Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
  • B29C39/02—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles
  • B29C39/12—Making multilayered or multicoloured articles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
  • B29C39/003—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor characterised by the choice of material
  • B29C39/006—Monomers or prepolymers
• • 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
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • 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
• • 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
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/40—Properties of the layers or laminate having particular optical properties
  • B32B2307/412—Transparent
• • 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
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/558—Impact strength, toughness
• • 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
  • B32B2457/00—Electrical equipment
  • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
  • B32B2457/202—LCD, i.e. liquid crystal displays
• • 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
  • B32B2457/00—Electrical equipment
  • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
  • B32B2457/208—Touch screens

Definitions

• the present invention relates to a resin laminate and a method for producing the same.
• This application claims priority based on Japanese Patent Application No. 2013-262527 filed in Japan on December 19, 2013, the contents of which are incorporated herein by reference.
• a transparent resin plate has been used as a display front plate in order to protect the surface of various displays such as CRT display devices, liquid crystal televisions and mobile phones.
• various displays such as CRT display devices, liquid crystal televisions and mobile phones.
• touch panel type display front plates have been adopted.
• a glass plate with excellent scratch resistance and surface hardness is used as the touch panel type display front plate.
• a glass plate is used as a display front plate, it is necessary to reduce the thickness of the display front plate in order to satisfy cost reduction and weight reduction.
• a resin plate that can be reduced in cost and weight as a display front plate.
• display front plates having various shapes have been demanded, and the use of a resin plate having better processability than glass as a display front plate has been studied.
• a curable composition containing a polyfunctional monomer such as polyfunctional (meth) acrylate is cured, and a cured film obtained thereby is obtained.
• a method of forming on the surface of a resin base material is known.
• Patent Document 1 discloses a compound having three isocyanate groups in a molecule, a hydroxyl group and a (meth) acryloyloxy group in the molecule.
• the scratch resistance of the coating layer which is a cured film provided on the display front plate, is improved, the surface hardness is not sufficient.
• Patent Document 2 uses a curable coating containing a compound having at least six (meth) acryloyloxy groups in the molecule.
• a scratch-resistant resin plate characterized in that a cured film is formed on the surface of a methacrylic resin plate has been proposed.
• the scratch resistance and surface hardness of the cured film are improved, the impact resistance is low and the film may be easily cracked.
• Patent Document 3 discloses a scratch-resistant film obtained by curing a curable paint on the surface of an acrylic resin film including an acrylic resin layer in which rubber particles are dispersed in methacrylic resin. A scratch-resistant acrylic resin film characterized in that is formed is proposed. However, in the method described in Patent Document 3, the impact resistance of the resin film itself is improved, but the scratch resistance and surface hardness are not sufficient.
• the object of the present invention is to be used as a low-cost and lightweight optical sheet by laminating a cured film excellent in transparency, scratch resistance, surface hardness and impact resistance on the surface of a resin substrate. It is to obtain a resin laminate excellent in design processability.
• a resin laminate including a cured coating layer (A), a cured coating layer (B), and a resin substrate layer (C), wherein the resin substrate layer (C) is a cured coating layer (A) and a cured coating layer.
• P (A) represents the pencil hardness of the cured coating layer (A)
• P (B) represents the pencil hardness of the cured coating layer (B).
• the cured coating layer (A) is (A-1) a polyfunctional monomer having 3 or more (meth) acryloyl groups, (A-2) A cured coating layer obtained by curing a curable composition (A) comprising a polyfunctional monomer having two (meth) acryloyl groups and (A-3) a polymerization initiator,
• the curable composition (A) contains 65 to 85 parts by mass of the component (A-1) and (A) with respect to 100 parts by mass of the total of the components (A-1) and (A-2).
• the cured coating layer (B) is (B-1) a polyfunctional monomer having three or more (meth) acryloyl groups excluding dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, (B-2) A cured coating layer obtained by curing a curable composition (B) containing a polyfunctional monomer having two (meth) acryloyl groups and (B-3) a polymerization initiator,
• the curable composition (B) contains 40 to 75 parts by mass of the component (B-1) and 100 parts by mass of the component (B-1) with respect to 100 parts by mass of the component (B-1) and the component (B-2).
• the resin laminate according to [1] which is a curable composition containing 25 to 60 parts by mass of the component.
• the resin base layer (C) A polymer containing only methyl methacrylate units, or a copolymer having 50 to 100% by mass of methyl methacrylate units and monomer units copolymerizable with methyl methacrylate with respect to the total mass of the copolymer.
• the resin base layer (C) contains 0.02 to 1 mass of an olefin-alkyl acrylate copolymer based on 100 mass parts of the polymer containing only the methyl methacrylate unit or 100 mass parts of the copolymer.
• the monomer unit copolymerizable with methyl methacrylate includes a monomer unit derived from (meth) acrylic acid ester having a hydrocarbon group having 2 to 20 carbon atoms other than methyl methacrylate [11].
• the main component of methyl methacrylate is a laminated mold obtained by placing the mold (A) and mold (B) shown below with the cured coating layer (A) and the cured coating layer (B) facing each other.
• the resin base material containing the radically polymerizable monomer is poured, the resin base material is cast polymerized to form the resin base material layer (C), and then the mold is removed.
• the mold (A) is a mold in which a film having a contact angle with water of 105 ° or more is formed on the surface of the mold that contacts the curable composition (A).
• a manufacturing method of a layered product [18] A laminated mold obtained by placing the following mold (A) and mold (B) with the cured film layer (A) and the cured film layer (B) facing each other, and methyl methacrylate as a main component.
• a resin base material obtained by pouring a resin base material containing a radical polymerizable monomer, cast polymerizing the resin base material to form a resin base layer (C), and then removing the mold is obtained.
• the resin laminate on which the cured film of the present invention is formed is excellent in transparency, scratch resistance, surface hardness and impact resistance, and therefore can be used as a low-cost and lightweight optical sheet.
• the resin substrate layer (C) used in the present invention is a layer located between the cured coating layer (A) and the cured coating layer (B).
• resin which comprises the resin base material of the resin base material layer (C) polyolefin resin, (meth) acrylic resin, epoxy resin, polyimide resin, phenol resin, polyester resin, and polycarbonate resin are mentioned, for example.
• the resin base material one obtained by laminating the above resin can be used as necessary.
• the resin constituting the resin base material is preferably a (meth) acrylic resin in terms of transparency.
• Examples of the (meth) acrylic resin include, for example, a polymer containing only methyl methacrylate units, or a methyl methacrylate unit of 50 to less than 100% by mass and a methacryl of more than 0 and less than 50% by mass based on the total mass of the copolymer.
• (Meth) acrylic resin containing a copolymer containing a monomer unit copolymerizable with methyl acid is mentioned.
• the sum total of the mass% of each compound shall not exceed 100 mass%.
• (meth) acryl represents at least one selected from “acryl” and “methacryl”.
• Examples of monomers copolymerizable with methyl methacrylate include the following.
• (meth) acrylic acid ester having a hydrocarbon group having 2 to 20 carbon atoms examples include ethyl (meth) acrylate and (meth) acrylic.
• a polymerizable monomer copolymerizable with methyl methacrylate and a (meth) acrylic acid ester having a hydrocarbon group having 2 to 20 carbon atoms is selected from methyl methacrylate and a hydrocarbon having 2 to 20 carbon atoms.
• Copolymerization can be carried out in the range of 0 to 10 parts by mass with respect to 100 parts by mass in total of the (meth) acrylic acid ester having a group.
• the above-mentioned monomers copolymerizable with methyl methacrylate can be used alone or in combination of two or more.
• examples of monomers copolymerizable with methyl methacrylate include the following.
• Alkanediol di (meta) such as ethylene glycol di (meth) acrylate, 1,2-propylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate ) Acrylate; polyoxyalkylene glycol di such as diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate (Meth) acrylate; vinyl monomer having two or more ethylenically unsaturated bonds in the molecule such as divinylbenzene; at least one polyvalent carboxylic acid containing ethylenically unsaturated polycarboxylic acid When at least one unsaturated polyester obtained from a diol prepolymer; and vinyl ester prep
• the above-mentioned monomers copolymerizable with methyl methacrylate can be used alone or in combination of two or more.
• the resin base material containing the copolymer containing a unit can be obtained, for example, by polymerizing a resin base material containing a radical polymerizable monomer whose main component is methyl methacrylate.
• the resin base material containing the copolymer containing the unit is, for example, a resin base material containing only methyl methacrylate, or methyl methacrylate of 50 or more and less than 100% by mass and more than 0 with respect to the total mass of the copolymer. It can be obtained by polymerizing a resin base material containing a radically polymerizable monomer containing a monomer copolymerizable with methyl methacrylate of not more than mass%.
• the radical polymerizable monomer means, for example, a compound containing a radical polymerizable double bond radical polymerizable double bond, for example, methyl methacrylate and a monomer copolymerizable with methyl methacrylate. Refers to the compound.
• a radical polymerizable monomer containing only methyl methacrylate or a monomer copolymerizable with 50 to 100% by mass of methyl methacrylate and 0 to 50% by mass or less of methyl methacrylate It is a partial polymer obtained by polymerizing a part of a resin base material containing a radical polymerizable monomer containing syrup, and syrup in which an unpolymerized radical polymerizable monomer remains can be used. .
• a resin base material a syrup of a type in which a (meth) acrylic resin is dissolved in a mixture of the above radical polymerizable monomers can be used.
• the polymer contained in the resin base material layer (C) obtained by polymerizing the resin base material contains 50 to 100% by weight of methyl methacrylate units and 0 to more than 50 with respect to the total weight of the copolymer.
• the composition and amount of the (meth) acrylic resin to be dissolved are not limited as long as it is a copolymer containing monomer units copolymerizable with less than or equal to mass% of methyl methacrylate.
• the impact resistance can be improved by adding the olefin-alkyl acrylate copolymer to the resin base material.
• the olefin-alkyl acrylate copolymer is preferably an ethylene-alkyl acrylate copolymer from the viewpoint of transparency.
• Examples of the alkyl acrylate unit in the olefin-alkyl acrylate copolymer used in the present invention include a methyl acrylate unit, an ethyl acrylate unit, a propyl acrylate unit, and a butyl acrylate unit.
• As the ethylene-alkyl acrylate copolymer an ethylene-methyl acrylate copolymer is preferred from the viewpoint of transparency and impact resistance.
• the olefin-alkyl acrylate copolymer may further be a copolymer with an acid anhydride such as maleic anhydride or itaconic anhydride.
• the resin base layer (C) having high solubility and high transparency of the ethylene-methyl acrylate copolymer in the resin base material
• the ethylene-methyl acrylate copolymer preferably contains 15% by mass or more of methyl acrylate units with respect to the total monomer units of the ethylene-methyl acrylate copolymer, and is preferably 20% by mass or more. More preferably.
• methyl acrylate in the ethylene-methyl acrylate copolymer is based on all monomer units in the ethylene-methyl acrylate copolymer.
• the unit is preferably contained in an amount of 40% by mass or less, and more preferably 30% by mass or less.
• the methyl acrylate unit is 15% by mass or more and 40% by mass or less in the ethylene-methyl acrylate copolymer with respect to all monomer units in the ethylene-methyl acrylate copolymer. It is preferably included, and more preferably 20% by mass or more and 30% by mass or less.
• the amount of the olefin-alkyl acrylate copolymer added is a polymer containing only methyl methacrylate units, or methyl methacrylate units and methyl methacrylate in an amount of 50% by mass to less than 100% by mass based on the total mass of the copolymer.
• the amount is preferably 0.02 to 1 part by mass, more preferably 0.02 to 0.4 part by mass with respect to 100 parts by mass of the copolymer having a monomer unit copolymerizable with. If the amount of the olefin-alkyl acrylate copolymer added is 0.02 parts by mass or more, a sufficient impact resistance improving effect tends to be obtained. If the amount is 1 part by mass or less, the solubility of the olefin-alkyl acrylate copolymer in the resin base material and the transparency of the resin base material tend to be good.
• the olefin-alkyl acrylate copolymer is preferably used by dissolving 0.1 to 10 parts by mass in 100 parts by mass of the polymerizable monomer in the resin base material.
• the polymerizable monomer is not particularly limited, and for example, a polymerizable monomer such as methyl methacrylate can be used.
• the olefin-alkyl acrylate copolymer is usually preferably dispersed with a diameter of 0.2 to 20 ⁇ m in the resin constituting the resin base layer (C).
• Polymerization initiator (a) can be added to the resin base material.
• polymerization initiator (a) examples include methyl ethyl ketone peroxide, benzoyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyoctate, and t-butyl peroxybenzoate.
• Organic peroxides such as lauroyl peroxide; azo compounds such as azobisisobutyronitrile; and amines such as N, N-dimethylaniline and N, N-dimethyl-p-toluidine to the peroxide.
• a combined redox polymerization initiator may be mentioned.
• the polymerization initiator (a) can be used alone or in combination of two or more.
• the addition amount of the polymerization initiator (a) is preferably 0.005 to 5 parts by mass with respect to 100 parts by mass of the radical polymerizable monomer in the resin base material.
• Resin base materials include colorants, mold release agents, antioxidants, stabilizers, flame retardants, impact modifiers, light stabilizers, UV absorbers, polymerization inhibitors, chain transfer agents as necessary.
• additives such as can be added.
• Examples of the polymerization method of the resin base material include a bulk polymerization method, a solution polymerization method, an emulsion polymerization method, and a suspension polymerization method.
• the resin base material preferably has a thickness of 0.2 mm to 3 mm, and more preferably 0.5 mm to 2 mm.
• the thickness of the resin base material is an average value obtained by photographing a cross section of the resin laminate in the vertical direction with a differential interference microscope and measuring the dimensions from the first surface to the second surface of the resin base material at five arbitrary locations.
• the first surface of the resin substrate refers to one of the two surfaces having the largest area among the surfaces of the resin substrate.
• the 2nd surface of a resin base material means the surface which opposes the 1st surface of a resin base material in a resin base material.
• the cured coating layer (A) in the present invention is provided on the first surface of the resin base material layer (C), and the pencil hardness on the first surface of the cured coating layer (A) is 6H or more. 9H.
• the cured coating layer (A) has a higher pencil hardness than the cured coating layer (B).
• the first surface of the cured coating layer (A) refers to the surface of the cured coating layer (A) that faces the surface in contact with the resin base material when the resin laminate is formed.
• the 2nd surface of a cured film layer (A) means the surface which contacts a resin base material in forming a resin laminated body in a cured film layer (A).
• the pencil hardness is a value obtained in accordance with JIS K5600-5-4.
• the pencil hardness of the first surface of the cured coating layer (A) of the resin laminate is 6H or more, it is difficult to be scratched when used by direct human touch.
• the pencil hardness of the first surface of the cured coating layer (A) of the resin laminate is preferably 6H or more and 9H or less, more preferably 7H or more and 9H or less, and more preferably 8H or more and 9H or less. More preferably it is.
• water repellency can be imparted to the cured coating layer (A) as necessary in order to improve the removability of dirt components such as fingerprints, sebum, sweat, and cosmetics.
• the contact angle with respect to water of the first surface of the cured coating layer (A) is preferably 70 degrees or more, and preferably 100 degrees or more. More preferably, it is 100 degrees or more and 120 degrees or less.
• oil repellency may be imparted to the first surface of the cured coating layer (A) as necessary. it can.
• the contact angle with respect to triolein on the first surface of the cured coating layer (A) is more preferably 60 degrees or more, 70 degrees More preferably, it is 90 degrees or less.
• the contact angle of water on the surface of a solid is 23 ° C. and a relative humidity of 50%.
• a drop of 0.2 ⁇ L of water is dropped on the surface of the solid, and a portable contact angle meter (Fibro system) is used. It was obtained using a product of ab company, trade name: PG-X).
• relative humidity refers to the ratio of the measured value of water vapor to the maximum amount of water vapor (saturated water vapor) that can be contained in the atmosphere at a certain temperature.
• the contact angle of triolein on the surface of a certain solid is determined by dropping one drop of 0.2 ⁇ L of triolein on the surface of the solid in an environment of 23 ° C. and 50% relative humidity. It was determined using a total (manufactured by Fibro system ab, trade name: PG-X).
• the cured coating layer (A) preferably has a thickness of 20 ⁇ m or more and 40 ⁇ m or less, and more preferably 25 ⁇ m or more and 40 ⁇ m or less.
• the thickness of the cured coating layer (A) is a cross section obtained by cutting the resin laminate in the vertical direction with a differential interference microscope, and from the first surface to the second surface of the cured coating layer (A) of the resin laminate. An average value obtained by measuring three arbitrary dimensions.
• the cured coating layer (A) can be obtained, for example, by curing a coating film of the curable composition (A).
• the curable composition (A) is applied to the first surface of the resin substrate, and the coating film of the curable composition (A) is heated, or the curable composition.
• the curable composition (A) includes a polyfunctional monomer (A-1) having three or more (meth) acryloyl groups and a polyfunctional monomer (A-2) having two (meth) acryloyl groups. And a composition containing a polymerization initiator (A-3).
• the polyfunctional monomer (A-1) includes, for example, a polyfunctional monomer in which the residue that binds each (meth) acryloyl group is a hydrocarbon group or a derivative thereof, and an ether is included in the molecule. Bonds, thioether bonds, ester bonds, amide bonds, urethane bonds, and the like can be included.
• polyfunctional monomer (A-1) examples include an esterified product obtained from 1 mol of a polyhydric alcohol and 3 mol or more of (meth) acrylic acid or a derivative thereof; and a polyhydric alcohol; And linear esterified products obtained from a monovalent carboxylic acid or an anhydride thereof and (meth) acrylic acid or a derivative thereof.
• polyhydric alcohol means an alcohol having two or more hydroxyl groups in the molecule.
• Polyvalent carboxylic acid means a carboxylic acid having two or more carboxyl groups in the molecule.
• the “derivative of (meth) acrylic acid” means a compound in which a hydrogen atom of (meth) acrylic acid is substituted with another functional group.
• Linear means linear and branched.
• esterified products obtained from 1 mol of polyhydric alcohol and 3 mol or more of (meth) acrylic acid or derivatives thereof include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, ethylene oxide Adduct trimethylolpropane tri (meth) acrylate, propylene oxide adduct trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaglycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, glycerin tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate , Tripentaerythritol tetra (meth)
• a linear esterified product obtained from a polyhydric alcohol, a polyhydric carboxylic acid or an anhydride thereof, and (meth) acrylic acid or a derivative thereof, the polyhydric alcohol, the polyhydric carboxylic acid or an anhydride thereof Preferred examples of combinations of (meth) acrylic acid include malonic acid / trimethylolethane / (meth) acrylic acid, malonic acid / trimethylolpropane / (meth) acrylic acid, malonic acid / glycerin / (meth) acrylic acid, malonic acid / Pentaerythritol / (meth) acrylic acid, succinic acid / trimethylolethane / (meth) acrylic acid, succinic acid / trimethylolpropane / (meth) acrylic acid, succinic acid / glycerin / (meth) acrylic acid, succinic acid / Pentaerythritol / (meth) acrylic acid, adipic acid
• polyfunctional monomer (A-1) examples include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate with respect to 1 mol of the polyisocyanate represented by the following formula (I).
• Urethane (meth) obtained by reacting 3 mol or more of an acrylic monomer having active hydrogen such as 2-hydroxy-3-methoxypropyl (meth) acrylate, N-methylol (meth) acrylamide, N-hydroxy (meth) acrylamide, etc.
• Acrylates poly [(meth) acryloyloxyethyl] isocyanurates such as tris (2-hydroxyethyl) isocyanuric acid tri (meth) acrylate; epoxy polyacrylates; and urethane polyacrylates.
• R represents a divalent hydrocarbon group having 1 to 12 carbon atoms which may contain a substituent.
• polyisocyanate represented by the following formula (I) examples include trimethylolpropane toluylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, trimethylhexa
• polyisocyanates obtained by trimerization of isocyanate compounds such as methylene diisocyanate are preferred.
• the polyfunctional monomer (A-1) includes dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) in terms of scratch resistance and surface hardness of the cured film.
• Preferred are acrylate and pentaerythritol tetra (meth) acrylate, and more preferred are dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.
• the contents of the polyfunctional monomer (A-1) and the polyfunctional monomer (A-2) in the curable composition (A) are respectively the polyfunctional monomer (A-1) and the polyfunctional monomer.
• the content of the polyfunctional monomer (A-1) is 65 to 85 parts by mass with respect to 100 parts by mass of the total amount of the body (A-2), and the content of the polyfunctional monomer (A-2)
• the amount is preferably 15 to 35 parts by mass.
• the content of the polyfunctional monomer (A-1) is 65 parts by mass or more with respect to 100 parts by mass of the total amount of the polyfunctional monomer (A-1) and the polyfunctional monomer (A-2). In this case, the scratch resistance and surface hardness of the cured coating layer (A) tend to be good. In addition, when the content of the polyfunctional monomer (A-1) is 85 parts by mass or less, the curing shrinkage rate when the curable composition is cured decreases, and the crack resistance of the cured coating layer (A) is reduced. Tends to be good, and the adhesion of the cured coating layer (A) to the resin base material layer (C) tends to be good.
• polyfunctional monomer (A-2) examples include ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, Polyethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, ethylene oxide adduct trimethylolpropane di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,4 -Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyester di (meth) acrylate, polyethylene glycol di (meth) acrylate, tricyclodecanedi Tyrol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth)
• the content of the polyfunctional monomer (A-2) in the curable composition (A) is 100 mass of the total amount of the polyfunctional monomer (A-1) and the polyfunctional monomer (A-2). In the case of 15 parts by mass or more with respect to the part, the curing shrinkage rate when curing the curable composition is lowered, and the crack resistance of the cured coating layer (A) tends to be good. Moreover, it exists in the tendency which can suppress the curvature of the resin laminated body which laminated
• Examples of the polymerization initiator (A-3) include the following.
• the polymerization initiator (A-3) can be used alone or in combination of two or more.
• the addition amount of the polymerization initiator (A-3) is 100 parts by mass of the total amount of the polyfunctional monomer (A-1) and the polyfunctional monomer (A-2) in the curable composition (A).
• the content is preferably 0.1 to 10 parts by mass.
• the curable composition (A) is a mold release agent, lubricant, plasticizer, antioxidant, antistatic agent, light stabilizer, ultraviolet absorber, flame retardant, flame retardant aid, polymerization inhibitor, if necessary.
• Various additives such as a filler, a pigment, a dye, a silane coupling agent, a leveling agent, an antifoaming agent, a fluorescent agent, and a chain transfer agent can be contained.
• curable composition (A) examples include a mixture of 20 to 50 parts by mass of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, or 20 to 50 parts by mass of caprolactone-modified dipentaerythritol pentaacrylate and caprolactone-modified diester.
• Examples of the method for applying the curable composition (A) to the first surface of the resin substrate layer (C) include a casting method, a roller coating method, a bar coating method, a spray coating method, and an air knife coating method. It is done.
• Examples of the method for laminating the cured coating layer (A) on the first surface of the resin base material layer (C) include the following two methods. (1) A method of curing the curable composition (A) after forming a coating film of the curable composition (A) on the first surface of the resin substrate layer (C) (2) A curable composition on the surface of the mold The mold (A) in which the curable composition (A) is cured after the coating film of the product (A) is formed and the cured film layer (A) is laminated on the surface of the mold, and the mold surface described later is curable.
• the mold (B) in which the curable composition (B) is cured and the cured film layer (B) is laminated on the surface of the mold is referred to as the cured film layer (A).
• the method (2) is preferable in that a cured coating layer (A) having high pencil hardness is obtained.
• the surface of the coating film of the curable composition (A) is resinized in that a cured coating layer (A) having a good appearance free from defects due to foreign matters and the like is obtained. It is preferable to coat with a film. Moreover, after covering the surface of a curable composition (A) with a resin film, it is preferable to perform a smooth process with respect to the resin film surface using rolls, such as a rubber roll of JIS hardness 40 degrees. There exists a tendency which can obtain the cured film layer (A) of a more uniform film thickness by the smooth process by a roll, and exists in the tendency which can obtain the cured film which has high smoothness and a desired film thickness.
• a curable composition is irradiated by irradiating an active energy ray after coat
• the crosslinking reaction of the product (A) is sufficiently advanced to obtain a cured film having a good degree of curing, and the scratch resistance and surface hardness of the cured film layer (A) tend to be good.
• the resin film examples include a polyethylene terephthalate (PET) film, a polypropylene (PP) film, a polyethylene (PE) film, and a polyvinylidene fluoride (PVDF) film.
• PET polyethylene terephthalate
• PP polypropylene
• PE polyethylene
• PVDF polyvinylidene fluoride
• a PET film is preferable in terms of cost and curability of the curable composition (A).
• the thickness of the resin film is preferably 8 to 125 ⁇ m from the viewpoint of the strength, handleability and cost of the resin film.
• the curable composition (A) is cured with active energy rays
• examples of the active energy rays include electron beams, ultraviolet rays, and visible rays, but ultraviolet rays are preferable from the viewpoint of apparatus cost and productivity.
• Examples of light sources for active energy rays include fluorescent ultraviolet lamps, ultra high pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, low pressure mercury lamps, metal halide lamps, Ar lasers, He-Cd lasers, solid state lasers, xenon lamps, and high frequency.
• Examples include induction mercury lamps and sunlight.
• a fluorescent ultraviolet lamp and a high-pressure mercury lamp are preferable in terms of the curing rate of the curable composition (A).
• the cumulative amount of active energy rays is preferably 5 to 2,000 mJ / cm 2 .
• a resin laminate can be obtained by the following method.
• a fluorine-containing coating film is formed on the mold surface.
• a curable composition (A) containing perfluoropolyether (meth) acrylate is applied onto the fluorine-containing coating film, and then cured to obtain a laminated mold having a cured film layer (A).
• a resin laminate is obtained by using the obtained laminate mold instead of the mold (A).
• Examples of the perfluoropolyether unit in the (meth) acrylate having a perfluoropolyether unit include — [CF 2 CF 2 O] — and — [CF 2 O] —.
• the (meth) acrylate having a perfluoropolyether unit is not particularly limited, and a known perfluoropolyether (meth) acrylate can be used.
• Examples of the (meth) acrylate having a perfluoropolyether unit include a triisocyanate represented by the following general formula (II), a compound (III-1) (X—CH 2 —OH), and a compound (III- 2) It can be obtained by reacting (CH 2 ⁇ CH—COO—C 2 H 4 —OH).
• X represents a perfluoroalkyl group or a perfluoropolyether group.
• the compound (III-1) reacts with one isocyanate group of the triisocyanate represented by the general formula (II), and the remaining two isocyanate groups react with the compound (III- It can be obtained by reacting 2).
• (III-1) and (III-2) may be reacted with triisocyanate simultaneously, or (III-1) and (III-2) may be reacted sequentially.
• the amount of each component to be reacted is preferably such that the total of the hydroxyl group of (III-1) and the hydroxyl group of (III-2) is 3 mol per 1 mol of triisocyanate.
• the amount of (III-1) is preferably 0.0001 to 2.0 mol (0.01 to 2.0 mol), preferably 0.01 to 1.2 mol (1 mol) relative to 1 mol of triisocyanate. 0.1 to 1.2 mol) is more preferable.
• the amount of (III-2) is preferably 1.0 to 2.5 mol, more preferably 1.2 to 2.0 mol, per 1 mol of triisocyanate.
• Examples of commercially available products of perfluoropolyether (meth) acrylate include “OPTOOL DAC-HP” (trade name) manufactured by Daikin Industries, Ltd., and “Fluorolink MD500” (trade name) manufactured by Solvay Solexis Co., Ltd. , Fluorolink MD700 (product name), Fluorolink 5105X (product name) and Fluorolink 5101X (product name), DIC Corporation's “Megafuck RS-75” (product name), “Megafuck RS-” 76-NS "(trade name) and” Megafuck RS-903-NST "(trade name). These can be used individually by 1 type or in combination of 2 or more types.
• the perfluoropolyether (meth) acrylate is based on 100 parts by mass of the total amount of the polyfunctional monomer (A-1) and the polyfunctional monomer (A-2) in the curable composition (A). 0.1 to 10 parts by mass is preferred.
• fluorine-containing coating agent used for forming the aforementioned fluorine-containing coating film for example, a coating agent containing a fluorine compound containing a perfluoroalkyl group or a perfluoropolyether group can be used.
• fluorine-containing coating agents include, for example, “Fluorosurf FG5010” (trade name) manufactured by Fluoro Technology Co., Ltd., “OPTOOL DSX” and “OPTOOL AES-4” (both trade names) manufactured by Daikin Industries, Ltd.
• “Novec EGC-1720” (trade name) manufactured by Sumitomo 3M Limited may be mentioned.
• an organic solvent can be appropriately added.
• organic solvent examples include non-fluorine solvents such as hydrocarbon solvents and fluorine-containing solvents, and fluorine-containing solvents are preferable in terms of excellent compatibility with fluorine-containing coating agents.
• non-fluorine solvents examples include the following.
• Ketones such as methyl ethyl ketone, acetone and methyl isobutyl ketone; monohydric alcohols such as ethanol, 1-propanol, 2-propanol, butanol and 1-methoxy-2propanol; polyhydric alcohols such as ethylene glycol, diethylene glycol and propylene glycol; Alcohols; esters such as ethyl acetate, butyl acetate and ⁇ -butyrolactone; ethers such as diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, tetrahydrofuran and 1,4-dioxane; aromatic hydrocarbons such as toluene and xylene; and Amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.
• monohydric alcohols such as ethanol, 1-propanol, 2-propanol, butanol and 1-methoxy-2propanol
• fluorine-containing solvent examples include fluorine-containing alcohols, fluorine-containing ethers, and ditrifluoromethylbenzene.
• fluorinated alcohol examples include compounds represented by the following formulas (IV-1) and (IV-2).
• fluorinated ether examples include compounds represented by the following formula (V).
• R 21 and R 22 are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, and hydrogen contained in at least one alkyl group of R 21 and R 22 An atom is substituted with a fluorine atom.
• fluorinated ether examples include hydrofluoroalkyl ether.
• fluorine-containing ethers examples include “HFE-7100” and “HFE-7200” (both trade names) manufactured by Sumitomo 3M Limited.
• ditrifluoromethylbenzene examples include o-ditrifluoromethylbenzene, m-ditrifluoromethylbenzene, p-ditrifluoromethylbenzene, and mixtures thereof.
• Organic solvents can be used alone or in combination of two or more.
• the first surface of the cured coating layer (A) of the resin laminate is subjected to hydrophilization treatment, solvent treatment or primer treatment. It is preferable.
• hydrophilic treatment method examples include chemical treatment methods such as acid treatment and alkali treatment, and physical treatment methods such as corona treatment, plasma treatment, atmospheric pressure plasma treatment, and flame treatment.
• chemical treatment methods such as acid treatment and alkali treatment
• physical treatment methods such as corona treatment, plasma treatment, atmospheric pressure plasma treatment, and flame treatment.
• corona treatment is preferable in terms of improving the wettability of the fluorine-containing coating agent.
• the above corona treatment refers to a treatment in which a discharge treatment is performed on the first surface of the cured coating layer (A) of the resin laminate to generate polar carboxyl groups and hydroxyl groups and roughen the surface.
• Examples of the method for primer treatment of the first surface of the cured film layer (A) of the resin laminate include a method of laminating a primer layer on the first surface of the cured film layer (A) of the resin laminate.
• Examples of the coating method of the fluorine-containing coating agent on the first surface of the cured coating layer (A) of the resin laminate include, for example, a casting method, a roller coating method, a bar coating method, a spray coating method, an air knife coating method, Examples include spin coating, flow coating, curtain coating, and dipping.
• the first surface of the cured coating layer (A) of the resin laminate may have various functional layers such as an antireflection layer, an antiglare layer, and an antistatic layer.
• the amount of reflected light of light incident in the direction toward the inside of the resin laminate on the first surface of the cured coating layer (A) of the resin laminate is 0% or more and 20% or less of the amount of incident light. What becomes 0% or more and 10% or less is more preferable, and what becomes 0% or more and 5% or less is still more preferable.
• an antireflection layer for example, a two-layer structure in which a low refractive index layer is laminated on a high refractive index layer, or a middle refractive index layer and a low refractive index layer on a high refractive index layer.
• a layered structure having a three-layer structure in which are sequentially stacked. The antireflection layer is disposed so that the high refractive index layer is in contact with the first surface of the cured coating layer (A) of the resin laminate.
• the antireflection layer has a two-layer structure in which a low refractive index layer is laminated on a high refractive index layer, for example, a low refractive index layer having a refractive index of 1.3 to 1.5 and a refractive index of 1. Those having a high refractive index layer of 6 to 2.0 are preferred. If it is this range, it exists in the tendency which can fully suppress the reflected light of incident light.
• the film thicknesses of the low refractive index layer and the high refractive index layer are each preferably 50 nm or more, and more preferably 70 nm or more. Moreover, as a film thickness of a low refractive index layer and a high refractive index layer, 200 nm or less is respectively preferable, and 150 nm or less is more preferable.
• the film thicknesses of the low refractive index layer and the high refractive index layer are each preferably 50 nm or more and 200 nm or less, and more preferably 70 nm or more and 150 nm or less. When the film thickness is within this range, reflected light having a visible wavelength tends to be sufficiently suppressed.
• the component forming the low refractive index layer examples include an active energy ray-curable composition such as an electron beam, radiation, and ultraviolet rays, and a thermosetting composition. These may be used alone or in combination of a plurality of curable compounds.
• Examples of the low refractive index layer having a refractive index of 1.3 to 1.5 include a siloxane bond-based layer obtained from a condensation polymerization curable compound such as alkoxysilane or alkylalkoxysilane.
• siloxane bond-based layer examples include those formed from a compound in which a part of the siloxane bond of the siloxane resin is substituted with a hydrogen atom, a hydroxyl group, an unsaturated group, or an alkoxyl group.
• colloidal silica can be contained as necessary for lowering the refractive index.
• the colloidal silica a colloidal solution obtained by dispersing at least one kind of fine particles selected from porous silica and non-porous silica in a dispersion medium can be used.
• the porous silica is low-density silica in which the inside of the particle is porous or hollow and contains air inside.
• the refractive index of porous silica include those of 1.20 to 1.40, which are lower than those of ordinary silica of 1.45 to 1.47.
• the colloidal silica by which the surface was processed with the silane coupling agent can be used as needed.
• Examples of the high refractive index layer having a refractive index of 1.6 to 2.0 include a metal oxide film obtained by condensing a metal alkoxide after hydrolysis.
• metal alkoxide examples include those represented by the following formula (VI).
• M represents a metal atom
• R represents a hydrocarbon group having 1 to 5 carbon atoms
• m represents the valence (3 or 4) of the metal atom M.
• the metal atom M titanium, aluminum, zirconium and tin are preferable, and titanium is more preferable in view of the refractive index of the high refractive index layer.
• metal alkoxide examples include the following.
• a high refractive index metal oxide ZrO 2 , TiO 2 , NbO, ITO, ATO, SbO 2, in 2 O 3, those obtained by dispersing at least one kind of fine particles selected from SnO 2 and ZnO are preferable.
• the high refractive index layer in addition to the above metal oxide film, for example, a high refractive index metal oxide fine particle dispersed in an ultraviolet curable mixture for forming a hard coat layer. Cured ones can be used. In this case, surface treated metal oxide fine particles having a high refractive index may be used.
• Examples of the method for forming the antireflection layer include a casting method, a roller coating method, a bar coating method, a spray coating method, an air knife coating method, a spin coating method, a flow coating method, a curtain coating method, a film cover method, and a dipping method.
• a method of laminating a low refractive film and a high refractive film is mentioned.
• the upper surface of the antiglare layer refers to a surface facing the surface in contact with the first surface of the cured coating layer (A) in the antiglare layer.
• Examples of the method for forming the antiglare layer include the following methods.
• the surface having the fine uneven shape of the active energy ray-transmitting film having the fine uneven shape formed thereon is coated with the antiglare layer forming composition on the first surface of the cured coating layer (A) of the resin laminate. It laminates
• the composition for forming the antiglare layer is cured, and a laminate in which the resin laminate, the antiglare layer obtained by curing the composition for forming the antiglare layer, and the active energy ray-transmitting film having fine irregularities are sequentially laminated. obtain.
• peeling off the active energy ray-permeable film a laminate in which an antiglare layer having a fine uneven surface is laminated on the surface of the cured coating layer (A) of the resin laminate is obtained.
• a release agent can be added to the antiglare layer forming composition as necessary.
• Examples of the method for forming a fine uneven shape on the surface of the active energy ray permeable film include, for example, a method of forming an uneven shape on the surface of the active energy ray permeable film itself and a coating method on the surface of the smooth active energy ray permeable film.
• corrugated shape by is mentioned.
• Examples of the method for providing the surface of the active energy ray permeable film with irregularities include, for example, a method of kneading particles in a resin for forming an active energy ray permeable film and an active energy ray permeable film.
• a method of kneading particles in a resin for forming an active energy ray permeable film and an active energy ray permeable film For example, there is a method of transferring the fine uneven shape on the surface of the mold by bringing the resin for heating to a glass transition temperature or higher into contact with a mold having the fine uneven shape.
• Examples of a method for providing a smooth active energy ray permeable film surface with a concavo-convex shape by a coating method include, for example, a method of applying an antiglare coating agent to an active energy ray permeable film surface and a coating composition as an active energy ray permeable film. And a method (2P method) of peeling from the mold after being poured and cured between the mold having a fine uneven surface.
• Examples of a method for producing a mold having a fine concavo-convex surface include a method of forming a fine concavo-convex shape by a method such as a sand blast method, a chemical etching method, or a lithography method.
• the shape of the mold is preferably a roll shape from the viewpoint of good productivity.
• the cured coating layer (B) in the present invention is provided on the second surface of the resin substrate layer (C), and the second surface of the cured coating layer (B), that is, the resin substrate layer (B) of the cured coating layer (B).
• the pencil hardness on the surface facing the surface in contact with C) is 3 to 6H.
• the 1st surface of a cured film layer (B) means the surface which contacts a resin base material in forming a resin laminated body in a cured film layer (B).
• the 2nd surface of the cured film layer (B) of a resin laminated body means the surface which opposes the surface which contacts a resin base material layer (C) in forming a resin laminated body in a cured film layer (B).
• the pencil hardness of the second surface of the cured coating layer (B) is 3H or more, the impact resistance of the resin laminate can be improved.
• the pencil hardness of the second surface of the cured coating layer (B) is preferably 3H or more and 6H or less, and more preferably 4H or more and 6H or less, from the viewpoint of improving the handleability for preventing damage during handling of the resin laminate. .
• the cured coating layer (B) preferably has a thickness of 10 ⁇ m or more and 50 ⁇ m or less, and more preferably 15 ⁇ m or more and 40 ⁇ m or less.
• the thickness of the cured coating layer (B) means that the cross section of the resin laminate cut in the vertical direction is photographed with a differential interference microscope, and the resin laminate is formed from the surface of the cured coating layer (B) in contact with the resin substrate layer (C).
• the average value which measured the dimension to the surface of the cured film layer (B) of a body in arbitrary three places is said.
• the cured coating layer (B) when used as a resin laminate is preferably one in which cracks do not occur when the radius of curvature is 40 mm in the following evaluation of crack resistance, and when the radius of curvature is 30 mm. It is more preferable that no crack occurs.
• the cured coating layer (B) of the resin laminate has a crack resistance that does not generate cracks when bent to a radius of curvature of 40 mm, the impact resistance of the resin laminate tends to be improved. is there.
• a resin laminate having a width of 30 mm and a length of 120 mm is a semi-cylindrical die, and the second surface of the cured coating layer (B) is vertical on a die having a radius of curvature R of the cross-section arc of 40 mm or 30 mm. Put it on the top of the direction.
• the resin laminate is bent along the mold and held for 30 seconds. Then, the 2nd surface of the cured film layer (B) of a resin laminated body is visually observed, and the presence or absence of the generation
• the thickness of the resin laminate used in the evaluation of crack resistance is, for example, not less than 0.2 mm and not more than 3 mm.
• the material of the mold used for evaluation of crack resistance is not particularly limited, and examples thereof include wood, resin, and steel.
• mold will not be specifically limited if it is the size in which the whole test piece used for evaluation is mounted. The act of bending the resin laminate along the mold is performed for 2 to 10 seconds, for example.
• the cured coating layer (B) includes, for example, a polyfunctional monomer (B-1) having three or more (meth) acryloyl groups excluding dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate. It can be obtained by curing a coating film of a curable composition (B) containing a polyfunctional monomer (B-2) having two (meth) acryloyl groups and a polymerization initiator (B-3). it can.
• curable composition (B) examples include polyfunctional monomers having 3 or more (meth) acryloyl groups excluding dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate (B-1 ), A polyfunctional monomer (B-2) having two (meth) acryloyl groups, and a polymerization initiator (B-3).
• Examples of the polyfunctional monomer (B-2) having two (meth) acryloyl groups are the same as those used for the polyfunctional monomer (A-2).
• the curable composition (B) may be selected so that the pencil hardness of the cured coating layer (B) is 3 to 6H.
• the contents of the polyfunctional monomer (B-1) and the polyfunctional monomer (B-2) are respectively the polyfunctional monomer (B-1) and the polyfunctional monomer.
• the content of the polyfunctional monomer (B-1) is 40 to 75 parts by mass with respect to 100 parts by mass of the total amount of the body (B-2), and the content of the polyfunctional monomer (B-2)
• the amount is preferably 25 to 60 parts by mass.
• the content of the polyfunctional monomer (B-1) is 40 parts by mass or more with respect to 100 parts by mass of the total amount of the polyfunctional monomer (B-1) and the polyfunctional monomer (B-2). In this case, the scratch resistance and surface hardness of the cured coating layer (B) tend to be good. Further, when the content of the polyfunctional monomer (B-1) is 75 parts by mass or less, the curing shrinkage rate when the curable composition (B) is cured decreases, and the cured coating layer (B) The crack resistance tends to be good, and the adhesiveness of the cured coating layer (B) to the resin base material layer (C) tends to be good.
• the content of the polyfunctional monomer (B-2) is 25 parts by mass or more with respect to 100 parts by mass of the total amount of the polyfunctional monomer (B-1) and the polyfunctional monomer (B-2).
• the curing shrinkage rate at the time of curing the curable composition (B) is lowered, and the crack resistance of the cured coating layer (B) tends to be good.
• the content of the polyfunctional monomer (A-2) in the resin cured composition (B) is 60 parts by mass or less, the cured coating layer (B) tends to have good scratch resistance and surface hardness. .
• Examples of the polymerization initiator (B-3) include those similar to the polymerization initiator (A-3) used in the curable composition (A).
• the addition amount of the polymerization initiator (B-3) is 100 mass of the total amount of the polyfunctional monomer (B-1) and the polyfunctional monomer (B-2) in the cured composition (B).
• the amount is preferably 0.1 to 10 parts by mass with respect to parts.
• the curable composition (B) can contain various additives similar to the additives that can be added to the curable composition (A) as necessary.
• Examples of the curable composition (B) include 40 to 70 parts by mass of a succinic acid / trimethylolethane / acrylic acid condensation mixture, 30 to 60 parts by mass of 1,6-hexanediol diacrylate, and 0.5
• Examples include a composition containing ⁇ 3 parts by mass of benzoin ethyl ether, and the total of the parts by mass of the compound is 95 to 115 parts by mass.
• the present composition when used as the curable composition (B), a mixture of 20 to 50 parts by mass of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate as the curable composition (A), Or a mixture of 20-50 parts by weight of caprolactone-modified dipentaerythritol pentaacrylate and caprolactone-modified dipentaerythritol hexaacrylate; 20-50 parts by weight of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate; 5-15 parts by weight of urethane This compound is obtained by reacting 3 mol of 3-acryloyloxy-2-hydroxypropyl methacrylate with 1 mol of triisocyanate obtained by trimerizing hexamethylene diisocyanate.
• a composition comprising 10 to 40 parts by mass of 1,6-hexanediol diacrylate; and 0.5 to 3 parts by mass of benzoin ethyl ether, wherein the total of the parts by mass of the compound is 90 to 110 parts by mass. You may use a thing (A ').
• Examples of the curable composition (B) include a mixture of 15 to 35 parts by mass of caprolactone-modified dipentaerythritol pentaacrylate and caprolactone-modified dipentaerythritol hexaacrylate; 20 to 40 parts by mass of pentaerythritol triacrylate and pentaerythritol tetra A mixture of acrylates; 5 to 25 parts by weight of a urethane acrylate compound; 20 to 40 parts by weight of 1,6-hexanediol diacrylate; and 0.5 to 3 parts by weight of benzoin ethyl ether; And a composition having a total of 70 to 110 parts by mass.
• the above-described composition (A ′) may be used as the curable composition (A).
• the curable composition (B) include a mixture of 20 to 40 parts by mass of pentaerythritol triacrylate and pentaerythritol tetraacrylate; 30 to 50 parts by mass of a urethane acrylate compound; 20 to 40 parts by mass of 1,6- Hexanediol diacrylate; and a composition containing 0.5 to 3 parts by mass of benzoin ethyl ether, and the total of the parts by mass of the compound is 70 to 110 parts by mass.
• the above-described composition (A ′) may be used as the curable composition (A).
• the method for laminating the cured coating layer (B) on the second surface of the resin substrate layer (C) is the same as the method for laminating the cured coating layer (A) on the first surface of the resin substrate layer (C). A method is mentioned.
• Examples of the method of laminating the cured coating layer (B) on the second surface of the resin base material layer (C) include the following two methods. (1) A method of curing the curable composition (B) after forming a coating film of the curable composition (B) on the second surface of the resin substrate layer (C) (2) A curable composition on the surface of the mold A mold (B) in which a curable composition (B) is cured after forming a coating film of the product (B) and a cured film layer (B) is laminated on the surface of the mold, and a curable composition on the surface of the mold After forming the coating film of (A), the curable composition (A) is cured and the mold (A) in which the cured film layer (A) is laminated on the surface of the mold, the cured film layer (A) and the cured film are formed.
• the cured coating layer (B) of the resin laminate has a crack resistance that does not generate cracks when bent to a radius of curvature of 40 mm, The method 2) is preferred.
• the surface of the coating film of the curable composition (B) is a resin in that a cured coating layer (B) having a good appearance free from defects due to foreign matters and the like is obtained. It is preferable to coat with a film. Moreover, after covering the surface of a curable composition (B) with a resin film, it is preferable to perform a smooth process with respect to the resin film surface using rolls, such as a rubber roll of JIS hardness 40 degrees. The cured film layer (B) having a more uniform film thickness can be obtained by the smoothing treatment using a roll, and a cured film having high smoothness and a desired film thickness tends to be obtained.
• an active energy ray curable composition as a curable composition (B)
• a curable composition is irradiated by irradiating an active energy ray after coat
• the crosslinking reaction of the product (B) sufficiently proceeds to obtain a cured film having a good degree of curing, and the scratch resistance and surface hardness of the cured film layer (B) tend to be improved.
• the same resin film as that used when obtaining the cured coating layer (A) by the same method as the methods (1) and (2) can be used.
• the active energy rays are the same as the active energy rays used when the curable composition (A) is cured with active energy rays. can do.
• the same light source as that used when the curable composition (A) is cured with the active energy ray can be used.
• various functional layers such as an antireflection layer, an antiglare layer, and an antistatic layer may be provided on the second surface of the cured coating layer (B) of the resin laminate as necessary.
• the 1st surface of a curable composition (B) means the surface which contacts a resin base material in a curable composition (B).
• the 2nd surface of a curable composition (B) means the surface facing the surface which contacts a resin base material in a curable composition (B).
• Examples of the various functional layers include the same functional layers as those laminated on the first surface of the cured coating layer (A) of the resin laminate.
• the resin laminate of the present invention comprises a cured coating layer (A) on the first surface of the resin substrate layer (C) and a cured coating layer (B) on the second surface of the resin substrate layer (C). It is a laminate.
• the thickness of the resin base layer (C) is from 0.2 mm to 3 mm
• the thickness of the cured coating layer (A) is from 20 ⁇ m to 40 ⁇ m
• the thickness of the cured coating layer (B) is preferably 10 ⁇ m or more and 50 ⁇ m or less.
• the cured coating layer (A) is laminated on the first surface of the resin substrate layer (C), and then the cured coating layer (B) is laminated on the second surface of the resin substrate layer (C), or the resin base
• a method of obtaining a resin laminate by laminating the cured coating layer (B) on the second surface of the material layer (C) and then laminating the cured coating layer (A) on the first surface of the resin substrate layer (C) (2 ) A mold (A) in which the cured film layer (A) is laminated on the surface of the mold, and a mold (B) in which the cured film layer (B) is laminated on the surface of the mold, the cured film layer (A) and the cured film.
• the method (2) will be further described below.
• Examples of the mold include a mold and a sheet.
• the surface on which the cured coating layer (A) or the cured coating layer (B) of the mold is laminated has a smooth surface.
• Examples of the mold material include stainless steel, glass, and resin.
• the mold used for the mold (A) and the mold (B) may be the same material or different materials.
• Examples of a method for producing a laminated mold include the following methods.
• the mold (A) and the mold (B) are arranged with the cured film layer (A) and the cured film layer (B) facing each other.
• the space formed between the peripheral portion of the mold (A) and the peripheral portion of the mold (B) is sealed by providing a gasket, thereby forming a stack composed of the mold (A) and the mold (B).
• a laminated mold having a certain volume of space inside the mold is produced.
• Examples of the casting polymerization method for the resin base material include a cell casting method in which the resin base material is poured into a laminated mold and heated.
• a continuous casting polymerization method using a stainless steel endless belt may be mentioned as a suitable method.
• a laminated stainless steel endless belt having a cured coating layer (A) laminated on the surface thereof and a laminated stainless steel endless belt having a cured coating layer (B) laminated on the surface thereof are arranged to face each other. Both end portions of these stainless steel endless belts are sealed with a gasket similar to the above gasket to form a space.
• Two laminated stainless steel endless belts run in the same direction and at the same speed, and the resin base material is continuously polymerized by pouring the resin base material upstream into the space and heating it.
• Examples of the method for heating the resin base material include a method in which the laminated mold into which the resin base material is poured is heated with a heat source such as hot water at 30 to 98 ° C.
• the polymerization time may be appropriately determined according to the progress of polymerization curing.
• the heating time is, for example, 3 minutes to 24 hours.
• heat treatment at 90 to 150 ° C. can be performed in an air atmosphere using a heat source such as a far infrared heater as necessary. Further, after the heat treatment, a cooling treatment such as blowing can be performed as necessary.
• part represents “part by mass”.
• film thickness of cured coating The thickness of the cured coating layer (A) and the cured coating layer (B) was measured using a differential interference micrograph of the cross section of the resin laminate.
• Haze The haze of the resin laminate was measured according to the measurement method shown in JIS K7136 using HAZE METER NDH4000 (trade name) manufactured by Nippon Denshoku Industries Co., Ltd.
• Scratch resistance The scratch resistance of the cured coating on the surface of the resin laminate was evaluated by the difference ⁇ haze (%) between the haze values of the resin laminate before and after the scratch test.
• a resin laminate having a width of 30 mm, a length of 120 mm, and a thickness of 1 mm is placed on a wooden mold having a semi-cylindrical shape and a radius of curvature R of a cross-sectional arc of 40 mm or 30 mm and a base length of 100 mm.
• the resin laminate was placed so that the second surface of the cured coating layer (B) of the resin laminate was on the upper side in the vertical direction.
• the entire resin laminate was bent along the arc of the mold and held for 30 seconds. Thereafter, the second surface of the cured coating layer (B) of the resin laminate was visually observed and judged according to the following criteria. “ ⁇ ”: No cracks are observed.
• Polyacrylate 1 A mixture of dipentaerythritol hexaacrylate (60 to 70% by mass based on the total mass of polyacrylate 1) and dipentaerythritol pentaacrylate (40 to 30% by mass based on the total mass of polyacrylate 1).
• Polyacrylate 2 caprolactone-modified dipentaerythritol pentaacrylate (60 to 70% by mass with respect to the total mass of polyacrylate 2) and caprolactone-modified dipentaerythritol hexaacrylate (40 to 30% by mass with respect to the total mass of polyacrylate 2) ).
• Polyacrylate 3 A mixture of pentaerythritol triacrylate (50 to 70 mass% with respect to the total mass of polyacrylate 3) and pentaerythritol tetraacrylate (50 to 30 mass% with respect to the total mass of polyacrylate 3)
• Polyacrylate 4 Succinic acid / trimethylolethane / acrylic acid molar ratio 1: 5: 4 condensation mixture urethane acrylate 1: 3-acryloyloxy-2-hydroxy with respect to 1 mole of triisocyanate obtained by trimerization of hexamethylene diisocyanate Urethane compound diacrylate obtained by reacting 3 mol of propyl methacrylate: 1,6-hexanediol diacrylate
• BEE Benzoin ethyl ether (trade name, manufactured by Seiko Chemical Co., Ltd.)
• HCPK 1-hydroxycyclohexyl phenyl ketone
• Megafuck 903NST Fluorine-containing acryl
• SUS304 plate stainless steel having a mirror surface is used as a mold, and the curable composition (A1) is applied on the mirror surface of the mold, and a PET film “NS” having a thickness of 12 ⁇ m (manufactured by Teijin DuPont Films Ltd., trade name) ) To obtain a laminate (1-1) before curing.
• a rubber roll having a JIS hardness of 40 ° is pressure-bonded onto the PET film of the laminate (1-1) before curing, and bubbles are contained in the curable composition (A1) while squeezing out the excessive curable composition (A1).
• a pre-cured laminate (1-2) was obtained.
• the pre-curing laminate (1-2) was placed 2 m / min at a position 20 cm below the fluorescent UV lamp (trade name: FL40BL, manufactured by Toshiba Corporation) with an output of 40 W with the PET film surface in the vertical direction.
• the curable composition (A1) was cured to obtain a cured coating layer (A), and a cured laminate (1-3) was obtained.
• the PET film of the laminate (1-3) after curing was peeled off to obtain a laminate (1-4) after curing.
• the cured laminate (1-4) was passed through a position 20 cm below the high-pressure mercury lamp with an output of 60 W / cm 2 with the cured coating layer (A) facing up, after curing,
• the laminate (1-4) was further cured by irradiating with ultraviolet rays.
• cured was laminated
• a curable composition (B1) for forming a cured coating layer (B) is applied on a mold of a SUS304 plate having a mirror surface in the same manner as the method for obtaining the mold (A1) and cured to a film thickness of 20 ⁇ m.
• a mold (B1) in which a cured coating layer (B1) obtained by curing the curable composition (B1) was laminated was obtained.
• the obtained mold (A1) and the obtained mold (B1) are opposed to the cured film layer (A1) laminated on the mold (A1) and the cured film layer (B1) laminated on the mold (B1). Arranged.
• the space formed between the peripheral edge of the mold (A1) and the peripheral edge of the mold (B1) was sealed with a soft polyvinyl chloride gasket to produce a laminated mold (1).
• methyl methacrylate monomer 100 parts was supplied to a reactor (polymerization kettle) equipped with a condenser, a thermometer and a stirrer, and after bubbling with nitrogen gas while stirring, heating was started.
• a reactor polymerization kettle
• 0.06 part of 2,2′-azobis- (2,4-dimethylvaleronitrile) as a radical polymerization initiator was added, and the mixture was further heated to an internal temperature of 100 ° C. For 13 minutes. Thereafter, the reactor was cooled to room temperature to obtain syrup (1).
• the polymerization rate of this syrup (1) was about 21 mass%.
• Examples 2-4, 7-9, Comparative Examples 1-2 Cured coating layers (A2), (A3), (A4), (A7) in the same manner as in Example 1 except that the curable compositions (A) and (B) having the compositions shown in Table 1 were used. , (A8), (A9), (A11) and (A12) and cured coating layers (B2), (B3), (B4), (B7), (B8), (B9), (B11) and (B12) Then, resin laminates (2), (3), (4), (7), (8), (9), (11) and (12) were obtained. The evaluation results are shown in Table 1.
• Example 5 “Fluorosurf FG5010Z130-0.1” (trade name, manufactured by Fluoro Technology Co., Ltd.) is used as a fluorine-containing coating agent on a SUS304 plate having a mirror surface as a mold for forming the cured coating layer (A), using a bar coater. Thus, a coating film forming mold having a fluorine-containing coating agent coating film was obtained. Next, this coating film forming mold was dried in a hot air drying oven at 60 ° C. for 10 minutes, and further allowed to stand at room temperature for 8 hours to obtain a SUS laminated mold whose surface was treated with fluorine.
• Example 6 The surface of the cured coating layer (A6) of the resin laminate (6 ′) obtained in the same manner as in Example 1 was subjected to corona treatment at a discharge amount of 135 W / m 2 .
• “Novec EGC1720” (trade name, manufactured by Sumitomo 3M Co., Ltd.) as a fluorine-containing coating agent was applied to the corona-treated surface using a bar coater so that the dry film thickness was 10 nm.
• a resin laminate (6 ′) having an agent coating was obtained.
• the resin laminate (6 ′) having a fluorine-containing coating agent coating film is dried in a hot air drying oven at 60 ° C. for 10 minutes, and is further allowed to stand at room temperature for 8 hours.
• the evaluation result of the cured film layer (A) of Example 6 shows the evaluation result on the fluorine-containing coating agent coating film. The evaluation results are shown in Table 1.
• Example 10 Comparative Example 4
• the cured coating layers (A10) and (A14) and the cured coating layers (B10) and (B10) were prepared in the same manner as in Example 1 except that the curable compositions (A) and (B) having the compositions shown in Table 1 were used. (B14) was obtained.
• EB050S ethylene-methyl acrylate copolymer
• Lexpearl EMA methyl acrylate unit content 24%, manufactured by Nippon Polyethylene Corporation
• a mixture of 68 parts of methyl methacrylate, 20 parts of isobornyl methacrylate, 3 parts of isobornyl acrylate, 8 parts of isobornyl acrylate, 8 parts of t-butyl methacrylate and 1 part of butyl acrylate is stirred and mixed with nitrogen gas. After bubbling, heating was started.
• the coated surface of the curable composition coating-coated methacrylic resin plate (A13) and the PET film “OX-50” (trade name, manufactured by Teijin DuPont Films Ltd.) are combined with the PET film “OX-”. Bonding and pressing with a press roll at a speed of 6 m / min so that the high smooth surface of 50 ”is in contact with the coated surface of the curable composition (A13), the cured coating layer (A13) of the curable composition The film thickness was adjusted to 18 ⁇ m.
• a methacrylic resin plate, a curable composition (A13) and a PET film were sequentially laminated for 1 minute to obtain a laminate. Thereafter, the obtained laminate was passed through a position 24 cm below the metal halide lamp with an output of 120 W / cm at a speed of 2.5 m / min to cure the curable composition (A13) to obtain a cured laminate. .
• the PET film was peeled from the cured laminate to obtain a laminated resin plate in which the cured coating layer (A13) was laminated on the methacrylic resin plate.
• the resin laminate on which the cured film of the present invention is formed is excellent in transparency, scratch resistance, surface hardness and impact resistance, and is therefore suitable for use by direct human contact.

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• 2014
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