつ、マイケル付加反応が一段階で終了し、反応による着色が少ない ため好ましい。  [0030] Among them, an aliphatic monoamine having only a secondary amino group is preferable because the dispersibility of the metal oxide is good, the Michael addition reaction is completed in one step, and coloring due to the reaction is small.
第二級ァミノ基のみを有する脂肪族モノアミンとしては、ジメチルァミン、ジェチルァ ミン、 N—メチルェチルァミン、 N メチルイソプロピルアミン、 N メチルへキシルアミ ン、ジイソプロピルァミン、ジ n—プロピルァミン、ジ n—ブチルァミン、ジ sec ブチル ァミン、 N ェチル—1,2 ジメチルプロピルァミン、ピぺリジン、 2 ピペコリン、 3— ピペコリン、 4 ピペコリン、 2,4—ルペチジン、 2,6—ルペチジン、 3,5—ルペチジン、 2 メチルアミノエタノール、 3 メチルアミノー 1,2 プロパンジオール、 1ーピペラジ ンエタノール、 3 ピペリジンメタノール、 2 ピペリジンエタノール、 4ーピペリジンェ タノール、 4ーピベリジノール、ピロリジン、 3—ァミノピロリジン、 3—ピロリジノール等 が挙げられる。特に、ジメチルァミン、ジェチルァミン、 N—メチルェチルァミン、 N— メチルイソプロピルァミン、 N—メチルへキシルァミン、ジイソプロピルァミン、ジ n—プ 口ピルァミン、ジ n プチルァミンは、金属酸ィ匕物の分散性と分散安定性がより良好と なることから好ましい。  Aliphatic monoamines having only secondary amino groups include dimethylamine, jetylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine, di-n-propylamine, di-n- Butyramine, Disec Butyramine, N-ethyl-1,2 Dimethylpropylamine, Piperidine, 2-Pipecoline, 3-Pipecoline, 4-Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, Examples include 2-methylaminoethanol, 3-methylamino-1,2-propanediol, 1-piperazine ethanol, 3-piperidinemethanol, 2-piperidineethanol, 4-piperidineethanol, 4-piperidinol, pyrrolidine, 3-aminopyrrolidine, and 3-pyrrolidinol. In particular, dimethylamine, jetylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine, di-n-pylamine, di-n-ptyramine are metal oxide dispersions. From the viewpoint of better properties and dispersion stability.
[0031] 光硬化後の鉛筆硬度が H以上になる (メタ)アタリレートイ匕合物と第一級または第二 級ァミンとは、前記 (メタ）アタリレートイ匕合物中のエチレン性不飽和二重結合 100モ ルに対して、第一級または第二級ァミンが 0. 5〜50モルとなる比率で反応させること が好ましぐ 1. 0〜30モルとなる比率で反応させることがより好ましい。すなわち、アミ ノ基含有光硬化性化合物中には、 0. 5〜50モル（より好ましくは 1. 0〜30モル）のァ ミノ基 (つまり、エチレン性不飽和二重結合と第一級または第二級ァミンとを反応させ た官能基）と、 50〜95. 5モル（より好ましくは 70〜99モル）の未反応のエチレン性 不飽和二重結合が含まれて 、ることが好ま 、。 [0031] The (meth) atareto toy compound and the primary or secondary ammine having a pencil hardness after photocuring of not less than H are an ethylenic defect in the (meth) atareto toy compound. 100 double saturated bonds It is preferable to react with the base at a ratio of primary or secondary amine of 0.5 to 50 mol, more preferably 1.0 to 30 mol. That is, in the amino group-containing photocurable compound, 0.5 to 50 mol (more preferably 1.0 to 30 mol) of amino groups (that is, ethylenically unsaturated double bonds and primary or A functional group reacted with a secondary amine) and 50 to 95.5 moles (more preferably 70 to 99 moles) of an unreacted ethylenically unsaturated double bond. .
第一級または第二級ァミンの反応比率が 0. 5モル未満の場合、得られるアミノ基含 有光硬化性ィ匕合物中のアミノ基の比率が小さいため、金属酸ィ匕物の良好な分散性 が得られに《なり、その硬化膜の透明性が悪ィ匕しやすくなる。また、この反応比率が 50モルを超える場合、得られるアミノ基含有光硬化性ィ匕合物中のアミノ基の比率が 非常に大きくなるため、良好な金属酸化物分散性は得られるが、一方でエチレン性 不飽和二重結合の比率が低くなるため、塗膜作成時の光硬化性が乏しくなり、その 硬化膜のハードコート性も低下しやすくなる。  When the reaction ratio of primary or secondary amine is less than 0.5 mol, the ratio of amino groups in the resulting amino group-containing photocurable compound is small, so that the metal acid compound is good. Therefore, the dispersibility of the cured film becomes low, and the transparency of the cured film tends to deteriorate. In addition, when the reaction ratio exceeds 50 mol, the ratio of amino groups in the resulting amino group-containing photocurable composite is very large, so that good metal oxide dispersibility can be obtained. Since the ratio of ethylenically unsaturated double bonds is low, the photocurability at the time of preparing the coating film becomes poor, and the hard coat property of the cured film tends to deteriorate.
[0032] アミノ基含有光硬化性化合物は、前記 (メタ)アタリレート化合物と前記第一級また は第二級ァミンとを、二成分が溶解可能な溶剤中にお 、て反応させることにより得ら れる。これは、第一級または第二級ァミン中のアミノ基が (メタ)アタリレートイ匕合物中 のエチレン性不飽和二重結合にマイケル付加することにより、分子の末端にアミノ基 を導入する反応である。 [0032] The amino group-containing photocurable compound is obtained by reacting the (meth) acrylate compound and the primary or secondary amine in a solvent in which two components can be dissolved. It is This introduces an amino group at the end of the molecule by Michael addition of the amino group in the primary or secondary amine to the ethylenically unsaturated double bond in the (meth) atalytoi compound. It is a reaction.
反応温度に関しては、室温下でも速やかに反応が進むため、 10〜110°Cが好まし ぐ 20〜80°Cがより好ましい。反応温度が 10°C未満の場合、原料となる (メタ)アタリ レート化合物、または反応物であるアミノ基含有光硬化性化合物の溶解性が低下し て析出しやすぐ反応速度が低下し反応時間が長時間化するため生産性が落ちるな どの問題が生じ易い。一方、反応温度が 110°Cを超えた場合、反応物が着色するた め、その着色したアミノ基含有光硬化性化合物を用いた硬化性組成物、およびその 硬化膜の色目〖こ影響を及ぼすことになる。  Regarding the reaction temperature, 10 to 110 ° C is preferable, and 20 to 80 ° C is more preferable because the reaction proceeds promptly even at room temperature. When the reaction temperature is less than 10 ° C, the solubility of the raw material (meth) acrylate compound or the reaction product amino group-containing photo-curing compound decreases, and the reaction rate decreases immediately and the reaction time decreases. The problem is likely to occur such as a drop in productivity due to the longer time required. On the other hand, when the reaction temperature exceeds 110 ° C, the reaction product is colored. Therefore, the curable composition using the colored amino group-containing photocurable compound and the color of the cured film are affected. It will be.
[0033] 前記 (メタ)アタリレートイ匕合物と前記第一級または第二級ァミンとを反応させる際に 用いる溶剤は、原料となる (メタ)アタリレートイ匕合物および第一級または第二級ァミン との反応性を有しないものであれば、特に限定するものではない。溶剤としては、例 えば、シクロへキサノン、メチルイソブチルケトン、メチルェチルケトン、アセトン、トル ェン、キシレン、ブタノール、イソプロパノール、プロピレングリコーノレモノメチノレエーテ ル、アジピン酸ジメチル、コハク酸ジメチル、グルタル酸ジメチルなどが挙げられる。こ れらのうち、複数種の溶剤を組み合わせて用いてもよい。 [0033] The solvent used in the reaction of the (meth) ataretoy compound with the primary or secondary amine is a raw material of the (meth) ateretoy compound and primary or There is no particular limitation as long as it does not have reactivity with the secondary amine. Examples of solvents Examples include cyclohexanone, methyl isobutyl ketone, methyl ethyl ketone, acetone, toluene, xylene, butanol, isopropanol, propylene glycol monomonomethylolate, dimethyl adipate, dimethyl succinate, and dimethyl glutarate. It is done. Of these, a plurality of solvents may be used in combination.
[0034] 硬化性組成物における金属酸ィ匕物の添加量は、特に制限されな!、が、金属酸ィ匕 物及びアミノ基含有光硬化性化合物の固形分合計量 100重量部中、好ましくは 1〜 80重量部、より好ましくは 10〜70重量部である。金属酸化物の添加量が 1重量部未 満では、金属酸ィ匕物由来の帯電防止性が劣る場合があり、 80重量部を超えると有機 成分量が少ないことにより成膜性が劣る場合がある。  [0034] The addition amount of the metal oxide in the curable composition is not particularly limited! However, it is preferable in 100 parts by weight of the total solid content of the metal oxide and the amino group-containing photocurable compound. Is 1 to 80 parts by weight, more preferably 10 to 70 parts by weight. If the addition amount of the metal oxide is less than 1 part by weight, the antistatic property derived from the metal oxide may be inferior, and if it exceeds 80 parts by weight, the film forming property may be inferior due to the small amount of the organic component. is there.
[0035] 硬化性組成物は、たとえば、上述のように、（メタ)アタリレートイ匕合物と第一級または 第二級ァミンとを、前記 (メタ)アタリレートイ匕合物中のエチレン性不飽和二重結合 10 0モルに対して、第一級または第二級ァミンが 0. 5〜50モルとなる比率で反応させて 、アミノ基含有光硬化性化合物を製造すること;および、前記アミノ基含有光硬化性 化合物と、平均一次粒子径が 5〜： LOOnmの金属酸ィ匕物とを混合すること；を含む製 造方法により製造することができる。  [0035] The curable composition includes, for example, as described above, a (meth) atalytoy compound and a primary or secondary ammine, and ethylene in the (meth) atalytoy compound. Reacting at 100 to 50 mol of primary or secondary amine with respect to 100 mol of the unsaturated double bond to produce an amino group-containing photocurable compound; and The amino group-containing photocurable compound and an average primary particle size of 5 to: a metal oxide having LOOnm can be mixed.
[0036] 本発明の硬化性組成物は、金属酸化物粉末とアミノ基含有光硬化性化合物を単に 混合して調製しても、十分に目的とする効果が得られる。ただし、ニーダー、ロール、 アトライター、スーパーミル、乾式粉砕処理機などにより機械的に混合するか、金属 酸化物粉末と有機溶剤などによるサスペンジョン系に、アミノ基含有光硬化性化合物 を含む溶液を添加し、金属酸化物表面にアミノ基含有光硬化性化合物を沈着させる などの緊密な混合系で行なえば、さらに良好な結果を得ることができる。  [0036] Even if the curable composition of the present invention is prepared by simply mixing the metal oxide powder and the amino group-containing photocurable compound, the intended effect can be obtained sufficiently. However, mechanically mixed with a kneader, roll, attritor, super mill, dry pulverizer, etc., or a solution containing an amino group-containing photocurable compound is added to a suspension system using a metal oxide powder and an organic solvent. If a close mixing system such as deposition of an amino group-containing photocurable compound on the surface of the metal oxide is performed, even better results can be obtained.
[0037] 有機溶剤などの非水系ビヒクル中への金属酸ィ匕物、アミノ基含有光硬化性化合物 または硬化性組成物の分散または溶解、及びこれらの混合などには、ペイントコンデ イショナー（レッドデビル社製）、ボールミル、サンドミル（シンマルエンタープライゼス 社製「ダイノーミル」等）、アトライター、パールミル (アイリツヒ社製「DCPミル」等）、コ ボールミル、ホモミキサー、ホモジナイザー（ェム 'テクニック社製「クレアミックス」等）、 湿式ジェットミル（ジーナス社製「ジーナス PY」、ナノマイザ一社製「ナノマイザ一」 )、 微小ビーズミル (寿工業 (株)製「スーパーァペックミル」、 「ウルトラァペックミル」）等の 分散機が使用できる。分散機にメディアを使う場合には、ガラスビーズ、ジルコ-アビ ーズ、アルミナビーズ、磁性ビーズ、スチレンビーズ等を用いることが好ましい。分散 に関しては、 2種類以上の分散機、または大きさの異なる 2種類以上のメディアをそれ ぞれ用い、段階的に使用しても差し支えない。 [0037] A paint conditioner (red devil) is used for dispersing or dissolving a metal oxide, an amino group-containing photocurable compound or curable composition in a non-aqueous vehicle such as an organic solvent, and mixing thereof. ), Ball mill, sand mill (such as “Dyno mill” manufactured by Shinmaru Enterprises), attritor, pearl mill (such as “DCP mill” manufactured by Eiritsuhi), coball mill, homomixer, homogenizer (“EM Technique”) CLEAMIX ”, etc.), wet jet mills (Genus PY, Genas PY, Nanomizer I, Nanomizer 1), microbead mills (Superapec Mill, Kotobuki Co., Ltd., Ultraapec Mill) Etc.) A disperser can be used. When using media in the disperser, it is preferable to use glass beads, zirco beads, alumina beads, magnetic beads, styrene beads, or the like. Regarding dispersion, two or more types of dispersers or two or more types of media of different sizes may be used and used in stages.
[0038] 本発明の硬化性組成物は、少なくとも金属酸化物、アミノ基含有光硬化性化合物 を含有するものであり、さらに溶剤や様々な添加剤を、本発明の目的や効果を損な わない範囲において含むことができる。具体的には、溶剤、光重合開始剤、光硬化 性化合物、重合禁止剤、光増感剤、レべリング剤、界面活性剤、抗菌剤、アンチプロ ッキング剤、可塑剤、紫外線吸収剤、赤外線吸収剤、酸化防止剤、シランカップリン グ剤、導電性ポリマー、導電性界面活性剤、無機充填剤、顔料、染料などが挙げら れる。 [0038] The curable composition of the present invention contains at least a metal oxide and an amino group-containing photocurable compound, and further, a solvent and various additives may impair the purpose and effect of the present invention. It can be included in a range that is not. Specifically, solvents, photopolymerization initiators, photocurable compounds, polymerization inhibitors, photosensitizers, leveling agents, surfactants, antibacterial agents, anti-blocking agents, plasticizers, UV absorbers, Examples include infrared absorbers, antioxidants, silane coupling agents, conductive polymers, conductive surfactants, inorganic fillers, pigments and dyes.
[0039] 金属酸化物およびアミノ基含有光硬化性化合物以外の成分を含む硬化性組成物 の製造方法としては、特に制限されないが、いくつかの方法が挙げられる。具体的に は、初めに金属酸化物及びアミノ基含有光硬化性化合物を有機溶剤中で混合分散 し、安定な金属酸化物分散体を得た後、他の様々な添加剤を添加及び調整し製造 する方法;初めから、金属酸化物、アミノ基含有光硬化性化合物、有機溶剤及びそ の他の添加剤の全てが混合された状態で、分散し製造する方法;などが挙げられる。  [0039] The production method of the curable composition containing components other than the metal oxide and the amino group-containing photocurable compound is not particularly limited, but there are several methods. Specifically, first, a metal oxide and an amino group-containing photocurable compound are mixed and dispersed in an organic solvent to obtain a stable metal oxide dispersion, and then various other additives are added and adjusted. From the beginning, a method of dispersing and manufacturing a metal oxide, an amino group-containing photocurable compound, an organic solvent and other additives are mixed.
[0040] 溶剤を加える場合は、溶剤を揮発させた後に硬化処理を行なうことが好ま ヽ。溶 剤としては、特に制限されるものでなぐ様々な公知の有機溶剤を用いることができる 。具体的には例えば、シクロへキサノン、メチルイソブチルケトン、メチルェチルケトン 、アセトン、ァセチルアセトン、トルエン、キシレン、 n—ブタノール、イソブタノール、 te rtーブタノール、 n—プロパノール、イソプロパノール、エタノール、メタノール、 3—メト キシー 1ーブタノール、 3—メトキシー 2 ブタノール、エチレングリコールモノメチルェ 一テル、エチレングリコールモノ n—ブチルエーテル、 2—エトキシエタノーノレ、 1ーメト キシ 2—プロパノール、ジアセトンアルコール、乳酸ェチル、乳酸ブチル、プロピレ ングリコーノレモノメチノレエーテノレ、エチレングリコーノレモノブチノレエーテノレアセテート[0040] When adding a solvent, it is preferable to perform a curing treatment after volatilizing the solvent. As the solvent, various known organic solvents that are not particularly limited can be used. Specifically, for example, cyclohexanone, methyl isobutyl ketone, methyl ethyl ketone, acetone, acetyl acetate, toluene, xylene, n-butanol, isobutanol, tert-butanol, n-propanol, isopropanol, ethanol, methanol, 3-methoxy 1-butanol, 3-methoxy-2-butanol, ethylene glycol monomethyl ether, ethylene glycol mono n -butyl ether, 2-ethoxyethanol, 1-methoxy 2-propanol, diacetone alcohol, lactyl acetate, butyl lactate, Propylene glycol monomono chinenoate ethere, ethylene glycol monobutino enoate acetate
、プロピレングリコールモノメチルエーテルアセテート、 2—エトキシェチルアセテート 、ブチルアセテート、イソアミルアセテート、アジピン酸ジメチル、コハク酸ジメチル、グ ルタル酸ジメチル、テトラヒドロフラン、メチルピロリドンなどが挙げられる。これらの有 機溶剤は、 2種類以上を併用しても差し支えない。 , Propylene glycol monomethyl ether acetate, 2-ethoxyethyl acetate, butyl acetate, isoamyl acetate, dimethyl adipate, dimethyl succinate, Examples include dimethyl rurate, tetrahydrofuran, and methylpyrrolidone. Two or more of these organic solvents may be used in combination.
[0041] なかでも、水酸基含有溶剤は、親水性の高い粒子表面物性を持つ金属酸化物に 対して濡れ性が良いことから、溶剤組成中に含有されることで、金属酸化物の分散性 及びその塗料 (硬化性組成物）の経時安定性の向上において非常に効果的であり、 かつ塗工工程のレべリング性も向上することから好ましい。全溶剤組成中の水酸基 含有溶剤含有量は、 10〜： LOO重量％であることが好ましい。具体体には、水酸基含 有溶剤としては、 n—ブタノール、イソブタノール、 tert—ブタノール、 n プロパノー ル、イソプロパノール、エタノール、メタノール、 3—メトキシ 1ーブタノール、 3—メト キシー 2—ブタノール、エチレングリコーノレモノメチノレエーテル、エチレングリコーノレモ ノ n—ブチルエーテル、 2—エトキシエタノール、 1ーメトキシ 2—プロパノール、ジァ セトンアルコール、乳酸ェチル、乳酸ブチル、プロピレングリコールモノメチルエーテ ル等が挙げられる。特に、 3—メトキシ一 1—ブタノール、プロピレングリコールモノメチ ノレエーテノレ、エチレングリコーノレモノメチノレエーテノレ、エチレングリコーノレモノ n—ブ チルエーテルは、金属酸ィ匕物の分散性と分散安定性がより良好となることから好まし い。 [0041] In particular, a hydroxyl group-containing solvent has good wettability with respect to a metal oxide having a highly hydrophilic particle surface property. Therefore, when it is contained in the solvent composition, the dispersibility of the metal oxide and This is preferable because it is very effective in improving the temporal stability of the coating material (curable composition) and also improves the leveling property of the coating process. The hydroxyl group-containing solvent content in the total solvent composition is preferably 10 to: LOO% by weight. Specific examples of the hydroxyl group-containing solvent include n-butanol, isobutanol, tert-butanol, n-propanol, isopropanol, ethanol, methanol, 3-methoxy 1-butanol, 3-methoxy 2-butanol, and ethylene glycolol. Examples thereof include monomethylol ether, ethylene glycol-no-mono n-butyl ether, 2-ethoxyethanol, 1-methoxy 2-propanol, diacetone alcohol, ethyl acetate, butyl lactate and propylene glycol monomethyl ether. In particular, 3-methoxy-1-butanol, propylene glycol monomethylenotenole, ethyleneglycololemonomethenoatenore, and ethyleneglycololemononole n-butyl ether have better dispersibility and dispersion stability of metal oxides. This is preferable.
[0042] 光重合開始剤としては、光励起によってビニル重合を開始できる機能を有するもの であれば特に限定はなぐ例えばモノカルボニル化合物、ジカルボニル化合物、ァセ トフエノン化合物、ベンゾインエーテル化合物、ァシルホスフィンォキシド化合物、アミ ノカルボ-ルイ匕合物などが使用できる。  [0042] The photopolymerization initiator is not particularly limited as long as it has a function capable of initiating vinyl polymerization by photoexcitation, for example, a monocarbonyl compound, a dicarbonyl compound, a acetophenone compound, a benzoin ether compound, a acylphosphine. Xoxide compounds and aminocarbo-Louis compounds can be used.
具体的には、モノカルボ-ル化合物としては、ベンゾフエノン、 4ーメチルーベンゾフ ェノン、 2,4,6 トリメチルベンゾフエノン、メチルー o ベンゾィルベンゾエート、 4ーフ ェニルベンゾフエノン、 4— (4—メチルフエ-ルチオ）フエ-ルーエタノン、 3,3'—ジメ チル一 4—メトキシベンゾフエノン、 4— (1, 3—アタリロイル一 1, 3, 3' ジメチルー 4 —メトキシベンゾフエノン、 4— (1,3—アタリロイル一 1,4,7, 10, 13 ペンタォキソトリ デシル）ベンゾフエノン、 3, 3',4, 4'ーテトラ（t ブチルペルォキシカルボ-ル）ベン ゾフエノン、 4—ベンゾィル—N, N, N トリメチル—1—プロパンァミン塩酸塩、 4— ベンゾィル N, N ジメチル N— 2— ( 1—ォキソ 2—プロべ-ルォキシェチル） メタアンモ-ゥムシユウ酸塩、 2— Z4—イソ一プロピルチォキサントン、 2, 4—ジェチ ルチオキサントン、 2, 4 ジクロ口チォキサントン、 1 クロロー 4 プロポキシチォキ サントン、 2 ヒドロキー 3— (3, 4 ジメチルー 9—ォキソ 9Hチォキサントン一 2— イロキシ— N, N, N トリメチル—1—プロパンァミン塩酸塩、ベンゾィルメチレン— 3 メチルナフト（1, 2— d)チアゾリン等が挙げられる。 Specific examples of monocarbon compounds include benzophenone, 4-methyl-benzophenone, 2,4,6 trimethylbenzophenone, methyl-o benzoylbenzoate, 4-phenylbenzophenone, 4- (4 —Methylphenol-thiophene-luethanone, 3,3′-dimethyl 4-methoxybenzophenone, 4- (1, 3--ataryloyl 1, 3, 3 ′ dimethyl 4--methoxybenzophenone, 4-— 1,3—Atarylloyl 1,4,7, 10, 13 pentaxotridecyl) benzophenone, 3, 3 ′, 4,4′-tetra (t-butylperoxycarbol) benzophenone, 4-benzoyl-N, N , N Trimethyl-1-propanamine hydrochloride, 4-benzoyl N, N dimethyl N— 2— (1-oxo-2-pro-loxychetyl) Methaammuum oxalate, 2—Z4—Isopropyl thioxanthone, 2, 4—Jetylthioxanthone, 2,4 Dichlorodithioxanthone, 1 Chloro-4 propoxythioxanthone, 2 Hydrokey 3— (3, 4 Dimethyl-9—Oxo 9H Thioxanthone-2-yloxy-N, N, N-trimethyl-1-propanamine hydrochloride, benzoylmethylene-3-methylnaphtho (1,2-d) thiazoline and the like.
[0043] ジカルボ-ル化合物としては、 1, 2, 2 トリメチル一ビシクロ [2.1.1]ヘプタン一 2, 3 ジオン、ベンザイル、 2 ェチルアントラキノン、 9, 10 フエナントレンキノン、メ チルー (X ォキソベンゼンアセテート、 4 フエ-ルペンザイル等が挙げられる。 ァセトフエノン化合物としては、 2—ヒドロキシ一 2—メチル 1—フエ-ルプロパン一 1—オン、 1— (4—イソプロピルフエ-ル） 2 ヒドロキシ一 2—メチル 1—フエ-ル プロパン一 1—オン、 1— (4—イソプロピルフエ-ル） 2 ヒドロキシ一ジ- 2—メチル —1—フエ-ルプロパン一 1—オン、 1—ヒドロキシ一シクロへキシルフエ-ルケトン、 2 ーヒドロキシ 2—メチルー 1ースチリルプロパン 1 オン重合物、ジェトキシァセト フエノン、ジブトキシァセトフエノン、 2, 2—ジメトキシ 1, 2—ジフエニルェタンー1 オン、 2, 2 ジエトキシ 1, 2 ジフエニルェタン 1 オン、 2—メチルー 1 [4 (メチルチオ）フエ-ル] 2—モルホリノプロパン 1 オン、 2—ベンジル 2—ジメ チルァミノ一 1— (4—モルホリノフエ-ル）ブタン一 1—オン、 1—フエ-ルー 1, 2—プ 口パンジオン— 2— (o エトキシカルボ-ル）ォキシム、 3, 6 ビス（2—メチル—2— モルホリノープロパノ -ル） 9 ブチルカルバゾール等が挙げられる。 [0043] Dicarbol compounds include 1, 2, 2 trimethyl monobicyclo [2.1.1] heptane 1, 2, 3 dione, benzyl, 2 ethyl anthraquinone, 9, 10 phenanthrenequinone, methyl (X o Examples include xenobenzene acetate, 4-phenol penzyl, etc. Examples of the acetophenone compound include 2-hydroxy-1-2-methyl-1-phenolpropane-1-one, 1- (4-isopropylphenol) 2-hydroxy-2- Methyl 1-phenol Propanone 1-one, 1— (4-Isopropylphenol) 2 Hydroxy di-2-methyl —1-phenol propane mono-1-one, 1-hydroxy monocyclohexyl phenol ketone , 2-Hydroxy-2-methyl-1-styrylpropane 1-one polymer, methoxyacetophenone, dibutoxyacetophenone, 2,2-dimethoxy 1,2-diphenylethane-1 1,2-diethoxy 1,2-diphenylethane 1-on, 2-methyl-1 [4 (methylthio) phenol] 2-morpholinopropane 1-on, 2-benzyl 2-dimethylaminoamino 1- (4-morpholinophenol ) Butane 1-one, 1-Ferro 1, 2—Puffed Pandione 2— (o Ethoxycarbol) oxime, 3, 6 Bis (2-methyl—2-morpholinopropanol) 9 Examples include butyl carbazole.
[0044] ベンゾインエーテル化合物としては、ベンゾイン、ベンゾインメチルエーテル、ベン ゾインェチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインィゾブチルエー テル、ベンゾインノルマルブチルエーテル等が挙げられる。 [0044] Examples of the benzoin ether compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin normal butyl ether.
ァシルホスフィンォキシド化合物としては、 2, 4, 6 トリメチルベンゾィルジフエ-ル ホスフィンォキシド、 4— n—プロピルフエ-ルージ（2, 6 ジクロロべンゾィル）ホスフ インォキシド等が挙げられる。  Examples of the acyl phosphine oxide compounds include 2,4,6 trimethyl benzoyl diphosphine phosphoxide, 4-n-propyl phenoyl (2, 6 dichlorobenzoyl) phosphine oxide, and the like.
ァミノカルボ-ル化合物としては、メチルー 4 （ジメトキシァミノ）ベンゾエート、ェチ ルー 4— (ジメチルァミノ）ベンゾエート、 2— n—ブトキシェチル— 4— (ジメチルァミノ )ベンゾェート、イソアミルー 4 （ジメチルァミノ）ベンゾエート、 2 （ジメチルァミノ）ェ チルベンゾエート、 4, 4'—ビス一 4—ジメチルァミノべンゾフエノン、 4, 4'—ビス一 4 ジェチルァミノべンゾフエノン、 2, 5' ビス（4 ジェチルァミノベンザル）シクロべ ンタノン等が挙げられる。 Examples of aminocarbole compounds include methyl-4- (dimethoxyamino) benzoate, ethyl 4- (dimethylamino) benzoate, 2-n-butoxetyl-4- (dimethylamino) benzoate, isoamiru 4 (dimethylamino) benzoate, 2 (dimethylamino) Ye Examples thereof include tilbenzoate, 4,4′-bis-4-dimethylaminobenzophenone, 4,4′-bis-4-jetylaminobenzophenone, 2,5′bis (4-jetylaminobenzal) cyclopentanone, and the like.
光重合開始剤の市販品としてはチバ 'スぺシャリティ ·ケミカルズ (株)製ィルガキュ ァ 184、 651、 500、 907、 127、 369、 784、 2959、 BASF社製ルシリン TPO、 日本 シィベルヘグナー (株)製エサキュアワン等があげられる。  Commercially available photopolymerization initiators include Ciba Specialty Chemicals Co., Ltd. Irgacure 184, 651, 500, 907, 127, 369, 784, 2959, BASF's Lucirin TPO, Japan Siebel Hegner Co., Ltd. ) Made Esacure One.
[0045] 光重合開始剤は、上記化合物に限定されず、紫外線により重合を開始させる能力 があれば、どのようなものでも構わない。これらの光重合開始剤は、一種類で用いら れるほ力、二種類以上を混合して用いてもよい。 [0045] The photopolymerization initiator is not limited to the above compound, and any photopolymerization initiator may be used as long as it has the ability to initiate polymerization by ultraviolet rays. These photopolymerization initiators may be used alone or in combination of two or more.
光重合開始剤の使用量に関しては、特に制限はされないが、光硬化性化合物の全 量 100重量部に対して 1〜20重量部の範囲内で使用することが好ましい。  The amount of the photopolymerization initiator used is not particularly limited, but it is preferably used within the range of 1 to 20 parts by weight with respect to 100 parts by weight of the total amount of the photocurable compound.
増感剤として、公知の有機アミン等を加えることもできる。  A known organic amine or the like can be added as a sensitizer.
さらに、上記ラジカル重合用開始剤のほかに、カチオン重合用の開始剤を併用す ることちでさる。  Furthermore, in addition to the radical polymerization initiator, a cationic polymerization initiator may be used in combination.
[0046] 硬化性組成物は、アミノ基含有光硬化性化合物の他に、その他のバインダー榭脂 や、光硬化性ィ匕合物を含んでいてもよい。  [0046] The curable composition may contain other binder resin or photocurable compound in addition to the amino group-containing photocurable compound.
ノインダー樹脂としては、例えば、ポリウレタン樹脂、ポリウレァ樹脂、ポリウレタンゥ レア榭脂、ポリエステル榭脂、ポリエーテル榭脂、ポリカーボネート榭脂、エポキシ榭 脂、アミノ榭脂、スチレン榭脂、アクリル榭脂、メラミン榭脂、ポリアミド榭脂、フエノール 榭脂、ビュル榭脂等が挙げられる。これらの榭脂は、一種類で用いても、二種類以上 を混合して用いてもよい。ノイダー榭脂は、硬化性組成物の固形分 (溶剤以外の成 分。以下、同じ。）の全量を基準（100重量部）として、 20重量部以下の範囲内で使 用することが好ましい。  Examples of the noinder resin include polyurethane resin, polyurethane resin, polyurethane urea resin, polyester resin, polyether resin, polycarbonate resin, epoxy resin, amino resin, styrene resin, acrylic resin, and melamine resin. Examples thereof include fat, polyamide resin, phenol resin, bull resin and the like. These coffins may be used alone or in combination of two or more. Noider rosin is preferably used within a range of 20 parts by weight or less based on the total amount (100 parts by weight) of the solid content of the curable composition (components other than the solvent; hereinafter the same).
[0047] 光硬化性ィ匕合物としては、例えば、（メタ）アクリル系化合物、脂肪酸ビニル化合物 、アルキルビュルエーテル化合物、 aーォレフイン化合物、ビュル化合物、ェチュル 化合物等の重合性不飽和二重結合基を有する化合物を用いることができる。これら の重合性不飽和二重結合基を有する化合物は、さらに水酸基、アルコキシ基、カル ボキシル基、アミド基、シラノール基等の官能基を有していてもよい。アミノ基含有光 硬化性化合物以外の光硬化性化合物は、硬化性組成物の固形分の全量を基準（1 00重量部）として、 50重量部未満の範囲内、特に 5〜40重量部の範囲内で使用す ることが好ましい。 [0047] Examples of the photocurable compound include polymerizable unsaturated double bond groups such as (meth) acrylic compounds, fatty acid vinyl compounds, alkyl butyl ether compounds, a-olefin compounds, bur compounds, and echul compounds. A compound having can be used. These compounds having a polymerizable unsaturated double bond group may further have a functional group such as a hydroxyl group, an alkoxy group, a carboxyl group, an amide group, or a silanol group. Amino group-containing light Photocurable compounds other than curable compounds are used in a range of less than 50 parts by weight, particularly in a range of 5 to 40 parts by weight, based on the total amount of solid content of the curable composition (100 parts by weight). It is preferable.
[0048] (メタ）アクリル系化合物としては、ベンジル (メタ）アタリレート、アルキル系（メタ）ァク リレート、アルキレングリコール系（メタ）アタリレート、カルボキシル基と重合性不飽和 二重結合とを有する化合物、水酸基を有する (メタ)アクリル系化合物、窒素含有 (メ タ)アクリル系化合物等がある。また、単官能、多官能の化合物を適宜使用することが できる。光硬化性、塗膜のハードコート性の点からは、多官能のものが好ましい。  [0048] (Meth) acrylic compounds include benzyl (meth) acrylate, alkyl (meth) acrylate, alkylene glycol (meth) acrylate, carboxyl group and polymerizable unsaturated double bond. Compounds, (meth) acrylic compounds having a hydroxyl group, and nitrogen-containing (meth) acrylic compounds. Monofunctional and polyfunctional compounds can be used as appropriate. From the viewpoint of photocurability and hard coat properties of the coating film, polyfunctional ones are preferred.
[0049] 単官能の (メタ)アクリル系化合物として具体的には、アルキル系（メタ）アタリレートと しては、メチル (メタ）アタリレート、ェチル (メタ）アタリレート、プロピル (メタ）アタリレー ト、ブチル (メタ）アタリレート、ペンチル (メタ）アタリレート、 2—ェチルへキシル (メタ） アタリレート、ヘプチル (メタ）アタリレート、へキシル (メタ）アタリレート、ォクチル (メタ） アタリレート、ノ-ル (メタ）アタリレート、デシル (メタ）アタリレート、ゥンデシル (メタ）ァ タリレート、ドデシル (メタ)アタリレート、トリデシル (メタ)アタリレート、テトラデシル (メタ )アタリレート、ペンタデシル (メタ）アタリレート、へキサデシル (メタ）アタリレート、ヘプ タデシル (メタ）アタリレート、ォクタデシル (メタ）アタリレート、ノナデシル (メタ）アタリレ ート、ィコシル (メタ）アタリレート、ヘンィコシル (メタ）アタリレート、ドコシル (メタ）アタリ レート等の炭素数 1〜22のアルキレン (メタ）アタリレートが挙げられる。極性の調整を 目的とする場合には、炭素数 2〜10、さらに好ましくは炭素数 2〜8のアルキル基を 有するアルキル基含有 (メタ)アタリレートを用いることが好ましい。また、レべリング性 の調節等を目的とする場合には、炭素数 6以上のアルキル基を有するアルキル (メタ )アタリレートを用いることが好まし!/、。  [0049] Specific examples of monofunctional (meth) acrylic compounds include methyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate. , Butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, no- (Meth) acrylate, Decyl (Meth) acrylate, Undecyl (Meth) acrylate, Dodecyl (Meth) atelate, Tridecyl (Meth) acrylate, Tetradecyl (meth) atelate, Pentadecyl (Meth) atelate Xadecyl (meth) atarylate, heptadecyl (meth) atalylate, octadecyl (meth) atarire And alkylene (meth) acrylates having 1 to 22 carbon atoms such as catechol, nonadecyl (meth) acrylate, icosyl (meth) acrylate, hencosyl (meth) acrylate and docosyl (meth) acrylate. For the purpose of adjusting the polarity, it is preferable to use an alkyl group-containing (meth) acrylate having an alkyl group having 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms. For the purpose of adjusting leveling properties, it is preferable to use alkyl (meth) acrylate with an alkyl group having 6 or more carbon atoms!
[0050] アルキレングリコール系（メタ）アタリレートとしては、ジエチレングリコールモノ（メタ） アタリレート、トリエチレングリコールモノ（メタ）アタリレート、テトラエチレングリコールモ ノ（メタ）アタリレート、へキサエチレングリコールモノ（メタ）アタリレート、ポリエチレング リコールモノ（メタ）アタリレート、ジプロピレングリコールモノ（メタ）アタリレート、トリプロ ピレンダリコールモノ（メタ）アタリレート、テトラプロピレングリコールモノ（メタ）アタリレ ート、ポリテトラメチレングリコール (メタ）アタリレート等の、末端に水酸基を有しポリオ キシアルキレン鎖を有するモノ (メタ）アタリレート;メトキシエチレングリコール (メタ）ァ タリレート、メトキシジエチレングリコール (メタ）アタリレート、メトキシトリエチレングリコ ール (メタ）アタリレート、メトキシテトラエチレングリコール (メタ）アタリレート、エトキシテ トラエチレングリコール (メタ）アタリレート、プロポキシテトラエチレングリコール (メタ）ァ タリレート、 n—ブトキシテトラエチレングリコール (メタ）アタリレート、 n—ペンタキシテト ラエチレングリコール (メタ）アタリレート、トリプロピレングリコール (メタ）アタリレート、テ トラプロピレングリコール (メタ）アタリレート、メトキシトリプロピレングリコール (メタ）ァク リレート、メトキシテトラプロピレングリコール (メタ）アタリレート、エトキシテトラプロピレ ングリコール (メタ）アタリレート、プロポキシテトラプロピレングリコール (メタ）アタリレー ト、 n—ブトキシテトラプロピレングリコール (メタ）アタリレート、 n—ペンタキシテトラプロ ピレンダリコール (メタ）アタリレート、ポリテトラメチレングリコール (メタ）アタリレート、メ トキシポリテトラメチレングリコール (メタ）アタリレート、メトキシポリエチレングリコール（ メタ）アタリレート、エトキシポリエチレングリコール (メタ）アタリレート等の、末端にアル コキシ基を有しポリオキシアルキレン鎖を有するモノ (メタ）アタリレート；フエノキシジェ チレングリコール (メタ）アタリレート、フエノキシエチレングリコール (メタ）アタリレート、 フエノキシトリエチレングリコール (メタ）アタリレート、フエノキシテトラエチレングリコー ル (メタ）アタリレート、フエノキシへキサエチレングリコール (メタ）アタリレート、フエノキ シポリエチレングリコール (メタ）アタリレート、フエノキシテトラプロピレンエチレングリコ ール (メタ）アタリレート等の、末端にフエノキシまたはァリールォキシ基を有するポリオ キシアルキレン系（メタ）アタリレートが挙げられる。 [0050] Examples of the alkylene glycol-based (meth) acrylate include diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meta) ) Atalylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, polytetramethylene glycol Polio having a hydroxyl group at the end, such as (meth) acrylate Mono (meth) acrylate with a xyalkylene chain; methoxy ethylene glycol (meth) acrylate, methoxy diethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, methoxy tetraethylene glycol (meth) acrylate , Ethoxytetraethylene glycol (meth) acrylate, propoxytetraethylene glycol (meth) acrylate, n-butoxytetraethylene glycol (meth) acrylate, n-pentoxytetraethylene glycol (meth) acrylate, tripropylene glycol (meta ) Atalylate, tetrapropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxytetrapropylene glycol (meth) Tallylate, ethoxytetrapropylene glycol (meth) acrylate, propoxytetrapropylene glycol (meth) acrylate, n-butoxytetrapropylene glycol (meth) acrylate, n-pentoxytetrapropylene glycol (meth) acrylate , Polytetramethylene glycol (meth) acrylate, methoxy polytetramethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate, etc. Mono (meth) acrylate with polyoxyalkylene chain; phenoxyethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxytriethylene Recall (Meth) Atalylate, Phenoxytetraethylene Glycol (Meth) Atalylate, Phenoxyhexaethylene Glycol (Meth) Atalylate, Phenoxypolyethylene Glycol (Meth) Atalylate, Phenoxytetrapropylene Ethylene Glycol Polyoxyalkylene-based (meth) acrylates having a phenoxy or aryloxy group at the terminal, such as (meth) acrylate.
[0051] カルボキシル基及び重合性不飽和二重結合を有する化合物としては、マレイン酸、 フマル酸、ィタコン酸、シトラコン酸、または、これらのアルキルもしくはァルケ-ルモノ エステル、フタル酸 j8 - (メタ）アタリロキシェチルモノエステル、イソフタル酸 j8 - (メ タ）アタリロキシェチルモノエステル、コハク酸 j8 - (メタ）アタリロキシェチルモノエステ ル、アクリル酸、メタクリル酸、クロトン酸、けい皮酸等が挙げられる。  [0051] Examples of the compound having a carboxyl group and a polymerizable unsaturated double bond include maleic acid, fumaric acid, itaconic acid, citraconic acid, or alkyl or alkyl monoesters thereof, phthalic acid j8- (meth) atalyst. Loxochetyl monoester, isophthalic acid j8-(metha) atalylochechetyl monoester, succinic acid j8-(meth) atalylochechetyl monoester, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, etc. Can be mentioned.
[0052] 水酸基含有 (メタ）アクリル系化合物としては、 2—ヒドロキシェチル (メタ)アタリレート 、 2—ヒドロキシプロピル (メタ）アタリレート、 4—ヒドロキシブチル (メタ）アタリレート、グ リセロールモノ（メタ）アタリレート、 4—ヒドロキシビュルベンゼン、 2—ヒドロキシ一 3— フエノキシプロピル (メタ)アタリレート等が挙げられる。 [0052] Examples of the hydroxyl group-containing (meth) acrylic compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meta) ) Atalylate, 4-hydroxybutyrene, 2-hydroxyl 3- Examples include phenoxypropyl (meth) acrylate.
[0053] 窒素含有 (メタ）アクリル系化合物としては、（メタ)アクリルアミド、 N—メチロール (メ タ）アクリルアミド、 N—メトキシメチル—（メタ）アクリルアミド、 N—エトキシメチル—（メ タ）アクリルアミド、 N—プロポキシメチル—（メタ）アクリルアミド、 N—ブトキシメチル— (メタ）アクリルアミド、 N—ペントキシメチルー（メタ）アクリルアミド等のモノアルキロー ル (メタ）アクリルアミド、 N, N—ジ (メチロール）アクリルアミド、 N—メチロール— N— メトキシメチル (メタ）アクリルアミド、 N, N—ジ (メチロール）アクリルアミド、 N—ェトキ シメチルー N—メトキシメチルメタアクリルアミド、 N, N—ジ（エトキシメチル）アクリルァ ミンド、 N—ェトキシメチルー N—プロポキシメチルメタアクリルアミド、 N, N—ジ（プロ ポキシメチル）アクリルアミド、 N—ブトキシメチル— N— (プロボキシメチル)メタアタリ ルアミド、 N, N—ジ（ブトキシメチル）アクリルアミド、 N—ブトキシメチル— N— (メトキ シメチル)メタアクリルアミド、 N, N—ジ（ペントキシメチル）アクリルアミド、 N—メトキシ メチル—N— (ペントキシメチル)メタアクリルアミド等のジアルキロール (メタ）アクリル アミド等のアクリルアミド系不飽和化合物；ジメチルアミノエチル (メタ)アタリレート、ジ ェチルアミノエチル (メタ）アタリレート、メチルェチルアミノエチル (メタ）アタリレート、 ジメチルアミノスチレン、ジェチルアミノスチレン等のジアルキルアミノ基を有する不飽 和化合物；及び、対イオンとして Cl—、 Br -、 Γ等のハロゲンイオンまたは QS03_ (Q : 炭素数 1〜12のアルキル基）を有するジアルキルアミノ基含有不飽和化合物の 4級 アンモニゥム塩等がある。 [0053] Nitrogen-containing (meth) acrylic compounds include (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, N —Propoxymethyl— (meth) acrylamide, N-butoxymethyl— (meth) acrylamide, N-pentoxymethyl- (meth) acrylamide, and other monoalkylol (meth) acrylamides, N, N—di (methylol) acrylamide, N-methylol — N— Methoxymethyl (meth) acrylamide, N, N-di (methylol) acrylamide, N-ethoxymethyl-N-methoxymethylmethacrylamide, N, N-di (ethoxymethyl) acrylamide, N-ethoxymethyl-N-propoxymethyl Methacrylamide, N, N—di Propoxymethyl) acrylamide, N-butoxymethyl—N— (propoxymethyl) methatalamide, N, N—di (butoxymethyl) acrylamide, N-butoxymethyl—N— (methoxymethyl) methacrylamide, N, N—di Acrylamide-type unsaturated compounds such as (pentoxymethyl) acrylamide, N-methoxymethyl-N- (pentoxymethyl) methacrylamide, dialalkylol (meth) acrylamide, etc .; dimethylaminoethyl (meth) acrylate, diethylamino Unsaturated compounds having a dialkylamino group such as ethyl (meth) acrylate, methylethylaminoethyl (meth) acrylate, dimethylaminostyrene, and jetylaminostyrene; and Cl—, Br −, Γ as counter ions Halogen ion such as QS03_ (Q: carbon number 1 There quaternary Anmoniumu salts of dialkylamino group-containing unsaturated compound having an alkyl group) of 12.
[0054] その他の不飽和化合物としては、パーフルォロメチルメチル (メタ）アタリレート、ノ 一フルォロェチルメチル（メタ）アタリレート、 2—パーフルォロブチルェチル（メタ）ァク リレート、 2—パーフルォ口へキシルェチル（メタ）アタリレート、 2—パーフルォロオタ チルェチル (メタ）アタリレート、 2—パーフルォロイソノ-ルェチル（メタ）アタリレート、 2—パーフルォロノ-ルェチル（メタ）アタリレート、 2—パーフルォロデシルェチル（メ タ）アタリレート、パーフルォロプロピルプロピル（メタ）アタリレート、パーフルォロオタ チルプロピル (メタ）アタリレート、パーフルォロォクチルァミル (メタ）アタリレート、パー フルォロォクチルゥンデシル (メタ）アタリレート等の、炭素数 1〜20のパーフルォロア ルキル基を有するパーフルォロアルキルアルキル (メタ)アタリレート類を挙げることが できる。 [0054] Other unsaturated compounds include perfluoromethylmethyl (meth) acrylate, monofluoroethyl methyl (meth) acrylate, 2-perfluorobutyl cetyl (meth) alkyl. Relate, 2-perfluohexyl hexyl (meth) acrylate, 2-perfluoro ota tilethyl (meth) acrylate, 2-perfluoro isono-ruethyl (meth) acrylate, 2-perfluorono-ruethyl (meth) acrylate, 2-Perfluorodecylethyl (meth) acrylate, perfluoropropylpropyl (meth) acrylate, perfluoro octyl propyl (meth) acrylate, perfluorooctylamyl (meth) acrylate, perfluoro Perfluoroalkyl having 1 to 20 carbon atoms, such as fluorooctyldecyl (meth) atarylate Be given per full O b alkyl (meth) Atari rates compound having a it can.
[0055] さらに、パーフルォロブチルエチレン、パーフルォ口へキシルエチレン、パーフルォ ロォクチルェチレン、パーフルォロデシルエチレン等のパーフルォロアルキル、アル キレン類等のパーフルォロアルキル基含有ビュルモノマー；ビュルトリクロルシラン、 ビュルトリス（ メトキシエトキシ)シラン、ビニルトリエトキシシラン、 y - (メタ）アタリ ロキシプロピルトリメトキシシラン等のアルコキシシリル基含有ビュルィ匕合物及びその 誘導体；グリシジルアタリレート、 3, 4 エポキシシクロへキシルアタリレート等のグリシ ジル基含有アタリレートが挙げられる。  [0055] Further, perfluoroalkyl groups such as perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, perfluorodecylethylene, and perfluoroalkyl groups such as alkylenes Bull monomer; Bull trichlorosilane, Buturis (methoxyethoxy) silane, Vinyl triethoxysilane, y- (meth) Atyloxypropyl trimethoxysilane, and other alkoxysilyl group-containing Bury compounds and derivatives thereof; Glycidyl acrylate, 3, 4 Examples include glycidyl group-containing acrylate, such as epoxycyclohexyl acrylate.
[0056] 脂肪酸ビ-ルイ匕合物としては、酢酸ビニル、酪酸ビニル、クロトン酸ビニル、カプリ ル酸ビュル、ラウリン酸ビュル、クロル酢酸ビュル、ォレイン酸ビュル、ステアリン酸ビ -ル等が挙げられる。 [0056] Examples of the fatty acid beryl compound include vinyl acetate, vinyl butyrate, vinyl crotonate, butyrate caprylate, laurate, chloroacetate, oleate and stearate.
アルキルビュルエーテル化合物としては、ブチルビ-ルエーテル、ェチルビ-ルェ 一テル等が挙げられる。  Examples of the alkyl butyl ether compound include butyl benzene ether and ethyl benzene ether.
a—ォレフイン化合物としては、 1—へキセン、 1—オタテン、 1—デセン、 1—ドデセ ン、 1ーテトラデセン、 1一へキサデセン等が挙げられる。  Examples of the a-olefin compound include 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, and 1-hexadecene.
ビュル化合物としては、ァリル酢酸、ァリルアルコール、ァリルベンゼン、シアン化ァ リル等のァリル化合物、シアン化ビュル、ビュルシクロへキサン、ビュルメチルケトン、 スチレン、 α—メチルスチレン、 2—メチルスチレン、クロロスチレン等が挙げられる。 ェチュル化合物としては、アセチレン、ェチュルベンゼン、ェチュルトルエン、 1 ェチニルー 1ーシクロへキサノール等が挙げられる。  Examples of the bur compound include allylic compounds such as allylic acetic acid, allylic alcohol, allylic benzene, and cyano cyanide, cyano cyanide, biscyclohexane, butyl methyl ketone, styrene, α-methyl styrene, 2-methyl styrene, chlorostyrene, and the like. Is mentioned. Examples of the ethul compound include acetylene, eth benzene, ethul toluene, 1 ethynyl-1-cyclohexanol, and the like.
これらは、一種類で用いてもよいし、二種類以上を混合して用いてもよい。  These may be used alone or in combination of two or more.
[0057] アミノ基含有光硬化性化合物以外の光硬化性化合物としては、塗膜強度、耐擦傷 性の観点より、少なくとも 3つの官能基を有するポリウレタンポリ（メタ)アタリレート、ポリ エポキシポリ（メタ）アタリレート等のポリ（メタ）アタリレート類、分子内に 3個以上のァク リロイル基を有する多官能のアタリレート類を好適に使用することができる。 [0057] Photocurable compounds other than amino group-containing photocurable compounds include polyurethane poly (meth) acrylate and polyepoxy poly (meta) having at least three functional groups from the viewpoint of coating film strength and scratch resistance. ) Poly (meth) acrylates such as acrylate and polyfunctional acrylates having 3 or more acryloyl groups in the molecule can be preferably used.
ポリエポキシポリ（メタ）アタリレートは、エポキシ榭脂のエポキシ基を (メタ）アクリル酸 でエステルイ匕して、官能基を (メタ）アタリロイル基としたものであり、ビスフエノール A 型エポキシ榭脂への (メタ）アクリル酸付加物、ノボラック型エポキシ榭脂への (メタ）ァ クリル酸付加物等がある。 Polyepoxy poly (meth) acrylate is an epoxy resin whose epoxy group is esterified with (meth) acrylic acid and the functional group is a (meth) taroloyl group. To bisphenol A type epoxy resin Of (meth) acrylic acid adducts, (meth) a to novolac epoxy resin There are adducts such as crylic acid.
[0058] ポリウレタンポリ（メタ)アタリレートは、例えば、ジイソシァネートと水酸基を有する (メ タ）アタリレート類とを反応させて得られるもの、ポリオールとポリイソシァネートとをイソ シァネート基過剰の条件下に反応させてなるイソシァネート基含有ウレタンプレボリマ 一を、水酸基を有する (メタ)アタリレート類と反応させて得られるものがある。あるいは 、ポリオールとポリイソシァネートとを水酸基過剰の条件下に反応させてなる水酸基 含有ウレタンプレボリマーを、イソシァネート基を有する (メタ）アタリレート類と反応さ せて得ることちでさる。  [0058] Polyurethane poly (meth) acrylate is obtained, for example, by reacting diisocyanate and (meth) acrylate having a hydroxyl group, under the condition that polyol and polyisocyanate are excessive in isocyanate group. There are those obtained by reacting an isocyanate group-containing urethane preform made by reacting with (meth) acrylates having a hydroxyl group. Alternatively, it may be obtained by reacting a hydroxyl group-containing urethane prepolymer obtained by reacting a polyol and a polyisocyanate under a hydroxyl group-excess condition with a (meth) acrylate having an isocyanate group.
[0059] ポリオールとしては、エチレングリコール、プロピレングリコール、ジエチレングリコー ル、ジプロピレングリコール、ブチレングリコール、 1, 6—へキサンジオール、 3—メチ ルー 1, 5—ペンタンダリコール、ネオペンチルグリコール、へキサントリオール、トリメリ ロールプロパン、ポリテトラメチレングリコール、アジピン酸とエチレングリコールとの縮 重合物等が挙げられる。  [0059] Examples of polyols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentandalol, neopentyl glycol, hexane. Examples include triol, trimellyl propane, polytetramethylene glycol, and a polycondensation product of adipic acid and ethylene glycol.
[0060] ポリイソシァネートとしては、トリレンジイソシァネート、イソホロンジイソシァネート、へ キサメチレンジイソシァネート等が挙げられる。  [0060] Examples of the polyisocyanate include tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and the like.
水酸基を有する (メタ)アタリレート類としては、 2—ヒドロキシェチル (メタ）アタリレー ペンタエリスリトールトリ（メタ）アタリレート、ジペンタエリスリトールペンタ（メタ）アタリレ ート、ジトリメチロールプロパンテトラ (メタ)アタリレート等が挙げられる。  Examples of (meth) atalylates having a hydroxyl group include 2-hydroxyethyl (meth) atalyl pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate. Etc.
イソシァネート基を有する (メタ)アタリレート類としては、 2— (メタ)アタリロイルォキシ ェチルイソシァネート、（メタ）アタリロイルイソシァネート等が挙げられる。  Examples of (meth) acrylates having an isocyanate group include 2- (meth) attalylooxyethylisocyanate, (meth) attalyloyl isocyanate, and the like.
[0061] 光硬化性ィ匕合物の市販品としては、以下のものが例示できる。 [0061] Examples of commercially available photocurable composites include the following.
東亜合成（株）製：ァロニックス M— 400、ァ口-ックス M— 402、ァ口-ックス M— 4 08、ァ口-ックス M— 450、ァ口-ックス M— 7100、ァロニックス M— 8030、ァ口-ッ タス M— 8060、  Toa Gosei Co., Ltd .: Alonix M-400, Aguchi-X M-402, Aguchi-X M-408, Aguchi-X M-450, Aguchi-X M-7100, Aronix M-8030,口 口 -tuss M—8060,
大阪有機化学工業 (株)製：ビスコート # 400、  Osaka Organic Chemical Industry Co., Ltd .: Biscote # 400,
化薬サートマ一 (株)製: SR— 295、  Kayaku Satomaichi Co., Ltd .: SR-295,
ダイセル UCB (株）製： DPHA、 Ebecryl 220、 Ebecryl 1290K、 Ebecryl 51 29, Ebecryl 2220、 Ebecryl 6602、 Daicel UCB Co., Ltd .: DPHA, Ebecryl 220, Ebecryl 1290K, Ebecryl 51 29, Ebecryl 2220, Ebecryl 6602,
新中村化学工業 (株）製： NKエステル A—TMMT、 NKオリゴ EA—1020、 NKォ ジゴ EMA— 1020、 NI Uゴ EA— 6310、 NI Uゴ EA— 6320、 NI Uゴ EA— 6 340、 NKオリゴ MA—6、 NKオリゴ U— 4HAゝ NKオリゴ U— 6HAゝ NKオリゴ U— 3 24A、  Shin-Nakamura Chemical Co., Ltd .: NK Ester A—TMMT, NK Oligo EA—1020, NK Odigo EMA—1020, NI U Go EA—6310, NI U Go EA—6320, NI U Go EA—6 340, NK Oligo MA-6, NK Oligo U— 4HA ゝ NK Oligo U— 6HA ゝ NK Oligo U— 3 24A,
BASF社製： LaromerEA81、  BASF: LaromerEA81,
サンノプコ（株）製：フォトマー 3016、  Made by San Nopco: Photomer 3016,
荒川化学工業 (株）製：ビームセット 371、ビームセット 575、ビームセット 577、ビー ムセット 700、ビームセット 710 ;  Arakawa Chemical Industries, Ltd .: Beam Set 371, Beam Set 575, Beam Set 577, Beam Set 700, Beam Set 710;
根上工業 (株）製：アートレジン UN— 3320HA、アートレジン UN— 3320HB、ァ 一トレジン UN—3320HC、アートレジン UN— 3320HS、アートレジン UN— 9000 H、アートレジン UN— 901T、アートレジン HDP、アートレジン HDP— 3、アートレジ ン H61、  Negami Kogyo Co., Ltd .: Art Resin UN-3320HA, Art Resin UN-3320HB, Art Resin UN-3320HC, Art Resin UN-3320HS, Art Resin UN—9000 H, Art Resin UN—901T, Art Resin HDP, Art Resin HDP-3, Art Resin H61,
日本合成化学工業 (株)製:紫光 UV—7600B、紫光 UV—7610B、紫光 UV—7 620EA、紫光 UV— 7630B、紫光 UV— 1400B、紫光 UV— 1700B、紫光 UV— 6 300B、  Nippon Synthetic Chemical Industry Co., Ltd .: Purple light UV—7600B, Purple light UV—7610B, Purple light UV—7 620EA, Purple light UV—7630B, Purple light UV—1400B, Purple light UV—1700B, Purple light UV—6 300B,
共栄社ィ匕学 (株)製:ライトアタリレート PE— 4A、ライトアタリレート DPE— 6A、 UA — 306H、 UA— 306T、 UA— 3061、  Kyoeisha Co., Ltd .: Light Attalate PE-4A, Light Attalate DPE-6A, UA-306H, UA-306T, UA-3061,
日本化薬（株）製： KAYARAD DPHA, KAYARAD DPHA2C, KAYARA D DPHA-40H, KAYARAD D— 310、 KAYARAD D— 330。  Nippon Kayaku Co., Ltd .: KAYARAD DPHA, KAYARAD DPHA2C, KAYARA D DPHA-40H, KAYARAD D-310, KAYARAD D-330.
次に、本発明の硬化膜とその積層体に関して説明する。  Next, the cured film and laminated body of the present invention will be described.
本発明の硬化膜は、本発明の硬化性組成物を硬化してなる膜である。その製造方 法は、たとえば、硬化性組成物を任意の基材に塗布すること、および活性エネルギ 一線を照射して、基材上の硬化性組成物を硬化させること、を含む。  The cured film of the present invention is a film formed by curing the curable composition of the present invention. The manufacturing method includes, for example, applying the curable composition to an arbitrary substrate, and irradiating an active energy line to cure the curable composition on the substrate.
より具体的には、この硬化性組成物を任意の基材上に、乾燥後の膜厚が好ましくは 0. 1〜30 111、ょり好ましくは0. 1〜20 /ζ πιになるように塗工後、硬化処理すること により形成することができる。  More specifically, the curable composition is deposited on an arbitrary substrate so that the film thickness after drying is preferably 0.1 to 30 111, more preferably 0.1 to 20 / ζ πι. It can be formed by applying a curing treatment after coating.
形成時において、硬化膜は、基材に直接塗工されてもよいし、硬化膜と基材との間 に 1層以上の下層が存在してもよい。 At the time of formation, the cured film may be applied directly to the substrate, or between the cured film and the substrate. There may be one or more lower layers.
この基材としては、金属、セラミックス、ガラス、プラスチック、木材、スレート等が挙げ られ、特に制限されるものではない。具体的なプラスチックの種類としては、ポリエス テル、ポリオレフイン、ポリカーボネート、ポリスチレン、ポリメチルメタタリレート、トリア セチルセルロース榭脂、 ABS榭脂、 AS榭脂、ポリアミド、エポキシ榭脂、メラミン榭脂 等が挙げられる。また基材の形状としてはフィルムシート、板状パネル、レンズ形状、 ディスク形状、ファイバー状の物が挙げられる力 特に制限されるものではない。  Examples of the substrate include metals, ceramics, glass, plastics, wood, slate and the like, and are not particularly limited. Specific plastic types include polyester, polyolefin, polycarbonate, polystyrene, polymethylmetatalylate, triacetyl cellulose resin, ABS resin, AS resin, polyamide, epoxy resin, and melamine resin. It is done. In addition, the shape of the substrate is not particularly limited, and includes a film sheet, a plate-like panel, a lens shape, a disk shape, and a fiber-like material.
[0063] 塗工方法としては、公知の方法を用いることができ、例えばロットまたはワイヤーバ 一などを用いた方法や、マイクログラビア、グラビア、ダイ、カーテン、リップ、スロットま たはスピンなどの各種コーティング方法を用いることができる。 [0063] As a coating method, a known method can be used, for example, a method using a lot or wire bar, or various coatings such as microgravure, gravure, die, curtain, lip, slot or spin. The method can be used.
硬化処理は、公知の技術を用いて、例えば、紫外線、電子線、波長 400〜500nm の可視光線等の活性エネルギー線を照射することにより行なうことができる。紫外線 および波長 400〜500nmの可視光線の線源（光源）には、例えば高圧水銀ランプ、 超高圧水銀ランプ、メタルハライドランプ、ガリウムランプ、キセノンランプ、カーボンァ 一クランプ等を使用することができる。電子線源には、熱電子放射銃、電解放射銃等 を使用することができる。  The curing treatment can be performed by irradiating active energy rays such as ultraviolet rays, electron beams, visible rays having a wavelength of 400 to 500 nm, using a known technique. For example, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon lamp clamp, or the like can be used as a source of ultraviolet light and visible light having a wavelength of 400 to 500 nm. As the electron beam source, a thermionic emission gun, an electrolytic emission gun, or the like can be used.
[0064] 照射する活性エネルギー線量は、 5〜2000miZcm2の範囲内であることが好まし く、さらには工程上管理しやすい点から、 50〜： LOOOmjZcm2の範囲内であることが 好ましい。 [0064] The active energy dose to be irradiated is preferably within the range of 5 to 2000 miZcm 2 , and more preferably within the range of 50 to: LOOOmjZcm 2 from the viewpoint of easy management in the process.
これらの活性エネルギー線照射に、赤外線、遠赤外線、熱風、高周波加熱等によ る熱処理を併用することができる。  These active energy rays can be used in combination with heat treatment by infrared rays, far infrared rays, hot air, high frequency heating or the like.
硬化膜は、基材に硬化性組成物を塗工し、 自然または強制乾燥させたあとに硬化 処理を行なって形成しても良!ヽし、塗工し硬化処理を行なったあとに自然または強制 乾燥させても良いが、自然または強制乾燥させたあとに硬化処理を行なう方がより好 ましい。  The cured film may be formed by applying a curable composition to a substrate and naturally or forcedly drying it, followed by a curing process. After coating and curing, Forced drying may be used, but it is more preferable to perform curing after natural or forced drying.
特に、電子線で硬化させる場合は、水による硬化阻害または有機溶剤の残留によ る塗膜の強度低下を防ぐため、自然または強制乾燥させたあとに硬化処理を行なう 方がより好ましい。 硬化処理のタイミングは、塗工と同時でもよいし、塗工後でもよい。 In particular, in the case of curing with an electron beam, it is more preferable to perform the curing treatment after natural or forced drying in order to prevent the curing inhibition by water or the decrease in the strength of the coating film due to the remaining organic solvent. The timing of the curing treatment may be simultaneous with coating or after coating.
[0065] 得られる硬化膜は、ハードコート性、透明性、耐光性、高屈折率性、帯電防止性に 優れるため、光学材料として好適に利用することが出来る。したがって、本発明の硬 化膜は、積層体として、陰極線管、フラットディスプレイパネル (液晶ディスプレイ、プ ラズマディスプレイ、エレクト口クロミックディスプレイ、発光ダイオードディスプレイ等） 等の各種表示装置の前面板あるいはこれらの入力装置としても利用できる。  [0065] The obtained cured film is excellent in hard coat property, transparency, light resistance, high refractive index property and antistatic property, and therefore can be suitably used as an optical material. Therefore, the cured film of the present invention is a laminated body, such as a cathode ray tube, a front panel of various display devices such as a flat display panel (liquid crystal display, plasma display, electoric chromic display, light emitting diode display, etc.) or an input thereof. It can also be used as a device.
その他、この硬化膜は、光学用レンズ、メガネ用レンズ、光記録ディスク (コンパクト ディスク、 DVDディスク、ブルーレイディスク等）、ライトケース等に広く利用できる。 硬化膜の表面抵抗値は、 1 X 1012ΩΖ口以下であることが好ましい。 In addition, this cured film can be widely used for optical lenses, eyeglass lenses, optical recording disks (compact disks, DVD disks, Blu-ray disks, etc.), light cases, and the like. The surface resistance value of the cured film is preferably 1 × 10 12 Ω or less.
硬化膜の厚みは、 0.1〜30/ζπιであることが好ましい。  The thickness of the cured film is preferably 0.1-30 / ζπι.
さらに、硬化膜の屈折率は、 1.5〜1.8の範囲であることが好ましい。  Furthermore, the refractive index of the cured film is preferably in the range of 1.5 to 1.8.
[0066] 本発明の積層体は、本発明の硬化膜と基材とを含むものである。基材としては、上 記例示のものを任意に使用することができ、特に、プラスチック基材であることが好ま しい。基材の形状は、フィルム形状、レンズ形状、またはディスク形状であることが好 ましい。 [0066] The laminate of the present invention includes the cured film of the present invention and a substrate. As the substrate, those exemplified above can be arbitrarily used, and a plastic substrate is particularly preferable. The shape of the substrate is preferably a film shape, a lens shape, or a disk shape.
この積層体は、これらに加え、屈折率の異なる膜、粘着層または情報記録層などを 1層以上含むことが好まし 、。  In addition to these, the laminate preferably includes one or more films having different refractive indexes, an adhesive layer or an information recording layer.
屈折率の異なる膜 (Μ)、粘着層 (Μ)または情報記録層 (Μ)を含む積層体は、たと えば、下記 (I)〜 (IX)などの層構成にすることができる。  For example, a laminate including a film (Μ), an adhesive layer (Μ) or an information recording layer (Μ) having different refractive indexes can have a layer structure such as the following (I) to (IX).
(I) 基材 Ζ(Μ)Ζ硬化膜  (I) Substrate Ζ (Μ) Ζ Cured film
(II) 基材 Ζ硬化膜 Ζ(Μ)  (II) Substrate Ζ Cured film Ζ (Μ)
(III) 基材 Z(M)Z硬化膜 Z(M)  (III) Substrate Z (M) Z cured film Z (M)
(IV) (M)Z基材 Z硬化膜  (IV) (M) Z substrate Z cured film
(V) ^)7基材7^)7硬化膜  (V) ^) 7 base material 7 ^) 7 cured film
(VI) (M)Z基材 Z硬化膜 Z(M)  (VI) (M) Z substrate Z cured film Z (M)
(VII) (M)Z基材Z(M)Z硬化膜Z(M)  (VII) (M) Z substrate Z (M) Z cured film Z (M)
(VIII) (M)Z硬化膜 Z基材 Z硬化膜  (VIII) (M) Z cured film Z substrate Z cured film
(IX) 硬化膜 Z(M)Z基材 Z硬化膜 [0067] 屈折率の異なる膜または情報記録層は、本発明の硬化物が有する機能以外の機 能を持つものである。その形成方法は特に限定されず、公知の方法で形成される。 例えば蒸着、スパッタなどのドライコーティング法、ロット、ワイヤーバーを用いた方法 や、マイクログラビア、グラビア、ダイ、カーテン、リップ、スロット、スピン等のウエットコ 一ティング方法を用いることができる。用いる材料も限定は無ぐ必要に応じて、情報 記録機能、防眩機能、ニュートンリング防止機能、粘着機能、特定波長の遮断、密着 向上、色調補正などの機能の 1種類以上を積層体に付与することができる任意の材 料を用いることができる。 (IX) Cured film Z (M) Z substrate Z cured film [0067] Films or information recording layers having different refractive indexes have functions other than the functions of the cured product of the present invention. The formation method is not particularly limited, and it is formed by a known method. For example, dry coating methods such as vapor deposition and sputtering, methods using lots and wire bars, and wet coating methods such as microgravure, gravure, die, curtain, lip, slot, and spin can be used. There are no restrictions on the materials used, and one or more functions such as information recording function, anti-glare function, Newton ring prevention function, adhesive function, blocking of specific wavelength, adhesion improvement, color correction, etc. are given to the laminate as necessary. Any material that can be used can be used.
[0068] 情報記録層としては、レーザー光などにより何らかの化学的変化を生じさせ、その 変化により情報を記録するものであればよぐ材料は特に限定されない。例えば有機 系の材料としては、ポリメチン色素、ナフタロシアニン系、フタロシアニン系、スクァリリ ゥム系、アントラキノン系、キサンテン系、トリフエ-ルメタン系金属錯体ィ匕合物が挙げ られ、上記の染料を 1種又は 2種以上の組合せで用いることができる。無機系の記録 層としては、 Te、 Ge、 Se、 In、 Sb、 Sn、 Zn、 Au、 Al、 Cu、 Pt等の金属、半金属を 1 種又は 2種以上の組合せで用いることができる。情報記録層は積層体などでも良ぐ 光化学変化の態様は相変化、バブル、穴あけタイプのいずれでも良い。さらに Fe、 T b、 Coを主体とした光磁気記録層であっても良いし、スピロピラン、フルキド系のフォト クロミック材料であっても良 、。 [0068] The information recording layer is not particularly limited as long as it is capable of causing some chemical change by laser light or the like and recording information by the change. Examples of organic materials include polymethine dyes, naphthalocyanine-based, phthalocyanine-based, squarylium-based, anthraquinone-based, xanthene-based, triphenylmethane-based metal complexes, and one or more of the above dyes. Two or more types can be used in combination. As the inorganic recording layer, metals such as Te, Ge, Se, In, Sb, Sn, Zn, Au, Al, Cu, and Pt, and semimetals can be used alone or in combination of two or more. The information recording layer may be a laminate or the like. The mode of photochemical change may be any of phase change, bubble, and punching type. Further, it may be a magneto-optical recording layer mainly composed of Fe, Tb, and Co, or may be a spiropyran or fluorinated photochromic material.
高屈折率の硬化膜は、反射防止の観点から、表層に低屈折率の被覆硬化膜を設 け、反射防止機能を付与した積層体として利用することも好ましい。すなわち、フィル ム等の基材上に硬化膜を形成し、さらに好ましくは被覆硬化膜を形成して得られる積 層体を、反射防止膜として用いることが好ましい。  From the viewpoint of antireflection, the high refractive index cured film is also preferably used as a laminate provided with a low refractive index coating cured film on the surface layer to provide an antireflection function. That is, it is preferable to use a laminate obtained by forming a cured film on a substrate such as a film, and more preferably forming a coated cured film, as the antireflection film.
反射干渉縞が問題となる積層体においては、本発明の硬化性組成物中の金属酸 化物の配合量を調整し、その硬化膜と基材との屈折率の差が、または、硬化膜と基 材との間に任意の層が存在する場合は硬化膜と硬化膜の接する下層との屈折率の 差が、 ±0. 02以内となるようにすることが好ましい。  In a laminate in which reflection interference fringes are a problem, the blending amount of the metal oxide in the curable composition of the present invention is adjusted, and the difference in the refractive index between the cured film and the substrate or the cured film and When an arbitrary layer is present between the base material and the base material, the difference in refractive index between the cured film and the lower layer in contact with the cured film is preferably within ± 0.02.
[0069] 本発明の硬化性組成物は、金属酸化物の種類や添加量を制御することにより、高 屈折率の硬化物を製造することが可能である。そのため、光半導体素子の光取り出 し効率を向上させるために、榭脂層の屈折率を光半導体素子側から最外層に向けて 順次小さくすることが要求される光半導体素子封止材として、好ましく利用できる。 光半導体素子としては、窒化ガリウム (GaN :屈折率 2. 5)、ガリウムリン (GaP :屈折 率 2. 9)、ガリウム砒素（GaAs :屈折率 3. 5)等が挙げられ、非常に屈折率が高い素 材である。そのため、光半導体素子封止材となる硬化物の屈折率は、光取り出し効 率を高める観点から、 1. 5以上であることが好ましぐより好ましくは 1. 5〜2. 1、さら に好ましくは 1. 7〜2. 1である。 [0069] The curable composition of the present invention can produce a cured product having a high refractive index by controlling the type and addition amount of the metal oxide. Therefore, the light extraction of the optical semiconductor element In order to improve the efficiency, the resin layer can be preferably used as an optical semiconductor element sealing material that is required to sequentially reduce the refractive index of the resin layer from the optical semiconductor element side toward the outermost layer. Examples of optical semiconductor elements include gallium nitride (GaN: refractive index 2.5), gallium phosphide (GaP: refractive index 2.9), and gallium arsenide (GaAs: refractive index 3.5). Is a high material. Therefore, the refractive index of the cured product that becomes the optical semiconductor element sealing material is preferably 1.5 or more, more preferably 1.5 to 2.1, and more preferably from the viewpoint of increasing the light extraction efficiency. Preferably it is 1.7-7.
硬化物の最適な屈折率を達成する方法としては、使用する金属酸化物として酸ィ匕 チタン (屈折率 2. 5〜2. 7)、酸化ジルコニウム (屈折率 2. 4)、酸ィ匕亜鉛 (屈折率 1. 95)などが好ましぐ分散剤にも高屈折率性が要求されることから、芳香族骨格を持 つたアミノ基含有光硬化性化合物が好ま ヽ。  To achieve the optimum refractive index of the cured product, the metal oxides used include titanium oxide (refractive index 2.5 to 2.7), zirconium oxide (refractive index 2.4), and zinc oxide. Since a dispersant having a refractive index of 1.95 is also required to have a high refractive index, an amino group-containing photocurable compound having an aromatic skeleton is preferred.
[0070] <実施例 > [0070] <Example>
以下、製造例、実施例に基づき本発明をさらに詳しく説明する。製造例、実施例中 、部および％は、重量部および重量％をそれぞれ表す。  Hereinafter, the present invention will be described in more detail based on production examples and examples. In the production examples and examples, parts and% represent parts by weight and% by weight, respectively.
(製造例 1)  (Production Example 1)
光硬化後の鉛筆硬度が 3Hのアタリレートイ匕合物 (根上工業 (株)製「UN - 3320H S」） 20部をメチルイソブチルケトン 31. 74部に溶解させた溶液に、ジブチルァミン 1 . 16部（エチレン性不飽和二重結合モル数 Zアミン化合物のモル数 = 100/15)を 添加し、 40°Cで 5時間攪拌したあと、室温まで冷却し、アミノ基含有光硬化性化合物 (1)のメチルイソプチルケトン溶液（固形分 40%)を得た。  Dibutylamine 1.16 in a solution of 20 parts of Atalertoy compound with a pencil hardness of 3H after photocuring (“UN-3320H S” manufactured by Negami Kogyo Co., Ltd.) in 31.74 parts of methyl isobutyl ketone Part (number of moles of ethylenically unsaturated double bonds Z number of moles of amine compound = 100/15), stirred at 40 ° C for 5 hours, cooled to room temperature, and photopolymerizable compound containing amino groups (1 ) Solution of methyl isobutyl ketone (solid content 40%).
[0071] (製造例 2) [0071] (Production Example 2)
光硬化後の鉛筆硬度が 3Hのアタリレートイ匕合物 (根上工業 (株)製「UN - 3320H S」） 20部をメチルイソブチルケトン 30.36部に溶解させた溶液に、 1—ァミノへキサン 0. 24部（エチレン性不飽和二重結合モル数 Zアミン化合物のモル数 = 100/10) を添加し、 40°Cで 5時間攪拌したあと、室温まで冷却し、アミノ基含有光硬化性化合 物（2)のメチルイソプチルケトン溶液（固形分 40%)を得た。  1-aminohexane in a solution in which 20 parts of a photo-cured pencil hardness of 3H ataler toy compound ("UN-3320H S" manufactured by Negami Kogyo Co., Ltd.) is dissolved in 30.36 parts of methyl isobutyl ketone. Add 24 parts (number of moles of ethylenically unsaturated double bond Z moles of amine compound = 100/10), stir at 40 ° C for 5 hours, cool to room temperature, and cure amino group-containing photocurable compound. A methyl isobutyl ketone solution (solid content 40%) of product (2) was obtained.
[0072] (製造例 3) [0072] (Production Example 3)
光硬化後の鉛筆硬度が 3Hのアタリレートイ匕合物（共栄社化学 (株)製「UA— 306T 」）20部をメチルイソブチルケトン 35. 19部に溶解させた溶液に、 1, 3—ジァミノプロ パン 3. 46部（エチレン性不飽和二重結合モル数 Zアミン化合物のモル数 = 100/ 30)を添加し、 40°Cで 5時間攪拌したあと、室温まで冷却し、アミノ基含有光硬化性 化合物（3)のメチルイソプチルケトン溶液（固形分 40%)を得た。 Ataleletoy compound with a pencil hardness of 3H after photocuring ("UA-306T" manufactured by Kyoeisha Chemical Co., Ltd.) ") In a solution obtained by dissolving 20 parts in 35. 19 parts of methyl isobutyl ketone, 3.46 parts of 1,3-diaminopropane (number of moles of ethylenically unsaturated double bonds Z number of moles of amine compound = 100/30) After stirring at 40 ° C. for 5 hours, the mixture was cooled to room temperature to obtain a methylisobutyl ketone solution (solid content: 40%) of the amino group-containing photocurable compound (3).
[0073] (製造例 4) [0073] (Production Example 4)
光硬化後の鉛筆硬度が 2Hのアタリレートイ匕合物 (荒川化学工業 (株)製「ビームセ ット 700」）20部をシクロへキサノン 34.04部に溶解させた溶液に、ピぺリジン 3. 59部 (エチレン性不飽和二重結合モル数 Zアミン化合物のモル数 = 100/20)を添カロし 、 40°Cで 5時間攪拌したあと、室温まで冷却し、アミノ基含有光硬化性化合物 (4)の シクロへキサノン溶液（固形分 40%)を得た。  Piperidine is added to a solution of 20 parts of Ataleletoy compound with a 2H pencil hardness after photo-curing ("Beamset 700" manufactured by Arakawa Chemical Industries, Ltd.) dissolved in 34.04 parts of cyclohexanone. 59 parts (number of moles of ethylenically unsaturated double bonds Z number of moles of amine compound = 100/20) was added and stirred at 40 ° C for 5 hours, then cooled to room temperature, and amino group-containing photocurable compound A cyclohexanone solution (solid content 40%) of (4) was obtained.
[0074] (製造例 5) [0074] (Production Example 5)
光硬化後の鉛筆硬度が 2Hのアタリレート化合物 (根上工業 (株)製「UN— 9000H 」）20部をシクロへキサノン 30. 24部に溶解させた溶液に、ジブチルァミン 0. 16部（ エチレン性不飽和二重結合モル数 Zアミン化合物のモル数 = 100/5)を添加し、 4 0°Cで 5時間攪拌したあと、室温まで冷却し、アミノ基含有光硬化性化合物（5)のシク 口へキサノン溶液（固形分 40%)を得た。  0.16 parts of dibutylamine (ethylenic) in a solution of 20 parts of an acrylate compound with a pencil hardness of 2H after photocuring (“UN-9000H” manufactured by Negami Kogyo Co., Ltd.) in 30.24 parts of cyclohexanone Unsaturated double bond moles Z moles of amine compound = 100/5), stirred at 40 ° C for 5 hours, cooled to room temperature, and the amino group-containing photocurable compound (5) An oral hexanone solution (solid content 40%) was obtained.
[0075] (製造例 6) [0075] (Production Example 6)
撹拌機、還流冷却管、ドライエアー導入管、温度計を備えた 4口フラスコに、ビフエ -ルテトラカルボン酸二無水物（三菱ィ匕学 (株)製) 80. 0部、ペンタエリスリトールトリ アタリレート（大阪有機化学工業 (株)製:ビスコート # 300) 250. 0部、ヒドロキノン 0. 16部、シクロへキサノン 141. 2部を仕込み、 85°Cまで昇温した。次いで触媒として 1 , 8—ジァザビシクロ [5. 4. 0]— 7—ゥンデセン (東京化成工業 (株)製） 1. 65部を 加え、 85°Cで 8時間撹拌し、グリシジルメタタリレート (ダウ'ケミカル日本 (株)製） 77. 3部、シクロへキサノン 33. 9部をカ卩え、次いで触媒として、ジメチルベンジルァミン 2. 65部を加え、 85°Cで 6時間撹拌し、室温まで冷却して、多官能 (メタ)アタリレートイ匕 合物（a)のシクロへキサノン溶液を得た。この反応溶液は淡黄色透明で固形分 70% 、数平均分子量（MN) 870、重量平均分子量（MW) 2, 830であった。  In a 4-neck flask equipped with a stirrer, reflux condenser, dry air inlet tube, and thermometer, biphenyl tetracarboxylic dianhydride (Mitsubishi Chemical Co., Ltd.) 80.0 parts, pentaerythritol triatari Rate (Osaka Organic Chemical Co., Ltd .: Biscoat # 300) 250.0 parts, hydroquinone 0.16 parts, cyclohexanone 141.2 parts were charged, and the temperature was raised to 85 ° C. Next, 1,8-diazabicyclo [5. 4. 0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) 1. 65 parts were added as a catalyst, and the mixture was stirred at 85 ° C for 8 hours, and glycidyl metatalylate (Dow 'Chemical Japan Co., Ltd.) 77. 3 parts and cyclohexanone 33.9 parts were added, then 2.65 parts dimethylbenzylamine as catalyst was added and stirred at 85 ° C for 6 hours at room temperature. The solution was cooled to a cyclohexanone solution of the polyfunctional (meth) ataretoy compound (a). This reaction solution was light yellow and transparent and had a solid content of 70%, a number average molecular weight (MN) of 870, and a weight average molecular weight (MW) of 2,830.
光硬化後の鉛筆硬度が 3Hの上記多官能 (メタ)アタリレート化合物 (a)を含有する シクロへキサノン溶液（固形分 70%) 28.6部をシクロへキサノン 23. 07部で希釈した 溶液（固形分 40%)に、ジブチルァミン 1. 1部（エチレン性不飽和二重結合モル数 Z ァミン化合物のモル数 = 100Z15)を添カ卩し、 40°Cで 5時間攪拌したあと、室温まで 冷却し、アミノ基含有光硬化性化合物（6)のシクロへキサノン溶液（固形分 40%)を 得た。 Contains the above polyfunctional (meth) acrylate compound (a) having a pencil hardness of 3H after photocuring Cyclohexanone solution (solid content 70%) 28.6 parts of cyclohexanone diluted with 23.07 parts of cyclohexanone (solid content 40%) were added to dibutylamine 1.1 parts (ethylenically unsaturated double bond moles Z-amin compound). The mixture was stirred at 40 ° C for 5 hours and then cooled to room temperature to obtain a cyclohexanone solution of amino group-containing photocurable compound (6) (solid content 40%). It was.
[0076] (製造例 7) [0076] (Production Example 7)
光硬化後の鉛筆硬度が 3Hの上記多官能 (メタ)アタリレート化合物 (a)を含有する シクロへキサノン溶液（固形分 70%) 28.6部をメチルイソブチルケトン 22. 4部で希釈 した溶液（固形分 40%)に、 N—メチルへキシルァミン 0. 65部（エチレン性不飽和二 重結合モル数 Zアミン化合物のモル数 = 100/10)を添加し、 40°Cで 5時間攪拌し たあと、室温まで冷却し、アミノ基含有光硬化性ィ匕合物（7)のメチルイソプチルケトン 溶液（固形分 40%)を得た。  Cyclohexanone solution (solid content 70%) containing the above polyfunctional (meth) atalylate compound (a) whose pencil hardness after photocuring is 3H (Solid content 70%) 28.6 parts diluted with methyl isobutyl ketone 22.4 parts (solid Min. 40%) N-methylhexylamine 0.65 parts (number of moles of ethylenically unsaturated double bonds Z moles of amine compound = 100/10) and after stirring at 40 ° C for 5 hours Then, the mixture was cooled to room temperature to obtain a methylisoptyl ketone solution (solid content 40%) of the amino group-containing photocurable compound (7).
[0077] (製造例 8) [0077] (Production Example 8)
撹拌機、還流冷却管、ドライエアー導入管、温度計を備えた 4口フラスコに、ブタン テトラカルボン酸二無水物 (新日本理化株式会社製:リカシッド BT-100) 100. 0部、 ペンタエリスリトールトリアタリレート（日本化薬株式会社製: KAYARAD PET- 30 ) 463. 2部、ヒドロキノン 0. 28部、シクロへキサノン 563. 2部を仕込み 85。Cまで昇温 した。次いで触媒として 1, 8—ジァザビシクロ [5. 4. 0]— 7—ゥンデセン (東京化成 工業 (株)製） 2. 82部をカ卩え、 85°Cで 8時間撹拌し、グリシジルメタタリレート (ダウ'ケ ミカル日本 (株)製） 143. 4部、シクロへキサノン 146. 5部を加え、次いで触媒として 、ジメチルベンジルァミン 4. 53部を加え、 85°Cで 6時間撹拌し、室温まで冷却し、多 官能 (メタ)アタリレートイ匕合物 (b)のシクロへキサノン溶液を得た。この反応溶液は淡 黄色透明で固形分 50%、数平均分子量 (MN) 920、重量平均分子量 (MW) 2, 20 0であった。  To a 4-neck flask equipped with a stirrer, reflux condenser, dry air inlet tube, and thermometer, butane tetracarboxylic dianhydride (manufactured by Shin Nippon Chemical Co., Ltd .: Ricacid BT-100), 100 parts, pentaerythritol tri Atarilate (Nippon Kayaku Co., Ltd .: KAYARAD PET-30) 463.2 parts, hydroquinone 0.28 parts, cyclohexanone 563.2 parts are charged 85. The temperature was raised to C. Next, 1, 8-diazabicyclo [5. 4. 0] — 7-undecene (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 2. 82 parts as a catalyst, stirred at 85 ° C for 8 hours, and glycidyl metatalylate (Dow's Chemical Japan Co., Ltd.) 143.4 parts and 146.5 parts of cyclohexanone were added, followed by 4.53 parts of dimethylbenzylamine as a catalyst and stirred at 85 ° C for 6 hours. The solution was cooled to room temperature to obtain a cyclohexanone solution of the polyfunctional (meth) attareito toy compound (b). This reaction solution was light yellow and transparent and had a solid content of 50%, a number average molecular weight (MN) of 920, and a weight average molecular weight (MW) of 2,200.
光硬化後の鉛筆硬度が 3Hの上記多官能 (メタ)アタリレート化合物 (b)を含有する シクロへキサノン溶液（固形分 50%) 30. 0部をシクロへキサノン 9. 1部で希釈した溶 液（固形分 40%)に、ジブチルァミン 1. 05部（エチレン性不飽和二重結合モル数 Z ァミン化合物のモル数 = 100Z15)を添カ卩し、 40°Cで 5時間攪拌したあと、室温まで 冷却し、アミノ基含有光硬化性化合物（8)のシクロへキサノン溶液（固形分 40%)を 得た。 Cyclohexanone solution (solid content 50%) containing the above polyfunctional (meth) acrylate compound (b) with a pencil hardness of 3H after photocuring 30.0 parts diluted with 9.1 parts of cyclohexanone To the liquid (solid content 40%) was added 1.05 parts of dibutylamine (number of moles of ethylenically unsaturated double bond Z moles of the amine compound = 100Z15) and stirred at 40 ° C for 5 hours. Until Upon cooling, a cyclohexanone solution (solid content 40%) of the amino group-containing photocurable compound (8) was obtained.
[0078] (製造例 9) [0078] (Production Example 9)
撹拌機、還流冷却管、ドライエアー導入管、温度計を備えた 4口フラスコに、 9、 9— ビス（3, 4—ジカルボキシフエ-ル）フルオレン二酸無水物（JFEケミカル株式会社製 、商品名 BPAF) 100. 0部、ペンタエリスリトールトリアタリレート（大阪有機化学ェ 業株式会社、商品名：ビスコート # 300) 200. 2部、ヒドロキノン 0. 15部（和光純薬 工業株式会社製）、シクロへキサノン 200. 1部を仕込み 85°Cまで昇温した。次いで 触媒として 1, 8—ジァザビシクロ [5. 4. 0]— 7—ゥンデセン (東京化成工業株式会 社製） 1. 50部を加え、 85°Cで 8時間撹拌し、グリシジルメタタリレート (ダウ'ケミカル 日本株式会社製) 62. 0部、シクロへキサノン 42. 4部をカ卩え、次いで触媒として、ジ メチルベンジルァミン (和光純薬工業株式会社製） 2. 41部をカ卩え、 85°Cで 6時間撹 拌し、室温まで冷却して、（メタ)アタリレートイ匕合物（c)のシクロへキサノン溶液を得た 。この反応溶液は淡黄色透明で固形分 60%、数平均分子量 (MN) 830、重量平均 分子量（MW) 2, 310であった。  In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, 9, 9-bis (3,4-dicarboxyphenyl) fluorene diacid anhydride (manufactured by JFE Chemical Co., Ltd.) (Product name BPAF) 100. 0 parts, Pentaerythritol Triatalylate (Osaka Organic Chemical Co., Ltd., trade name: Biscote # 300) 200. 2 parts, Hydroquinone 0.15 parts (manufactured by Wako Pure Chemical Industries, Ltd.) 200.1 parts of cyclohexanone was charged and the temperature was raised to 85 ° C. Next, 1,8-diazabicyclo [5. 4. 0] — 7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) 1. Add 50 parts, stir at 85 ° C for 8 hours, and add glycidyl metatalylate (Dow 'Chemicals made in Japan Co., Ltd.) 62. 0 parts, cyclohexanone 42. 4 parts, followed by dimethylbenzylamine (made by Wako Pure Chemical Industries) 2. 41 parts as catalyst The mixture was stirred at 85 ° C. for 6 hours and cooled to room temperature to obtain a cyclohexanone solution of the (meth) atalytoi compound (c). This reaction solution was light yellow and transparent and had a solid content of 60%, a number average molecular weight (MN) of 830, and a weight average molecular weight (MW) of 2,310.
光硬化後の鉛筆硬度が 3Hの上記多官能 (メタ)アタリレート化合物 (c)を含有する シクロへキサノン溶液（固形分 60%) 20. 0部をシクロへキサノン 10. 4部で希釈した 溶液（固形分 40%)に、ジェチルァミン 0. 3部（エチレン性不飽和二重結合モル数 Z ァミン化合物のモル数 = 100Z10)を添カ卩し、 40°Cで 5時間攪拌したあと、室温まで 冷却し、アミノ基含有光硬化性化合物（9)のシクロへキサノン溶液（固形分 40%)を 得た。  Cyclohexanone solution (solid content 60%) containing the above polyfunctional (meth) acrylate compound (c) having a pencil hardness of 3H after photocuring 20. A solution obtained by diluting 20. 0 parts with cyclohexanone 10.4 parts (Solid content: 40%) Add 0.3 parts of jetylamine (number of moles of ethylenically unsaturated double bond: moles of Z-amine compound = 100Z10) and stir at 40 ° C for 5 hours. Upon cooling, a cyclohexanone solution (solid content 40%) of the amino group-containing photocurable compound (9) was obtained.
[0079] (製造例 10) [0079] (Production Example 10)
撹拌機、還流冷却管、ドライエアー導入管、温度計を備えた 4口フラスコに、ビフエ -ルテトラカルボン酸二無水物（三菱ィ匕学 (株)製) 80. 0部、ペンタエリスリトールトリ アタリレート（日本化薬株式会社製: KAYARAD PET— 30) 124. 8部、ジペンタ エリスリトールペンタアタリレート（日本化薬株式会社製: KAYARAD DPHA) 222 . 8部、ヒドロキノン 0. 21部、シクロへキサノン 430. 0部を仕込み 85°Cまで昇温した。 次いで触媒として 1, 8—ジァザビシクロ [5. 4. 0]— 7—ゥンデセン (東京化成工業（ 株)製） 2. 14部をカ卩え、 85°Cで 8時間撹拌し、グリシジルメタタリレート (ダウ'ケミカル 日本 (株)製） 77. 3部、シクロへキサノン 80. 7部をカ卩え、次いで触媒として、ジメチル ベンジルァミン 3. 42部をカ卩え、 85°Cで 6時間撹拌し、室温まで冷却して、（メタ）ァク リレート化合物（d)のシクロへキサノン溶液を得た。この反応溶液は淡黄色透明で固 形分 50%、数平均分子量（MN) 1, 050、重量平均分子量（MW) 3, 830であった。 光硬化後の鉛筆硬度が 3Hの上記多官能 (メタ)アタリレート化合物（d)を含有する シクロへキサノン溶液（固形分 50%) 30. 0部をシクロへキサノン 9. 1部で希釈した溶 液（固形分 40%)に、 2—ピペリジンエタノール 1. 05部（エチレン性不飽和二重結合 モル数 Zアミン化合物のモル数 = 100/15)を添カ卩し、 40°Cで 5時間攪拌したあと、 室温まで冷却し、アミノ基含有光硬化性化合物（10)のシクロへキサノン溶液（固形分 40%)を得た。 In a 4-neck flask equipped with a stirrer, reflux condenser, dry air inlet tube, and thermometer, biphenyl tetracarboxylic dianhydride (Mitsubishi Chemical Co., Ltd.) 80.0 parts, pentaerythritol triatari Rate (Nippon Kayaku Co., Ltd .: KAYARAD PET—30) 124.8 parts, dipentaerythritol pentaatalylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) 222.8 parts, Hydroquinone 0.21 part, Cyclohexanone 430 0 parts were charged and the temperature was raised to 85 ° C. Next, 1, 8—diazabicyclo [5. 4. 0] — 7—undecene (Tokyo Chemical Industry ( 2. Prepare 14 parts, stir at 85 ° C for 8 hours, and add 77.3 parts of glycidyl metatalylate (manufactured by Dow Chemical Japan Co., Ltd.) and 80.7 parts of cyclohexanone. Then, as a catalyst, 3.42 parts of dimethyl benzylamine was added, stirred at 85 ° C for 6 hours, and cooled to room temperature to obtain a cyclohexanone solution of (meth) acrylate compound (d). It was. This reaction solution was light yellow and transparent with a solid content of 50%, a number average molecular weight (MN) of 1,050, and a weight average molecular weight (MW) of 3,830. Cyclohexanone solution (solid content 50%) containing the above polyfunctional (meth) acrylate compound (d) having a pencil hardness of 3H after photocuring 30.0 parts of cyclohexanone diluted with 9.1 parts of cyclohexanone To the liquid (solid content: 40%), add 1.05 parts of 2-piperidineethanol (number of moles of ethylenically unsaturated double bond, moles of Z amine compound = 100/15), and continue at 40 ° C for 5 hours. After stirring, the mixture was cooled to room temperature to obtain a cyclohexanone solution (solid content 40%) of the amino group-containing photocurable compound (10).
[0080] (製造例 11) [0080] (Production Example 11)
光硬化後の鉛筆硬度が HBのアタリレートイ匕合物 (荒川化学工業 (株)製「ビームセ ット 750」）20部をメチルイソブチルケトン 32. 27部に溶解させた溶液に、ジブチルァ ミン 1. 51部（エチレン性不飽和二重結合モル数 Zアミン化合物のモル数 = 100/1 5)を添加し、 40°Cで 5時間攪拌したあと、室温まで冷却し、アミノ基含有光硬化性ィ匕 合物（8)のメチルイソプチルケトン溶液（固形分 40%)を得た。  Dibutylamine 1 was prepared by dissolving 20 parts of Atalile Toy Compound with a pencil hardness of HB after photo-curing ("Beamset 750" manufactured by Arakawa Chemical Industry Co., Ltd.) in 32.27 parts of methyl isobutyl ketone. Add 51 parts (number of moles of ethylenically unsaturated double bond Z moles of amine compound = 100/1 5), stir at 40 ° C for 5 hours, cool to room temperature, and contain amino group-containing photocuring property A methyl isobutyl ketone solution (solid content 40%) of the compound (8) was obtained.
[0081] (金属酸ィヒ物分散ペーストの作成：実施例 1〜13、比較例 1及び 2)  [0081] (Preparation of metal-acid dispersion paste: Examples 1 to 13, Comparative Examples 1 and 2)
上記製造例により作成した各ァミノ基含有光硬化性化合物を用い、表 1に示す配 合により金属酸化物分散を行ない、金属酸化物分散ペーストを作成した。分散方法 は、仮分散（ジルコ-ァビーズ（1. 25mm)をメディアとして用い、ペイントシエイカ一 で 1時間分散）と、本分散 (ジルコ-ァビーズ (0. 1mm)をメディアとして用い、寿工業 (株)製分散機 UAM— 015で分散)の 2段階で行なった。  Using each amino group-containing photocurable compound prepared in the above production example, metal oxide dispersion was performed by the combination shown in Table 1 to prepare a metal oxide dispersion paste. Dispersion methods include temporary dispersion (using zirca beads (1.25 mm) as media and dispersion with paint shaker for 1 hour) and main dispersion (zirco beads (0.1 mm) as media). The dispersion was carried out in two stages using a dispersion machine UAM-015.
[0082] [表 1] 表 1 金 K酸化物分散ペーストの配合 [0082] [Table 1] Table 1 Composition of gold K oxide dispersion paste
Figure imgf000037_0001
Figure imgf000037_0001
[0083] 表 1において、 [0083] In Table 1,
Sb O：日産化学工業 (株)製「サンエポック EFR— 6N」（平均一次粒子径： 20η Sb O: “San-Epoque EFR-6N” manufactured by Nissan Chemical Industries, Ltd. (average primary particle size: 20η
2 5 twenty five
m)  m)
ATO：石原産業 (株)製「SN - 100PJ (平均一次粒子径： 20nm)  ATO: “SN-100PJ (average primary particle size: 20nm) manufactured by Ishihara Sangyo Co., Ltd.
ITO：シーアィ化成 (株)製「ナノテック ITO」（平均一次粒子径： 30nm) ITO: “Nanotech ITO” manufactured by Shi Kasei Co., Ltd. (average primary particle size: 30 nm)
PTO：触媒化成工業 (株)製「TL - 30SJ (平均一次粒子径： 30nm)PTO: "TL-30SJ (average primary particle size: 30nm) by Catalytic Chemical Industry Co., Ltd."
A1ドープ ZnO：ハクスィテック（株）製「PazetCK」（平均一次粒子径： 30nm)A1 doped ZnO: “PazetCK” (average primary particle size: 30 nm) manufactured by Hux Tech Co., Ltd.
ZrO：日本電工 (株)製「PCS」（平均一次粒子径： 30nm) ZrO: “PCS” (average primary particle size: 30 nm) manufactured by Nippon Denko Co., Ltd.
2  2
TiO：石原産業 (株)製「TTO - 51 (A) ] (平均一次粒子径： 20nm)  TiO: “TTO-51 (A)] manufactured by Ishihara Sangyo Co., Ltd. (average primary particle size: 20nm)
2  2
ZnO：堺化学工業 (株)製「FINEX— 50」（平均一次粒子径： 20nm) ZnO: “FINEX-50” manufactured by Sakai Chemical Industry Co., Ltd. (average primary particle size: 20 nm)
Al O：日本ァエロジル (株）製「Aluminium Oxide C」（平均一次粒子径： 13Al O: Nippon Aerosil Co., Ltd. “Aluminium Oxide C” (average primary particle size: 13
2 5 twenty five
nm)  nm)
市販多官能モノマー：荒 J 11化学工業 (株)製「ビームセット 750」（ビスフエノール A エチレンオキサイド変性アタリレート、分子量 (MW) 512、光硬化後の鉛筆硬度 HB) MIBK：メチノレイソブチノレケトン  Commercially available multifunctional monomer: Ara J 11 Chemical Industry Co., Ltd. “Beamset 750” (Bisphenol A ethylene oxide modified acrylate, molecular weight (MW) 512, pencil hardness after photocuring HB) MIBK: methinoreisobutinore Ketone
メトブタ： 3—メトキシー 1 ブタノール  Methobuta: 3-Methoxy-1-butanol
[0084] (塗料化及び硬化膜評価：実施例 1〜13、比較例 1及び 2) [0084] (Coating and evaluation of cured film: Examples 1 to 13, Comparative Examples 1 and 2)
上記で調整した金属酸ィ匕物分散ペーストを用いて、表 2に示す組成の硬化性組成 物を調整した。得られた硬化性組成物を、 100 /z m厚の易接着処理 PETフィルム（ 東洋紡 (株)製「コスモシャイン A— 4100」）に、バーコ一ターで、乾燥後の膜厚が 5 μ mになるように塗工した後、メタルハライドランプで 400miZcm2の紫外線を照射し 、帯電防止用ハードコート層 (硬化膜)を形成した。得られた帯電防止用ハードコート 層について、下記の方法で表面抵抗、耐擦傷性、鉛筆硬度、透明性 (ヘイズ)および 耐光性を評価した。その結果を表 2に示す。 A curable composition having the composition shown in Table 2 was prepared using the metal oxide dispersion paste prepared above. The obtained curable composition was applied to a 100 / zm thick easy-to-adhesive PET film ("Cosmo Shine A-4100" manufactured by Toyobo Co., Ltd.) with a bar coater to a film thickness after drying of 5 μm. After coating, an antistatic hard coat layer (cured film) was formed by irradiating 400 miZcm 2 ultraviolet rays with a metal halide lamp. The obtained antistatic hard coat layer was evaluated for surface resistance, scratch resistance, pencil hardness, transparency (haze) and light resistance by the following methods. The results are shown in Table 2.
[0085] [表 2] 表 2 硬化性組成物の E合と 化瞎の評《 [0085] [Table 2] Table 2 Evaluation of chemical composition and chemical composition of curable composition <<
Figure imgf000039_0001
Figure imgf000039_0001
[0086] 表 2において、 [0086] In Table 2,
光硬化性化合物（ 1)：共栄社化学 (株)製「UA— 306TJ  Photo-curable compound (1): “UA-306TJ” manufactured by Kyoeisha Chemical Co., Ltd.
光硬化性化合物（2)：日本化薬 (株)製「KAYARAD DPHA」  Photo-curing compound (2): “KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.
光重合開始剤：チバ 'スぺシャリティ ·ケミカルズ (株)製「ィルガキュア 184」 溶剤： PGME (プロピレングリコールモノメチルエーテル）  Photopolymerization initiator: Ciba Specialty Chemicals "Irgacure 184" Solvent: PGME (propylene glycol monomethyl ether)
* 1：金属酸ィヒ物ペーストが分散不良だったので未測定  * 1: Not measured because the metal acid paste paste was poorly dispersed
[0087] (反射防止膜 (積層体)の作製及び評価:実施例 14〜19) [0087] (Preparation and evaluation of antireflection film (laminate): Examples 14 to 19)
(低屈折率塗液の作製）  (Preparation of low refractive index coating liquid)
1,2,9, 10—テトラアタリロイルォキシ— 4, 4, 5, 5, 6, 6, 7, 7—ォクタフルォロデ カン 50重量部、シリカゾル 30%分散液（日産化学工業 (株)製 MEK-ST) 120重量  1,2,9,10—Tetraatalylooxy— 4, 4, 5, 5, 6, 6, 7, 7—Octafluorodecane 50 parts by weight, silica sol 30% dispersion (MEK manufactured by Nissan Chemical Industries, Ltd.) -ST) 120 weight
, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 11, 11, 11—ノナデカフルォロウンデ シル 10重量部、ブチルアルコール 900重量部、光重合開始剤（日本化薬 (株)製 KA YACURE BMS) 5重量部を混合し、低屈折率塗液を調整した。 , 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 11, 11, 11—Nonadecafluoroundecyl 10 parts by weight, Butyl alcohol 900 parts by weight, 5 parts by weight of a photopolymerization initiator (Nippon Kayaku Co., Ltd. KA YACURE BMS) was mixed to prepare a low refractive index coating solution.
[0088] 実施例 3の金属酸化物分散ペーストを用い、表 3に示す配合による組成の各硬化 性組成物を調整した。この硬化性組成物を、 100 m厚の易接着処理 PETフィルム (易接着処理層の屈折率 = 1. 60)の易接着処理面に、バーコ一ターを用いて乾燥 膜厚で 6 /z mとなるよう塗布した。得られた塗布層を、 100°C1分で乾燥したのち、メタ ルハライドランプで 400miZcm2の紫外線を照射した。得られた硬化膜上にさらに、 上記低屈折塗料液をスピンコーターにて、乾燥膜厚で λ /4を示す光の波長が 550η m程度になるように層の厚さを調整して塗布した。得られた塗布層を、 100°C1分で 乾燥したのち、メタルハライドランプで 400miZcm2の紫外線を照射し、積層体を得 た。 [0088] Using the metal oxide dispersion paste of Example 3, each curable composition having the composition shown in Table 3 was prepared. This curable composition was applied to an easy-adhesion-treated surface of a 100-m thick easy-adhesion-treated PET film (refractive index of the easy-adhesion-treated layer = 1.60) using a bar coater to give a dry film thickness of 6 / zm It applied so that it might become. The obtained coating layer was dried at 100 ° C. for 1 minute, and then irradiated with 400 miZcm 2 ultraviolet rays with a metal halide lamp. Further, the low refractive coating liquid was applied on the obtained cured film with a spin coater while adjusting the layer thickness so that the wavelength of light having a dry film thickness of λ / 4 was about 550 ηm. . The obtained coating layer was dried at 100 ° C. for 1 minute, and then irradiated with 400 miZcm 2 ultraviolet rays with a metal halide lamp to obtain a laminate.
得られた積層体について、下記の方法で硬化膜の屈折率を測定するとともに、硬 化膜の耐擦傷性、鉛筆硬度、透明性 (ヘイズ)、屈折率、反射干渉縞を評価した。そ の結果を表 3に示す。  Regarding the obtained laminate, the refractive index of the cured film was measured by the following method, and the scratch resistance, pencil hardness, transparency (haze), refractive index, and reflection interference fringes of the cured film were evaluated. The results are shown in Table 3.
[0089] [表 3] 表 3 硬化性組成物の配合と硬化膜の評価 [0089] [Table 3] Table 3 Composition of curable composition and evaluation of cured film
Figure imgf000041_0001
Figure imgf000041_0001
[0090] 表 3において [0090] In Table 3
光硬化性化合物（ 1 )：共栄社化学 (株)製「UA— 306TJ  Photocurable compound (1): “UA-306TJ” manufactured by Kyoeisha Chemical Co., Ltd.
光重合開始剤：チパ'スぺシャリティ ·ケミカルズ (株)製「ィルガキュア 184」 基材： 100 m厚の易接着処理 PETフィルム（東洋紡 (株)製「コスモシャイン A— 4100」、易接着処理面 (屈折率 1. 60)に塗工）  Photopolymerization initiator: “Irgacure 184” manufactured by Chipa's Specialty Chemicals Co., Ltd. Base material: 100 m thick easily treated PET film (“Cosmo Shine A-4100” manufactured by Toyobo Co., Ltd.) (Coating to refractive index 1.60)
溶剤： PGME (プロピレングリコールモノメチルエーテル）  Solvent: PGME (propylene glycol monomethyl ether)
[0091] (評価方法）  [0091] (Evaluation method)
(1)表面抵抗  (1) Surface resistance
硬化膜の表面抵抗（ Ω Z口）を、以下の基準に従って評価した。  The surface resistance (Ω Z port) of the cured film was evaluated according to the following criteria.
表面抵抗が 1 X 1012以下の場合: A If the surface resistance is 1 X 10 12 or less: A
表面抵抗が 1 X 1012より高く 1 X 1014以下の場合: B If the surface resistance is higher than 1 X 10 12 and lower than 1 X 10 14, B
表面抵抗が 1 X 1014を超える場合: D If the surface resistance exceeds 1 X 10 14 : D
(2)耐擦傷性  (2) Scratch resistance
塗工物を学振試験機にセットし、スチールウールの No.0000を用いて、荷重 250g で 10回学振させた。取り出した塗工物について、キズのっき具合を以下の 5段階の 目視評価に従って判断した。数値が大きいほど、硬化膜の耐擦傷性が良好であるこ とを示す。  The coated product was set on a Gakushin Tester and shook 10 times with a load of 250g using steel wool No.0000. The removed coating was judged for scratching according to the following five-step visual evaluation. The larger the value, the better the scratch resistance of the cured film.
5 :キズが全くない 4：僅か〖こキズが付いている 5: No scratch 4: There are slight scratches
3：キズは付!ヽて!ヽるが、基材は見えて!/ヽな!ヽ  3: Scratches are attached! Come on! You can see the base material!
2 :キズが付き、一部硬化膜が剥がれている  2: Scratched and part of the cured film is peeled off
1：硬化膜が剥がれてしまい、基材が剥き出しの状態  1: The cured film is peeled off and the substrate is exposed
[0092] (3)鉛筆硬度 [0092] (3) Pencil hardness
JIS— K5600に準拠し、鉛筆硬度試験機（HEIDON社製 Scratching Tester HEIDON- 14)を用い、鉛筆の芯の硬さを種々変えて、荷重 500gにて 5回試験を した。 5回中、 1回も傷がつかない、もしくは 1回のみ傷が付く時の芯の硬さを、その硬 化膜の鉛筆硬度とした。実用的な要求物性を考慮して、硬化膜の鉛筆硬度が、 2H以上: A  In accordance with JIS K5600, a pencil hardness tester (Scratching Tester HEIDON-14 manufactured by HEIDON) was used, and the test was performed five times at a load of 500 g with various changes in pencil core hardness. The pencil hardness of the hardened film was defined as the hardness of the core when the scratch was not scratched once or was scratched only once. In consideration of practical required physical properties, the pencil hardness of the cured film is 2H or more: A
2Hより低い： D  Lower than 2H: D
と判定した。  It was determined.
(4)透明性 (Haze値）  (4) Transparency (Haze value)
得られた塗工物における濁度 (Haze値)を、 Hazeメーターを用いて測定した。  Turbidity (Haze value) in the obtained coated product was measured using a Haze meter.
[0093] (5)耐光性 [0093] (5) Light resistance
光連続照射時の経時での黄変は、用途展開上、非常に好ましくない。そこで、光連 続照射時の黄変性を確認した。  Yellowing with the passage of time during continuous light irradiation is very undesirable for application development. Therefore, yellowing during continuous light irradiation was confirmed.
まず、耐光性試験機 (光源:キセノンランプ、照度： 100WZcm2、ブラックパネル温 度： 60°C、 60%RH)にて塗工物を 24時間暴露した。その後、白色紙上に塗工物を 置き、測色機 (ミノルタ CR— 300)を用いて着色を測定した。測色値は L*a*b*にて 表示し、硬化膜の黄変性の目安を b*値にて判断した。 b*値の値が小さいほど、黄変 の程度が小さぐ耐光性が良好であることを表す。実用的な要求物性を考慮して、硬 化膜の b*値が、 First, the coated material was exposed for 24 hours with a light resistance tester (light source: xenon lamp, illuminance: 100 WZcm 2 , black panel temperature: 60 ° C, 60% RH). Thereafter, the coated material was placed on white paper, and the color was measured using a colorimeter (Minolta CR-300). The colorimetric value was displayed as L * a * b *, and the guideline for yellowing of the cured film was judged from the b * value. The smaller the b * value, the smaller the degree of yellowing and the better the light resistance. Considering the practical properties required, the b * value of the cured film is
3. 5未満のもの： A  3. Less than 5: A
3. 5以上のもの： D  3. More than 5: D
と判定した。  It was determined.
[0094] (6)屈折率 [0094] (6) Refractive index
得られた硬化膜の屈折率を、株式会社ァタゴ製アッベ屈折率計を用いて測定した (7)反射干渉縞 The refractive index of the obtained cured film was measured using an Abbe refractometer manufactured by Atago Co., Ltd. (7) Reflective interference fringes
得られた硬化膜の反射干渉縞を、以下の基準に従い目視にて評価した。  The reflection interference fringes of the obtained cured film were visually evaluated according to the following criteria.
A：反射干渉縞が観察できなレヽ  A: Rays where reflection interference fringes cannot be observed
D :反射干渉縞が観察できる  D: Reflected interference fringes can be observed

Claims

請求の範囲 The scope of the claims
[1] 平均一次粒子径が 5〜： LOOnmの金属酸化物と、  [1] Average primary particle size is 5 ~: Metal oxide of LOOnm,
エチレン性不飽和二重結合と第一級ァミンまたは第二級ァミンとを反応させた官能 基、および、未反応のエチレン性不飽和二重結合を有するアミノ基含有光硬化性ィ匕 合物と、  A functional group obtained by reacting an ethylenically unsaturated double bond with a primary amine or a secondary amine, and an amino group-containing photocurable compound having an unreacted ethylenically unsaturated double bond; ,
を含有する硬化性組成物。  A curable composition containing
[2] アミノ基含有光硬化性化合物が、光硬化後の鉛筆硬度が H以上になるアタリレート 化合物またはメタクリレートイ匕合物と第一級ァミンまたは第二級ァミンとを反応させた ものである、請求項 1記載の硬化性組成物。 [2] The amino group-containing photocurable compound is obtained by reacting an atylate compound or methacrylate compound having a pencil hardness after photocuring of H or higher with a primary amine or secondary amine. The curable composition according to claim 1.
[3] アミノ基含有光硬化性ィ匕合物が、アタリレートイ匕合物またはメタタリレートイ匕合物と第 一級アミンまたは第二級ァミンとを、前記アタリレートイ匕合物またはメタクリレートイ匕合 物中のエチレン性不飽和二重結合 100モルに対して、第一級ァミンまたは第二級ァ ミンが 0. 5〜50モルとなる比率で反応させたものである、請求項 1または 2記載の硬 化性組成物。 [3] The amino group-containing photo-curable compound is an atareto toy compound or a meta talari toy compound and a primary amine or a secondary ammine, and the atalyto toy compound or the methacrylate compound. The primary or secondary amine is reacted at a ratio of 0.5 to 50 moles per 100 moles of ethylenically unsaturated double bonds in the product. Hardening composition.
[4] アミノ基含有光硬化性ィ匕合物が、下記一般式（1)で表される化合物と第一級ァミン または第二級ァミンとを反応させたものである、請求項 1〜3のいずれか 1項に記載の 硬化性組成物。  [4] The amino group-containing photocurable compound is obtained by reacting a compound represented by the following general formula (1) with a primary or secondary amine. The curable composition according to any one of the above.
一般式 (1)  General formula (1)
[化 1]  [Chemical 1]
Figure imgf000044_0001
Figure imgf000044_0001
(式中、 I^〜R4は、それぞれ独立に水素原子またはメチル基を示し、 R5〜R8は、そ れぞれ独立に非置換もしくは置換の、直鎖もしくは分岐鎖のアルキレン基を示し、 R! は、 4価の脂肪族基もしくは芳香族基を示す。 ) (In the formula, I ^ to R 4 each independently represents a hydrogen atom or a methyl group, and R 5 to R 8 each independently represents an unsubstituted or substituted linear or branched alkylene group. Show, R ! Represents a tetravalent aliphatic group or an aromatic group. )
[5] 第一級ァミンまたは第二級ァミンが、脂肪族モノアミンである、請求項 1〜4のいず れか 1項に記載の硬化性組成物。 [5] The curable composition according to any one of claims 1 to 4, wherein the primary or secondary amine is an aliphatic monoamine.
[6] 金属酸化物が、チタニウム、亜鉛、ジルコニウム、アンチモン、インジウム、スズ、ァ ルミ-ゥム及び珪素力 なる群力 選ばれる少なくとも一種の元素を含有するもので ある、請求項 1〜5のいずれか 1項に記載の硬化性組成物。 [6] The metal oxide according to any one of claims 1 to 5, wherein the metal oxide contains at least one element selected from the group force of titanium, zinc, zirconium, antimony, indium, tin, aluminum and silicon power. The curable composition of any one of Claims 1.
[7] さらに溶剤を含み、かつ溶剤が、全溶剤に対して 10〜： L00重量％の水酸基含有溶 剤を含む、請求項 1〜6の!ヽずれか 1項に記載の硬化性組成物。 [7] The curable composition according to any one of claims 1 to 6, further comprising a solvent, wherein the solvent comprises 10 to L00% by weight of a hydroxyl group-containing solvent with respect to the total solvent. .
[8] 請求項 1〜7の ヽずれか 1項に記載の硬化性組成物を硬化してなる硬化膜。 [8] A cured film obtained by curing the curable composition according to any one of claims 1 to 7.
[9] 表面抵抗値が、 1 X 1012ΩΖ口以下である、請求項 8記載の硬化膜。 [9] The cured film according to claim 8, wherein the surface resistance value is 1 × 10 12 Ω or lower.
[10] 厚さが、 0. 1〜30 μ mである、請求項 8または 9記載の硬化膜。 [10] The cured film according to claim 8 or 9, which has a thickness of 0.1 to 30 μm.
[11] 屈折率が、 1. 5〜1. 8の範囲である、請求項 8〜 10のいずれ力 1項に記載の硬化 膜。 [11] The cured film according to any one of claims 8 to 10, wherein the refractive index is in the range of 1.5 to 1.8.
[12] 基材と、請求項 8〜11のいずれか 1項に記載の硬化膜とを含む積層体。  [12] A laminate comprising a base material and the cured film according to any one of claims 8 to 11.
[13] 基材が、プラスチック基材である、請求項 12記載の積層体。  13. The laminate according to claim 12, wherein the substrate is a plastic substrate.
[14] 基材が、レンズ形状である、請求項 12または 13記載の積層体。  [14] The laminate according to [12] or [13], wherein the substrate has a lens shape.
[15] 硬化膜が基材上に、他の層を介することなく形成されており、硬化膜と基材との屈 折率の差が ±0. 02以内である、請求項 12〜14のいずれか 1項に記載の積層体。  [15] The cured film according to any one of claims 12 to 14, wherein the cured film is formed on the substrate without any other layer, and a difference in refractive index between the cured film and the substrate is within ± 0.02. The laminate according to any one of the above.
[16] 硬化膜と基材との間にさらに一層以上の下層を有し、硬化膜と、硬化膜の接する下 層との屈折率の差が ±0. 02以内である、請求項 12〜 14のいずれ力 1項に記載の 積層体。 [16] The invention further comprises one or more lower layers between the cured film and the substrate, and the difference in refractive index between the cured film and the lower layer in contact with the cured film is within ± 0.02. 14. The laminate according to any one of 14 items 1.
[17] 情報記録層を含む、請求項 12〜16のいずれか 1項に記載の積層体。  [17] The laminate according to any one of claims 12 to 16, comprising an information recording layer.
[18] 反射防止膜である、請求項 12〜16のいずれか 1項に記載の積層体。 [18] The laminate according to any one of claims 12 to 16, which is an antireflection film.
[19] 請求項 1〜7の 、ずれか 1項に記載の硬化性組成物を含む光半導体素子封止材。 [19] An optical semiconductor element sealing material comprising the curable composition according to any one of [1] to [7].
[20] 請求項 1〜7の ヽずれか 1項に記載の硬化性組成物を基材に塗布すること；および 活性エネルギー線を照射して硬化性組成物を硬化させること； [20] Applying the curable composition according to claim 1 to a substrate; and irradiating active energy rays to cure the curable composition;
を含む硬化膜の製造方法。  The manufacturing method of the cured film containing this.
PCT/JP2006/314087 2005-07-19 2006-07-14 Curable composition, cured film and multilayer body WO2007010865A1 (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007138946A1 (en) * 2006-05-29 2007-12-06 Toyo Ink Mfg. Co., Ltd. Metal oxide composition, cured film and laminate
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JP2009157233A (en) * 2007-12-27 2009-07-16 Riken Technos Corp Antireflection film
JP2009242497A (en) * 2008-03-28 2009-10-22 Arisawa Mfg Co Ltd Photosensitive resin composition, hard coat film using it, and reflection preventing film
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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4045416A (en) * 1971-01-21 1977-08-30 Union Carbide Corporation Amine acrylate addition reaction product compositions
US5596669A (en) * 1995-04-21 1997-01-21 Dsm N.V. Radiation curable coating composition and coated optical fiber
JPH11193321A (en) * 1997-10-27 1999-07-21 Toyo Ink Mfg Co Ltd Multi-branched compound and curable composition
JP2000109454A (en) * 1998-10-05 2000-04-18 Toyo Ink Mfg Co Ltd Vinyl group-containing polyfunctional compound, its production and curable composition
JP2000109522A (en) * 1998-10-06 2000-04-18 Toyo Ink Mfg Co Ltd Active energy ray-curable composition, formation of cured coating film using the same and cured product
WO2000044734A1 (en) * 1999-01-29 2000-08-03 Sartomer Company, Inc. Compounds comprising acrylate and cyclic sec.-amine functionalities
WO2003031502A1 (en) * 2001-10-12 2003-04-17 Ashland Inc. Self-photoinitiating multifunctional acrylates
WO2003047871A1 (en) * 2001-12-06 2003-06-12 Nippon Kores K.K. Coated object, print, coating material and ink for these, and layered product
JP2003238898A (en) * 2002-02-15 2003-08-27 Fujifilm Arch Co Ltd Photocurable coloring composition and color filter
JP2004204174A (en) * 2002-12-26 2004-07-22 Catalysts & Chem Ind Co Ltd Coating liquid for forming transparent electeroconductive film, substrate with transparent electroconductive film and displaying device

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4045416A (en) * 1971-01-21 1977-08-30 Union Carbide Corporation Amine acrylate addition reaction product compositions
US5596669A (en) * 1995-04-21 1997-01-21 Dsm N.V. Radiation curable coating composition and coated optical fiber
JPH11193321A (en) * 1997-10-27 1999-07-21 Toyo Ink Mfg Co Ltd Multi-branched compound and curable composition
JP2000109454A (en) * 1998-10-05 2000-04-18 Toyo Ink Mfg Co Ltd Vinyl group-containing polyfunctional compound, its production and curable composition
JP2000109522A (en) * 1998-10-06 2000-04-18 Toyo Ink Mfg Co Ltd Active energy ray-curable composition, formation of cured coating film using the same and cured product
WO2000044734A1 (en) * 1999-01-29 2000-08-03 Sartomer Company, Inc. Compounds comprising acrylate and cyclic sec.-amine functionalities
WO2003031502A1 (en) * 2001-10-12 2003-04-17 Ashland Inc. Self-photoinitiating multifunctional acrylates
WO2003047871A1 (en) * 2001-12-06 2003-06-12 Nippon Kores K.K. Coated object, print, coating material and ink for these, and layered product
JP2003238898A (en) * 2002-02-15 2003-08-27 Fujifilm Arch Co Ltd Photocurable coloring composition and color filter
JP2004204174A (en) * 2002-12-26 2004-07-22 Catalysts & Chem Ind Co Ltd Coating liquid for forming transparent electeroconductive film, substrate with transparent electroconductive film and displaying device

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007138946A1 (en) * 2006-05-29 2007-12-06 Toyo Ink Mfg. Co., Ltd. Metal oxide composition, cured film and laminate
JP2008207477A (en) * 2007-02-27 2008-09-11 Riken Technos Corp Antireflection film and its manufacturing process
JP2009157233A (en) * 2007-12-27 2009-07-16 Riken Technos Corp Antireflection film
JP2009242497A (en) * 2008-03-28 2009-10-22 Arisawa Mfg Co Ltd Photosensitive resin composition, hard coat film using it, and reflection preventing film
JP2015105325A (en) * 2013-11-29 2015-06-08 住友大阪セメント株式会社 Transparent resin composition, coating film, and heat ray shielding film
JP5910782B1 (en) * 2015-08-10 2016-04-27 東洋インキＳｃホールディングス株式会社 Laminated body having transparent conductive film and method for producing the laminated body

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