[go: up one dir, main page]

WO2014084093A1 - Composition pour revêtement dur et article moulé comportant une couche de revêtement dur - Google Patents

Composition pour revêtement dur et article moulé comportant une couche de revêtement dur Download PDF

Info

Publication number
WO2014084093A1
WO2014084093A1 PCT/JP2013/081236 JP2013081236W WO2014084093A1 WO 2014084093 A1 WO2014084093 A1 WO 2014084093A1 JP 2013081236 W JP2013081236 W JP 2013081236W WO 2014084093 A1 WO2014084093 A1 WO 2014084093A1
Authority
WO
WIPO (PCT)
Prior art keywords
meth
acrylate
compound
group
hard coat
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2013/081236
Other languages
English (en)
Japanese (ja)
Inventor
笑美 小佐
尊信 内木場
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kyoeisha Chemical Co Ltd
Original Assignee
Kyoeisha Chemical 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 Kyoeisha Chemical Co Ltd filed Critical Kyoeisha Chemical Co Ltd
Priority to KR1020157017156A priority Critical patent/KR102180159B1/ko
Priority to CN201380061291.9A priority patent/CN104812853B/zh
Priority to JP2014550140A priority patent/JP6345599B2/ja
Publication of WO2014084093A1 publication Critical patent/WO2014084093A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/343—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links

Definitions

  • the present invention relates to a hard coat composition and a molded article on which a hard coat layer is formed. More specifically, the present invention relates to a hard material having good durability, chemical resistance, anti-blocking properties, transparency, curling properties, adhesion, and the like. The present invention relates to a coating composition and a molded article on which a hard coat layer is formed.
  • plastics are used in many fields such as home appliances and automobile industries.
  • plastic has various advantages such as light weight and low cost.
  • plastic has a disadvantage that it is softer than a material such as glass and the surface is easily scratched.
  • a technique for coating the surface of a plastic with a hard coat material and improving the scratch resistance of the surface without impairing the transparency and lightness of the plastic has been used.
  • thermosetting hard coat materials such as silicon-based, acrylic-based, and melamine-based resins are used.
  • acrylic resins that can be cured by light such as ultraviolet rays are advantageous from the viewpoint of curing time, raw material cost, and the like, and are becoming mainstream.
  • acrylic resins are generally inferior in scratch resistance, wear resistance, and the like as compared with silicon-based paints. Therefore, a method using a polyfunctional (meth) acrylate having at least two (meth) acrylic groups in the molecule has been proposed (for example, JP-A-9-48934).
  • high hardness is aimed at by adding additives, such as an inorganic material.
  • Such polyfunctional (meth) acrylates and the like have a large cure shrinkage rate, and there is a problem that curling properties become remarkable particularly when formed into a thin film.
  • the polyfunctional (meth) acrylates of adjacent films or the like stick to each other due to its high static friction resistance and surface smoothness.
  • a phenomenon of blocking firmly occurs, that is, a state in which the particles are firmly attached and cannot be easily separated.
  • silica powder is generally widely used.
  • silica particle size is large, the transparency is remarkably impaired.
  • the particle size is small, there is a trade-off relationship that the anti-blocking effect cannot be sufficiently exhibited. Therefore, it is required to maintain high transparency while effectively preventing the occurrence of the blocking phenomenon.
  • the present invention has been made in order to solve the above-mentioned problems, while maximizing hard coat performance such as scratch resistance and at the same time minimizing curling property, anti-blocking property and It aims at providing the resin composition for hard coats and the molded article which were excellent also in transparency.
  • the present invention includes the following inventions.
  • the (A) urethane (meth) acrylate is (1) a compound having a polyether as a main chain; (2) an isocyanate compound; (3) The composition for hard coat as described in [1], which is a polymer obtained by a reaction with a hydroxyl group-containing (meth) acrylate compound.
  • the isocyanate compound is a polyisocyanate obtained by polycondensation of diisocyanates or diisocyanate monomers, or has a urethane structure in which an alcohol compound is added to an isocyanate group and / or a urea structure in which an amine compound is added.
  • the compound having (1) the polyether as the main chain is a polyalkylene glycol compound having one terminal hydroxyl group composed of alkoxy polyalkylene glycols, (meth) acrylic acid added with alkylene oxide or polyalkylene glycol mono (meta) )
  • the (C) fluorine-containing (meth) acrylic resin is (4) a fluorine-substituted alkyl (meth) acrylate monomer; (5) an alkyl (meth) acrylate monomer; (6) The composition for hard coat as described in any one of [1] to [7], which is a resin obtained by a reaction with an ether group-substituted alkyl (meth) acrylate monomer. [9] The hard coat composition as described in [8], wherein the (5) alkyl (meth) acrylate monomer has a C 4 to C 20 alkyl group.
  • the ether group-substituted alkyl (meth) acrylate monomer is (6) CH 2 ⁇ C (R 21 ) —CO—OA (II)
  • R 21 is a hydrogen atom or a methyl group
  • A is a C 1 -C 20 alkoxy group-containing C 1 -C 20 alkyl group
  • a C 1 -C 20 alkyl group-containing mono- and poly- (C 2 ⁇ C 20 alkylene glycol) is a monomer represented by a group.
  • the hard coat composition of the present invention while exhibiting the hard coat performance such as scratch resistance to the maximum, at the same time, the curling property is also minimized, and the anti-blocking property and the transparency are also excellent.
  • a resin composition for hard coat and a molded product can be provided.
  • the composition for hard coat of the present invention is mainly composed of (A) urethane (meth) acrylate, (B) a polyfunctional (meth) acrylate; (C) a polymer obtained by polymerizing fluorine-containing (meth) acrylate (hereinafter sometimes referred to as “fluorine-containing (meth) acrylate resin”); (D) metal oxide fine particles.
  • (C) fluorine-containing (meth) acrylate is effective for exhibiting antiblocking properties.
  • by using the (D) metal oxide particles in combination it is possible to secure even better antiblocking properties.
  • “(meth) acryl” represents “methacryl” and / or “acryl”
  • “(meth) acrylate” represents “methacrylate” and / or “acrylate”.
  • the urethane (meth) acrylate may be one having one or more hydrophilic groups (for example, hydroxyl group, carboxyl group, ethylene glycol group, propylene glycol group, etc.).
  • hydrophilic groups for example, hydroxyl group, carboxyl group, ethylene glycol group, propylene glycol group, etc.
  • the resin obtained by reaction of an isocyanate compound, a compound having a polyether as a main chain, and / or a hydroxyl group-containing (meth) acrylate compound can be mentioned.
  • m may be 0, but is preferably 1 or more.
  • the plurality of R 1 may be the same or two or more.
  • the molecular weight of the substituent constituting R 1 is suitably about 100 to 2000, and preferably about 100 to 1000. This is because if the molecular weight of the polyether chain is too large, the hardness tends to decrease.
  • the molecular weight of the substituent constituting R 2 is suitably about 150 to 5,000, and preferably about 500 to 3,000. This is because if the molecular weight is too large, the hardness tends to decrease.
  • n may be 0, but is suitably an integer greater than 0, that is, 1 or more.
  • the plurality of R 3 may be the same or two or more.
  • the molecular weight of the substituent constituting R 3 is suitably about 150 to 2,000, and preferably about 100 to 1,000. This is because if the molecular weight is too large, the hardness decreases.
  • m + n is preferably 2 or more, more preferably 3 or more, 4 or more, 5 or more, or 6 or more.
  • Examples of the compound having a polyether as a main chain include compounds having an ether group, preferably a polyether group in the main chain, and having a hydroxyl group (including a hydroxyl group containing one terminal hydroxyl group).
  • the ether group includes a hydroxyl group.
  • it is a compound different from the (3) hydroxyl group-containing (meth) acrylate compound described later.
  • one or more compounds selected from the group consisting of alkylene glycol compounds and alkylene oxide addition compounds can be mentioned.
  • polyalkylene glycols alkoxy polyalkylene glycols, (meth) acryloxy polyalkylene glycols, reaction products of polyalkylene and polytetramethylene glycol, epoxy compounds having an oxirane ring and (meth) acrylic acid are added.
  • (Meth) acryloyl group-containing polyethers obtained by reacting alkylene oxides such as ethylene oxide and propylene oxide with hydroxyl group-containing (meth) acrylic acid derivatives obtained by reaction, (meth) acrylic acid alkylene oxide addition compounds, etc. Can be mentioned.
  • polyalkylene glycols one-end hydroxyl group-containing polyalkylene glycols, alkoxy polyalkylene glycols and (meth) acryloyl group-containing polyethers, (meth) acrylic acid alkylene oxide addition compounds are preferred, and one-end hydroxyl group
  • the containing polyalkylene glycol compound or the (meth) acrylic acid alkylene oxide addition compound is preferred.
  • the one-terminal hydroxyl group-containing polyalkylene glycol compound is preferably an alkoxy polyalkylene glycol
  • the (meth) acrylic acid alkylene oxide addition compound is a compound obtained by adding (meth) acrylic acid to an alkylene oxide or polyalkylene. It is preferable that the glycol is mono (meth) acrylated.
  • the number of carbon atoms of the alkylene and alkoxy groups in these compounds is, for example, about 1 to 6, preferably about 1 to 4, and more preferably about 1 to 3.
  • polyalkylene glycols examples include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
  • Alkoxy polyalkylene glycols are, for example, polyalkylene glycols containing an alkoxy group having about 1 to 6 carbon atoms (alkylene has about 1 to 6 carbon atoms, for example), specifically methoxy polyethylene glycol, methoxy Examples thereof include polypropylene glycol and methoxypolytetramethylene glycol.
  • the molecular weight of the alkoxypolyalkylene glycols can be arbitrarily selected, but is preferably 100 to 2,000.
  • Examples of (meth) acryloxypolyalkylene glycols include (meth) acryloxypolyethylene glycol and (meth) acryloxypolypropylene glycol.
  • the reaction product of polyalkylene and polytetramethylene glycol is, for example, a reaction product of polyethylene and polytetramethylene glycol, a reaction product of methoxypolyethylene and polytetramethylene glycol, (meth) acryloxypolyethylene and polytetramethylene glycol, These reactants can be mentioned.
  • the (meth) acryloyl group-containing polyether is an acrylate containing an alkyl group having about 1 to 6 carbon atoms substituted with a hydroxy group, for example, an ethylene oxide adduct of 2-hydroxyethyl acrylate (for example, the added mole number is 1 to 20).
  • Examples of the (meth) acrylic acid alkylene oxide addition compound include those obtained by adding alkylene oxide (eg, about 2 to 6 carbon atoms) represented by ethylene oxide, propylene oxide, and butylene oxide to (meth) acrylic acid. It is done.
  • alkylene oxide eg, about 2 to 6 carbon atoms
  • propylene oxide e.g., propylene oxide
  • butylene oxide e.g., butylene oxide
  • Diisocyanates for example, polyisocyanates obtained by polycondensation of diisocyanate monomers, urethane structures in which alcohol compounds are added to isocyanate groups and / or urea structures in which amine compounds are added as isocyanate compounds Etc.
  • polyisocyanate, a urethane structure, and / or a urea structure is preferable.
  • Diisocyanates include, for example, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, (ortho, meta, para) xylene diisocyanate, methylene bis (cyclohexyl isocyanate), trimethylhexamethylene diisocyanate. Cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene isocyanate, 1,5-naphthalene diisocyanate, norbornane diisocyanate, and the like.
  • Polyisocyanates obtained by polycondensation of polyisocyanates and / or diisocyanate monomers are, for example, isophorone diisocyanate, hexamethylene diisocyanate, norbornane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, trimethylhexamethylene diisocyanate, as polyisocyanate compounds.
  • Examples thereof include bifunctional isocyanates such as hydrogenated xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate, and trifunctional or higher functional isocyanates which are burettes or uretrates thereof.
  • polyisocyanate compounds having 3 or more, 4 or more, 5 or more, and 6 or more isocyanate groups in one molecule, such as chain or cyclic alkyl or aryl groups (for example, about 6 to 12 carbon atoms)
  • polyisocyanate compounds containing nurate compounds such as hexamethylene diisocyanate, isophorone diisocyanate, and tolylene diisocyanate are preferable.
  • Examples of the alcohol compound include divalent to tetravalent alcohols having about 2 to 10 carbon atoms, such as ethylene glycol, propylene glycol, tetramethylene glycol, glycerin, trimethylolpropane, and pentaerythritol.
  • Examples of the amine compound include diaminoethane, diaminopropane, and tetramethylenediamine.
  • the number of functional groups per molecule of the isocyanate compound can be increased.
  • These alcohol compounds and amine compounds are preferably those having a small molecular weight per functional group from the viewpoint of increasing the scratch resistance of the cured polymer.
  • the hydroxyl group-containing (meth) acrylate compound is a compound different from the above-described compound having the polyether of component (1) as the main chain, and examples thereof include hydroxyalkyl (meth) acrylates and polyol (meth) acrylates. And those derived from an epoxy resin and a carboxylic acid.
  • hydroxyalkyl (meth) acrylates examples include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and hydroxyphenoxypropyl (meth) acrylate.
  • polyol (meth) acrylates examples include divalent to tetravalent polyol (meth) acrylates having about 2 to 10 carbon atoms, such as glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, Examples include ditrimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate.
  • Examples of those derived from an epoxy resin and a carboxylic acid include a (meth) acrylic acid adduct of glycidyl (meth) acrylate.
  • urethane (meth) acrylate may be used independently and may use 2 or more types together.
  • the urethane (meth) acrylate of the present invention has (2) an isocyanate compound having a urethane structure in which an alcohol compound is added to a polyisocyanate, an isocyanate group, and (1) a polyether.
  • the main chain compound polyalkylene glycols, alkoxy polyalkylene glycols and (meth) acryloyl group-containing polyethers, (meth) acrylic acid alkylene oxide addition compounds and / or (3) hydroxyl group-containing (meth) acrylate compounds
  • hydroxyalkyl (meth) acrylates and polyol (meth) acrylates are preferable.
  • the combination provided with all of (1), (2) and (3) described here is more preferable.
  • the urethane (meth) acrylate of the present invention suitably has, for example, a molecular weight of about 500 to 5,000. If the molecular weight is too large, the hardness tends to decrease.
  • Such urethane (meth) acrylate can be produced, for example, by the method described in JP-A No. 2000-264936.
  • the molar ratio of (1) a compound having a polyether as the main chain, for example, a single-end hydroxyl group-containing polyalkylene glycol compound is (3) the molar ratio of a hydroxyl group-containing (meth) acrylate compound.
  • the following is preferable.
  • the higher the molecular weight of the polyether chain the lower the hardness when cross-linked.
  • a polyfunctional (meth) acrylate is a (meth) acrylate resin containing two or more functional groups, and refers to those other than the (meth) acrylate having a urethane structure shown in (A).
  • a compound having two or more (meth) acryloyl groups in one molecule is preferable.
  • pentaerythritol tri (meth) acrylate pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dimethyloltricyclodecanedi (meth) acrylate, trimethylolpropane (Ethylene oxide adduct) Tri (meth) acrylate, polyester di (meth) acrylate, tetraethylene glycol di (meth) acrylate, glycerin di (meth) acrylate, (meth) acrylate of glycerin ethylene oxide adduct, glycerin propylene oxide addition (Meth) acrylate, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene Polyalkylene glycol diacrylates such as glycol, dipropylene glycol
  • the polyfunctional (meth) acrylate is 10 to 500 parts by weight, 10 to 200 parts by weight, 20 to 300 parts by weight, 20 to 200 parts by weight, 20 parts by weight based on 100 parts by weight of the urethane (meth) acrylate (A) described above. It is preferably used in an amount of ⁇ 100 parts by weight, 20 to 80 parts by weight, 20 to 50 parts by weight, and the like. By using in such a range, a cure shrinkage rate can be adjusted effectively together with other components.
  • the fluorine-containing (meth) acrylic resin may be a polymer containing a structural unit derived from (meth) acrylate and containing a fluorine atom.
  • the fluorine-containing (meth) acrylic resin may be a polymer containing a structural unit derived from (meth) acrylate and containing a fluorine atom.
  • a fluorine-substituted alkyl (meth) acrylate monomer (5) an alkyl (meth) acrylate monomer; (6)
  • the polymer obtained by reaction with an ether group substituted alkyl (meth) acrylate monomer is mentioned.
  • Examples of the fluorine-substituted alkyl (meth) acrylate monomer include (meth) acrylate monomers having a fluoroalkyl group having 1 to 18 carbon atoms. Of these, those having a fluoroalkyl group having 2 to 18 carbon atoms are preferred. Specific examples include perfluoromethyl acrylate, perfluoroethyl acrylate, tetrafluoropropyl acrylate, perfluorooctyl acrylate, perfluoromethyl methacrylate, perfluoroethyl methacrylate, tetrafluoropropyl methacrylate, perfluorooctyl methacrylate, and the like.
  • Fluoromethyl methacrylate, perfluoroethyl methacrylate, tetrafluoropropyl methacrylate, perfluorooctyl methacrylate, perfluorooctyl acrylate and the like are preferable.
  • alkyl (meth) acrylate monomers examples include (meth) acrylate monomers containing an alkyl group having 4 to 20 carbon atoms. Of these, a (meth) acrylate monomer having 4 to 18 carbon atoms is preferable.
  • (meth) acrylate monomers having n-butyl, dodecyl, octadecyl groups and the like are preferable, and n-butyl acrylate, dodecyl methacrylate, octadecyl methacrylate, dodecyl acrylate, and octadecyl acrylate are more preferable.
  • ether group-substituted alkyl (meth) acrylate monomer a monomer represented by the following formula (II) may be mentioned.
  • CH 2 ⁇ C (R 21 ) —CO—OA (II) (In the formula (II), R 21 represents a hydrogen atom or a methyl group, A represents an ether group-substituted alkyl group. )
  • ether group-substituted alkyl group specifically, (i) a C 1 -C 20 alkyl group substituted with a C 1 -C 20 alkoxy group or a C 1 -C 20 aryloxy group, (ii) A mono (C 2 -C 20 alkylene glycol) group substituted with a C 1 -C 20 alkyl group, (iii) a mono substituted with a C 1 -C 20 alkoxy group or a C 1 -C 20 aryloxy group A (C 2 -C 20 alkylene glycol) group, (iv) a poly (C 2 -C 20 alkylene glycol) group substituted with a C 1 -C 20 alkyl group, (v) a C 1 -C 20 alkoxy group or Represents a poly (C 2 -C 20 alkylene glycol) group substituted with a C 1 -C 20 aryloxy group.
  • the ether group may contain a hydroxyl group.
  • C 1 -C 20 alkoxy group-containing C 1 -C 20 alkyl groups C 1 -C 20 alkyl group-containing mono- and poly (C 2 -C 20 alkylene glycol) groups are preferred.
  • examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, a tert-butoxy group, a sec-butoxy group, and a pentyloxy group.
  • examples of the aryloxy group include a phenoxy group and a benzyloxy group.
  • the alkoxy group and the aryloxy group may be substituted with a halogen atom.
  • examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a chlorine atom is preferable.
  • Examples of the alkyl group are the same as those described above.
  • alkyl group substituted with an alkoxy group examples include methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, (2-chloroethoxy) ethyl, n-propoxyethyl, butoxyethyl, cyclohexyloxyethyl, (2- Cyclohexylethoxy) ethyl, (2-ethylhexyloxy) ethyl and the like.
  • alkyl group substituted with an aryloxy group examples include phenoxyethyl and benzyloxyethyl.
  • alkylene glycol examples include ethylene glycol, propylene glycol, butylene glycol and the like.
  • Monoalkylene glycol groups substituted with alkyl groups and polyalkylene glycols substituted with alkyl groups) include methoxymonoethylene glycol, ethoxymonoethylene glycol, methoxydiethylene glycol, methoxytriethylene glycol, methoxynonaethylene glycol, methoxypolyethylene Examples include glycol, methoxydipropylene glycol, methoxytripropylene glycol, phenoxydiethylene glycol, phenoxypolyethylene glycol, ethoxydiethylene glycol, and butoxydiethylene glycol.
  • ether group-substituted alkyl (meth) acrylate monomers include butoxyethyl (meth) acrylate, methoxymethyl (meth) acrylate, ethoxymethyl (meth) acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl (meth) ) Acrylate, (2-chloroethoxy) ethyl (meth) acrylate, (2-ethylhexyloxy) ethyl (meth) acrylate, n-propoxyethyl (meth) acrylate, cyclohexyloxyethyl (meth) acrylate, (2-cyclohexylethoxy) Ethyl (meth) acrylate, phenoxyethyl (meth) acrylate, benzyloxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, ethoxydi
  • fluorine-containing (meth) acrylic resins are (4) (meth) acrylic monomers having a fluoroalkyl group having 2 to 10 carbon atoms as fluorine-substituted alkyl (meth) acrylate monomers, and (5) alkyl (meth) acrylates.
  • a resin obtained by a reaction such as a (meth) acrylate monomer containing an alkyl group having 4 to 20 carbon atoms as a monomer and (6) an alkoxyalkyl (meth) acrylate as an ether group-substituted alkyl (meth) acryl monomer is preferred.
  • Fluorine-containing (meth) acrylic resins are (4) structural units derived from fluorine-substituted alkyl (meth) acrylate monomers, (5) alkyl (meth) acrylate monomers, and (6) ether group-substituted alkyl (meth) acrylate monomers.
  • Those having a weight ratio of 1 to 60:40 to 99 to 3 to 60:40 to 97 are preferable, and 1 to 30:70 to 99, 1.5 to 30:70 to 98.5 are preferable.
  • Those having a ratio of 1 to 20:80 to 99, 1.5 to 20:80 to 98.5, and 2 to 20:80 to 98 are more preferable.
  • the fluorine-containing (meth) acrylic resin preferably has a weight average molecular weight of 1,500 to 300,000, for example. By setting it as this range, while being able to maintain the physical property of the obtained composition, since a moderate viscosity can be maintained, handling becomes easy.
  • the fluorine-containing (meth) acrylic resin is 0.1 to 50 parts by weight, 0.1 to 20 parts by weight, 0.1 to 10 parts by weight with respect to 100 parts by weight of the urethane (meth) acrylate (A) described above.
  • 0.5 to 20 parts by weight, 0.5 to 19 parts by weight, 0.3 to 5 parts by weight, 1 to 19 parts by weight or 2 to 19 parts by weight are preferred.
  • composition for hard coats of this invention it is preferable not to contain the monomer or polymer containing a fluorine other than the fluorine-containing (meth) acrylic resin mentioned above, and also among fluorine-containing (meth) acrylic resins (4) It is preferable not to have a fluorine-containing monomer other than the fluorine-substituted alkyl (meth) acrylate.
  • the metal oxide fine particles are not particularly limited, and those having a particle size of 5 nm to 50 nm are suitable, and 10 nm to 20 nm are particularly preferable. Thereby, the hardness of the film
  • Metal oxide fine particles include silicon oxide, zirconium oxide, titanium oxide, zinc oxide, antimony pentoxide, tin oxide, aluminum oxide, indium oxide, indium tin oxide, ferric oxide, cerium oxide, yttrium oxide, manganese oxide, Holmium oxide, copper oxide, bismuth oxide, cobalt oxide, cobalt trioxide, iron tetroxide, magnesium oxide, lanthanum oxide, praseodymium oxide, neodymium oxide, samarium oxide, eurobium oxide, gadolinium oxide, terbium oxide, dysprosium oxide, oxide Examples thereof include erbium, thulium oxide, ytterbium oxide, lutetium oxide, scandium oxide, tantalum pentoxide, niobium pentoxide, iridium oxide, rhodium oxide, ruthenium oxide, and composite oxides obtained by combining these.
  • R 9 a R 8 b Si ( OR 7) 4-ab (IV) (Where R 7 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 1 to 10 carbon atoms, R 8 is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, or an acyl group having 1 to 8 carbon atoms, R 9 is an organic group having 1 to 12 carbon atoms which may contain an epoxy group, a methacryl group, an acrylic group, an amino group, a ureido group or a mercapto group, a is 0 or 1, and b is 0, 1 or 2. )
  • examples of the organic group include alkyl, alkenyl, aryl and the like.
  • examples of the alkyl group include methyl, ethyl, propyl, n-butyl, t-butyl, sec-butyl, isobutyl, pentyl, hexyl, heptyl and octyl groups.
  • examples of the aryl group include phenyl, tolyl, and xylyl groups.
  • alkenyl groups include vinyl, allyl, 2-propenyl, prop-2-en-1-yl groups and the like.
  • acyl group examples include formyl, acetyl, propionyl, butyryl, valeryl, oxalyl, malonyl, succinyl, benzoyl, trioyl, phthaloyl and the like.
  • the compound include trimethylmethoxysilane, triphenylmethoxysilane, diphenylmethylmethoxysilane, phenyldimethylmethoxysilane, vinyldimethylethoxysilane, dimethyldimethoxysilane, phenylmethyldiethoxysilane, and ⁇ -mercaptopropyltrimethoxysilane.
  • ⁇ -glycidoxypropyltriethoxysilane, tetraethylorthosilicate, tetramethylorthosilicate, and the like, and known silicon compounds exemplified in JP-A-2006-70120 or partial hydrolysates thereof are exemplified.
  • a silicon compound in which R 9 is a methacryl group or an acryl group is preferable because the hardness of the film is further increased.
  • silicon compounds include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acrylonitrile. Examples include roxypropyltrimethoxysilane.
  • the metal oxide fine particles may be used alone or in combination of two or more.
  • the metal oxide fine particles are preferably used in an amount of 30 to 500 parts by weight, more preferably 50 to 350 parts by weight, in terms of solid content, with respect to 100 parts by weight of the above-mentioned (A) urethane (meth) acrylate. By using in such a range, a cure shrinkage rate can be adjusted with other components.
  • the metal oxide fine particles can be dispersed in an organic solvent and used as an organosol.
  • solvent species include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-methoxy-2-propanol, and isopropyl alcohol.
  • glycols include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl Ether acetate, propylene glycol monobutyl ether acetate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Distearate propyl ether, diethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol
  • Examples of the aliphatic cyclic ketones include cyclohexanone, ortho, meta, and para-methylcyclohexanone.
  • Examples of acetic acid esters include ethyl acetate n-propyl acetate and n-butyl acetate.
  • solvent naphtha, methyl ethyl ketone, methyl isobutyl ketone and the like may be used.
  • organosol those having a solid content of 5 to 100% using these solvents can be used.
  • composition of the present invention may further contain a (meth) acrylic acid compound or a vinyl group-containing compound.
  • a (meth) acrylic acid compound or a vinyl group-containing compound for example, it is preferable to contain 0.1 to 50 parts by weight with respect to 100 parts by weight of the total composition.
  • These compounds may be used alone or in combination of two or more.
  • (Meth) acrylic acid compounds include, for example, acrylic amides, alkyl (meth) acrylates, aminoalkyl (meth) acrylates, quaternary salts of aminoalkyl (meth) acrylates, alkoxy polyalkylene glycol (meth) acrylates Hydroxyalkyl (meth) acrylates, acid anhydride adducts of hydroxyalkyl (meth) acrylates, polyalkylene glycol di (meth) acrylates, alkyldiol di (meth) acrylates, polyol poly (meth) acrylates, Examples include alkylene oxide-added polyol poly (meth) acrylates. Examples of these compounds include those described in JP-A No. 2000-264939.
  • vinyl group-containing compound examples include vinyl acetate, N-vinylacetamide, vinyl pyrrolidone, vinyl alkyl ethers, vinyl sulfonic acid, vinyl sulfonic acid salts, and the like.
  • composition of the present invention may be mixed with a polymerization initiator, a diluent, a leveling agent, a lubricity imparting agent, and other additives.
  • the polymerization initiator is not particularly limited, but a photopolymerization initiator that generates radicals by active energy rays is preferable.
  • a photopolymerization initiator that generates radicals by active energy rays is preferable.
  • Diluents include alkylene glycol monoalkyl ethers, alkyl alcohols, alkylene glycol monoalkyl alcohol alkyl carboxylic acid esters, ketones, alkyl alcohol alkyl carboxylic acid esters, and the like. Examples of these are those described in JP-A-2004-43790.
  • the hard coat composition of the present invention may contain a solvent as necessary.
  • a solvent as necessary.
  • alcohols, glycols, aliphatic cyclic ketones, acetate esters, etc. as described above can be used.
  • leveling agent and the lubricity-imparting agent examples include a copolymer of polyoxyalkylene and polydimethylsiloxane, a copolymer of polyoxyalkylene and fluorocarbon, and the like.
  • the composition for hard coats of the present invention can be cured by irradiating active energy rays such as ultraviolet rays, radiation, infrared rays, X-rays and electron beams.
  • active energy rays such as ultraviolet rays, radiation, infrared rays, X-rays and electron beams.
  • the cured polymer of this composition exhibits a hard coat function on the surface of the molded product.
  • the molded products here are not limited to plastic molded products made of general-purpose resins such as polystyrene resin, polyolefin resin, ABS resin, AS resin, AN resin, etc., but wood, glass, metal, ceramic, paper, cement, and composites of these And those formed of various materials such as the above.
  • you may comprise a molded article with the composition itself of this invention.
  • the hard coat composition of the present invention is formed on the surface as a hard coat layer.
  • the hard coat composition of the present invention may be in the form of a film, a transfer foil or the like constituting the hard coat layer.
  • the hard coat composition of the present invention may be applied to a transparent base material to form a film, which may be a hard coat transfer foil and a hard coat film, or these transfer foils or films. May be applied to the surface of the molded product.
  • a film which may be a hard coat transfer foil and a hard coat film, or these transfer foils or films. May be applied to the surface of the molded product.
  • the hard coat composition of the present invention is mixed with the plastic constituting the molded product unless the intended properties of the plastic molded product are affected. It is good.
  • a hard coat layer is formed by applying a hard coat composition to one or both surfaces of a transparent substrate and irradiating the coating film with light.
  • Transparent substrates include polyurethane resins, polyepisulfide resins, (meth) acrylic polymers such as polymethyl methacrylate (PMMA), allyl polymers, diethylene glycol bisallyl carbonate, polycarbonate, MS resin, cyclic polyolefin Examples include a base material made of a resin.
  • the substrate may have any shape such as a flat plate shape, a curved plate shape, and a film shape.
  • Application may be performed by, for example, dip coating, flow coating, spray coating, gravure coating, bar coating, spin coating, roll coating, flexographic printing, screen printing, brush coating, and the like. it can.
  • the coating thickness is suitably about 0.01 to 100 ⁇ m after curing.
  • the light irradiation is about 100 to 1,500 mJ / cm 2 by ultraviolet rays or the like.
  • a primer layer is previously provided on the surface of the transparent substrate or molded product, or pretreatment such as alkali treatment, acid treatment, plasma treatment, corona treatment, flame treatment, etc. You may go.
  • the primer layer include urethane resin and acrylic resin.
  • the thickness of the primer layer is suitably about 2 to 50 nm.
  • the primer layer can be formed by applying these resin solutions by any method such as a dipping method, a spray method, a flow coating method, a roll coating method, or a spin coating method. Examples of the hard coat composition of the present invention will be described in detail below.
  • Production Example 2 Production of fluorine-containing (meth) acrylic resin 2 Into a container equipped with a reflux condenser, a thermometer, a stirrer and a dropping tank, 150 parts by weight of Solfit (trade name, manufactured by Kuraray Co., Ltd.) The liquid temperature was kept at 120 ° C. Under a nitrogen atmosphere, 40 parts by weight of light ester M-3F (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), 30 parts by weight of ethylhexyl methacrylate, 30 parts by weight of 2-hydroxyethyl acrylate, perbutyl D (manufactured by NOF Corporation) (Product Name) 1 part by weight of the mixed solution was dropped into Solfit over about 1 hour.
  • Solfit trade name, manufactured by Kuraray Co., Ltd.
  • Production Example 3 Production of fluorine-containing (meth) acrylic resin 3 Into a container equipped with a reflux condenser, a thermometer, a stirrer, and a dropping tank, 150 parts by weight of Solfit (trade name, manufactured by Kuraray Co., Ltd.) The liquid temperature was kept at 120 ° C. Under a nitrogen atmosphere, 15 parts by weight of light ester M-3F (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), 30 parts by weight of butyl methacrylate, 55 parts by weight of 2-hydroxyethyl acrylate, perbutyl D (manufactured by NOF Corporation) (Product Name) 1 part by weight of the mixed solution was dropped into Solfit over about 1 hour.
  • Solfit trade name, manufactured by Kuraray Co., Ltd.
  • Production Example 4 Production of fluorine-containing (meth) acrylic resin 4 In a container equipped with a reflux condenser, a thermometer, a stirrer and a dropping tank, 200 parts by weight of Solfit (trade name, manufactured by Kuraray Co., Ltd.) The liquid temperature was kept at 110 ° C.
  • composition for hard coats obtained in Examples and Comparative Examples was applied to a substrate, and the solvent was dried. This is loaded on a conveyor at a speed of 6 m / min, and irradiated with UV rays twice from a position of 10 cm with a 80 W / cm high-pressure mercury lamp to cause cross-linking polymerization to form a coating layer having a thickness of about 5 ⁇ m containing a cured polymer. Formed. About the obtained coating layer, the coating-film state (transparency), pencil hardness, steel wool resistance, curl property, antiblocking property, adhesiveness, transmittance
  • ⁇ Pencil hardness> The test was conducted with a load of 500 g of a pencil hardness meter, and the hardness of the pencil that was not scratched was shown.
  • ⁇ Steel wool resistance> The coating layer thus obtained was rubbed 10 times with steel wool (# 0000) loaded with a weight of about 1 kg. When visually observed, the evaluation was made in four stages: ⁇ for those that were not scratched, ⁇ for those that were hardly scratched, ⁇ for those that were slightly scratched, and ⁇ for those that were scratched.
  • ⁇ Curl properties> The coated film was cut into a 10 cm square, and the average value of the floating heights at the four corners was measured. Evaluations were made in four stages, with an average floating height of 10 mm or less: ⁇ : 10-20 mm: ⁇ , 20-30 mm: ⁇ , 30 mm: x.
  • ⁇ Anti-blocking property> A 1 kg load was applied with the coating film and the back surface (non-coating surface) or the coating surface adhered to each other, and it was allowed to stand for 1 day, and it was visually confirmed that the combined surfaces were not in close contact with each other.
  • ⁇ Adhesion> A cross-cut test was carried out, and the evaluation was made in four stages: ⁇ for 100/100, ⁇ for 90/100 or more, ⁇ for 50/100 or more, and ⁇ for less than 50/100.
  • Total light transmittance and haze value The total light transmittance and the haze value were measured using a haze value measuring device (colorimetric colorimeter, Ultrascan XE).
  • Example 5 For the evaluation of the coating film state (transparency), pencil hardness, steel wool resistance, curling property, adhesion, antiblocking property, transmittance, and haze value of the hard coat composition obtained in Example 1 In the same manner as above, it was applied to a substrate and formed as a coat layer to prepare a hard coat film. The obtained film was sandwiched between injection molds, and an acrylic resin was injected by a simultaneous injection molding method. After cooling, a molded product having a hard coat layer was obtained.
  • the composition of the present invention can reduce the curling property while maximizing the transparency, scratch resistance and durability of the acrylic resin. Moreover, while obtaining good hard coat properties by containing metal oxide fine particles, in particular, while ensuring the transmittance and / or transparency, the balance with the polyfunctional (meth) acrylate is aimed at, and the good anti-coating property is obtained. Blocking performance can be exhibited. Furthermore, chemical resistance and antifouling properties can be imparted by the fluorine-containing (meth) acrylic resin.
  • the composition for hard coat of the present invention can be applied to molded products made of plastic, glass, paper, wood, etc., and has adhesion, transparency, scratch resistance, moisture resistance, etc. to these molded products.
  • durability, chemical resistance, anti-blocking property, etc. it is possible to provide a stable and excellent coating layer for a long period of time, and also reduce the curling property of the hard coat composition, that is, the cure shrinkage rate, A good coating layer can be obtained while maintaining the anti-blocking property. Therefore, it can be used in parts and molded products that require these characteristics.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention a pour objectif de fournir une composition pour revêtements durs et un article moulé, la composition permettant aux constituants utilisés de montrer une transparence, une résistance à la rayure, une résistance chimique et des propriétés anti-grippage du plus haut degré, tout en étant efficaces avec celle-ci dans la minimisation des propriétés de bouclage. La composition pour revêtements durs comprend (A) un uréthane (méth)acrylate, (B) un (méth)acrylate polyfonctionnel, (C) une résine (méth)acrylique contenant du fluor, et (D) des particules d'oxyde métallique fines.
PCT/JP2013/081236 2012-11-27 2013-11-20 Composition pour revêtement dur et article moulé comportant une couche de revêtement dur Ceased WO2014084093A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020157017156A KR102180159B1 (ko) 2012-11-27 2013-11-20 하드코트용 조성물 및 하드코트층이 형성된 성형품
CN201380061291.9A CN104812853B (zh) 2012-11-27 2013-11-20 硬涂用组合物以及形成有硬涂层的成型品
JP2014550140A JP6345599B2 (ja) 2012-11-27 2013-11-20 ハードコート用組成物及びハードコート層が形成された成形品

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012258649 2012-11-27
JP2012-258649 2012-11-27

Publications (1)

Publication Number Publication Date
WO2014084093A1 true WO2014084093A1 (fr) 2014-06-05

Family

ID=50827736

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/081236 Ceased WO2014084093A1 (fr) 2012-11-27 2013-11-20 Composition pour revêtement dur et article moulé comportant une couche de revêtement dur

Country Status (5)

Country Link
JP (1) JP6345599B2 (fr)
KR (1) KR102180159B1 (fr)
CN (1) CN104812853B (fr)
TW (1) TWI604024B (fr)
WO (1) WO2014084093A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016051718A1 (fr) * 2014-09-30 2016-04-07 日本板硝子株式会社 Revêtement à faible réflexion, feuille de verre équipée de revêtement à faible réflexion, feuille de verre présentant un revêtement à faible réflexion, substrat de verre et dispositif de conversion photoélectrique
WO2018093975A1 (fr) 2016-11-21 2018-05-24 3M Innovative Properties Company Revêtement dur souple comprenant de l'hydrogène oligomère d'uréthane lié à un polymère acrylique
US11629269B2 (en) * 2018-04-02 2023-04-18 Sumitomo Electric Industries, Ltd. Resin composition, secondary coating material for optical fiber, and optical fiber
US11914186B2 (en) 2018-04-16 2024-02-27 Sumitomo Electric Industries, Ltd. Optical fiber

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017206008A1 (fr) * 2016-05-30 2017-12-07 Dow Global Technologies Llc Interpolymère d'éthylène/alpha-oléfine/diène
CN106634761B (zh) * 2016-12-30 2020-01-21 袁慧雅 一种紫外光固化组合物及母版的制备方法
KR102166844B1 (ko) 2017-09-15 2020-10-16 주식회사 엘지화학 하드 코팅 필름
KR102166845B1 (ko) 2017-09-15 2020-10-16 주식회사 엘지화학 하드 코팅 필름
WO2019138600A1 (fr) * 2018-01-15 2019-07-18 共栄社化学株式会社 Composé ester contenant un groupe insaturé, polymère, composition de résine durcissable à la chaleur et film durci
US20200347236A1 (en) * 2018-01-24 2020-11-05 3M Innovative Properties Company Flexible hardcoat comprising urethane oligomer hydrogen bonded to an acrylic polymer suitable for stretchable films
JP7138447B2 (ja) * 2018-02-21 2022-09-16 株式会社ダイセル 伸長性ハードコートフィルムならびに成形体およびその製造方法
CN110838379B (zh) * 2019-12-17 2021-05-18 王震 一种电离辐射防护服

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002069333A (ja) * 2000-06-13 2002-03-08 Nippon Kayaku Co Ltd 放射線硬化型樹脂組成物の硬化皮膜を有するフィルム
WO2005003246A1 (fr) * 2003-07-08 2005-01-13 Kyoeisha Chemical Co., Ltd. Agent de controle de tension de surface pour materiau de revetement et materiau de revetement contenant cet agent
US20060167170A1 (en) * 2003-07-08 2006-07-27 Kyoeisha Chemical Co., Ltd Surface tension control agent for coating material and coating material containing same
KR20100036944A (ko) * 2008-09-30 2010-04-08 교에이샤 케미칼 주식회사 하드코트용 조성물 및 하드코트층이 형성된 성형품
JP2011190343A (ja) * 2010-03-15 2011-09-29 Kyoeisha Chem Co Ltd ハードコート用組成物及びハードコート層が形成された成形品

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002069333A (ja) * 2000-06-13 2002-03-08 Nippon Kayaku Co Ltd 放射線硬化型樹脂組成物の硬化皮膜を有するフィルム
WO2005003246A1 (fr) * 2003-07-08 2005-01-13 Kyoeisha Chemical Co., Ltd. Agent de controle de tension de surface pour materiau de revetement et materiau de revetement contenant cet agent
EP1642947A1 (fr) * 2003-07-08 2006-04-05 Kyoeisha Chemical Co., Ltd. Agent de controle de tension de surface pour materiau de revetement et materiau de revetement contenant cet agent
US20060167170A1 (en) * 2003-07-08 2006-07-27 Kyoeisha Chemical Co., Ltd Surface tension control agent for coating material and coating material containing same
JP4147245B2 (ja) * 2003-07-08 2008-09-10 共栄社化学株式会社 コーティング剤用表面張力制御剤およびそれを含有するコーティング剤
KR20100036944A (ko) * 2008-09-30 2010-04-08 교에이샤 케미칼 주식회사 하드코트용 조성물 및 하드코트층이 형성된 성형품
JP2010107956A (ja) * 2008-09-30 2010-05-13 Kyoeisha Chem Co Ltd ハードコート用組成物及びハードコート層が形成された成形品
CN101712844A (zh) * 2008-09-30 2010-05-26 共荣社化学株式会社 硬涂层用组合物和形成了硬涂层的成型品
JP2011190343A (ja) * 2010-03-15 2011-09-29 Kyoeisha Chem Co Ltd ハードコート用組成物及びハードコート層が形成された成形品

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016051718A1 (fr) * 2014-09-30 2016-04-07 日本板硝子株式会社 Revêtement à faible réflexion, feuille de verre équipée de revêtement à faible réflexion, feuille de verre présentant un revêtement à faible réflexion, substrat de verre et dispositif de conversion photoélectrique
WO2018093975A1 (fr) 2016-11-21 2018-05-24 3M Innovative Properties Company Revêtement dur souple comprenant de l'hydrogène oligomère d'uréthane lié à un polymère acrylique
JP2020512415A (ja) * 2016-11-21 2020-04-23 スリーエム イノベイティブ プロパティズ カンパニー アクリルポリマーに水素結合したウレタンオリゴマーを含む可撓性ハードコート
EP3541881A4 (fr) * 2016-11-21 2020-06-24 3M Innovative Properties Company Revêtement dur souple comprenant de l'hydrogène oligomère d'uréthane lié à un polymère acrylique
US10941313B2 (en) 2016-11-21 2021-03-09 3M Innovative Properties Company Flexible hardcoat comprising urethane oligomer hydrogen bonded to an acrylic polymer
JP7088599B2 (ja) 2016-11-21 2022-06-21 スリーエム イノベイティブ プロパティズ カンパニー アクリルポリマーに水素結合したウレタンオリゴマーを含む可撓性ハードコート
US11629269B2 (en) * 2018-04-02 2023-04-18 Sumitomo Electric Industries, Ltd. Resin composition, secondary coating material for optical fiber, and optical fiber
US11914186B2 (en) 2018-04-16 2024-02-27 Sumitomo Electric Industries, Ltd. Optical fiber

Also Published As

Publication number Publication date
JPWO2014084093A1 (ja) 2017-01-05
JP6345599B2 (ja) 2018-06-20
TWI604024B (zh) 2017-11-01
KR20150092202A (ko) 2015-08-12
KR102180159B1 (ko) 2020-11-18
TW201428066A (zh) 2014-07-16
CN104812853B (zh) 2018-05-15
CN104812853A (zh) 2015-07-29

Similar Documents

Publication Publication Date Title
JP6345599B2 (ja) ハードコート用組成物及びハードコート層が形成された成形品
JP5658869B2 (ja) ハードコート用組成物及びハードコート層が形成された成形品
JP5479170B2 (ja) ハードコート用組成物及びハードコート層が形成された成形品
TWI450939B (zh) 塑膠基材用塗料組成物、其所形成之塗膜、以及形成體
JP4638954B2 (ja) 耐指紋性光硬化性組成物および耐指紋性コーティング層が設けられた塗装物
JP2013173871A (ja) 組成物、帯電防止性コート剤及び帯電防止性積層体
JP5684444B2 (ja) 帯電防止ハードコート用組成物及び帯電防止ハードコート層が形成された成形品
JP5815235B2 (ja) ハードコーティング組成物およびこれを含む積層体
CN101395191A (zh) 高能射线固化性组合物
CN105733434A (zh) 光固化性树脂组合物、及固化膜、带膜基材及其制造方法
KR20160079641A (ko) 광경화성 수지 조성물, 이 조성물로 형성되는 경화 피막 및 피막을 갖는 기재, 및 경화 피막 및 피막을 갖는 기재의 제조방법
JP6826417B2 (ja) 活性エネルギー線硬化型樹脂組成物
WO2018235816A1 (fr) Composition de résine photodurcissable, film de revêtement durci, substrat comprenant un film de revêtement durci, procédé pour sa production, et méthode d'inactivation de virus
JP6623744B2 (ja) 水性樹脂組成物、それを用いた積層体及び物品
JP6147130B2 (ja) 耐指紋性を有する硬化被膜を形成可能な光硬化性組成物、その被膜およびその被覆基材
JP5693543B2 (ja) コーティング剤用スリップ剤
JP6710508B2 (ja) 活性エネルギー線硬化型ハードコート用樹脂組成物、ハードコート付き透明プラスチックシート及び光学部材
JP6874787B2 (ja) 活性エネルギー線硬化型樹脂組成物、硬化物及び積層体
JP2017171726A (ja) 硬化性組成物及びその硬化物並びに積層体
JPWO2005092991A1 (ja) 活性エネルギ線硬化性被覆用組成物及び成形品
JP7009973B2 (ja) 活性エネルギー線硬化性樹脂組成物、硬化物、積層フィルム、加飾フィルム及び物品
JP5821271B2 (ja) 活性エネルギー線硬化性含水被覆塗料
JP2012031312A (ja) 光硬化型塗料組成物
JP5560693B2 (ja) 成型用ハードコートフィルム及び成型体
JP7035506B2 (ja) 積層フィルム、加飾フィルム及び物品

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13858706

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2014550140

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20157017156

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 13858706

Country of ref document: EP

Kind code of ref document: A1