WO2014208477A1 - (メタ)アクリル重合体、(メタ)アクリル樹脂組成物、(メタ)アクリル樹脂シート、(メタ)アクリル樹脂積層体及び複合シート - Google Patents
(メタ)アクリル重合体、(メタ)アクリル樹脂組成物、(メタ)アクリル樹脂シート、(メタ)アクリル樹脂積層体及び複合シート Download PDFInfo
- Publication number
- WO2014208477A1 WO2014208477A1 PCT/JP2014/066500 JP2014066500W WO2014208477A1 WO 2014208477 A1 WO2014208477 A1 WO 2014208477A1 JP 2014066500 W JP2014066500 W JP 2014066500W WO 2014208477 A1 WO2014208477 A1 WO 2014208477A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- meth
- acrylic resin
- monomer
- unit
- acrylic
- Prior art date
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—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
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
-
- 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
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
-
- 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
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
-
- 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
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
-
- 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
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- 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
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/106—Esters of polycondensation macromers
- C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
Definitions
- the present invention relates to a (meth) acrylic polymer, a (meth) acrylic resin composition, a (meth) acrylic resin sheet, a (meth) acrylic resin laminate, and a composite sheet.
- Transparent resins such as acrylic resins and polycarbonate resins are widely used as various materials such as industrial materials and building materials. Particularly in recent years, it has been used as a front plate for various displays such as CRTs, liquid crystal televisions, and plasma displays from the viewpoint of transparency and impact resistance.
- a dipping method As a method for producing such a resin sheet having various surface functions, for example, a dipping method may be mentioned.
- the dipping method has a problem of low productivity due to batch processing.
- UV laminate transfer method As another manufacturing method, after the functional layer formed on the base film is bonded to the surface to be transferred via the ultraviolet curable adhesive layer, and the adhesive layer is solidified by irradiating with ultraviolet rays (UV) And a method of peeling the base film and transferring the functional layer to the transfer surface (hereinafter referred to as “UV laminate transfer method”). Such a method is disclosed in Patent Document 1, for example.
- acrylic resin has high water absorption, and particularly when applied to the front plate of a display, there is a problem that shape change such as warpage due to water absorption is likely to occur.
- Patent Document 2 discloses a polymer obtained by polymerizing a polymerizable monomer containing methyl methacrylate, methyl methacrylate, a (meth) acrylic ester having a specific alicyclic hydrocarbon group, and a specific A mixture of two or more (meth) acrylic acid esters selected from the group consisting of (meth) acrylic acid esters having a straight chain or branched hydrocarbon group, and having a specific composition ratio and specific refractive index conditions
- a method for producing an acrylic resin plate by polymerizing acrylic syrup satisfying the above is described.
- An object of the present invention is a (meth) acrylic resin sheet excellent in low water absorption, heat resistance and transparency, and having good adhesion to a functional layer, and a (meth) acrylic polymer suitable for forming this resin sheet, and The object is to provide a (meth) acrylic resin composition.
- Another object of the present invention is a (meth) acrylic resin laminate in which a functional layer is laminated on the (meth) acrylic resin sheet, and the (meth) acrylic resin laminate is a surface layer of a thermoplastic resin substrate. It is in providing the composite sheet laminated
- Monomer (a) unit 4.5 to 7.5% by mass, Monomer (b) units of 0.3 to 3.2% by mass, Containing 89.3 to 95.2% by mass of monomer (c) units
- the monomer (a) unit is an acrylate unit having a hydrocarbon group having 1 to 11 carbon atoms and having one ethylenically unsaturated bond in the molecule
- the monomer (b) unit is a monomer unit having two or more ethylenically unsaturated bonds in the molecule
- the monomer (c) unit is a (meth) acrylic polymer (A) that is a (meth) acrylic acid ester unit other than the monomer unit.
- the (meth) acrylic polymer (A) 100 parts by mass and the olefin- (meth) alkyl acrylate copolymer (B) 0.002 to 0.7 parts by mass (meth) are contained.
- An acrylic resin composition is provided.
- a (meth) acrylic resin sheet containing the (meth) acrylic polymer (A) is provided.
- the (meth) acrylic resin sheet containing the said (meth) acrylic resin composition is provided.
- a (meth) acrylic resin laminate including the (meth) acrylic resin sheet and a functional layer laminated on at least one surface of the (meth) acrylic resin sheet.
- thermoplastic resin base material contains the thermoplastic resin base material and the said (meth) acrylic resin laminated body laminated
- thermoplastic resin substrate the (meth) acrylic resin laminate laminated on one surface of the thermoplastic resin substrate, and the functional layer laminated on the other surface of the thermoplastic resin substrate.
- a (meth) acrylic resin sheet excellent in low water absorption, heat resistance and transparency, and having good adhesion to a functional layer, and (meth) acrylic suitable for forming this resin sheet A polymer and a (meth) acrylic resin composition can be provided.
- stacked on this (meth) acrylic resin sheet and this (meth) acrylic resin laminated body laminated
- Composite sheets can be provided.
- FIG. 1 is a conceptual diagram showing a method for measuring a deflection ratio of a sheet test piece.
- the (meth) acrylic polymer (A) according to an embodiment of the present invention has an acrylic ester (a) unit having a hydrocarbon group having 1 to 11 carbon atoms and having one ethylenically unsaturated bond in the molecule.
- the content of the monomer (a) unit is in the range of 4.5 to 7.5% by mass.
- the content of the monomer (b) unit is in the range of 0.3 to 3.2% by mass
- the content of the monomer (c) unit is in the range of 89.3 to 95.2% by mass.
- Monomer (c) units include methyl methacrylate (c1) units, methacrylic acid ester (c2) units having an alicyclic hydrocarbon group having 6 to 20 carbon atoms, and methacrylic acid other than methacrylic acid ester (c2) units. It may contain an acid ester unit and a methacrylic acid ester (c3) unit having a hydrocarbon group having 3 to 10 carbon atoms.
- the monomer (c2) is preferably isobornyl methacrylate, and the monomer (c3) is preferably t-butyl methacrylate.
- the (meth) acrylic resin composition according to an embodiment of the present invention includes a (meth) acrylic polymer (A) and an olefin- (meth) acrylic acid alkyl copolymer (B).
- This composition may contain 0.002 to 0.7 parts by mass of the olefin- (meth) alkyl acrylate copolymer (B) with respect to 100 parts by mass of the (meth) acrylic polymer (A). preferable.
- the olefin- (meth) alkyl acrylate copolymer (B) is preferably an ethylene- (meth) alkyl acrylate copolymer (B-1), preferably an ethylene-alkyl acrylate copolymer (B-2). ) Is more preferable.
- the content of the alkyl acrylate unit in the ethylene-alkyl acrylate copolymer (B-2) is preferably in the range of 15 to 40% by mass.
- the (meth) acrylic resin sheet according to an embodiment of the present invention includes the above (meth) acrylic polymer (A) or (meth) acrylic resin composition.
- a (meth) acrylic resin laminate according to an embodiment of the present invention includes the above (meth) acrylic resin sheet and a functional layer laminated on at least one surface of the sheet. Functional layers may be laminated on both sides of this sheet.
- a composite sheet according to an embodiment of the present invention includes a thermoplastic resin base material and the (meth) acrylic resin laminate laminated on at least one surface of the thermoplastic resin base material.
- the (meth) acrylic resin laminate is laminated so that the surface of the (meth) acrylic resin sheet is in contact with the surface of the thermoplastic resin substrate.
- a (meth) acrylic resin laminate can be laminated on one surface of this thermoplastic resin substrate, and a functional layer can be laminated on the other surface.
- the thickness of the thermoplastic resin substrate is preferably in the range of 0.5 mm to 2 mm.
- the thickness of the (meth) acrylic resin sheet is preferably in the range of 0.03 mm to 0.2 mm.
- the functional layer in the (meth) acrylic resin laminate and the composite sheet is preferably a layer having at least one function selected from an antireflection function, an antiglare function, a hard coat function, an antistatic function and an antifouling function.
- the (meth) acrylic resin laminate and the composite sheet have a deflection ratio of 0. when left in an environment of 50 ° C. and a relative humidity of 90% for 24 hours and then in an environment of 23 ° C. and a relative humidity of 50% for 5 hours. It is preferably 2% or less, and the residual ratio of the functional layer is preferably 90% or more when a cross-cut peel test is performed in accordance with JIS K5600-5-6.
- Acrylic resin laminate and composite sheet including the same are suitable as an image display member used indoors and outdoors, and as a front plate of a display such as a mobile phone, a touch panel display, a solar cell protective plate, a portable information terminal, and a notebook personal computer. It is.
- the monomer (a) constituting the monomer (a) unit is an acrylate ester having a hydrocarbon group having 1 to 11 carbon atoms and having one ethylenically unsaturated bond in the molecule.
- the monomer (a) include the following monomers. Methyl acrylate, ethyl acrylate, isopropyl acrylate, t-butyl acrylate, i-butyl acrylate, n-butyl acrylate, cyclohexyl acrylate, bornyl acrylate, norbornyl acrylate, isobornyl acrylate, adamantyl acrylate, Dimethyl adamantyl acrylate, methyl cyclohexyl acrylate, norbornyl methyl acrylate, menthyl acrylate, fentyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, cyclodecyl acrylate, Acrylic acid esters such as 4-t-butylcyclohexyl acrylate and trimethylcyclohexyl acrylate;
- the monomer (b) constituting the monomer (b) unit is a monomer having two or more ethylenically unsaturated bonds in the molecule.
- the monomer (b) include the following monomers. 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, neopentyl glycol di (meth) ) Alkanediol di (meth) acrylate such as acrylate; diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di ( Polyoxyalkylene glycol di (meth) acrylates such as (meth) acrylate; polyfunctional polymerizable compounds having two or more ethylenically unsaturated bonds in the molecule such as divinylbenzene; At least one polycarboxylic acid and at least one poly
- alkanediol di (meth) acrylate is preferable from the viewpoint of heat resistance of the (meth) acrylic resin sheet of the present invention.
- (meth) acrylate means at least one selected from “acrylate” and “methacrylate”, and “(meth) acryl” is selected from “acryl” and “methacryl”.
- At least one means “(meth) acryloyloxy” means at least one selected from “acryloyloxy” and “methacryloyloxy”.
- the monomer (c) constituting the monomer (c) unit is a (meth) acrylic acid ester other than the monomer (a) and the monomer (b).
- monomer (c2) constituting the monomer (c2) unit include the following monomers.
- the monomer (c3) constituting the monomer (c3) unit include the following monomers.
- Methacrylic acid esters such as isopropyl methacrylate, t-butyl methacrylate, i-butyl methacrylate, and n-butyl methacrylate. Of these, t-butyl methacrylate is preferred because of its low water absorption and high heat resistance.
- the (meth) acrylic polymer (A) according to the embodiment of the present invention has an acrylic ester (a) unit of 4.5 to 7.5% by mass and a monomer (b) unit of 0.3 to 3.2% by mass. And a (meth) acrylic acid ester (c) copolymer containing 89.3 to 95.2% by mass of units.
- the adhesion between the functional layer described later and the (meth) acrylic polymer (A) can be improved.
- the content of the monomer (a) unit in the (meth) acrylic polymer (A) 7.5% by mass or less the heat resistance of the (meth) acrylic polymer (A) can be improved, The water absorption of the (meth) acrylic polymer (A) can be lowered, and as a result, the amount of deflection of the (meth) acrylic resin laminate and the composite sheet using the (meth) acrylic polymer (A) can be suppressed. it can.
- the lower limit of the content of the monomer (a) unit is preferably 4.6% by mass or more, and more preferably 5.0% by mass or more. Moreover, 7.1 mass% or less is preferable and, as for the upper limit of content of a monomer (a) unit, 7.0 mass% or less is more preferable.
- the content of the monomer (b) unit in the (meth) acrylic polymer (A) 0.3% by mass or more By making the content of the monomer (b) unit in the (meth) acrylic polymer (A) 0.3% by mass or more, the heat resistance of the (meth) acrylic polymer (A) can be improved, The water absorption of the (meth) acrylic polymer (A) can be lowered, and as a result, the amount of deflection of the (meth) acrylic resin laminate and the composite sheet using the (meth) acrylic polymer (A) can be suppressed. it can. By setting the content of the monomer (b) unit to 3.2% by mass or less, the adhesion between the functional layer and the (meth) acrylic polymer (A) can be improved.
- 0.4 mass% or more is preferable and, as for the lower limit of content of a monomer (b) unit, 0.5 mass% or more is more preferable. Moreover, 3.1 mass% or less is preferable and, as for the upper limit of content of a monomer (b) unit, 3.0 mass% or less is more preferable.
- the content of the monomer (c) unit is as follows: the monomer (a) unit and the monomer (B) It corresponds to the ratio of the remainder excluding the total content of units.
- the monomer (a) unit content is in the range of 4.5 to 7.5% by mass and the monomer (b) unit content is in the range of 0.3 to 3.2% by mass
- the content of the monomer (c) unit can be set in the range of 89.3 to 95.2% by mass.
- the monomer (a) unit content is in the range of 4.6 to 7.1% by mass and the monomer (b) unit content is in the range of 0.4 to 3.1% by mass.
- the content of the monomer (c) unit can be set in the range of 89.8 to 95.0% by mass.
- the monomer (a) unit content is in the range of 5.0 to 7.0 mass% and the monomer (b) unit content is in the range of 0.5 to 3.0 mass%
- the content of the monomer (c) unit can be set in the range of 90.0 to 94.5% by mass.
- the monomer (c) unit in the (meth) acrylic polymer (A) contains a monomer (c1) unit, a monomer (c2) unit, and a monomer (c3) unit, )
- the content of the monomer (c1) unit, monomer (c2) unit and monomer (c3) unit in the acrylic polymer (A) the following amounts are preferred.
- the content of the monomer (c1) unit in the (meth) acrylic polymer (A) is preferably 65 to 77% by mass.
- the content of the monomer (c1) unit in the (meth) acrylic polymer (A) is 65% by mass or more, the transparency of the (meth) acrylic resin sheet tends to be good, and the monomer (C1)
- the lower limit of the content of the monomer (c1) unit is more preferably 67% by mass or more, and further preferably 69% by mass or more.
- the upper limit of the content of the monomer (c1) unit is more preferably 75% by mass or less, and further preferably 74% by mass or less.
- the content of the monomer (c2) unit in the (meth) acrylic polymer (A) is preferably 10 to 20% by mass.
- the content of the monomer (c2) unit in the (meth) acrylic polymer (A) is preferably 10 to 20% by mass.
- the lower limit of the content of the monomer (c2) unit is more preferably 11% by mass or more, and further preferably 12% by mass or more. Further, the upper limit of the content of the monomer (c2) unit is more preferably 19% by mass or less, and further preferably 18% by mass or less.
- the content of the monomer (c3) unit in the (meth) acrylic polymer (A) is preferably 3 to 7% by mass.
- the content of the monomer (c3) unit in the (meth) acrylic polymer (A) is 3% by mass or more, the transparency of the (meth) acrylic polymer (A) tends to be good,
- the strength of the (meth) acrylic polymer (A) tends to be good.
- the lower limit of content of a monomer (c3) unit 4 mass% or more is more preferable.
- the upper limit of content of a monomer (c3) unit 6 mass% or less is more preferable.
- Examples of the form of the (meth) acrylic polymer (A) include powder and pellets.
- Examples of the method for producing the (meth) acrylic polymer (A) include a bulk polymerization method, a solution polymerization method, an emulsion polymerization method, and a suspension polymerization method.
- bulk polymerization is preferable from the viewpoint of the production cost of the (meth) acrylic polymer (A), the environmental load due to the use of a solvent, and the productivity.
- the method for producing the pellets of the (meth) acrylic polymer (A) includes, for example, a method of obtaining pellets by extruding the powder obtained by the above method, and JP-A-2000-26507. As in the above method, there is a method of obtaining pellets by bulk polymerization of a monomer mixture in a reactor and extruding while separating and removing unreacted monomers.
- polymerization format known formats such as radical polymerization and anionic polymerization can be used.
- radical polymerization initiator examples include the following. 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), etc.
- Azo-based polymerization initiator lauroyl peroxide, diisopropyl peroxydicarbonate, benzoyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxyneodecanoate t-hexylperoxypivalate
- Organic peroxide polymerization initiators such as
- the addition amount of the radical polymerization initiator is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the total amount of raw material monomers for obtaining the (meth) acrylic polymer (A).
- the polymerization temperature is preferably 40 ° C. or higher, more preferably 50 ° C. or higher.
- the polymerization temperature is preferably 180 ° C. or lower, and more preferably 150 ° C. or lower.
- Polymerization time is appropriately determined according to the progress of polymerization.
- various additives such as a chain transfer agent, an antioxidant, a stabilizer such as an ultraviolet absorber, a flame retardant, a dye, a pigment, and a release agent can be added as necessary.
- the addition amount of the chain transfer agent is preferably 0.001 to 0.015 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer (A).
- the amount of chain transfer agent added is 0.001 part by mass or more, and the deflection temperature under load of the (meth) acrylic polymer (A) when measured according to the edgewise method of JIS K 7191-1 is 103 ° C. or lower. There is a tendency, and the adhesion between the functional layer and the (meth) acrylic polymer (A) tends to be good.
- the addition amount of a chain transfer agent is 0.015 mass part or less, and it exists in the tendency for the heat resistance of a (meth) acrylic polymer (A) to become favorable.
- chain transfer agent examples include compounds having an —SH group at the terminal, such as terpinolene, ⁇ -methylstyrene dimer, n-dodecyl mercaptan, 1,2-ethanedithiol, 1,10-dimethylcaptodecane; Compounds having a structure in which two or more —OH groups of polyhydric alcohols such as mercaptan, 1,4-dimercapto-2,3-butanediol, 2,3-dimercapto-1-propanol are substituted with —SH groups; thioglycolic acid , 2-mercaptopropionic acid, 3-mercaptopropionic acid, thioglycerol, thioglycol, etc., a compound having one —SH group and at least one —OH group and COOH group in the molecule; ethylene glycol dithioglycolate , Trimethylolpropane tris ( ⁇ -thiopropionate), tri Methy
- the (meth) acrylic resin composition according to the embodiment of the present invention comprises a (meth) acrylic polymer (A) and an olefin- (meth) alkyl acrylate copolymer (B) (hereinafter referred to as “copolymer (B)” as appropriate. ”)).
- the copolymer (B) is a copolymer containing an olefin unit and an alkyl (meth) acrylate unit.
- Examples of the olefin that is a raw material of the olefin unit constituting the copolymer (B) include ethylene, propylene, isoprene, and butadiene.
- the olefin unit may be a single olefin unit or two or more olefin units.
- examples of the alkyl (meth) acrylate used as a raw material for the alkyl (meth) acrylate unit constituting the copolymer (B) include the following monomers.
- an ethylene- (meth) alkyl acrylate copolymer ( B-1) is preferred, ethylene-alkyl acrylate copolymer (B-2) is more preferred, and ethylene-methyl acrylate copolymer is still more preferred.
- These copolymers may be copolymers with acid anhydride monomers such as maleic anhydride and itaconic anhydride (copolymers further comprising units derived from acid anhydride monomers). . Further, these copolymers may be random copolymers or block copolymers.
- the content of the alkyl (meth) acrylate unit in the copolymer (B) is the solubility in the monomer mixture of the copolymer (B), the (meth) acrylic resin sheet or (meth) acrylic resin laminate formed 15 mass% or more is preferable from a viewpoint of the transparency of a body. Moreover, this content is preferably 40% by mass or less from the viewpoint of the transparency and impact resistance of the (meth) acrylic resin sheet or (meth) acrylic resin laminate.
- the ethylene-alkyl acrylate copolymer (B-2) is used as the copolymer (B)
- the ethylene-alkyl acrylate copolymer contains 15 to 40% by mass of alkyl acrylate units. Preferably it is.
- the copolymer (B) has good solubility in the monomer mixture, and the (meth) acrylic resin sheet or the (meth) acrylic resin laminate is transparent. Tend to be good. Moreover, when the alkyl acrylate unit is contained in an amount of 40% by mass or less, the transparency and impact resistance of the (meth) acrylic resin sheet or (meth) acrylic resin laminate tend to be good.
- the content of the copolymer (B) in the (meth) acrylic resin sheet and the content of the copolymer (B) in the (meth) acrylic resin composition forming the (meth) acrylic resin sheet are particularly (
- the (meth) acrylic resin sheet or the (meth) acrylic resin laminate containing the same is used as a protective plate or front plate for a display or the like, it is 0.002-0. 7 parts by mass is preferable, 0.005 to 0.5 parts by mass is more preferable, 0.01 to 0.5 parts by mass is further preferable, and 0.01 to 0.1 parts by mass is particularly preferable.
- the content of the copolymer (B) is 0.002 parts by mass or more, the impact resistance of the (meth) acrylic resin sheet or the (meth) acrylic resin laminate containing the copolymer can be improved, and 0.7 parts by mass below, the transparency of a (meth) acrylic resin sheet or a (meth) acrylic resin laminate including the same can be improved.
- the content of the copolymer (B) is preferably 0.005 parts by mass or less.
- the compound (C) represented by the following formula (1) can be contained in the (meth) acrylic polymer (A) according to the purpose.
- R 1 represents an alkyl group having 4 to 8 carbon atoms, a phenyl group or a phenyl group having a substituent, and X represents phosphorus
- Examples of the compound (C) include triphenylphosphine, tri-n-octylphosphine, tri-n-butylphosphine, tri (1,3,5-trimethylphenyl) phosphine and tri (1,3,5-tri Methoxyphenyl) phosphine.
- Examples of the substituent of the phenyl group include an alkyl group having 1 to 5 carbon atoms or an alkoxy group.
- the content of the compound (C) in the (meth) acrylic resin sheet is preferably 0.01 to 0.05 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer (A).
- the content of the compound (C) is 0.01 parts by mass or more, the adhesion between the (meth) acrylic resin sheet or (meth) acrylic resin laminate and the functional layer tends to be good, and 0.05 parts by mass below, it exists in the tendency for the light resistance of a (meth) acrylic resin sheet or a (meth) acrylic resin laminated body to become favorable.
- the (meth) acrylic polymer (A) can contain a release agent (D) for peeling from the mold depending on the purpose.
- a release agent (D) for peeling from the mold depending on the purpose.
- the release agent (D) include organic salts, and sodium dioctyl sulfosuccinate (AOT) (d-1) is preferable from the viewpoint of less template contamination.
- a phosphate ester compound (d-2) represented by the following formula (2) can be contained.
- n represents an integer of 1 to 3
- R represents an alkyl group having 1 to 4 carbon atoms
- the phosphoric acid ester compounds (d-2) are preferable in that the (meth) acrylic resin sheet can be easily peeled from the mold.
- the content of the release agent (D) in the (meth) acrylic resin sheet is preferably 0.005 to 1.0 part by mass, and 0.02 to 0 part per 100 parts by mass of the (meth) acrylic polymer (A). 0.5 parts by mass is more preferable, and 0.04 to 0.3 parts by mass is still more preferable.
- the content of the release agent (D) is 0.005 parts by mass or more, the (meth) acrylic resin sheet tends to be peelable from the mold, and the mold contamination is suppressed at 1.0 parts by mass or less. And a (meth) acrylic resin sheet excellent in appearance tends to be obtained.
- the (meth) acrylic resin sheet according to the embodiment of the present invention is a sheet obtained from the (meth) acrylic polymer (A) or the (meth) acrylic resin composition.
- the thickness of the (meth) acrylic resin sheet is preferably 0.2 mm to 15 mm.
- Examples of the method for producing the (meth) acrylic resin sheet include a casting polymerization method, an extrusion molding method, and an injection molding method. Among these, since a transparent resin sheet is obtained, the cast polymerization method is preferable particularly in applications requiring transparency such as optical applications.
- the casting polymerization method uses a mold formed by two plate-like bodies arranged opposite to each other at a predetermined interval and a sealing material arranged at the edge thereof, and a (meth) acrylic resin sheet is placed in the mold.
- a polymerizable raw material to be obtained is injected and polymerized to form a sheet, and the obtained sheet is peeled from the mold.
- the casting polymerization mold is not particularly limited, and a conventionally used mold can be used.
- Examples of the mold for obtaining a plate-shaped resin molded product include a cell casting mold and a continuous casting mold.
- a casting mold for cell casting for example, two plate-like bodies such as an inorganic glass plate, a chrome-plated metal plate, and a stainless steel plate are arranged to face each other at a predetermined interval, and a gasket is arranged on the edge thereof to form a plate-like body. And a sealed space formed by a gasket.
- a sealed space is formed by the opposing surfaces of a pair of endless belts that run at the same speed in the same direction and gaskets that run at the same speed as the endless belt on both sides. Things.
- Examples of the polymerizable raw material injected into the mold include the following raw material composition (1), raw material composition (2), or raw material composition (3).
- a copolymer (B), a compound (C), and a mold release agent (D) can be added to a raw material composition (1), a raw material composition (2), or a raw material composition (3).
- Raw material composition (1) a composition comprising a monomer mixture (1) having monomer (a), monomer (b) and monomer (c)
- Raw material composition (2) syrup (1) obtained by polymerizing a part of monomer mixture (1) having monomer (a), monomer (b) and monomer (c)
- a composition comprising, Raw material composition (3): a polymer obtained by polymerizing the first monomer mixture (2) having monomer (a), monomer (b) and monomer (c), A composition comprising syrup (2) obtained by dissolving in a second monomer mixture (2 ') having monomer (a), monomer (b) and monomer (c);
- the first monomer mixture (2) and the second monomer mixture (2 ′) may have the same composition or different compositions, and the composition of the resulting (meth) acrylic polymer (A) has a predetermined composition. What is necessary is just to become a composition.
- the above syrup (1) and syrup (2) are viscous liquids in which a polymer is dissolved in a monomer.
- the content of the polymer in the syrup (1) or syrup (2) is preferably 5 to 45% by mass.
- the content of the polymer in the syrup is 5% by mass or more, the polymerization time during cast polymerization tends to be shortened, and there is a tendency that appearance defects are less likely to occur in the (meth) acrylic resin sheet.
- the content of the polymer in the syrup is 45% by mass or less, the viscosity of the syrup tends to be appropriate, and the handleability of the syrup tends to be good.
- the polymerization rate of syrup is preferably as high as possible.
- the polymerization rate of syrup is preferably as low as possible.
- the content of the polymer in the syrup is preferably 5 to 45% by mass, more preferably 10 to 40% by mass.
- Examples of a method for adjusting the content of the polymer in the syrup within the range of 5 to 45% by mass include, for example, the above monomer mixture in a reactor equipped with a cooling pipe, a thermometer and a stirrer. After a predetermined amount of the composition containing (1) or the monomer mixture (2) is weighed in and heated with stirring, a polymerization initiator is added, and the polymerization is progressed while maintaining the predetermined temperature. And a cooling method.
- a polymerization inhibitor can be added as necessary to avoid coloring and spontaneous curing.
- polymerization inhibitor examples include hydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-4-methylphenol and 2,4-dimethyl-6-t-butylphenol. These can be used alone or in combination of two or more.
- Examples of the polymerization reaction mode of cast polymerization include radical polymerization and anionic polymerization.
- radical polymerization is preferred from the viewpoints of versatility of raw materials, easy management of production conditions, and simple production with general-purpose equipment.
- the same radical polymerization initiator and various additives as in the case of obtaining the (meth) acrylic polymer (A) can be added to the polymerizable raw material.
- the addition amount of the radical polymerization initiator is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the total amount of monomers.
- the polymerization temperature of the polymerizable raw material is preferably 40 ° C. or higher, more preferably 50 ° C. or higher. Further, the polymerization temperature of the polymerizable raw material is preferably 180 ° C. or lower, and more preferably 150 ° C. or lower.
- the polymerization time is appropriately determined according to the progress of polymerization curing.
- the (meth) acrylic resin sheet according to the embodiment of the present invention is produced by the casting polymerization method
- a raw material composition ( 1) and (2) are preferable, and the raw material composition (1) is more preferable.
- the raw material compositions (1) and (2) are preferable, and the raw material composition (2) is more preferable.
- the (meth) acrylic resin laminate according to the embodiment of the present invention is a laminate in which a functional layer described later is laminated on at least one surface of a (meth) acrylic resin sheet.
- the (meth) acrylic resin laminate preferably has a deflection ratio of 0.2% or less.
- the deflection ratio is 0.2% or less, the (meth) acrylic resin laminate tends to suppress appearance defects such as interference patterns without contacting the image display side.
- the deflection ratio is shown in FIG. 1 after the deflection test (after leaving in a high temperature and high humidity environment of 50 ° C. and 90% relative humidity for 24 hours and then in a normal environment of 23 ° C. and 50% relative humidity).
- the vertical displacement amount (bending amount: a) of the center portion of the sheet test piece with respect to the end portion of the sheet test piece (ends of the four sides of the fixed test piece) is obtained, and the value obtained by the following equation (deflection) It refers to the ratio of the deflection amount (a) to the long side (b) of the sheet test piece before the test.
- Deflection ratio (%) Deflection amount (a) ⁇ Long side of test piece (b) ⁇ 100
- the (meth) acrylic resin sheet and the functional layer of the (meth) acrylic resin laminate have a functional layer residual ratio of 90% or more when a cross-cut peel test is performed in accordance with JIS K5600-5-6. It is preferable to have adhesiveness.
- the residual ratio of the functional layer is 90% or more, there is a tendency that problems such as deterioration in image visibility due to film peeling can be suppressed when the functional layer is used as a protective plate of an image display device.
- the (meth) acrylic resin laminate preferably has a haze based on JIS K 7136 of 0.5% or less and a 50% impact fracture height based on JIS K 7211 in a falling ball test of 300 mm or more.
- Various functional layers include scratch resistance (hard coat function), antireflection, antiglare, antifouling (stain prevention function), antistatic, scattering prevention, adhesiveness, adhesiveness, softness, etc.
- a layer having at least one function can be given.
- the functional layer is preferably a layer having at least one function selected from an antireflection function, an antiglare function, a hard coat function, an antistatic function, and an antifouling function.
- a functional layer can be made into a single
- the functional layer can be a layer of a cured product of the curable composition, for example.
- a layer of a cured product has a hard coat function and can improve scratch resistance.
- curable composition examples include a thermosetting composition and an active energy ray curable composition.
- thermosetting composition examples include a radical polymerizable composition such as a vinyl monomer and a condensation polymerization curable composition such as an alkoxysilane and an alkylalkoxysilane. These can be used alone or in combination of two or more.
- Examples of the active energy ray when using the active energy ray-curable composition include an electron beam, radiation, and ultraviolet rays.
- An active energy ray curable composition can be used individually by 1 type or in combination of 2 or more types.
- an ultraviolet curable composition is preferable from the viewpoint of productivity and physical properties of the (meth) acrylic resin laminate.
- the ultraviolet curable composition include a composition containing a compound having at least two (meth) acryloyloxy groups in the molecule and a photoinitiator (ultraviolet polymerization initiator).
- Examples of the compound having at least two (meth) acryloyloxy groups in the molecule include the same monomers as the monomer (b) and the following compounds. From esterified product obtained from 1 mol of polyhydric alcohol and 2 mol or more of (meth) acrylic acid or derivative thereof, and from polyhydric alcohol, polyvalent carboxylic acid or anhydride thereof and (meth) acrylic acid or derivative thereof The esterified product obtained.
- esterified product obtained from 1 mol of polyhydric alcohol and 2 mol or more of (meth) acrylic acid or a derivative thereof include the following compounds. Trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaglycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerol tri (meth) acrylate, di Pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (met) acryl
- Examples of the combination of the polyhydric alcohol, the polyvalent carboxylic acid or its anhydride, and (meth) acrylic acid or its derivative include the following combinations. 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 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 / Trimethylolethane / (meth) acrylic acid, adipic acid / trimethylolpropane / (meth) acrylic acid
- the compound having at least two (meth) acryloyloxy groups in the molecule include the following compounds. Trimerization of diisocyanates (for example, trimethylolpropane toluylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, trimethylhexamethylene diisocyanate, etc.
- diisocyanates for example, trimethylolpropane toluylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, trimethylhexamethylene diisocyanate
- Acrylic monomers having active hydrogen per mole of the resulting polyisocyanate for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-methoxypropyl (meth) acrylate, N -Methylol (meth) acrylamide, N-hydroxy (meth) acrylamide, 1,2,3-propanetrio 1,3-di (meth) acrylate, 3-acryloyloxy-2-hydroxypropyl (meth) acrylate, etc.) urethane (meth) acrylate obtained by reacting 3 mol or more; Tris (2-hydroxyethyl) Poly [(meth) acryloyloxyethylene] isocyanurates such as di (meth) acrylate or tri (meth) acrylate of isocyanuric acid; epoxy poly (meth) acrylate; and urethane poly (meth) acrylate.
- photoinitiator used in the ultraviolet curable composition include the following compounds. Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, acetoin, butyroin, toluoin, benzyl, benzophenone, p-methoxybenzophenone, 2,2-diethoxyacetophenone, ⁇ , ⁇ -dimethoxy- ⁇ -phenyl Acetophenone, methylphenylglyoxylate, ethylphenylglyoxylate, 4,4'-bis (dimethylamino) benzophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenylpropane-1 A carbonyl compound such as --one; a sulfur compound such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; and 2,4,6
- the thickness of the functional layer is preferably 1 to 100 ⁇ m, more preferably 1 to 30 ⁇ m from the viewpoint of the surface hardness and appearance of the (meth) acrylic resin laminate.
- Examples of the method for applying the curable composition on the surface of the (meth) acrylic resin sheet include a casting method, a gravure coating method, a reverse gravure coating method, a vacuum slot die coating method, a roller coating method, a bar coating method, and a spraying method.
- Examples thereof include a coating method, an air knife coating method, a spin coating method, a flow coating method, a curtain coating method, a film cover method (for example, a UV laminate transfer method), and a dipping method.
- the film cover method is preferable in that the obtained coating film has few foreign matter defects and good surface smoothness.
- a cover film is bonded to a (meth) acrylic resin sheet via a curable composition.
- a step of forming a film laminate formation step of a laminate before curing
- a step of curing a curable composition to form a functional layer formation step of a laminate after curing
- peeling off the cover film (meth) acrylic resin The manufacturing method which has the process of obtaining a laminated body is mentioned.
- a curable composition can be applied to one side of a (meth) acrylic resin sheet, and a cover film can be bonded to the applied surface to form a film laminate.
- a functional layer that can be peeled is formed in advance on the surface of the cover film, and the cover film with the functional layer and the (meth) acrylic resin sheet are bonded together, and then the cover film is peeled off, so that the (meth) acrylic resin sheet side
- the functional layer is transferred to the (meth) acrylic resin laminate.
- an active energy ray transmissive film is used, and a known film can be used. Moreover, if it is a film which has peelability with respect to a functional layer, if a peelability is inadequate, you may provide a peeling layer on the surface of a cover film.
- the active energy ray permeable film examples include synthetic resin films such as polyethylene terephthalate film, polypropylene film, polycarbonate film, polystyrene film, polyamide film, polyamideimide film, polyethylene film, and polyvinyl chloride film; Cellulosic films; film-like materials such as cellophane paper, glassine paper, western paper, and Japanese paper; and composite film-like materials and composite sheet-like materials containing two or more of these films. Moreover, what provided the peeling layer in these films and composite film-like materials is mentioned.
- the thickness of the active energy ray transmissive film is preferably 4 to 500 ⁇ m. By setting the thickness of the active energy ray transmissive film to 4 to 500 ⁇ m, a transfer film free from wrinkles and cracks tends to be obtained.
- the lower limit of the thickness of the active energy ray transmissive film is preferably 4 ⁇ m or more, more preferably 12 ⁇ m or more, and further preferably 30 ⁇ m or more.
- the upper limit value of the thickness of the active energy ray transmissive film is preferably 500 ⁇ m or less, more preferably 150 ⁇ m or less, and still more preferably 120 ⁇ m or less.
- release agent for forming the release layer known release agents such as polymers and waxes can be appropriately selected and used.
- the release layer for example, paraffin wax; acrylic, urethane, silicon, melamine, urea, urea-melamine, cellulose, benzoguanamine, and the like; and at least one surfactant A coating in which seeds are dissolved in an organic solvent or water is applied onto a cover film by a normal printing method such as gravure printing, screen printing, or offset printing, and dried (thermosetting resin, ultraviolet curable resin, Examples of the method include a method of forming a curable coating film such as an electron beam curable resin or a radiation curable resin by curing.
- the thickness of the release layer is preferably about 0.1 to 3 ⁇ m. If the release layer is too thin, it tends to be difficult to peel off. Conversely, if the release layer is too thick, it tends to peel off too much, and the layers on the cover film tend to be detached before transfer.
- the antireflection layer has a reflected light of the (meth) acrylic resin laminate surface of 20% or less of incident light, preferably 10% or less, more preferably 5 %, It may be made of any material as long as it is a layer having a function of suppressing the content to less than or equal to%.
- a method of forming a laminated structure of films having two or more different refractive indexes can be cited.
- the refractive index of each film is, for example, the refractive index of the outermost surface facing air is about 1.3 to 1.5.
- a laminated structure of a low refractive index layer and a high refractive index layer having a refractive index of 1.6 to 2.0 existing on the (meth) acrylic resin sheet side is preferable. If it is this range, it exists in the tendency which can fully suppress the reflected light of incident light.
- the film thickness of the low refractive index layer and the high refractive index layer is not particularly limited, but is preferably 50 nm or more, and more preferably 70 nm or more. Moreover, 200 nm or less is preferable and 150 nm or less is more preferable. When the film thickness is within this range, reflected light having a visible wavelength tends to be sufficiently suppressed.
- the low refractive index layer preferably has a refractive index of about 1.3 to 1.5.
- the low refractive index layer include a siloxane bond-based layer made of a condensation polymerization curable compound such as alkoxysilane or alkylalkoxysilane, and specific examples thereof include a part of the siloxane bond of a siloxane-based resin. Examples thereof include those formed from a compound substituted with a hydrogen atom, a hydroxyl group, an unsaturated group, or an alkoxyl group.
- 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.
- colloidal silica is a colloidal solution in which at least one kind of fine particles selected from porous silica and non-porous silica is dispersed in a dispersion medium.
- 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 is 1.20 to 1.40, which is lower than that of ordinary silica 1.45 to 1.47.
- porous silica as colloidal silica.
- the colloidal silica by which the surface was processed with the silane coupling agent can be used as needed.
- the high refractive index layer preferably has a refractive index of about 1.6 to 2.0.
- Examples of the high refractive index layer include metal oxide films obtained by condensing metal alkoxide after hydrolysis.
- Examples of the metal alkoxide include those represented by the following formula (3).
- M represents a metal
- R represents a hydrocarbon group having 1 to 5 carbon atoms
- m represents the valence (3 or 4) of the metal 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 alkoxides include titanium methoxide, titanium ethoxide, titanium n-propoxide, titanium isopropoxide, titanium n-butoxide, titanium isobutoxide, aluminum ethoxide, aluminum isopropoxide, aluminum butoxide, aluminum Examples include t-butoxide, tin t-butoxide, zirconium ethoxide, zirconium n-propoxide, zirconium isopropoxide and zirconium n-butoxide.
- a high refractive index metal oxide such as ZrO 2 , TiO 2 , NbO, ITO, ATO, SbO 2 , in 2 O 3, that at least one kind of fine particles selected from SnO 2 and ZnO is dispersed is preferable.
- high refractive index metal oxide fine particles are dispersed in an ultraviolet curable composition for forming a hard coat layer.
- the cured product can be used.
- 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. Is mentioned.
- an adhesive layer and a hard coat layer on the (meth) acrylic resin sheet side of the antireflection layer.
- the adhesive layer By forming the adhesive layer, the adhesion between the antireflection layer and the (meth) acrylic resin sheet becomes good, and by forming the hard coat layer, the surface hardness of the antireflection layer becomes good.
- Anti-glare layer When laminating an anti-glare layer having an anti-glare function as a functional layer, a method of forming fine irregularities on the surface of the anti-glare layer and adding light diffusing fine particles into the string layer to diffuse external light by internal scattering Reflection of outside light can be suppressed by at least one of the methods.
- Examples of the method for forming a functional layer having an antiglare layer include the following methods.
- an ultraviolet curable composition for forming a hard coat layer described above is applied to an active energy ray transmissive film having a fine uneven shape and then cured to obtain a film having a hard coat layer formed thereon. Then, after laminating this film so that the surface of the hard coat layer contacts the surface of the (meth) acrylic resin sheet, the surface of the (meth) acrylic resin sheet is peeled off from the active energy ray permeable film. It is possible to obtain a laminate in which an antiglare layer having a fine uneven surface is laminated.
- an adhesive can be used as necessary.
- a mold release agent can be added in a hard-coat layer as needed.
- Examples of a 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, and a coating on the surface of the smooth active energy ray permeable film.
- corrugated shape by a method is mentioned.
- Examples of a method for forming an uneven shape on the surface of the active energy ray permeable film include, for example, a method of kneading particles in a resin for forming an active energy ray permeable film, and a resin for forming an active energy ray permeable film.
- corrugated surface in the state heated more than the glass transition temperature is mentioned.
- Examples of a method for imparting a concavo-convex shape to a smooth active energy ray permeable film surface by a coating method include, for example, a method of applying an antiglare coating agent, and a curable composition having an active energy ray permeable film and a fine concavo-convex surface.
- a method for applying an antiglare coating agent and a curable composition having an active energy ray permeable film and a fine concavo-convex 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 function of the anti-smudge layer may be water repellency or oil repellency and may be hydrophilic or oleophilic, but water repellency from the viewpoint of easy removal of dirt. Or it is preferable to have oil repellency.
- a compound having at least two (meth) acryloyloxy groups in the molecule, a (meth) acrylate having a fluorine atom, and an ultraviolet polymerization initiator are used as a raw material for forming a stain-proofing layer having water repellency or oil repellency. It is preferable from a viewpoint of productivity to use the ultraviolet curable composition containing.
- the compound having at least two (meth) acryloyloxy groups in the molecule the above-mentioned compound having two (meth) acryloyloxy groups can be used.
- the ultraviolet polymerization initiator the aforementioned ultraviolet polymerization initiator can be used.
- Fluorine atom-containing (meth) acrylate is an essential component for developing the water / oil repellency (antifouling property) of the water repellent layer.
- the (meth) acrylate having a fluorine atom a known (meth) acrylate having a fluorine atom can be used.
- Examples of commercially available (meth) acrylates having a fluorine atom include “Biscoat 17F” (trade name) manufactured by Osaka Organic Chemical Industry, which is heptadecane fluorodecyl acrylate, and Kyoeisha Chemical Co., Ltd., which is perfluorooctylethyl acrylate.
- Light acrylate FA-108 (trade name) manufactured by Co., Ltd., 1,10-bis (meth) acryloyloxy-2,2,3,3,4,4,5,5,6,6,7,7 , 8, 8, 9, 9-hexadecafluorodecane "16-FDA” (trade name) manufactured by Kyoeisha Chemical Co., Ltd.
- a (meth) acrylate having a perfluoropolyether group is preferable from the viewpoint of improving the water / oil repellency of the antifouling layer.
- Examples of commercially available (meth) acrylates having a perfluoropolyether group include “OPTOOL DAC” (trade name) manufactured by Daikin Industries, Ltd., “EXP RS-503” and “EXP RS-” manufactured by DIC Corporation. 751-k ”.
- Fluorine atom-containing (meth) acrylates can be used alone or in combination of two or more.
- the addition amount of the (meth) acrylate having a fluorine atom is preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the compound having at least two (meth) acryloyloxy groups in the molecule.
- the addition amount of the (meth) acrylate having a fluorine atom is 0.1 parts by mass or more, the water / oil repellency of the antifouling layer tends to be sufficient.
- the addition amount of the (meth) acrylate having a fluorine atom is 2 parts by mass or less, and the curability and transparency of the antifouling layer tend to be good.
- the addition amount of the ultraviolet polymerization initiator is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the compound having at least two (meth) acryloyloxy groups in the molecule.
- the film thickness of the antifouling layer is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more. Further, the film thickness of the antifouling layer is preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less. When the film thickness is in the above range, a stain preventing layer having sufficient surface hardness and transparency can be obtained, the film is less warped by the stain preventing layer, and the appearance tends to be good.
- the (meth) acrylate having a fluorine atom in the ultraviolet curable composition described above has a low surface tension, it tends to gather at an air interface having a lower surface tension than an active energy ray transmissive film having a relatively high surface tension. is there. Therefore, when the antifouling layer is laminated on the surface of the (meth) acrylic resin sheet by a transfer method, more (meth) acrylate having fluorine atoms is present on the (meth) acrylic resin sheet (A) side (hereinafter referred to as “ Therefore, the water / oil repellency of the antifouling layer of the surface layer of the obtained resin laminate tends to be insufficient.
- a film having fluorine atoms is formed on the active energy ray permeable film, and on that, It is preferable to form a stain prevention layer.
- a film having fluorine atoms can be obtained by applying a fluorine-containing coating agent containing a known fluorine-containing compound and an organic solvent on the film, and then volatilizing the organic solvent.
- a fluorine-containing compound represented by the following formula (4) is preferable in that a film having a low surface tension can be formed.
- Rf represents an organic functional group having a fluorine atom, and R represents an alkyl group having 1 to 3 carbon atoms.
- the fluorine-containing compound contained in the above-mentioned fluorine-containing coating agent is a component for forming a film described later having a low surface tension and high water and oil repellency on the film surface.
- Rf is preferably a perfluoroalkyl group or a perfluoropolyether group in terms of oil repellency and adhesion to the film.
- the carbon number of the perfluoroalkyl group is preferably in the range of 2-16.
- X represents a fluorine atom
- Y and Z each independently represent a fluorine atom or a trifluoromethyl group
- a to h are each independently an integer
- a is an integer from 1 to 16
- c is from 0 to 5
- B, d, e, f and g are integers from 0 to 200
- h is an integer from 0 to 16.
- Fluorine-containing compounds can be used alone or in combination of two or more.
- the fluorine-containing compound is preferably contained in an amount of 0.02 to 0.2% by mass in the fluorine-containing coating agent from the viewpoint of obtaining a film having high water and oil repellency.
- the organic solvent contained in the fluorine-containing coating agent those having excellent compatibility with the fluorine-containing compound can be used. Moreover, the organic solvent contained in the fluorine-containing coating agent is used for controlling the viscosity, the drying speed, and the film thickness of the coating film of the fluorine-containing coating agent.
- the film thickness of the coating having fluorine atoms is preferably 2 nm or more, and more preferably 5 nm or more. Further, the film thickness of the film having fluorine atoms is preferably 20 nm or less, and more preferably 15 nm or less. When the film thickness is in the above range, the appearance is good and there is a tendency that an effective film for forming the antifouling layer can be obtained.
- organic solvent examples include non-fluorine solvents such as hydrocarbon solvents and fluorine-containing solvents, but fluorine-containing solvents are preferable in terms of excellent compatibility with fluorine-containing compounds.
- Non-fluorine solvents include, for example, ketones such as methyl ethyl ketone, acetone, and methyl isobutyl ketone; monohydric alcohols such as ethanol, 1-propanol, 2-propanol, butanol, 1-methoxy-2propanol, ethylene glycol, diethylene glycol, propylene Alcohols such as polyhydric alcohols such as glycol; 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; toluene, xylene and the like And amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.
- ketones such as methyl ethyl ketone, acetone, and methyl isobutyl ketone
- fluorine-containing solvent examples include fluorine-containing alcohols, fluorine-containing ethers, and ditrifluoromethylbenzene.
- the organic solvent contained in the fluorine-containing coating agent can be used alone or in combination of two or more.
- the fluorine-containing coating agent is prepared by mixing the necessary amounts of the fluorine-containing compound and organic solvent and adjusting the concentration and viscosity as appropriate, and using a commercially available product in which the fluorine-containing compound and organic solvent are already mixed. Any method of adding an organic solvent as necessary may 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.
- the content of the fluorine-containing compound can be adjusted by appropriately adding an organic solvent.
- Examples of the method for applying the fluorine-containing coating agent to the film surface include the same method as the method for forming the antireflection layer.
- a method for forming a film having a fluorine atom for example, it can be obtained by applying a fluorine-containing coating agent on a film and then carrying out a drying treatment for volatilizing an organic solvent.
- the fluorine-containing coating agent Since the fluorine-containing coating agent has a low surface tension and the film surface easily repels the fluorine-containing coating agent at the time of application, it is preferably applied by a film cover method.
- the fluorine-containing coating agent is anaerobic from which polymerization is not hindered by oxygen or the like from the viewpoint of improving the scratch resistance of the antifouling layer, and from the viewpoint of preventing mixing of bubbles, dust, etc. that cause defective finishes. It is preferable to cure in an atmosphere.
- the resulting film containing fluorine atoms has low surface tension and high water and oil repellency, so when transferring the antifouling layer, the (meth) acrylate containing fluorine atoms contained in the fluorine-containing coating agent contains fluorine. It becomes easy to orient in the surface layer of the coating film side of the coating film of the coating agent, and the water / oil repellency of the antifouling layer on the resulting (meth) acrylic resin laminate is improved.
- the contact angle of water on the surface of the antifouling layer on the (meth) acrylic resin laminate is preferably 100 ° or more, and more preferably 105 ° or more.
- fluorine-containing coating agent examples include those that are cured with active energy rays such as electron beams, radiation, and ultraviolet rays.
- an arbitrary surface of another active energy ray transmissive film as a cover film and a coating surface of the ultraviolet curable composition of the active energy ray transmissive film coated with the ultraviolet curable composition described above are made to face each other.
- a press roll By pressing with a press roll, a laminate in which an active energy ray transmissive film, a film having fluorine atoms, an ultraviolet curable composition coating film, and a cover film are sequentially laminated is formed.
- the laminate is irradiated with ultraviolet rays using an ultraviolet irradiation device through the film from the cover film surface side to cure the ultraviolet curable composition.
- the holding time is preferably 0.5 to 5 minutes considering that the (meth) acrylate having fluorine atoms is oriented on the surface side of the coating film having fluorine atoms in the ultraviolet curable composition.
- the cover film is peeled off to obtain a laminated film on which the antifouling layer is laminated.
- Antistatic layer The case where an antistatic layer having an antistatic function is laminated as a functional layer will be described below.
- the antistatic layer uses an ultraviolet curable composition for an antistatic layer containing a compound having at least two (meth) acryloyloxy groups in the molecule, an antistatic component and an ultraviolet polymerization initiator. preferable.
- the compound having at least two (meth) acryloyloxy groups in the molecule the above-mentioned compound having two (meth) acryloyloxy groups can be used.
- the ultraviolet polymerization initiator the aforementioned ultraviolet polymerization initiator can be used.
- the antistatic component examples include an electron conductive organic compound, conductive particles, and an ion conductive organic compound.
- an antistatic component it is less susceptible to environmental changes, has a stable conductive performance, and expresses a good conductive performance even in a low-humidity environment.
- it is an electron conductive type such as a ⁇ -conjugated conductive organic compound or conductive fine particles.
- the antistatic component is preferred.
- Examples of the ⁇ -conjugated conductive organic compound include aliphatic conjugated polyacetylene, aromatic conjugated poly (paraphenylene), heterocyclic conjugated polypyrrole, polythiophene, polythiophene conductive polymer, and heteroatom-containing conjugate. And poly (phenylene vinylene) of mixed conjugated system.
- polythiophene-based conductive polymers are preferable from the viewpoint of transparency of the antistatic layer.
- Examples of conductive fine particles include carbon-based, metal-based, metal oxide-based, and conductive coating-based various particles.
- Examples of the carbon-based fine particles include carbon powders such as carbon black, ketjen black, and acetylene black, carbon fibers such as PAN-based carbon fibers and pitch-based carbon fibers, and carbon flakes of pulverized expanded graphite products.
- metal-based fine particles examples include metals such as aluminum, copper, gold, silver, nickel, chromium, iron, molybdenum, titanium, tungsten, and tantalum, and powders of alloys containing these metals, metal flakes, iron, copper, Examples thereof include metal fibers such as stainless steel, silver-plated copper, and brass.
- metal oxide fine particles examples include tin oxide, tin oxide doped with antimony (ATO), indium oxide, indium oxide doped with tin (ITO), zinc oxide, zinc oxide doped with aluminum, zinc antimonate, Fine particles such as antimony pentoxide are listed.
- the conductive coated fine particles include the surface of various fine particles such as titanium oxide (spherical, needle-shaped), potassium titanate, aluminum borate, barium sulfate, mica, silica and the like, and antistatic components such as tin oxide, ATO, and ITO.
- Resin beads such as polystyrene, acrylic resin, epoxy resin, polyamide resin, polyurethane resin surface-treated with metal such as conductive fine particles coated with gold, gold, nickel and the like.
- Suitable conductive fine particles include, for example, metal fine particles such as gold, silver, silver / palladium alloy, copper, nickel, and aluminum, and metals such as tin oxide, ATO, ITO, zinc oxide, and zinc oxide doped with aluminum. Examples thereof include oxide-based fine particles.
- the primary particle mass average particle diameter of the conductive fine particles is preferably 1 nm or more from the viewpoint of the conductivity of the antistatic layer. Moreover, the mass average particle diameter of the primary particles of the conductive fine particles is preferably 200 nm or less, more preferably 150 nm or less, still more preferably 100 nm or less, and particularly preferably 80 nm or less, from the viewpoint of the transparency of the antistatic layer.
- the mass average particle diameter of the conductive fine particles can be measured by a light scattering method or an electron micrograph.
- the addition amount of the ultraviolet polymerization initiator is preferably 0.1 parts by mass or more with respect to 100 parts by mass of the ultraviolet curable composition for the antistatic layer from the viewpoint of curability by ultraviolet irradiation, and the antistatic layer has a good color tone. From the viewpoint of maintenance, the amount is preferably 10 parts by mass or less with respect to 100 parts by mass of the ultraviolet curable composition for an antistatic layer.
- various additives such as a slip improver, a leveling agent, inorganic fine particles, and a light stabilizer (such as an ultraviolet absorber and HALS) can be added to the ultraviolet curable composition for the antistatic layer.
- the amount added is preferably 10 parts by mass or less with respect to 100 parts by mass of the ultraviolet curable composition for an antistatic layer.
- the thickness of the antistatic layer is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more.
- the film thickness of the antistatic layer is preferably 10 ⁇ m or less, more preferably 7 ⁇ m or less. When the film thickness of the antistatic layer is within the above range, it has sufficient surface hardness, antistatic performance and transparency, and the (meth) acrylic resin laminate tends to have little warpage and good appearance.
- the surface resistance value of the antistatic layer, (meth) from the viewpoint of antistatic property of the acrylic resin laminate preferably 10 10 ⁇ / ⁇ or less, more preferably 10 8 ⁇ / ⁇ or less.
- Examples of the method for forming the antistatic layer include the same method as the method for forming the antireflection layer.
- the functional layer can be laminated with the (meth) acrylic resin sheet via an adhesive layer as necessary.
- Examples of the resin forming the adhesive layer include (meth) acrylic resin, chlorinated olefin resin, vinyl chloride-vinyl acetate copolymer, maleic acid resin, chlorinated rubber resin, cyclized rubber resin, polyamide resin, and the like.
- examples thereof include thermoplastic resins such as resins, coumarone indene resins, ethylene-vinyl acetate copolymers, polyester resins, polyurethane resins, styrene resins, butyral resins, rosin resins, and epoxy resins.
- the above thermoplastic resin is preferably a resin composition in which at least one resin selected from a butyral resin, a rosin resin and an epoxy resin is mixed with a polyamide resin.
- the thermoplastic resin may be a resin composition in which at least one resin selected from a butyral resin, a rosin resin, and an epoxy resin is mixed with a polyurethane resin.
- a polyamide resin and a polyurethane resin may be used. It is good also as a resin composition which mixed at least 1 sort (s) of resin chosen from butyral resin, rosin-type resin, and epoxy-type resin into this mixture. In any case, there is a tendency that an adhesive layer having good adhesiveness can be obtained even at a low temperature.
- Examples of the method for forming the adhesive layer include the same method as the method for forming the antireflection layer.
- the composite sheet according to the embodiment of the present invention has a thermoplastic resin substrate and a (meth) acrylic resin so that the surface of the (meth) acrylic resin sheet of the (meth) acrylic resin laminate is in contact with one surface of the thermoplastic resin substrate. It is a sheet in which a laminate is laminated. Another (meth) acrylic resin laminate may be laminated on the other surface (opposite surface) of the thermoplastic resin substrate. In that case, the surface of the (meth) acrylic resin sheet of the (meth) acrylic resin laminate contacts the surface of the thermoplastic resin substrate.
- stacked on both sides of the thermoplastic resin base material may have the mutually same structure, or may have a mutually different structure. Moreover, you may laminate
- thermoplastic resin base material examples include aromatic vinyl monomer unit-containing resins such as polystyrene and styrene-methyl methacrylate copolymer, olefin resins such as cyclic polyolefin, polycarbonate resins such as polycarbonate, and polycarbonate and different materials.
- aromatic vinyl monomer unit-containing resins such as polystyrene and styrene-methyl methacrylate copolymer
- olefin resins such as cyclic polyolefin
- polycarbonate resins such as polycarbonate
- polycarbonate and different materials A multilayer material is mentioned.
- the thickness of the thermoplastic resin substrate and the (meth) acrylic resin sheet in the composite sheet may be in the range of 0.5 mm to 2 mm from the viewpoint of suppressing warpage and maintaining high pencil hardness.
- the thickness of the (meth) acrylic resin sheet is preferably in the range of 0.03 mm to 0.2 mm.
- the deflection ratio of the composite sheet is preferably 0.2% or less.
- the composite sheet tends to be able to suppress appearance defects such as interference patterns without contacting the image display side.
- the deflection rate is a value obtained in the same manner as the above-described deflection rate.
- the (meth) acrylic resin sheet and the functional layer of the composite sheet have adhesion that the residual rate of the functional layer is 90% or more when a cross-cut peel test is performed in accordance with JIS K5600-5-6. It is preferable.
- the residual ratio of the functional layer is 90% or more, there is a tendency that problems such as deterioration in image visibility due to film peeling can be suppressed when the functional layer is used as a protective plate of an image display device.
- the composite sheet preferably has a haze based on JIS K 7136 of 0.5% or less and a 50% impact fracture height based on JIS K 7211 in a falling ball test of 300 mm or more.
- E / MA copolymer ethylene-methyl acrylate copolymer (methyl acrylate unit content: 24 mass%)
- MMA methyl methacrylate
- IBXMA isobornyl methacrylate
- IBXA isobornyl acrylate
- TBMA t-butyl methacrylate
- BA n-butyl acrylate
- NPG neopentyl glycol dimethacrylate
- HPP perhexyl PV (t-hexyl peroxypivalate, purity 70% by mass)
- PBPV perbutyl PV (t-butyl peroxypivalate, purity 70% by mass)
- AOT sodium dioctyl sulfosuccinate
- urethane (meth) acrylate 1 3 mol of 3-acryloyloxy-2-hydroxypropyl (meth) acrylate is reacted per mol of polyisocyanate obtained by trimerization of
- test piece Place the test piece on the support base so that the center of the hole on the support base matches the center of the test piece, fix the left and right sides of the test piece to the support base with cellophane tape, and test the stainless steel ball Dropped into the center of the piece.
- the drop height was changed in units of 25 mm, the number of test pieces at each drop height was 20, and the height at which 50% or more of the test pieces were cracked (50% impact fracture height) was determined.
- Specimen size Square with a side of 50 mm Support base size: 5 mm thick acrylic plate with a circular hole with a diameter of 20 mm Falling ball size: Stainless steel ball (sphere diameter 20.0 mm ⁇ , mass 18.5 g) Temperature of measurement atmosphere: 23 ° C Relative humidity of measurement atmosphere: 50% The standing time in the measurement atmosphere of the test piece before the measurement: 24 hours or more.
- a fixing jig (fixing frame) was bonded to the center of the glass base using a double-sided tape.
- a test piece of a predetermined size was attached to the central portion of the fixing jig using a double-sided tape to produce a sample for measuring water absorption displacement.
- the obtained sample for measuring water absorption displacement is kept in a predetermined high temperature and high humidity environment for 24 hours, and further left in a predetermined normal environment for 5 hours, and then a laser displacement meter (LK-085) manufactured by Keyence Corporation is used.
- the amount of deflection (amount of water absorption) in the vertical direction at the center of the sample was measured.
- the amount of deflection was measured by how much the center of the sheet test piece was displaced in the vertical direction with respect to the four corners of the sheet test piece.
- the displacement to the glass base side is plus, and the displacement to the opposite side is minus.
- -Test piece size 45mm length and 65mm width
- Fixing jig a rectangular frame having a width of 5 mm, the short side outside the frame is 45 mm, the long side outside the frame is 65 mm, the short side inside the frame is 35 mm, and the long side inside the frame is 55 mm, 3 mm thick metal frame, -Base: glass plate with a length of 80 mm, a width of 80 mm, and a thickness of 5 mm-Double-sided tape: Double-sided tape manufactured by 3M Corporation with a width of 5 mm
- peeling of 25 square grids was conducted at 4 locations in accordance with JIS K5600-5-6. The number of cells that remained was calculated.
- Example 1 Two glass plates (length 300 mm, width 300 mm, thickness 5 mm) were made to face each other, and the edges thereof were sealed with a soft polyvinyl chloride gasket to produce a casting polymerization mold.
- MMA 28.7 parts, BA 3 parts and NPG 0.3 parts were added to 68 parts of the original syrup 1 to obtain diluted syrup, and 0.08 parts of PBPV, 0.03 parts of triphenylphosphine (compound (C)) and AOT. 0.08 part of (release agent (D)) was added to obtain a polymerizable raw material.
- the above-mentioned polymerizable raw material was injected into the mold, and the distance between the opposing glass plates was adjusted to 1.6 mm.
- this mold was heated in a water bath at 84 ° C. for 30 minutes, and further heated in an air furnace at 130 ° C. for 30 minutes to polymerize and cure the polymerizable raw material in the mold to obtain a sheet-like polymer. Thereafter, the mold was cooled, and the sheet polymer was peeled from the glass plate to obtain an acrylic resin sheet having a thickness of 1 mm.
- urethane (meth) acrylate 1 20 parts of urethane (meth) acrylate 1, 30 parts of diacrylate 1, 25 parts of polyacrylate 1, 25 parts of polyacrylate 2 and 2 parts of TDPO were mixed to obtain a curable composition for forming a functional layer. . After this curable composition is heated to 50 ° C., the curable composition is applied to one side of the acrylic resin sheet, and the PET surface side of the PET film having an easy-adhesion layer is superimposed on the applied surface. To obtain a laminate before curing.
- the position of 20 cm below the metal halide lamp with an output of 9.6 kW is 2.5 m so as to be irradiated through the PET film.
- the curable composition was cured under conditions of an integrated light amount of 570 mJ / cm 2 and a peak illuminance of 220 mW / cm 2 to obtain a post-curing laminate in which a functional layer was formed.
- the PET film was peeled from the laminate after curing to obtain a (meth) acrylic resin laminate.
- the film thickness of the functional layer in the obtained (meth) acrylic resin laminate was 13 ⁇ m.
- the evaluation results are shown in Table 2.
- Example 2 A (meth) acrylic resin laminate was prepared in the same manner as in Example 1 except that the diluted syrup composition, the monomer composition of the (meth) acrylic polymer (A), and the auxiliary agent were changed as shown in Table 2. did. The evaluation results are shown in Table 2.
- Example 14 An acrylic resin sheet having a thickness of 0.1 mm was obtained in the same manner as in Example 1 except that the distance between the glass plates facing each other was adjusted to 0.3 mm. Using the obtained acrylic resin sheet, a (meth) acrylic resin laminate was obtained in the same manner as in Example 1. The film thickness of the functional layer in the obtained (meth) acrylic resin laminate was 13 ⁇ m.
- the adhesive composition heated to 50 ° C. is applied to one surface of a polycarbonate sheet having a thickness of 0.6 mm, and the functional layer of the (meth) acrylic resin laminate is not laminated on the coated surface. Were laminated to obtain a composite sheet before curing.
- the composite sheet before curing was heated to 43 ° C. for 60 seconds and then irradiated through the (meth) acrylic resin laminate at a position 20 cm below the metal halide lamp with an output of 9.6 kW.
- the composite sheet was passed through the pre-curing composite sheet at a speed of 2.5 m / min, and the adhesive composition was cured under the conditions of an integrated light amount of 570 mJ / cm 2 and a peak illuminance of 220 mW / cm 2 on one side of the polycarbonate sheet (Metal )
- a composite sheet laminated with an acrylic resin laminate was obtained.
- the same operation as described above was performed on the other surface of the polycarbonate sheet on which the (meth) acrylic resin laminate was not laminated to obtain a composite sheet in which the (meth) acrylic resin laminate was laminated on both sides of the polycarbonate sheet.
- the total light transmittance of the obtained composite sheet was 88%, and the haze was 0.8%. Further, the 50% impact fracture height of the composite sheet was 500 mm, the ⁇ haze after the scratch test was 0.1%, the deflection ratio was 0.1%, and the adhesion was 100%.
- Comparative Example 2 contains more than 3.2% by mass of monomer (b) unit, the adhesion between the functional layer (cured layer) and the (meth) acrylic resin sheet was insufficient.
- Comparative Example 4 contained more than 7.5% by mass of the acrylic ester (a) unit, so the deflection ratio (water absorption displacement) of the (meth) acrylic resin laminate was large.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Laminated Bodies (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Abstract
Description
単量体(a)単位4.5~7.5質量%と、
単量体(b)単位0.3~3.2質量%と、
単量体(c)単位89.3~95.2質量%とを含有し、
単量体(a)単位は、炭素数1~11の炭化水素基を有し、分子中に1個のエチレン性不飽和結合を有するアクリル酸エステル単位であり、
単量体(b)単位は、分子中に2個以上のエチレン性不飽和結合を有する単量体単位であり、
単量体(c)単位は、前記の単量体単位以外の他の(メタ)アクリル酸エステル単位である、(メタ)アクリル重合体(A)が提供される。
単量体(a)単位を構成する単量体(a)は、炭素数1~11の炭化水素基を有し、分子中に1個のエチレン性不飽和結合を有するアクリル酸エステルである。
アクリル酸メチル、アクリル酸エチル、アクリル酸イソプロピル、アクリル酸t-ブチル、アクリル酸i-ブチル、アクリル酸n-ブチル、アクリル酸シクロヘキシル、アクリル酸ボルニル、アクリル酸ノルボルニル、アクリル酸イソボルニル、アクリル酸アダマンチル、アクリル酸ジメチルアダマンチル、アクリル酸メチルシクロヘキシル、アクリル酸ノルボルニルメチル、アクリル酸メンチル、アクリル酸フェンチル、アクリル酸ジシクロペンタニル、アクリル酸ジシクロペンテニル、アクリル酸ジシクロペンテニルオキシエチル、アクリル酸シクロデシル、アクリル酸4-t-ブチルシクロヘキシル、アクリル酸トリメチルシクロヘキシル等のアクリル酸エステル。
単量体(b)単位を構成する単量体(b)は、分子中に2個以上のエチレン性不飽和結合を有する単量体である。
エチレングリコールジ(メタ)アクリレート、1,2-プロピレングリコールジ(メタ)アクリレート、1,3-ブチレングリコールジ(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート等のアルカンジオールジ(メタ)アクリレート;ジエチレングリコールジ(メタ)アクリレート、ジプロピレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(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、ポリエチレングリコールジ(メタ)アクリレート等のポリオキシアルキレングリコールジ(メタ)アクリレート;ジビニルベンゼン等の分子中に2個以上のエチレン性不飽和結合を有する多官能重合性化合物;エチレン系不飽和ポリカルボン酸を含む少なくとも1種の多価カルボン酸と少なくとも1種のジオール類とから誘導された不飽和ポリエステルプレポリマー。
単量体(c)単位を構成する単量体(c)は、単量体(a)及び単量体(b)以外の(メタ)アクリル酸エステルである。
メタクリル酸イソプロピル、メタクリル酸t-ブチル、メタクリル酸i-ブチル、メタクリル酸n-ブチル等のメタクリル酸エステル。なかでも、吸水率が低く、耐熱性が高い理由から、メタクリル酸t-ブチルが好ましい。
本発明の実施形態による(メタ)アクリル重合体(A)は、アクリル酸エステル(a)単位4.5~7.5質量%、単量体(b)単位0.3~3.2質量%及び(メタ)アクリル酸エステル(c)単位89.3~95.2質量%を含有する共重合体である。
2,2'-アゾビス(4-メトキシ-2,4-ジメチルバレロニトリル)、2,2'-アゾビスイソブチロニトリル、2,2'-アゾビス-(2,4-ジメチルバレロニトリル)等のアゾ系重合開始剤;ラウロイルパーオキサイド、ジイソプロピルパーオキシジカーボネート、ベンゾイルパーオキサイド、ビス(4-t-ブチルシクロヘキシル)パーオキシジカーボネート、t-ブチルパーオキシネオデカノエートt-ヘキシルパーオキシピバレート等の有機過酸化物系重合開始剤。
本発明の実施形態による(メタ)アクリル樹脂組成物は、(メタ)アクリル重合体(A)とオレフィン-(メタ)アクリル酸アルキル共重合体(B)(以下、適宜「共重合体(B)」という)を含有するものである。
本発明の実施形態による(メタ)アクリル樹脂シートは、(メタ)アクリル重合体(A)又は(メタ)アクリル樹脂組成物から得られるシートである。
原料組成物(2):単量体(a)、単量体(b)及び単量体(c)を有する単量体混合物(1)の一部を重合して得られたシラップ(1)を含む組成物、
原料組成物(3):単量体(a)、単量体(b)及び単量体(c)を有する第1の単量体混合物(2)を重合させて得られた重合物を、単量体(a)、単量体(b)及び単量体(c)を有する第2の単量体混合物(2′)に溶解させて得られたシラップ(2)を含む組成物、
ここで、第1の単量体混合物(2)と第2の単量体混合物(2′)は同じ組成でも異なる組成でもよく、得られる(メタ)アクリル重合体(A)の組成が所定の組成となればよい。
本発明の実施形態による(メタ)アクリル樹脂積層体は、(メタ)アクリル樹脂シートの少なくとも一方の表面に後述する機能層が積層された積層体である。
(メタ)アクリル樹脂積層体の(メタ)アクリル樹脂シートと機能層とは、JIS K5600-5-6に準拠して碁盤目剥離試験を行ったときの機能層の残存率が90%以上となる密着性を有していることが好ましい。機能層の残存率が90%以上であると、画像表示装置の保護板として使用している際に、膜剥離に伴う画像の視認性悪化等の問題を抑制できる傾向にある。
機能層としては、耐擦傷性(ハードコート機能)、反射防止性、防眩性、防汚性(汚れ防止機能)、帯電防止性、飛散防止性、粘着性、接着性、軟質性等の各種機能を少なくとも一つ有する層が挙げられる。機能層としては、特に、反射防止機能、防眩機能、ハードコート機能、帯電防止機能及び汚れ防止機能から選ばれる少なくとも一つの機能を有する層であることが好ましい。また、機能層は、必要に応じて単層又は2層以上の多層とすることができる。2層以上の多層とする場合は、2種以上の機能を有する機能層を得ることができる。
1モルの多価アルコールと2モル以上の(メタ)アクリル酸又はその誘導体とから得られるエステル化物、及び多価アルコールと多価カルボン酸又はその無水物と(メタ)アクリル酸又はその誘導体とから得られるエステル化物。
トリメチロールプロパントリ(メタ)アクリレート、トリメチロールエタントリ(メタ)アクリレート、ペンタグリセロールトリ(メタ)アクリレート、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、グリセリントリ(メタ)アクリレート、ジペンタエリスリトールトリ(メタ)アクリレート、ジ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ペンタ(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、トリペンタエリスリトールテトラ(メタ)アクリレート、トリペンタエリスリトールペンタ(メタ)アクリレート、トリペンタエリスリトールヘキサ(メタ)アクリレート、トリペンタエリスリトールヘプタ(メタ)アクリレート等の3官能以上のポリオールのポリ(メタ)アクリレート。
マロン酸/トリメチロールエタン/(メタ)アクリル酸、マロン酸/トリメチロールプロパン/(メタ)アクリル酸、マロン酸/グリセリン/(メタ)アクリル酸、マロン酸/ペンタエリスリトール/(メタ)アクリル酸、コハク酸/トリメチロールエタン/(メタ)アクリル酸、コハク酸/トリメチロールプロパン/(メタ)アクリル酸、コハク酸/グリセリン/(メタ)アクリル酸、コハク酸/ペンタエリスリトール/(メタ)アクリル酸、アジピン酸/トリメチロールエタン/(メタ)アクリル酸、アジピン酸/トリメチロールプロパン/(メタ)アクリル酸、アジピン酸/グリセリン/(メタ)アクリル酸、アジピン酸/ペンタエリスリトール/(メタ)アクリル酸、グルタル酸/トリメチロールエタン/(メタ)アクリル酸、グルタル酸/トリメチロールプロパン/(メタ)アクリル酸、グルタル酸/グリセリン/(メタ)アクリル酸、グルタル酸/ペンタエリスリトール/(メタ)アクリル酸、セバシン酸/トリメチロールエタン/(メタ)アクリル酸、セバシン酸/トリメチロールプロパン/(メタ)アクリル酸、セバシン酸/グリセリン/(メタ)アクリル酸、セバシン酸/ペンタエリスリトール/(メタ)アクリル酸、フマル酸/トリメチロールエタン/(メタ)アクリル酸、フマル酸/トリメチロールプロパン/(メタ)アクリル酸、フマル酸/グリセリン/(メタ)アクリル酸、フマル酸/ペンタエリスリトール/(メタ)アクリル酸、イタコン酸/トリメチロールエタン/(メタ)アクリル酸、イタコン酸/トリメチロールプロパン/(メタ)アクリル酸、イタコン酸/グリセリン/(メタ)アクリル酸、イタコン酸/ペンタエリスリトール/(メタ)アクリル酸、無水マレイン酸/トリメチロールエタン/(メタ)アクリル酸、無水マレイン酸/トリメチロールプロパン/(メタ)アクリル酸、無水マレイン酸/グリセリン/(メタ)アクリル酸、及び無水マレイン酸/ペンタエリスリトール/(メタ)アクリル酸。
ジイソシアネート(例えば、トリメチロールプロパントルイレンジイソシアネート、ヘキサメチレンジイソシアネート、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、キシレンジイソシアネート、4,4'-メチレンビス(シクロヘキシルイソシアネート)、イソホロンジイソシアネート、及びトリメチルヘキサメチレンジイソシアネート等)の3量化により得られるポリイソシアネート1モル当たり、活性水素を有するアクリル系モノマー(例えば、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシ-3-メトキシプロピル(メタ)アクリレート、N-メチロール(メタ)アクリルアミド、N-ヒドロキシ(メタ)アクリルアミド、1,2,3-プロパントリオール-1,3-ジ(メタ)アクリレート、及び3-アクリロイルオキシ-2-ヒドロキシプロピル(メタ)アクリレート等)3モル以上を反応させて得られるウレタン(メタ)アクリレート;トリス(2-ヒドロキシエチル)イソシアヌル酸のジ(メタ)アクリレート又はトリ(メタ)アクリレート等のポリ[(メタ)アクリロイルオキシエチレン]イソシアヌレート;エポキシポリ(メタ)アクリレート;並びに、ウレタンポリ(メタ)アクリレート。
ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、アセトイン、ブチロイン、トルオイン、ベンジル、ベンゾフェノン、p-メトキシベンゾフェノン、2,2-ジエトキシアセトフェノン、α,α-ジメトキシ-α-フェニルアセトフェノン、メチルフェニルグリオキシレート、エチルフェニルグリオキシレート、4,4′-ビス(ジメチルアミノ)ベンゾフェノン、1-ヒドロキシ-シクロヘキシル-フェニル-ケトン、2-ヒドロキシ-2-メチル-1-フェニルプロパン-1-オン等のカルボニル化合物;テトラメチルチウラムモノスルフィド、テトラメチルチウラムジスルフィド等の硫黄化合物;及び、2,4,6-トリメチルベンゾイルジフェニルフォスフィンオキサイド、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド、ベンゾイルジエトキシフォスフィンオキサイド等のリン化合物。
機能層として反射防止機能を有する反射防止層を積層する場合、反射防止層は、(メタ)アクリル樹脂積層体表面の反射光を入射光の20%以下、好ましくは10%以下、更に好ましくは5%以下に抑える機能を有する層であれば、どのような材料から構成されていてもよい。このような機能を付与するためには、例えば、2以上の異なる屈折率を有する膜の積層構造とする方法が挙げられる。
機能層として防眩機能を有する防眩層を積層する場合、防眩層の表面に微細凹凸を形成する方法及び防弦層中に光拡散性微粒子を添加して内部散乱により外光を乱反射させる方法の少なくとも1つの方法により外光の映りこみを抑制することができる。防眩層を有する機能層の形成方法としては、例えば、以下の方法が挙げられる。
機能層として汚れ防止機能を有する汚れ防止層を積層する場合、汚れ防止層が有する機能は、撥水性又は撥油性でもよく、親水性又は親油性でもよいが、汚れを除去し易い観点から撥水性又は撥油性を有することが好ましい。
機能層として帯電防止機能を有する帯電防止層を積層する場合について以下に説明する。
本発明の実施形態においては、機能層は、必要に応じて、接着層を介して(メタ)アクリル樹脂シートと積層することができる。
本発明の実施形態による複合シートは、熱可塑性樹脂基材の一面に(メタ)アクリル樹脂積層体の(メタ)アクリル樹脂シートの面が接するように、熱可塑性樹脂基材と(メタ)アクリル樹脂積層体が積層されたシートである。熱可塑性樹脂基材の他の面(反対側の面)に他の(メタ)アクリル樹脂積層体が積層されてもよい。その際、その(メタ)アクリル樹脂積層体の(メタ)アクリル樹脂シートの面が熱可塑性樹脂基材の面に接触する。このように熱可塑性樹脂基材の両側に積層された複合シートは互いに同じ構造を有するものであっても、互いに異なる構造を有するものであってもよい。また、熱可塑性樹脂基材の他の面(反対側の面)に機能層を積層してもよい。
機能層/(メタ)アクリル樹脂シート/熱可塑性樹脂基材、
機能層/(メタ)アクリル樹脂シート/熱可塑性樹脂基材/(メタ)アクリル樹脂シート/機能層、
機能層/(メタ)アクリル樹脂シート/熱可塑性樹脂基材/(メタ)アクリル樹脂シート、
機能層/(メタ)アクリル樹脂シート/熱可塑性樹脂基材/機能層。
「MMA」:メタクリル酸メチル
「IBXMA」:メタクリル酸イソボルニル
「IBXA」:アクリル酸イソボルニル
「TBMA」:メタクリル酸t-ブチル
「BA」:アクリル酸n-ブチル
「NPG」:ジメタクリル酸ネオペンチルグリコール
「HPP」:パーヘキシルPV(t-ヘキシルパーオキシピバレート、純度70質量%)
「PBPV」:パーブチルPV(t-ブチルパーオキシピバレート、純度70質量%)
「AOT」:ジオクチルスルホコハク酸ナトリウム
「ウレタン(メタ)アクリレート1」:ヘキサメチレンジイソシアネートの3量化により得られるポリイソシアネート1モル当たり、3-アクリロイルオキシ-2-ヒドロキシプロピル(メタ)アクリレート3モルを反応させて得られるウレタン(メタ)アクリレート、
「ジアクリレート1」:1,6-ヘキサンジオールジアクリレート
「ポリアクリレート1」:ペンタエリスリトールトリアクリレート(50~70質量%)とペンタエリスリトールテトラアクリレート(50~30質量%)の混合物
「ポリアクリレート2」:ジペンタエリスリトールヘキサアクリレート(60~70質量%)とジペンタエリスリトールペンタアクリレート(40~30質量%)の混合物、
「TDPO」:2,4,6-トリメチルベンゾイル-ジフェニル-フォスフィンオキサイド
「リン酸エステル1」モノエチルアシッドフォスフェート(50質量%)とジエチルアシッドフォスフェートとトリエチルアシッドフォスフェート(50質量%)の混合物
「リン酸エステル2」モノエチルアシッドフォスフェート(50質量%)とジエチルアシッドフォスフェートとトリエチルアシッドフォスフェート(50質量%)の混合物。
(メタ)アクリル樹脂積層体、複合シートから45~65mm角の試験片を切り出して全光線透過率及びヘーズを測定した。(メタ)アクリル樹脂積層体、複合シートの全光線透過率及びヘーズは、日本電色工業(株)製のHAZE METER NDH2000(商品名)を用いてJIS K7136の測定法に準拠して測定した。
(メタ)アクリル樹脂積層体、複合シートの耐衝撃性の評価は落球試験により行った。この落球試験による耐衝撃性の評価は、JIS K 7211-1に準拠し、以下に示す落球試験条件にて以下の方法により行った。
試験片サイズ:一辺50mmの正方形
支持台サイズ:直径20mmの円形の穴が空いた5mm厚のアクリル板
落球サイズ:ステンレス鋼製の球(球径20.0mmφ、質量18.5g)
測定雰囲気の温度:23℃
測定雰囲気の相対湿度:50%
測定前の試験片の測定雰囲気中での放置時間:24hr以上。
#000のスチールウールを装着した直径25.4mmの円形パッドを(メタ)アクリル樹脂積層体の機能層、複合シートの機能層の表面上に置き、9.8Nの荷重下で、20mmの距離を100回往復させて擦傷処理し、擦傷処理前のヘーズ(擦傷前ヘーズ)及び、擦傷処理後のヘーズ(擦傷後ヘーズ)を求めた。耐擦傷性は、次式より求められるヘーズの変化量(Δヘーズ(%))により評価した。
[Δヘーズ(%)]=[擦傷後ヘーズ(%)]-[擦傷前ヘーズ(%)]
(メタ)アクリル樹脂積層体及び複合シートのたわみ比率は、以下の条件で、(メタ)アクリル樹脂積層体及び複合シートを50℃及び相対湿度90%の高温多湿環境下で24時間放置した後、23℃及び相対湿度50%の通常環境下で5時間放置したときのシート試験片のたわみ量(a)を測定し、高温多湿環境下での放置前の試験片の長辺(b)(固定枠と重ならない部分の長さ:55mm)に対するたわみ量(a)の比率を下式により求めた。(図1参照)
たわみ比率(%)=たわみ量(a)÷試験片の長辺(b)×100
ガラス製の土台の中心部に、固定治具(固定枠)を、両面テープを用いて貼り合わせた。次いで、上記固定治具の中央部に、所定サイズの試験片を、両面テープを用いて貼り付け、吸水変位測定用サンプルを作製した。得られた吸水変位測定用サンプルを所定の高温多湿環境下に24時間保持し、更に所定の通常環境下に5時間放置した後、キーエンス(株)製レーザー変位計(LK-085)を用いて、サンプルの中央部の鉛直方向のたわみ量(吸水変位量)を測定した。たわみ量は、シート試験片の4隅に対してシート試験片の中央がどの程度鉛直方向に変位しているかを測定した。尚、ガラス製土台側への変位をプラス、逆側への変位をマイナスとする。
・固定治具:幅5mmの矩形状の枠であって、枠の外側の短辺が45mm、枠の外側の長辺が65mm、枠の内側の短辺が35mm、枠の内側の長辺が55mm、厚み3mmの金属枠、
・土台:縦80mm、横80mm及び厚み5mmのガラスプレート
・両面テープ:幅5mmの3M(株)製両面テープ。商品名:VHB(TM)
・高温多湿環境:50℃及び相対湿度90%
・通常環境:23℃及び相対湿度50%。
(メタ)アクリル樹脂積層体及び複合シートにおける機能層の密着性は以下の碁盤目剥離試験により評価した。
冷却管、温度計及び攪拌機を備えた反応器中に、表1に示すように、E/MA共重合体0.038部、MMA60部、IBXMA24部、IBXA6.5部、TBMA8.2部、BA1.1部及びNPG0.08部の混合物を供給し、撹拌しながら窒素ガスでバブリングした後、加熱を開始した。液温が60℃になった時点で、HPP0.034部を添加し、更に液温を100℃まで上昇させ、この温度を13分間維持した。次いで、液温を室温まで冷却し、元シラップ1を得た。元シラップ1中の重合体の含有量は20質量%であった。
二枚のガラス板(縦300mm、横300mm、厚み5mm)を対向させ、その縁部を軟質ポリ塩化ビニル製のガスケットで封じ、注型重合用の鋳型を作製した。
希釈シラップ組成、(メタ)アクリル重合体(A)の単量体組成、助剤を表2に示すように変更したこと以外は、実施例1と同様にして(メタ)アクリル樹脂積層体を作製した。評価結果を表2に示す。
鋳型の対向するガラス板の間隔を0.3mmに調整する以外は実施例1と同様にして厚み0.1mmのアクリル樹脂シートを得た。得られたアクリル樹脂シートを使用し、実施例1と同様にして(メタ)アクリル樹脂積層体を得た。得られた(メタ)アクリル樹脂積層体中の機能層の膜厚は13μmであった。
希釈シラップ組成、(メタ)アクリル重合体の単量体組成を表3に示すように変更したこと以外は、実施例1と同様にして(メタ)アクリル樹脂積層体を作製した。評価結果を表3に示す。
Claims (20)
- 単量体(a)単位4.5~7.5質量%と、
単量体(b)単位0.3~3.2質量%と、
単量体(c)単位89.3~95.2質量%とを含有し、
単量体(a)単位は、炭素数1~11の炭化水素基を有し、分子中に1個のエチレン性不飽和結合を有するアクリル酸エステル単位であり、
単量体(b)単位は、分子中に2個以上のエチレン性不飽和結合を有する単量体単位であり、
単量体(c)単位は、前記の単量体単位以外の他の(メタ)アクリル酸エステル単位である、(メタ)アクリル重合体(A)。 - 単量体(c)単位が、単量体(c1)単位、単量体(c2)単位及び単量体(c3)単位を含有し、
単量体(c1)単位は、メタクリル酸メチル単位であり、
単量体(c2)単位は、炭素数6~20の脂環式炭化水素基を有するメタクリル酸エステル単位であり、
単量体(c3)単位は、メタクリル酸エステル(c2)単位以外のメタクリル酸エステル単位であって、炭素数3~10の炭化水素基を有するメタクリル酸エステル単位である、請求項1に記載の(メタ)アクリル重合体(A)。 - 単量体(c2)がメタクリル酸イソボルニルであり、単量体(c3)がメタクリル酸t-ブチルである請求項2に記載の(メタ)アクリル重合体(A)。
- 請求項1~3のいずれかに記載の(メタ)アクリル重合体(A)100質量部及びオレフィン-(メタ)アクリル酸アルキル共重合体(B)0.002~0.7質量部を含有する(メタ)アクリル樹脂組成物。
- オレフィン-(メタ)アクリル酸アルキル共重合体(B)が、エチレン-(メタ)アクリル酸アルキル共重合体(B-1)である請求項4に記載の(メタ)アクリル樹脂組成物。
- エチレン-(メタ)アクリル酸アルキル共重合体(B-1)が、エチレン-アクリル酸アルキル共重合体(B-2)である請求項5に記載の(メタ)アクリル樹脂組成物。
- エチレン-アクリル酸アルキル共重合体(B-2)中のアクリル酸アルキル単位の含有量が15~40質量%である請求項6に記載の(メタ)アクリル樹脂組成物。
- 請求項1~3のいずれかに記載の(メタ)アクリル重合体(A)を含有する(メタ)アクリル樹脂シート。
- 請求項4に記載の(メタ)アクリル樹脂組成物を含有する(メタ)アクリル樹脂シート。
- 請求項8に記載の(メタ)アクリル樹脂シートと、
(メタ)アクリル樹脂シートの少なくとも片面に積層された機能層とを含む(メタ)アクリル樹脂積層体。 - 請求項8に記載の(メタ)アクリル樹脂シートと、
(メタ)アクリル樹脂シートの両面に積層された機能層とを含む(メタ)アクリル樹脂積層体。 - 熱可塑性樹脂基材と、
熱可塑性樹脂基材の少なくとも一面に積層された請求項10に記載の(メタ)アクリル樹脂積層体とを含み、
(メタ)アクリル樹脂積層体の(メタ)アクリル樹脂シートの面と、熱可塑性樹脂基材の面とが接するように積層された複合シート。 - 熱可塑性樹脂基材と、
熱可塑性樹脂基材の一面に積層された請求項10に記載の(メタ)アクリル樹脂積層体と、
熱可塑性樹脂基材の他の一面に積層された機能層とを含み、
(メタ)アクリル樹脂積層体の(メタ)アクリル樹脂シートの面と、熱可塑性樹脂基材の面とが接するように積層された複合シート。 - 50℃及び相対湿度90%の環境下で24時間放置した後に23℃及び相対湿度50%の環境下で5時間放置したときの(メタ)アクリル樹脂積層体のたわみ比率が0.2%以下であり、JIS K5600-5-6に準拠して碁盤目剥離試験を行ったときの機能層の残存率が90%以上である請求項10に記載の(メタ)アクリル樹脂積層体。
- 50℃及び相対湿度90%の環境下で24時間放置した後に23℃及び相対湿度50%の環境下で5時間放置したときの(メタ)アクリル樹脂積層体のたわみ比率が0.2%以下であり、JIS K5600-5-6に準拠して碁盤目剥離試験を行ったときの機能層の残存率が90%以上である請求項11に記載の(メタ)アクリル樹脂積層体。
- 50℃及び相対湿度90%の環境下で24時間放置した後に23℃及び相対湿度50%の環境下で5時間放置したときの複合シートのたわみ比率が0.2%以下であり、JIS K5600-5-6に準拠して碁盤目剥離試験を行ったときの機能層の残存率が90%以上である請求項12に記載の複合シート。
- 50℃及び相対湿度90%の環境下で24時間放置した後に23℃及び相対湿度50%の環境下で5時間放置したときの複合シートのたわみ比率が0.2%以下であり、JIS K5600-5-6に準拠して碁盤目剥離試験を行ったときの機能層の残存率が90%以上である請求項13に記載の複合シート。
- 機能層が反射防止機能、防眩機能、ハードコート機能、帯電防止機能及び汚れ防止機能から選ばれる少なくとも一つの機能を有する層である請求項10に記載の(メタ)アクリル樹脂積層体。
- 機能層が反射防止機能、防眩機能、ハードコート機能、帯電防止機能及び汚れ防止機能から選ばれる少なくとも一つの機能を有する層である請求項12に記載の複合シート。
- 熱可塑性樹脂基材の厚みが0.5mm~2mmであり、(メタ)アクリル樹脂シートの厚みが0.03mm~0.2mmである請求項12に記載の複合シート。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201480034667.1A CN105324400B (zh) | 2013-06-24 | 2014-06-23 | (甲基)丙烯酸类聚合物、(甲基)丙烯酸类树脂组合物、(甲基)丙烯酸类树脂片材、(甲基)丙烯酸类树脂层积体以及复合片材 |
US14/900,871 US20160137766A1 (en) | 2013-06-24 | 2014-06-23 | (meth)acrylic polymer, (meth)acrylic resin composition, (meth)acrylic resin sheet, (meth)acrylic resin laminated article and composite sheet |
KR1020157036029A KR20160013924A (ko) | 2013-06-24 | 2014-06-23 | (메트)아크릴 중합체, (메트)아크릴 수지 조성물, (메트)아크릴 수지 시트, (메트)아크릴 수지 적층체 및 복합 시트 |
JP2014532166A JP6361506B2 (ja) | 2013-06-24 | 2014-06-23 | (メタ)アクリル重合体、(メタ)アクリル樹脂組成物、(メタ)アクリル樹脂シート、(メタ)アクリル樹脂積層体及び複合シート |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013-131319 | 2013-06-24 | ||
JP2013131319 | 2013-06-24 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014208477A1 true WO2014208477A1 (ja) | 2014-12-31 |
Family
ID=52141814
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2014/066500 WO2014208477A1 (ja) | 2013-06-24 | 2014-06-23 | (メタ)アクリル重合体、(メタ)アクリル樹脂組成物、(メタ)アクリル樹脂シート、(メタ)アクリル樹脂積層体及び複合シート |
Country Status (6)
Country | Link |
---|---|
US (1) | US20160137766A1 (ja) |
JP (1) | JP6361506B2 (ja) |
KR (1) | KR20160013924A (ja) |
CN (1) | CN105324400B (ja) |
TW (1) | TW201510047A (ja) |
WO (1) | WO2014208477A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017193641A (ja) * | 2016-04-21 | 2017-10-26 | 三菱ケミカル株式会社 | (メタ)アクリル系樹脂組成物、樹脂成形体及び(メタ)アクリル系樹脂組成物の製造方法 |
JP2021169634A (ja) * | 2020-06-24 | 2021-10-28 | 三菱ケミカル株式会社 | (メタ)アクリル系樹脂組成物及び樹脂成形体 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20170050078A (ko) * | 2015-10-29 | 2017-05-11 | 주식회사 엘지화학 | 리튬-황 이차전지 양극용 아크릴 바인더 |
JP7018931B2 (ja) * | 2016-08-09 | 2022-02-14 | ソルベイ スペシャルティ ポリマーズ イタリー エス.ピー.エー. | 多孔質膜 |
CN108192254A (zh) * | 2017-12-28 | 2018-06-22 | 珠海市盛西源机电设备有限公司 | 高抗污亚克力实体面材及其制备方法 |
CN114231112A (zh) * | 2021-12-20 | 2022-03-25 | 哈尔滨工程大学 | 钒酸铋/3d石墨烯泡沫/丙烯酸硼异冰片酯聚合物基复合涂层及其制备方法 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5063085A (ja) * | 1972-06-20 | 1975-05-29 | ||
JPS6259657A (ja) * | 1985-09-11 | 1987-03-16 | Denki Kagaku Kogyo Kk | 熱可塑性樹脂組成物 |
JPS6259613A (ja) * | 1985-09-09 | 1987-03-16 | Denki Kagaku Kogyo Kk | 重合体の製造方法 |
JPH0247107A (ja) * | 1988-08-09 | 1990-02-16 | Kansai Paint Co Ltd | ゲル化微粒子重合体の水分散液の製造方法 |
JPH0717843A (ja) * | 1993-07-02 | 1995-01-20 | Nippon Shokubai Co Ltd | ゲル状芳香剤組成物 |
JPH0812787A (ja) * | 1994-06-27 | 1996-01-16 | Mitsubishi Rayon Co Ltd | ハードコート層を有する熱可塑性ノルボルネン系樹脂成形品及びその製造方法 |
JP2000159821A (ja) * | 1998-11-27 | 2000-06-13 | Sumitomo Chem Co Ltd | メタクリル酸メチル系重合体ビーズの製造方法 |
JP2008016702A (ja) * | 2006-07-07 | 2008-01-24 | Mitsubishi Paper Mills Ltd | 樹脂組成物 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3856894A (en) * | 1970-12-26 | 1974-12-24 | Mitsubishi Rayon Co | Vinyl chloride polymer composition containing a cross-linked methyl methacrylate copolymer |
DE10354379A1 (de) * | 2003-11-20 | 2005-06-23 | Röhm GmbH & Co. KG | Formmasse, enthaltend ein Mattierungsmittel |
CN101092469A (zh) * | 2007-05-28 | 2007-12-26 | 周伯涛 | 一种太阳光辐照交联核壳聚合物乳液及其制备方法和应用 |
KR20140034815A (ko) * | 2011-05-10 | 2014-03-20 | 미쯔비시 레이온 가부시끼가이샤 | 아크릴 수지 조성물, 아크릴 수지 시트, 아크릴 수지 적층체, 및 그들의 제조 방법 |
-
2014
- 2014-06-23 CN CN201480034667.1A patent/CN105324400B/zh not_active Expired - Fee Related
- 2014-06-23 KR KR1020157036029A patent/KR20160013924A/ko not_active Application Discontinuation
- 2014-06-23 US US14/900,871 patent/US20160137766A1/en not_active Abandoned
- 2014-06-23 JP JP2014532166A patent/JP6361506B2/ja not_active Expired - Fee Related
- 2014-06-23 TW TW103121487A patent/TW201510047A/zh unknown
- 2014-06-23 WO PCT/JP2014/066500 patent/WO2014208477A1/ja active Application Filing
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5063085A (ja) * | 1972-06-20 | 1975-05-29 | ||
JPS6259613A (ja) * | 1985-09-09 | 1987-03-16 | Denki Kagaku Kogyo Kk | 重合体の製造方法 |
JPS6259657A (ja) * | 1985-09-11 | 1987-03-16 | Denki Kagaku Kogyo Kk | 熱可塑性樹脂組成物 |
JPH0247107A (ja) * | 1988-08-09 | 1990-02-16 | Kansai Paint Co Ltd | ゲル化微粒子重合体の水分散液の製造方法 |
JPH0717843A (ja) * | 1993-07-02 | 1995-01-20 | Nippon Shokubai Co Ltd | ゲル状芳香剤組成物 |
JPH0812787A (ja) * | 1994-06-27 | 1996-01-16 | Mitsubishi Rayon Co Ltd | ハードコート層を有する熱可塑性ノルボルネン系樹脂成形品及びその製造方法 |
JP2000159821A (ja) * | 1998-11-27 | 2000-06-13 | Sumitomo Chem Co Ltd | メタクリル酸メチル系重合体ビーズの製造方法 |
JP2008016702A (ja) * | 2006-07-07 | 2008-01-24 | Mitsubishi Paper Mills Ltd | 樹脂組成物 |
Non-Patent Citations (2)
Title |
---|
LUDOVIC VALETTE: "Meth)acrylic Cross-Linked Polymer Microparticles: Synthesis by Dispersion Polymerization and Particle Characterization", MACROMOL. MATER. ENG., vol. 287, no. 1, 2002, pages 31 - 40 * |
WEN-CHANG CHEN: "Synthesis and characterization of large diameter acrylic polymer light conduits", J. MATER. CHEM., vol. 9, no. 10, 1999, pages 2307 - 2312 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017193641A (ja) * | 2016-04-21 | 2017-10-26 | 三菱ケミカル株式会社 | (メタ)アクリル系樹脂組成物、樹脂成形体及び(メタ)アクリル系樹脂組成物の製造方法 |
JP2021169634A (ja) * | 2020-06-24 | 2021-10-28 | 三菱ケミカル株式会社 | (メタ)アクリル系樹脂組成物及び樹脂成形体 |
JP7298654B2 (ja) | 2020-06-24 | 2023-06-27 | 三菱ケミカル株式会社 | (メタ)アクリル系樹脂組成物及び樹脂成形体 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2014208477A1 (ja) | 2017-02-23 |
KR20160013924A (ko) | 2016-02-05 |
CN105324400B (zh) | 2017-09-22 |
CN105324400A (zh) | 2016-02-10 |
US20160137766A1 (en) | 2016-05-19 |
TW201510047A (zh) | 2015-03-16 |
JP6361506B2 (ja) | 2018-07-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6361506B2 (ja) | (メタ)アクリル重合体、(メタ)アクリル樹脂組成物、(メタ)アクリル樹脂シート、(メタ)アクリル樹脂積層体及び複合シート | |
JP5747439B2 (ja) | アクリル系樹脂シートを連続的に製造する方法 | |
JP5728945B2 (ja) | 防汚組成物、防汚膜、防汚積層膜、転写フィルム及び樹脂積層体、並びに樹脂積層体の製造方法 | |
JP6007789B2 (ja) | アクリル樹脂組成物、アクリル樹脂シート、アクリル樹脂積層体、及びそれらの製造方法 | |
TWI404629B (zh) | 樹脂疊層體的製造方法 | |
JP6597302B2 (ja) | 樹脂組成物、樹脂シート、及び樹脂積層体 | |
JP5656054B2 (ja) | アクリル樹脂板の製造方法、アクリル樹脂板、アクリル樹脂積層体及び表示装置 | |
WO2015045200A1 (ja) | 光硬化性樹脂組成物及びその硬化膜 | |
JP5594509B2 (ja) | 積層体及び積層体の製造方法 | |
JP6079234B2 (ja) | 金属酸化物微粒子含有膜、転写フィルムおよびその製造方法並びに積層体およびその製造方法 | |
WO2014189075A1 (ja) | 積層体 | |
JP5484082B2 (ja) | 積層体の製造方法 | |
JP4818682B2 (ja) | 樹脂積層体の製造方法 | |
JP6016009B2 (ja) | 転写フィルム、積層体及びそれらの製造方法 | |
JP5700245B2 (ja) | アクリル樹脂板、アクリル樹脂積層体及び表示装置 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201480034667.1 Country of ref document: CN |
|
ENP | Entry into the national phase |
Ref document number: 2014532166 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14816712 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20157036029 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14900871 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 14816712 Country of ref document: EP Kind code of ref document: A1 |