WO2007010865A1 - 硬化性組成物、硬化膜及び積層体 - Google Patents

硬化性組成物、硬化膜及び積層体 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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Prior art keywords
compound
meth
cured film
curable composition
group
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PCT/JP2006/314087
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English (en)
French (fr)
Japanese (ja)
Inventor
Jun Kaneda
Hayato Takahashi
Shinsuke Tsurutani
Kazunori Shigemori
Hiroshi Tominaga
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Toyo Ink Mfg. Co., Ltd.
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Application filed by Toyo Ink Mfg. Co., Ltd. filed Critical Toyo Ink Mfg. Co., Ltd.
Priority to CN2006800259024A priority Critical patent/CN101223198B/zh
Priority to JP2007525998A priority patent/JP4924425B2/ja
Priority to KR1020087003658A priority patent/KR101276736B1/ko
Publication of WO2007010865A1 publication Critical patent/WO2007010865A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
    • 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.

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PCT/JP2006/314087 2005-07-19 2006-07-14 硬化性組成物、硬化膜及び積層体 WO2007010865A1 (ja)

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WO2007138946A1 (ja) * 2006-05-29 2007-12-06 Toyo Ink Mfg. Co., Ltd. 金属酸化物組成物、硬化膜及び積層体
JP2008207477A (ja) * 2007-02-27 2008-09-11 Riken Technos Corp 反射防止フィルムおよびその製造方法
JP2009157233A (ja) * 2007-12-27 2009-07-16 Riken Technos Corp 反射防止フィルム
JP2009242497A (ja) * 2008-03-28 2009-10-22 Arisawa Mfg Co Ltd 感光性樹脂組成物及び該樹脂組成物を用いたハードコートフィルム並びに反射防止フィルム
JP2015105325A (ja) * 2013-11-29 2015-06-08 住友大阪セメント株式会社 透明樹脂組成物及び塗膜並びに熱線遮蔽フィルム
JP5910782B1 (ja) * 2015-08-10 2016-04-27 東洋インキＳｃホールディングス株式会社 透明導電膜を有する積層体および積層体の製造方法

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JP5401824B2 (ja) 2007-04-09 2014-01-29 デクセリアルズ株式会社 画像表示装置
JP5470735B2 (ja) 2007-04-10 2014-04-16 デクセリアルズ株式会社 画像表示装置の製造方法
CN102012532B (zh) * 2009-09-03 2015-05-20 株式会社巴川制纸所 光学层叠体、偏振片及使用其的显示装置
CN110408159B (zh) * 2014-06-30 2022-02-08 日产化学工业株式会社 固化膜形成用组合物、取向材料和相位差材料
CN106154358A (zh) * 2015-03-24 2016-11-23 陈国樑 具过滤降低蓝光穿透率的镜片成份及依该成份所制成的镜片
CN105722254A (zh) * 2016-02-24 2016-06-29 东莞珂洛赫慕电子材料科技有限公司 一种柔性电热膜用光固化型电阻浆料及其制备方法
KR101959510B1 (ko) 2016-03-04 2019-03-18 주식회사 엘지화학 반사 방지 필름
WO2018194032A1 (ja) * 2017-04-18 2018-10-25 株式会社トクヤマデンタル 硬化性組成物
KR20210068434A (ko) * 2018-09-27 2021-06-09 닛산 가가쿠 가부시키가이샤 무기산화물입자를 포함하는 아크릴계 코팅 조성물
JP6750666B2 (ja) * 2018-12-27 2020-09-02 東洋インキＳｃホールディングス株式会社 積層体、及び積層体の製造方法

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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 (ja) * 1997-10-27 1999-07-21 Toyo Ink Mfg Co Ltd 多分岐化合物および硬化性組成物
JP2000109454A (ja) * 1998-10-05 2000-04-18 Toyo Ink Mfg Co Ltd ビニル基含有多官能化合物、その製造方法および硬化性組成物
JP2000109522A (ja) * 1998-10-06 2000-04-18 Toyo Ink Mfg Co Ltd 活性エネルギー線硬化性組成物、それを用いた硬化皮膜の形成方法および硬化物
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WO2003031502A1 (en) * 2001-10-12 2003-04-17 Ashland Inc. Self-photoinitiating multifunctional acrylates
WO2003047871A1 (fr) * 2001-12-06 2003-06-12 Nippon Kores K.K. Objet revetu, impression, materiau de revetement et encre associee, et produit en couches
JP2003238898A (ja) * 2002-02-15 2003-08-27 Fujifilm Arch Co Ltd 光硬化性着色組成物及びカラーフィルター
JP2004204174A (ja) * 2002-12-26 2004-07-22 Catalysts & Chem Ind Co Ltd 透明導電性被膜形成用塗布液および透明導電性被膜付基材、表示装置

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007138946A1 (ja) * 2006-05-29 2007-12-06 Toyo Ink Mfg. Co., Ltd. 金属酸化物組成物、硬化膜及び積層体
JP2008207477A (ja) * 2007-02-27 2008-09-11 Riken Technos Corp 反射防止フィルムおよびその製造方法
JP2009157233A (ja) * 2007-12-27 2009-07-16 Riken Technos Corp 反射防止フィルム
JP2009242497A (ja) * 2008-03-28 2009-10-22 Arisawa Mfg Co Ltd 感光性樹脂組成物及び該樹脂組成物を用いたハードコートフィルム並びに反射防止フィルム
JP2015105325A (ja) * 2013-11-29 2015-06-08 住友大阪セメント株式会社 透明樹脂組成物及び塗膜並びに熱線遮蔽フィルム
JP5910782B1 (ja) * 2015-08-10 2016-04-27 東洋インキＳｃホールディングス株式会社 透明導電膜を有する積層体および積層体の製造方法

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