WO2014084093A1 - Composition for hardcoat and molded article with hardcoat layer - Google Patents
Composition for hardcoat and molded article with hardcoat layer Download PDFInfo
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- 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
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- 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
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- 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
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- 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
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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
- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—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.
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Abstract
Description
これらの欠点を改良するために、プラスチック表面にハードコート材料をコーティングし、プラスチックが有する透明性及び軽量性等を損なうことなく、表面の耐擦傷性等を改善する技術が用いられている。 Conventionally, various plastics are used in many fields such as home appliances and automobile industries. In addition to processability and transparency, plastic has various advantages such as light weight and low cost. However, plastic has a disadvantage that it is softer than a material such as glass and the surface is easily scratched.
In order to improve these drawbacks, 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.
しかし、アクリル系樹脂は、一般的にシリコン系塗料と比べて耐擦傷性や耐摩耗性などに劣る。
そのため、分子中に少なくとも2個以上の(メタ)アクリル基を有する多官能(メタ)アクリレート等を用いる方法等が提案されている(例えば、特開平9-48934号公報等)。
また、無機材料等の添加剤を添加することにより、高い硬度を図っている。 As such hard coat materials, for example, thermosetting hard coat materials such as silicon-based, acrylic-based, and melamine-based resins are used. Among these, 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.
However, 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).
Moreover, high hardness is aimed at by adding additives, such as an inorganic material.
また、このような多官能(メタ)アクリレート等を、フィルム状に成形した場合、その高い静摩擦抵抗と表面の平滑性とに起因して、隣接するフィルム等の多官能(メタ)アクリレート同士がくっつき、強固に付着して容易に引き離すことができない状態となる現象、つまりブロッキング現象が起こることがある。このようなブロッキング現象を防止するために使用されるアンチブロッキング剤としては、一般にシリカ粉末が広く使用されている。しかし、シリカの粒径が大きい場合には、透明性が著しく損なわれ、一方、粒径が小さい場合には、アンチブロッキング効果を充分に発揮させることができないというトレードオフの関係がある。よって、ブロッキング現象の発生を有効に防止しながら、高い透明性を維持することが求められている。 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.
In addition, when such a polyfunctional (meth) acrylate or the like is formed into a film shape, the polyfunctional (meth) acrylates of adjacent films or the like stick to each other due to its high static friction resistance and surface smoothness. In some cases, a phenomenon of blocking firmly occurs, that is, a state in which the particles are firmly attached and cannot be easily separated. As an antiblocking agent used for preventing such a blocking phenomenon, silica powder is generally widely used. However, when the silica particle size is large, the transparency is remarkably impaired. On the other hand, when 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.
〔1〕(A)ウレタン(メタ)アクリレートと、
(B)多官能(メタ)アクリレートと、
(C)フッ素含有(メタ)アクリレートを重合した重合体と、
(D)金属酸化物微粒子とを含むことを特徴とするハードコート用組成物。
〔2〕前記(A)ウレタン(メタ)アクリレートが、
(1)ポリエーテルを主鎖とする化合物と、
(2)イソシアネート化合物と、
(3)水酸基含有(メタ)アクリレート化合物との反応によって得られる重合体である〔1〕に記載のハードコート用組成物。
〔3〕前記(A)ウレタン(メタ)アクリレートが、下記式(I)
(R1O-CONH-)m-R2-(-NHCO-OR3)n (I)
(式(I)中、R1O-はポリエーテルを主鎖とする化合物の脱水素残基、
-R2-はイソシアネート化合物の脱イソシアネート基残基、
R3O-は水酸基含有(メタ)アクリレート化合物の脱水素残基、
m+n=1~50の整数を表す。)で表されるウレタン(メタ)アクリレートオリゴマーを含む〔1〕又は〔2〕に記載のハードコート用組成物。
〔4〕前記(2)イソシアネート化合物が、ジイソシアネート類又はジイソシアネートモノマーを重縮合したポリイソシアネート類であるか、またはイソシアネート基にアルコール化合物を付加したウレタン構造及び/又はアミン化合物を付加したウレア構造を有している〔2〕又は〔3〕に記載のハードコート用組成物。
〔5〕前記(3)水酸基含有(メタ)アクリレート化合物が、ヒドロキシアルキル(メタ)アクリレート類、ポリオール(メタ)アクリレート類である〔2〕から〔4〕のいずれか1つに記載のハードコート用組成物。
〔6〕前記(1)ポリエーテルを主鎖とする化合物が、アルキレングリコール化合物及びアルキレンオキサイド付加化合物からなる群から選択される1種以上の化合物である〔3〕から〔5〕のいずれか1つに記載のハードコート用組成物。
〔7〕前記(1)ポリエーテルを主鎖とする化合物が、アルコキシポリアルキレングリコール類からなる片末端水酸基含有ポリアルキレングリコール化合物、(メタ)アクリル酸をアルキレンオキサイド付加又はポリアルキレングリコールのモノ(メタ)アクリレート化されたものである〔6〕に記載のハードコート用組成物。
〔8〕前記(C)フッ素含有(メタ)アクリル系樹脂が、
(4)フッ素置換アルキル(メタ)アクリレートモノマーと、
(5)アルキル(メタ)アクリレートモノマーと、
(6)エーテル基置換アルキル(メタ)アクリレートモノマーとの反応によって得られる樹脂である〔1〕から〔7〕のいずれか1つに記載のハードコート用組成物。
〔9〕前記(5)アルキル(メタ)アクリレートモノマーが、C4~C20のアルキル基を有する〔8〕に記載のハードコート用組成物。
〔10〕前記(6)エーテル基置換アルキル(メタ)アクリレートモノマーが、
CH2=C(R21)-CO-O-A (II)
(式(II)中、R21は水素原子又はメチル基
Aは、C1~C20のアルコキシ基含有C1~C20のアルキル基、C1~C20のアルキル基含有モノ及びポリ(C2~C20アルキレングリコール)基を表す。)で表されるモノマーである〔9〕又は〔10〕に記載のハードコート用組成物。
〔11〕前記(B)多官能(メタ)アクリレートが、1分子中に(メタ)アクリロイル基を少なくとも2個有する化合物である〔1〕から〔10〕のいずれか1つに記載のハードコート用組成物。
〔12〕上記〔1〕から〔11〕のいずれか1つに記載のハードコート用組成物の硬化重合体がハードコート層として形成されてなることを特徴とする成形品。 The present invention includes the following inventions.
[1] (A) urethane (meth) acrylate;
(B) a polyfunctional (meth) acrylate;
(C) a polymer obtained by polymerizing fluorine-containing (meth) acrylate;
(D) A hard coat composition comprising metal oxide fine particles.
[2] 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.
[3] The (A) urethane (meth) acrylate is represented by the following formula (I)
(R 1 O—CONH—) m —R 2 — (— NHCO—OR 3 ) n (I)
(In the formula (I), R 1 O— represents a dehydrogenated residue of a compound having a polyether as the main chain;
—R 2 — is a deisocyanate group residue of the isocyanate compound,
R 3 O— is a dehydrogenated residue of a hydroxyl group-containing (meth) acrylate compound,
m + n = 1 represents an integer of 1 to 50. The composition for hard coat as described in [1] or [2] containing the urethane (meth) acrylate oligomer represented by this.
[4] (2) 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 composition for hard coat as described in [2] or [3].
[5] The hard coat according to any one of [2] to [4], wherein the (3) hydroxyl group-containing (meth) acrylate compound is a hydroxyalkyl (meth) acrylate or a polyol (meth) acrylate. Composition.
[6] Any one of [3] to [5], wherein the compound having (1) the polyether as the main chain is at least one compound selected from the group consisting of an alkylene glycol compound and an alkylene oxide addition compound. The composition for hard coats described in 1.
[7] 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 composition for hard coat as set forth in [6], which is acrylated.
[8] 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.
[10] The ether group-substituted alkyl (meth) acrylate monomer is (6)
CH 2 ═C (R 21 ) —CO—OA (II)
(In the formula (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.) [9] or the hard coat composition according to [10].
[11] The hard coat as set forth in any one of [1] to [10], wherein the (B) polyfunctional (meth) acrylate is a compound having at least two (meth) acryloyl groups in one molecule. Composition.
[12] A molded article comprising a cured polymer of the hard coat composition as described in any one of [1] to [11] as a hard coat layer.
(A)ウレタン(メタ)アクリレートと、
(B)多官能(メタ)アクリレートと、
(C)フッ素含有(メタ)アクリレートを重合した重合体(以下、「フッ素含有(メタ)アクリレート系樹脂」ということがある)と、
(D)金属酸化物微粒子とを含む。
このように、(C)フッ素含有(メタ)アクリレートは、アンチブロッキング性を発揮させるために有効である。加えて(D)金属酸化物粒子を併用することで、より一層良好なアンチブロッキング性を確保することができる。さらに、(A)ウレタン(メタ)アクリレートの作用により低カール、高硬度のバランスを図ることが可能となる。
なお、本明細書においては、「(メタ)アクリル」は「メタクリル」及び/又は「アクリル」、「(メタ)アクリレート」は「メタクリレート」及び/又は「アクリレート」を表す。 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.
Thus, (C) fluorine-containing (meth) acrylate is effective for exhibiting antiblocking properties. In addition, by using the (D) metal oxide particles in combination, it is possible to secure even better antiblocking properties. Furthermore, it is possible to achieve a balance between low curl and high hardness by the action of (A) urethane (meth) acrylate.
In the present specification, “(meth) acryl” represents “methacryl” and / or “acryl”, and “(meth) acrylate” represents “methacrylate” and / or “acrylate”.
(A)ウレタン(メタ)アクリレートは、例えば、1以上の親水性基(例えば、ヒドロキシル基、カルボキシル基、エチレングリコール基、プロピレングリコール基等)を有しているものであればよい。例えば、イソシアネート化合物と、ポリエーテルを主鎖とする化合物及び/又は水酸基含有(メタ)アクリレート化合物との反応によって得られる樹脂が挙げられる。具体的には、
(1)ポリエーテルを主鎖とする化合物と、
(2)イソシアネート化合物と、
(3)水酸基含有(メタ)アクリレート化合物との反応によって得られる樹脂、
(1)ポリエーテルを主鎖とする化合物と、
(2)イソシアネート化合物との反応によって得られる樹脂、または
(2)イソシアネート化合物と、
(3)水酸基含有(メタ)アクリレート化合物との反応によって得られる樹脂が挙げられる。 [(A) Urethane (meth) acrylate]
(A) 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.). For example, 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. In particular,
(1) a compound having a polyether as a main chain;
(2) an isocyanate compound;
(3) a resin obtained by reaction with a hydroxyl group-containing (meth) acrylate compound,
(1) a compound having a polyether as a main chain;
(2) a resin obtained by reaction with an isocyanate compound, or (2) an isocyanate compound;
(3) Resin obtained by reaction with a hydroxyl-containing (meth) acrylate compound is mentioned.
(R1O-CONH-)m-R2-(-NHCO-OR3)n (I)
(式中、R1O-はポリエーテルを主鎖とする化合物の脱水素残基、-R2-はイソシアネート化合物の脱イソシアネート基残基、R3O-は水酸基含有(メタ)アクリレート化合物の脱水素残基、m+n=1~50の整数)で表される化合物が挙げられる。 For example, as an example of urethane (meth) acrylate, the following formula (I)
(R 1 O—CONH—) m —R 2 — (— NHCO—OR 3 ) n (I)
(Wherein R 1 O— is a dehydrogenation residue of a polyether-based compound, —R 2 — is a deisocyanate group residue of an isocyanate compound, and R 3 O— is a hydroxyl group-containing (meth) acrylate compound) A dehydrogenation residue, m + n = 1 to an integer of 1 to 50).
R2を構成する置換基の分子量は、150~5,000程度であることが適しており、500~3,000程度であることが好ましい。この分子量が大きくなりすぎると硬度が低下する傾向があるからである。
nは0であってもよいが、0より大きい整数、つまり1以上であることが適している。nが2以上の場合、複数のR3は同一であってもよいし、2種以上であってもよい。
R3を構成する置換基の分子量は、150~2,000程度であることが適しており、100~1,000程度であることが好ましい。この分子量が大きくなりすぎると硬度が低下するからである。
m+nは、2以上が好ましく、3以上、4以上、5以上又は6以上がより好ましい。あるいは、m=0及びn=1、m=1及びn=0、m=2及びn=0、m=0及びn=2、m=1以上及びn=1以上等であってもよい。 In formula (I), m may be 0, but is preferably 1 or more. When m is 2 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. When n is 2 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. Alternatively, m = 0 and n = 1, m = 1 and n = 0, m = 2 and n = 0, m = 0 and n = 2, m = 1 or more, n = 1 or more, or the like may be used.
なかでも、ポリアルキレングリコール類、片末端水酸基含有ポリアルキレングリコール類、アルコキシポリアルキレングリコール類及び(メタ)アクリロイル基含有ポリエーテル類、(メタ)アクリル酸アルキレンオキサイド付加化合物が好ましく、さらに、片末端水酸基含有ポリアルキレングリコール化合物又は(メタ)アクリル酸アルキレンオキサイド付加化合物が好ましい。
特に、片末端水酸基含有ポリアルキレングリコール化合物が、アルコキシポリアルキレングリコール類であるものが好ましく、また、(メタ)アクリル酸アルキレンオキサイド付加化合物が、(メタ)アクリル酸をアルキレンオキサイド付加したもの又はポリアルキレングリコールをモノ(メタ)アクリレート化したものであることが好ましい。
これらの化合物のアルキレン及びアルコキシ基の炭素数は、例えば、1~6程度が挙げられ、1~4程度が好ましく、1~3程度がより好ましい。 (1) 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). Here, the ether group includes a hydroxyl group. However, it is a compound different from the (3) hydroxyl group-containing (meth) acrylate compound described later. In particular, one or more compounds selected from the group consisting of alkylene glycol compounds and alkylene oxide addition compounds can be mentioned. For example, 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.
Among these, 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.
In particular, the one-terminal hydroxyl group-containing polyalkylene glycol compound is preferably an alkoxy polyalkylene glycol, and 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.
アミン化合物は、例えば、ジアミノエタン、ジアミノプロパン、テトラメチレンジアミンが挙げられる。 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.
なお、ウレタン(メタ)アクリレートは、単独で用いてもよいし、2種以上を併用してもよい。 Examples of those derived from an epoxy resin and a carboxylic acid include a (meth) acrylic acid adduct of glycidyl (meth) acrylate.
In addition, urethane (meth) acrylate may be used independently and may use 2 or more types together.
(B)多官能(メタ)アクリレートは、官能基を2以上含む(メタ)アクリレート樹脂ものであって、(A)で示した、ウレタン構造を有する(メタ)アクリレート以外のものを指す。1分子中に(メタ)アクリロイル基を2個以上有する化合物であることが好ましい。
例えば、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジメチロールトリシクロデカンジ(メタ)アクリレート、トリメチロールプロパン(エチレンオキサイド付加体)トリ(メタ)アクリレート、ポリエステルジ(メタ)アクリレート、テトラエチレングリコールジ(メタ)アクリレート、グリセリンジ(メタ)アクリレート、グリセリンエチレンオキサイド付加物の(メタ)アクリレート、グリセリンプロピレンオキサイド付加物の(メタ)アクリレート、エチレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、テトラプロピレングリコール等のポリアルキレングリコールのジアクリレート、多価アルコールと多塩基酸を縮合して得られる化合物の(メタ)アクリレート及び上述したポリイソシアネートと水酸基含有(メタ)アクリレートとの反応によって得られる化合物、水酸基含有ポリマーと水酸基含有(メタ)アクリレートがイソシアネートによるウレタン化反応によって得られる化合物が挙げられる。これら化合物は単独で用いてもよく、2種以上を併用してもよい。 [(B) Multifunctional (meth) acrylate]
(B) 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.
For example, 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, tripropylene glycol and tetrapropylene glycol, (meth) acrylates of compounds obtained by condensation of polyhydric alcohols and polybasic acids, and polyisocyanates and hydroxyl groups ( Examples thereof include compounds obtained by reaction with (meth) acrylate, and compounds obtained by urethanization reaction of an hydroxyl group-containing polymer and a hydroxyl group-containing (meth) acrylate with isocyanate. These compounds may be used alone or in combination of two or more.
(C)フッ素含有(メタ)アクリル系樹脂は、(メタ)アクリレートに由来する構造単位を含み、フッ素原子を含有する重合体であればよい。例えば、
(4)フッ素置換アルキル(メタ)アクリレートモノマーと、
(5)アルキル(メタ)アクリレートモノマーと、
(6)エーテル基置換アルキル(メタ)アクリレートモノマーとの反応によって得られる重合体が挙げられる。 [(C) Fluorine-containing (meth) acrylic resin]
(C) The fluorine-containing (meth) acrylic resin may be a polymer containing a structural unit derived from (meth) acrylate and containing a fluorine atom. For example,
(4) 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.
具体的には、パーフルオロメチルアクリレート、パーフルオロエチルアクリレート、テトラフルオロプロピルアクリレート、パーフルオロオクチルアクリレート、パーフルオロメチルメタクリレート、パーフルオロエチルメタクリレート、テトラフルオロプロピルメタクリレート、パーフルオロオクチルメタクリレート等が挙げられ、パーフルオロメチルメタクリレート、パーフルオロエチルメタクリレート、テトラフルオロプロピルメタクリレート、パーフルオロオクチルメタクリレート、パーフルオロオクチルアクリレート等が好ましい。 (4) 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.
具体的には、n-ブチル(C4)、sec-ブチル、tert-ブチル、n-ペンチル、n-ヘキシル、ヘプチル、2-エチルヘキシル、オクチル、ノニル、デシル、ウンデシル、ドデシル(ラウリル:C12)、テトラデシル、ペンタデシル、ヘキサデシル、ヘプタデシル、オクタデシル(ステアリル:C18)基等のアルキル基を有する(メタ)アクリレートモノマーが挙げられる。なかでも、n-ブチル、ドデシル、オクタデシル基等を有する(メタ)アクリレートモノマーが好ましく、n-ブチルアクリレート、ドデシルメタクリレート、オクタデシルメタクリレート、ドデシルアクリレート、オクタデシルアクリレートがより好ましい。 Examples of (5) alkyl (meth) acrylate monomers 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.
Specifically, n-butyl (C 4 ), sec-butyl, tert-butyl, n-pentyl, n-hexyl, heptyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl (lauryl: C 12 ) , (Meth) acrylate monomers having an alkyl group such as tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl (stearyl: C 18 ) group. Of these, (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.
CH2=C(R21)-CO-O-A (II)
(式(II)中、R21は水素原子又はメチル基、
Aは、エーテル基置換アルキル基を表す。) (6) As an example of an 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. )
なかでも、C1~C20のアルコキシ基含有C1~C20のアルキル基、C1~C20のアルキル基含有モノ及びポリ(C2~C20アルキレングリコール)基が好ましい。 As the 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.
Of these, 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.
アリールオキシ基としては、フェノキシ基、ベンジルオキシ基等が挙げられる。
アルコキシ基及びアリールオキシ基は、ハロゲン原子で置換されていてもよい。
ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。なかでも、塩素原子が好ましい。
アルキル基としては、上記と同様のものが挙げられる。 Here, 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.
アリールオキシ基が置換されたアルキル基としては、フェノキシエチル、ベンジルオキシエチル等が挙げられる。 Examples of the alkyl group substituted with an alkoxy group include methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, (2-chloroethoxy) ethyl, n-propoxyethyl, butoxyethyl, cyclohexyloxyethyl, (2- Cyclohexylethoxy) ethyl, (2-ethylhexyloxy) ethyl and the like.
Examples of the alkyl group substituted with an aryloxy group include phenoxyethyl and benzyloxyethyl.
アルキル基が置換されたモノアルキレングリコール基及びアルキル基が置換されたポリアルキレングリコール)基としては、メトキシモノエチレングリコール、エトキシモノエチレングリコール、メトキシジエチレングリコール、メトキシトリエチレングリコール、メトキシノナエチレングリコール、メトキシポリエチレングリコール、メトキシジプロピレングリコール、メトキシトリプロピレングリコール、フェノキシジエチレングリコール、フェノキシポリエチレングリコール、エトキシジエチレングリコール、ブトキシジエチレングリコール等が挙げられる。 Examples of the alkylene glycol 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.
なお、本発明のハードコート用組成物では、上述したフッ素含有(メタ)アクリル系樹脂以外はフッ素を含有するモノマー又はポリマーを含有しないことが好ましく、さらに、フッ素含有(メタ)アクリル系樹脂のうち、(4)フッ素置換アルキル(メタ)アクリレート以外は、フッ素を含有するモノマーを有しないことが好ましい。 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. By using in such a range, while being able to improve hardness and scratch resistance, chemical resistance, antiblocking property, and transparency can also be provided.
In addition, in the 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.
(D)金属酸化物微粒子は、特に限定されるものではなく、粒子径が5nm~50nmのものを使用することが適しており、特には10nm~20nmが好ましい。これにより、組成物による膜の硬度を増大させることができる。また、塗膜の屈折率を調整することも可能となるとともに、透明性を確保することができる。 [(D) Metal oxide fine particles]
(D) 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 | membrane by a composition can be increased. In addition, the refractive index of the coating film can be adjusted, and transparency can be ensured.
R9 aR8 bSi(OR7)4-a-b (IV)
(式中、
R7は水素原子、炭素原子数1~10のアルキル基又は炭素数1~10のアシル基であり、
R8は炭素数1~8のアルキル基、炭素数6~8のアリール基、炭素数1~8のアルケニル基又は炭素数1~8のアシル基、
R9はエポキシ基、メタクリル基、アクリル基、アミノ基、ウレイド基又はメルカプト基を含有していてもよい炭素数1~12の有機基、
aは0又は1、bは0、1又は2である。) For example, those containing a silicon compound represented by the following formula (IV) or a partial hydrolyzate thereof are suitable.
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. )
アルキル基としては、メチル、エチル、プロピル、n-ブチル、t-ブチル、sec-ブチル、イソブチル、ペンチル、ヘキシル、ヘプチル、オクチル基等が挙げられる。
アリール基としては、フェニル、トリル、キシリル基等が挙げられる。
アルケニル基としては、ビニル、アリル、2-プロペニル、プロパ-2-エンー1-イル基等が挙げられる。
アシル基としては、ホルミル、アセチル、プロピオニル、ブチリル、バレリル、オキサリル、マロニル、スクシニル、ベンゾイル、トリオイル、フタロイル等が挙げられる。 Here, 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.
Examples of alkenyl groups include vinyl, allyl, 2-propenyl, prop-2-en-1-yl groups and the like.
Examples of the acyl group include formyl, acetyl, propionyl, butyryl, valeryl, oxalyl, malonyl, succinyl, benzoyl, trioyl, phthaloyl and the like.
なお、金属酸化物微粒子は、・BR>P独で用いてもよく、2種以上を併用してもよい。 In particular, 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. Examples of such 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.
その溶剤種は、アルコール類としては、例えば、メタノール、エタノール、1-プロパノール、2-プロパノール、1-メトキシ-2-プロパノール、イソプロピルアルコール等が挙げられる。 The metal oxide fine particles can be dispersed in an organic solvent and used as an organosol.
Examples of the solvent species include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-methoxy-2-propanol, and isopropyl alcohol.
酢酸エステル類としては、例えば、酢酸エチル酢酸n-プロピル、酢酸n-ブチルが挙げられる。
さらに、ソルベントナフサ、メチルエチルケトン、メチルイソブチルケトン等を用いてもよい。
オルガノゾルは、これら溶剤を用いて固形分が5~100%の濃度範囲のものが使用可能である。 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.
Further, solvent naphtha, methyl ethyl ketone, methyl isobutyl ketone and the like may be used.
As the organosol, those having a solid content of 5 to 100% using these solvents can be used.
本発明のハードコート用組成物は、紫外線、放射線、赤外線、X線、電子線の活性エネルギー線を照射すること等により硬化させることが可能である。この組成物の硬化重合体は、成形品の表面においてハードコート機能を発揮させる。 〔Molding〕
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. The cured polymer of this composition exhibits a hard coat function on the surface of the molded product.
さらに、成形品がプラスチックからなる場合は、そのプラスチック成形品の意図する特性に影響を及ぼさない限り、成形品を構成するプラスチックに、本発明のハードコート用組成物を混合して、ハードコート層としてもよい。 Therefore, for example, 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.
Further, when the molded product is made of plastic, 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.
透明基材としては、ポリウレタン樹脂、ポリエピスルフィド樹脂、ポリメチルメタクリレート(PMMA)のような(メタ)アクリル系重合体、アリル系重合体、ジエチレングリコールビスアリルカーボネート、ポリカーボネート、MS樹脂、環状ポリオレフィン等各種合成樹脂からなる基材が挙げられる。基材は、平板状、曲板状、フィルム状等のいずれの形状であってもよい。 For example, 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.
塗布の厚みは、硬化後に0.01~100μm程度とすることが適している。
光照射は、紫外線等により約100~1,500mJ/cm2程度が挙げられる。 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 μm after curing.
The light irradiation is about 100 to 1,500 mJ / cm 2 by ultraviolet rays or the like.
プライマー層としては、例えば、ウレタン樹脂、アクリル樹脂が挙げられる。プライマー層の厚みは2~50nm程度が適している。プライマー層は、これらの樹脂溶液を、ディッピング法、スプレー法、フローコート法、ロールコート法、スピンコート法などいずれかの方法で塗布することにより形成することができる。
以下に、本発明のハードコート用組成物の実施例を詳細に説明する。 In order to improve the adhesion of the hard coat layer, 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.
Examples of 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.
還流冷却器、温度計、攪拌機および滴下槽を備えた容器に3-メチル-3-メトキシブタノールであるソルフィット((株)クラレ製の商品名)150重量部を入れて、液温を120℃に保温した。窒素雰囲気下で、トリフルオロエチルメタクリレートであるライトエステルM-3F(共栄社化学(株)製の商品名)5重量部、メチルメタクリレート47.5重量部、2-ヒドロキシエチルアクリレート47.5重量部、パーブチルD(日本油脂(株)製の商品名)1重量部の混合溶液を約1時間かけてソルフィットに滴下した。120℃で2時間反応させ、フッ素含有(メタ)アクリル系共重合物液を得た。
得られたフッ素含有(メタ)アクリル系共重合物液について重量平均分子量をゲルパーミエーションクロマトグラフ法によりポリスチレン換算した値で求めたところ、11000であった。 Production Example 1 Production of Fluorine-Containing (Meth) acrylic Resin 1 A container equipped with a reflux condenser, thermometer, stirrer, and dropping tank was added to Solfite (manufactured by Kuraray Co., Ltd.) which is 3-methyl-3-methoxybutanol Product name) 150 parts by weight were added, and the liquid temperature was kept at 120 ° C. Under nitrogen atmosphere, 5 parts by weight of light ester M-3F (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) which is trifluoroethyl methacrylate, 47.5 parts by weight of methyl methacrylate, 47.5 parts by weight of 2-hydroxyethyl acrylate, A mixed solution of 1 part by weight of perbutyl D (trade name, manufactured by Nippon Oil & Fats Co., Ltd.) was dropped onto Solfit over about 1 hour. It was made to react at 120 degreeC for 2 hours, and the fluorine-containing (meth) acrylic-type copolymer liquid was obtained.
It was 11000 when the weight average molecular weight was calculated | required by the value converted into polystyrene by the gel permeation chromatography method about the obtained fluorine-containing (meth) acrylic-type copolymer liquid.
還流冷却器、温度計、攪拌機および滴下槽を備えた容器にソルフィット((株)クラレ製の商品名)150重量部を入れて、液温を120℃に保温した。窒素雰囲気下で、ライトエステルM-3F(共栄社化学(株)製の商品名)40重量部、エチルヘキシルメタクリレート30重量部、2-ヒドロキシエチルアクリレート30重量部、パーブチルD(日本油脂(株)製の商品名)1重量部の混合溶液を約1時間かけてソルフィットに滴下した。120℃で2時間反応させ、フッ素含有(メタ)アクリル系共重合物液を得た。
得られたフッ素含有(メタ)アクリル系共重合物液について重量平均分子量をゲルパーミエーションクロマトグラフ法によりポリスチレン換算した値で求めたところ、35000であった。 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. It was made to react at 120 degreeC for 2 hours, and the fluorine-containing (meth) acrylic-type copolymer liquid was obtained.
It was 35000 when the weight average molecular weight was calculated | required by the value converted into polystyrene by the gel permeation chromatography method about the obtained fluorine-containing (meth) acrylic-type copolymer liquid.
還流冷却器、温度計、攪拌機および滴下槽を備えた容器にソルフィット((株)クラレ製の商品名)150重量部を入れて、液温を120℃に保温した。窒素雰囲気下で、ライトエステルM-3F(共栄社化学(株)製の商品名)15重量部、ブチルメタクリレート30重量部、2-ヒドロキシエチルアクリレート55重量部、パーブチルD(日本油脂(株)製の商品名)1重量部の混合溶液を約1時間かけてソルフィットに滴下した。120℃で2時間反応させ、フッ素含有(メタ)アクリル系共重合物液を得た。
得られたフッ素含有(メタ)アクリル系共重合物液について重量平均分子量をゲルパーミエーションクロマトグラフ法によりポリスチレン換算した値で求めたところ、15000であった。 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. It was made to react at 120 degreeC for 2 hours, and the fluorine-containing (meth) acrylic-type copolymer liquid was obtained.
It was 15000 when the weight average molecular weight was calculated | required by the value converted into polystyrene by the gel permeation chromatography method about the obtained fluorine-containing (meth) acrylic-type copolymer liquid.
還流冷却器、温度計、攪拌機および滴下槽を備えた容器にソルフィット((株)クラレ製の商品名)200重量部を入れて、液温を110℃に保温した。窒素雰囲気下で、パーフルオロオクチルエチルメタクリレートであるライトエステルFM-108(共栄社化学(株)製の商品名)20重量部、n-ブチルアクリレート15重量部、2-ヒドロキシエチルアクリレート65重量部、パーブチルO(日本油脂(株)製の商品名)5.0重量部の混合溶液を約1時間かけてソルフィットに滴下した。110℃で2時間反応させ、フッ素含有(メタ)アクリル系共重合物液を得た。
得られたフッ素含有(メタ)アクリル系共重合物液について重量平均分子量をゲルパーミエーションクロマトグラフ法によりポリスチレン換算した値で求めたところ、5000であった。 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. Under a nitrogen atmosphere, 20 parts by weight of light ester FM-108 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) which is perfluorooctylethyl methacrylate, 15 parts by weight of n-butyl acrylate, 65 parts by weight of 2-hydroxyethyl acrylate, perbutyl A mixed solution of 5.0 parts by weight of O (trade name, manufactured by Nippon Oil & Fats Co., Ltd.) was dropped onto Solfit over about 1 hour. It was made to react at 110 degreeC for 2 hours, and the fluorine-containing (meth) acrylic-type copolymer liquid was obtained.
It was 5000 when the weight average molecular weight was calculated | required by the value converted into polystyrene by the gel permeation chromatography method about the obtained fluorine-containing (meth) acrylic-type copolymer liquid.
(A)ウレタン(メタ)アクリレート
(B)多官能(メタ)アクリレートと、
(C)フッ素含有(メタ)アクリル系樹脂と、
(D)金属酸化物微粒子とを、表1に示す組成比(重量部)で混練し、約30重量%の樹脂分を含むハードコート用組成物を得た。 Examples and Comparative Examples (A) Urethane (meth) acrylate (B) Polyfunctional (meth) acrylate,
(C) a fluorine-containing (meth) acrylic resin;
(D) Metal oxide fine particles were kneaded at a composition ratio (parts by weight) shown in Table 1 to obtain a composition for hard coat containing about 30% by weight of resin.
樹脂(A)-1 ポリイソシアネート(コロネートHK)/2-ヒドロキシエチルアクリレート/ペンタエリスリトールトリアクリレート(特開2010-107956号公報の合成例1により製造)
樹脂(A)-2 商品名:UA-306H(共栄社化学株式会社製、ペンタエリスリトールトリアクリレートヘキサメチレンジイソシアネート ウレタンプレポリマー)
樹脂(A)-3 ポリイソシアネート(コロネートHK)/2-ヒドロキシエチルアクリレート/ペンタエリスリトールトリアクリレート/アクリル酸エチレンオキサイド10モル付加物
樹脂(B) ペンタエリスリトールトリアクリレート、商品名:ライトアクリレートPE-3A(共栄社化学株式会社製)
樹脂(C)-1 製造例1で製造したフッ素含有(メタ)アクリル系樹脂1、
樹脂(C)-2 製造例2で製造したフッ素含有(メタ)アクリル系樹脂2、
樹脂(C)-3 製造例3で製造したフッ素含有(メタ)アクリル系樹脂3
樹脂(C)-4 製造例4で製造したフッ素含有(メタ)アクリル系樹脂4
樹脂(C)-5 アルキル系共重合体、商品名:ポリフロー99C(共栄社化学株式会社製)
樹脂(C)-6 シリコン系共重合体、商品名:ポリフローKL-401(共栄社化学株式会社製)
オルガノシリカゾル溶液1 商品名:PL-2L-MEK(扶桑化学工業株式会社製、粒子径10nm、固形分20.0%)の微粒子にメタクリル基を導入したもの(式(IV)におけるR9がメタクリル基のものに相当)
オルガノシリカゾル溶液2 PL-2L-MEK(扶桑化学工業株式会社製、粒子径10nm、固形分20.0%)の微粒子にアクリル基を導入したもの(式(IVにおけるR9がアクリル基のものに相当)
アンチブロッキングフィラー 商品名:PL-20(扶桑化学工業株式会社製、粒子径220nm)
光重合開始剤1 商品名:イルガキュア184、BASFジャパン株式会社製
光重合開始剤2 商品名:LucirinTPO、BASFジャパン株式会社製
塗布基材:100μmPET(未処理) The components in Table 1 are as follows.
Resin (A) -1 Polyisocyanate (Coronate HK) / 2-hydroxyethyl acrylate / pentaerythritol triacrylate (manufactured according to Synthesis Example 1 of JP 2010-107956 A)
Resin (A) -2 Product name: UA-306H (Kyoeisha Chemical Co., Ltd., pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer)
Resin (A) -3 Polyisocyanate (Coronate HK) / 2-hydroxyethyl acrylate / pentaerythritol triacrylate / acrylic acid ethylene oxide 10 mol adduct Resin (B) Pentaerythritol triacrylate, trade name: Light acrylate PE-3A ( (Kyoeisha Chemical Co., Ltd.)
Resin (C) -1 Fluorine-containing (meth) acrylic resin 1 produced in Production Example 1
Resin (C) -2 Fluorine-containing (meth) acrylic resin 2 produced in Production Example 2
Resin (C) -3 Fluorine-containing (meth) acrylic resin 3 produced in Production Example 3
Resin (C) -4 Fluorine-containing (meth) acrylic resin 4 produced in Production Example 4
Resin (C) -5 Alkyl copolymer, trade name: Polyflow 99C (manufactured by Kyoeisha Chemical Co., Ltd.)
Resin (C) -6 Silicone copolymer, trade name: Polyflow KL-401 (manufactured by Kyoeisha Chemical Co., Ltd.)
Organosilica sol solution 1 Product name: PL-2L-MEK (manufactured by Fuso Chemical Industry Co., Ltd., particle diameter 10 nm, solid content 20.0%) having methacrylic groups introduced therein (R 9 in formula (IV) is methacrylic) Equivalent to the basic one)
Organosilica sol solution 2 PL-2L-MEK (manufactured by Fuso Chemical Industry Co., Ltd., particle size 10 nm, solid content 20.0%) having an acrylic group introduced therein (where R 9 in IV is an acrylic group) Equivalent)
Anti-blocking filler Product name: PL-20 (manufactured by Fuso Chemical Industry Co., Ltd., particle size 220 nm)
Photopolymerization initiator 1 Product name: Irgacure 184, manufactured by BASF Japan Co., Ltd. Photopolymerization initiator 2 Product name: Lucirin TPO, manufactured by BASF Japan Co., Ltd. Application substrate: 100 μm PET (untreated)
得られたコート層について、塗膜状態(透明性)、鉛筆硬度、耐スチールウール性、カール性、アンチブロッキング性、密着性、透過率及びヘイズ値の評価を行った。 The 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 μm 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 | permeability, and haze value were evaluated.
目視による観察によって、白化が全くないものを◎、ほとんどないものを○、部分的にあるものを△、全面的にあるものを×とする4段階で評価した。 <Coating state>
By visual observation, evaluation was made in four stages, with ◎ indicating no whitening, ◯ indicating almost none, Δ indicating partial, and × indicating overall.
鉛筆硬度計500g荷重にて試験を行い、傷の付かなかった鉛筆の硬度を示した。 <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.
得られたコート層に約1kg重の負荷をかけたスチールウール(#0000)で10往復、擦ることにより行った。目視により観察したとき、傷が付かなかったものを◎、ほとんど傷が付かなかったものを○、少し傷が付いたものを△、傷が付いたものを×とする4段階で評価した。 <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.
塗工フィルムを10cm四方に切り出し、その四隅の浮き高さの平均値を計測した。浮き高さの平均値が10mm以下のものを◎、10~20mmのものを○、20~30mmのものを△、30mm以上を×とする4段階で評価した。 <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: Δ, 30 mm: x.
コーティングフィルムと裏面(非コーティング面)又はコーティング面を張り合わせた状態で1kg荷重をかけ1日静置し、合わせた面同士が密着していないことを目視により確認した。 <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.
碁盤目試験を行い、100/100のものを◎、90/100以上のものを○、50/100以上のものを△、50/100未満のものを×とする4段階で評価した。 <Adhesion>
A cross-cut test was carried out, and the evaluation was made in four stages: ◎ for 100/100, ○ for 90/100 or more, Δ for 50/100 or more, and × for less than 50/100.
ヘイズ値測定機器(測色色彩計、ウルトラスキャン XE)を用い、全光線透過率及びヘイズ値を測定した。 <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).
一方、比較例では、特にアンチブロッキング効果に劣っていることがわかった。 From Table 1, in Examples, satisfactory results can be obtained in all evaluations by blending polyfunctional (meth) acrylate, fluorine-containing (meth) acrylic resin and metal oxide fine particles with urethane acrylate. did it.
On the other hand, in the comparative example, it turned out that it is especially inferior to the antiblocking effect.
実施例1で得られたハードコート用組成物を、上述した塗膜状態(透明性)、鉛筆硬度、耐スチールウール性、カール性、密着性、アンチブロッキング性、透過率、ヘイズ値の評価用と同様に、基材に塗布し、コート層として形成し、ハードコートフィルムを作製した。
得られたフィルムを、射出成形金型に挟みこみ、成形同時射出成型法にてアクリル樹脂を射出した。冷却後、ハードコート層を有する成型品を得た。 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.
Claims (12)
- (A)ウレタン(メタ)アクリレートと、
(B)多官能(メタ)アクリレートと、
(C)フッ素含有(メタ)アクリレートを重合した重合体と、
(D)金属酸化物微粒子とを含むことを特徴とするハードコート用組成物。 (A) urethane (meth) acrylate,
(B) a polyfunctional (meth) acrylate;
(C) a polymer obtained by polymerizing fluorine-containing (meth) acrylate;
(D) A hard coat composition comprising metal oxide fine particles. - 前記(A)ウレタン(メタ)アクリレートが、
(1)ポリエーテルを主鎖とする化合物と、
(2)イソシアネート化合物と、
(3)水酸基含有(メタ)アクリレート化合物との反応によって得られる重合体である請求項1に記載のハードコート用組成物。 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 according to claim 1, which is a polymer obtained by a reaction with a hydroxyl group-containing (meth) acrylate compound. - 前記(A)ウレタン(メタ)アクリレートが、下記式(I)
(R1O-CONH-)m-R2-(-NHCO-OR3)n(I)
(式(I)中、R1O-はポリエーテルを主鎖とする化合物の脱水素残基、
-R2-はイソシアネート化合物の脱イソシアネート基残基、
R3O-は水酸基含有(メタ)アクリレート化合物の脱水素残基、
m+n=1~50の整数を表す。)で表されるウレタン(メタ)アクリレートオリゴマーを含む請求項1又は2に記載のハードコート用組成物。 The (A) urethane (meth) acrylate is represented by the following formula (I)
(R 1 O—CONH—) m —R 2 — (— NHCO—OR 3 ) n (I)
(In the formula (I), R 1 O— represents a dehydrogenated residue of a compound having a polyether as the main chain;
—R 2 — is a deisocyanate group residue of the isocyanate compound,
R 3 O— is a dehydrogenated residue of a hydroxyl group-containing (meth) acrylate compound,
m + n = 1 represents an integer of 1 to 50. The composition for hard-coats of Claim 1 or 2 containing the urethane (meth) acrylate oligomer represented by this. - 前記(2)イソシアネート化合物が、ジイソシアネート類又はジイソシアネートモノマーを重縮合したポリイソシアネート類であるか、またはイソシアネート基にアルコール化合物を付加したウレタン構造及び/又はアミン化合物を付加したウレア構造を有している請求項2又は3に記載のハードコート用組成物。 (2) The isocyanate compound is a diisocyanate or a polyisocyanate obtained by polycondensation of a diisocyanate monomer, 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 composition for hard-coats of Claim 2 or 3.
- 前記(3)水酸基含有(メタ)アクリレート化合物が、ヒドロキシアルキル(メタ)アクリレート類、ポリオール(メタ)アクリレート類である請求項2から4のいずれか1つに記載のハードコート用組成物。 The hard coat composition according to any one of claims 2 to 4, wherein the (3) hydroxyl group-containing (meth) acrylate compound is a hydroxyalkyl (meth) acrylate or a polyol (meth) acrylate.
- 前記(1)ポリエーテルを主鎖とする化合物が、アルキレングリコール化合物及びアルキレンオキサイド付加化合物からなる群から選択される1種以上の化合物である請求項3から5のいずれか1つに記載のハードコート用組成物。 The hard according to any one of claims 3 to 5, wherein the compound (1) having a polyether as a main chain is at least one compound selected from the group consisting of an alkylene glycol compound and an alkylene oxide addition compound. Coat composition.
- 前記(1)ポリエーテルを主鎖とする化合物が、アルコキシポリアルキレングリコール類からなる片末端水酸基含有ポリアルキレングリコール化合物、(メタ)アクリル酸をアルキレンオキサイド付加又はポリアルキレングリコールのモノ(メタ)アクリレート化された化合物である請求項6に記載のハードコート用組成物。 (1) The compound having a polyether as the main chain is a polyalkylene glycol compound containing one terminal hydroxyl group composed of alkoxy polyalkylene glycols, (meth) acrylic acid is added with alkylene oxide, or polyalkylene glycol is mono (meth) acrylated The composition for hard coats according to claim 6, which is a prepared compound.
- 前記(C)フッ素含有(メタ)アクリル系樹脂が、
(4)フッ素置換アルキル(メタ)アクリレートモノマーと、
(5)アルキル(メタ)アクリレートモノマーと、
(6)エーテル基置換アルキル(メタ)アクリレートモノマーとの反応によって得られる樹脂である請求項1から7のいずれか1つに記載のハードコート用組成物。 The (C) fluorine-containing (meth) acrylic resin is
(4) a fluorine-substituted alkyl (meth) acrylate monomer;
(5) an alkyl (meth) acrylate monomer;
(6) The hard coat composition according to any one of claims 1 to 7, which is a resin obtained by a reaction with an ether group-substituted alkyl (meth) acrylate monomer. - 前記(5)アルキル(メタ)アクリレートモノマーが、C4~C20のアルキル基を有する請求項8に記載のハードコート用組成物。 The hard coat composition according to claim 8, wherein the (5) alkyl (meth) acrylate monomer has a C 4 to C 20 alkyl group.
- 前記(6)エーテル基置換アルキル(メタ)アクリレートモノマーが、
CH2=C(R21)-CO-O-A (II)
(式(II)中、R21は水素原子又はメチル基
Aは、C1~C20のアルコキシ基含有C1~C20のアルキル基、C1~C20のアルキル基含有モノ及びポリ(C2~C20アルキレングリコール)基を表す。)で表されるモノマーである請求項8又は9に記載のハードコート用組成物。 The (6) ether group-substituted alkyl (meth) acrylate monomer is
CH 2 ═C (R 21 ) —CO—OA (II)
(In the formula (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) represents a group.) for hard coat composition according to claim 8 or 9, which is a monomer represented by. - 前記(B)多官能(メタ)アクリレートが、1分子中に(メタ)アクリロイル基を少なくとも2個有する化合物である請求項1から10のいずれか1つに記載のハードコート用組成物。 The hard coat composition according to any one of claims 1 to 10, wherein the (B) polyfunctional (meth) acrylate is a compound having at least two (meth) acryloyl groups in one molecule.
- 請求項1から11のいずれか1つに記載のハードコート用組成物の硬化重合体がハードコート層として形成されてなることを特徴とする成形品。 A molded product comprising a cured polymer of the hard coat composition according to any one of claims 1 to 11 formed as a hard coat layer.
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