WO2011145630A1 - 合成樹脂積層体 - Google Patents
合成樹脂積層体 Download PDFInfo
- Publication number
- WO2011145630A1 WO2011145630A1 PCT/JP2011/061348 JP2011061348W WO2011145630A1 WO 2011145630 A1 WO2011145630 A1 WO 2011145630A1 JP 2011061348 W JP2011061348 W JP 2011061348W WO 2011145630 A1 WO2011145630 A1 WO 2011145630A1
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- WIPO (PCT)
- Prior art keywords
- layer
- vinyl copolymer
- laminate
- resin
- copolymer resin
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
- B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31507—Of polycarbonate
Definitions
- the present invention relates to a synthetic resin laminate, and more specifically, is used for a transparent substrate material and a transparent protective material, and includes a polycarbonate resin layer and a vinyl copolymer resin layer having a specific structure.
- the present invention relates to a synthetic resin laminate excellent in shape stability, surface hardness and impact resistance in a wet environment.
- Patent Document 2 discloses a laminate in which a resin having a low water absorption rate is laminated on a polycarbonate resin in order to suppress warpage of the laminate.
- Patent Document 3 discloses a laminate excellent in impact resistance, heat resistance, weather resistance, and scratch resistance obtained by laminating a vinyl copolymer resin containing a specific (meth) acrylate structural unit and a polycarbonate resin.
- peeling may occur at the interface of the laminate depending on the use conditions.
- a laminate in which an acrylic resin layer is laminated on both sides of a polycarbonate resin layer is known, but when a surface impact is applied to one side of the laminate, a crack occurs in the acrylic resin layer on the opposite side. It is easy and may become a problem depending on the method of use.
- the present invention is a synthetic resin laminate that is excellent in interlayer adhesion, shape stability in a high-temperature and high-humidity environment, surface hardness, and impact resistance, which is used for transparent substrate materials and transparent protective materials from the above situation.
- the purpose is to provide.
- the present inventors have obtained a synthetic resin laminate in which a vinyl copolymer resin having a specific structure is laminated on one side of a polycarbonate resin layer.
- the inventors have found that a synthetic resin laminate having properties can be obtained, and have reached the present invention. That is, the present invention provides the following synthetic resin laminate and a transparent material using the synthetic resin laminate.
- a synthetic resin laminate having a vinyl copolymer resin (A) layer and a polycarbonate resin (B) layer, wherein the (A) layer is directly laminated on one side of the (B) layer,
- the vinyl copolymer resin (A) is a (meth) acrylic acid ester structural unit (a) represented by the following general formula (1) and an aliphatic vinyl structural unit (b) represented by the following general formula (2).
- the total ratio of the (meth) acrylic ester structural unit (a) and the aliphatic vinyl structural unit (b) is based on the total of all structural units in the vinyl copolymer resin (A) 90 to 100 mol%, and the proportion of the (meth) acrylic ester structural unit (a) is 65 to 80 mol% with respect to the total of all the structural units in the vinyl copolymer resin (A).
- a synthetic resin laminate is based on the total of all structural units in the vinyl copolymer resin (A) 90 to 100 mol%, and the proportion of the (meth) acrylic ester structural unit (a) is 65 to 80 mol% with respect to the total of all the structural units in the vinyl copolymer resin (A).
- R1 is a hydrogen atom or a methyl group
- R2 is an alkyl group having 1 to 18 carbon atoms.
- R3 is a hydrogen atom or a methyl group
- R4 is a cyclohexyl group that may have a hydrocarbon substituent of 1 to 4 carbon atoms.
- the synthetic resin laminated body which is excellent in the shape stability in high temperature, high humidity environment, and surface hardness and impact resistance is provided, and this synthetic resin laminated body is used as a transparent substrate material and a transparent protective material.
- this synthetic resin laminated body is suitably used for portable display devices such as mobile phone terminals, portable electronic play equipment, portable information terminals, and mobile PCs, and stationary display devices such as notebook PCs, desktop PC liquid crystal monitors, and liquid crystal televisions. Is done.
- the synthetic resin laminate of the present invention has a vinyl copolymer resin (A) layer and a polycarbonate resin (B) layer, and the vinyl copolymer resin (A) layer is directly on one side of the polycarbonate resin (B) layer.
- a synthetic resin laminate laminated on The vinyl copolymer resin (A) is a (meth) acrylic acid ester structural unit (a) represented by the following general formula (1) and an aliphatic vinyl structural unit (b) represented by the following general formula (2).
- the total ratio of the (meth) acrylic ester structural unit (a) and the aliphatic vinyl structural unit (b) is based on the total of all structural units in the vinyl copolymer resin (A) 90 to 100 mol%, and the proportion of the (meth) acrylic ester structural unit (a) is 65 to 80 mol% with respect to the total of all the structural units in the vinyl copolymer resin (A). It is a feature.
- R1 is a hydrogen atom or a methyl group
- R2 is an alkyl group having 1 to 18 carbon atoms.
- R3 is a hydrogen atom or a methyl group
- R4 is a cyclohexyl group that may have a hydrocarbon substituent of 1 to 4 carbon atoms.
- the vinyl copolymer resin (A) layer is laminated only on one side of the polycarbonate resin (B) layer.
- a polycarbonate resin (B) having a soft structure on the opposite side when a surface impact is applied to the vinyl copolymer resin (A) layer side which is a hard structure
- the impact is mitigated and the damage due to the impact is less likely to occur.
- a laminate in which a vinyl copolymer resin (A) layer is laminated on both sides of a polycarbonate resin (B) layer has a structure in which the opposite surface is hard when a surface impact is applied to one side of the laminate.
- R2 is an alkyl group having 1 to 18 carbon atoms, specifically, methyl group, ethyl group, butyl group, lauryl group, stearyl. Group, cyclohexyl group, isobornyl group and the like.
- R2 is a methyl group and / or an ethyl group
- R1 is a methyl group
- R2 is It is a methyl methacrylate structural unit which is a methyl group.
- R3 is a hydrogen atom or a methyl group
- R4 is a cyclohexyl group or a cyclohexyl group having a hydrocarbon substituent having 1 to 4 carbon atoms. Things.
- the vinyl copolymer resin (A) used in the present invention is mainly composed of a (meth) acrylic acid ester structural unit (a) represented by the general formula (1) and an aliphatic vinyl represented by the general formula (2). It consists of a structural unit (b).
- the vinyl copolymer resin (A) may contain one or more of the (meth) acrylic ester structural unit (a), and one or two of the aliphatic vinyl structural unit (b). You may contain above.
- the total proportion of the (meth) acrylic ester structural unit (a) and the aliphatic vinyl structural unit (b) is 90 to 100 mol based on the total of all the structural units in the vinyl copolymer resin (A).
- the vinyl copolymer resin (A) is in the range of 10 mol% or less with respect to the total of all the structural units, and the (meth) acrylic ester structural unit (a) and the aliphatic vinyl structural unit (b). Other structural units may be contained.
- the structural unit other than the (meth) acrylic ester structural unit (a) and the aliphatic vinyl structural unit (b) include, for example, a polymer obtained by polymerizing a (meth) acrylic ester monomer and an aromatic vinyl monomer.
- Examples of the vinyl copolymer resin (A) obtained by hydrogenating an aromatic double bond derived from an aromatic vinyl monomer include structural units derived from an aromatic vinyl monomer containing an unhydrogenated aromatic double bond. .
- the proportion of the (meth) acrylate structural unit (a) represented by the general formula (1) is 65 to 80 mol% with respect to the total of all the structural units in the vinyl copolymer resin (A). Preferably, it is 70 to 80 mol%.
- the ratio of the (meth) acrylic ester structural unit (a) to the total of all structural units in the vinyl copolymer resin (A) is less than 65 mol%, the adhesion and surface hardness with the polycarbonate resin (B) are reduced. May be impractical.
- it exceeds 80 mol% the laminate is warped due to water absorption, which may not be practical.
- the method for producing the vinyl copolymer resin (A) is not particularly limited, but after the polymerization of at least one (meth) acrylic acid ester monomer and at least one aromatic vinyl monomer, the vinyl copolymer resin (A) is derived from the aromatic vinyl monomer. Those obtained by hydrogenating aromatic double bonds are preferred.
- (meth) acrylic acid shows methacrylic acid and / or acrylic acid.
- Specific examples of the aromatic vinyl monomer used at this time include styrene, ⁇ -methylstyrene, p-hydroxystyrene, alkoxystyrene, chlorostyrene, and derivatives thereof. Of these, styrene is preferred.
- a known method can be used for the polymerization of the (meth) acrylic acid ester monomer and the aromatic vinyl monomer, and for example, it can be produced by a bulk polymerization method or a solution polymerization method.
- the bulk polymerization method is carried out by a method in which the monomer composition containing the monomer and the polymerization initiator is continuously supplied to a complete mixing tank and continuously polymerized at 100 to 180 ° C.
- the monomer composition may contain a chain transfer agent as necessary.
- the polymerization initiator is not particularly limited, but t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, t-hexylpropoxyisopropyl monocarbonate, t-amylperoxynormal Organic peroxides such as octoate, t-butylperoxyisopropyl monocarbonate, di-t-butyl peroxide, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile) ), 2,2'-azobis (2,4-dimethylvaleronitrile) and
- the chain transfer agent is used as necessary, and examples thereof include ⁇ -methylstyrene dimer.
- Examples of the solvent used in the solution polymerization method include hydrocarbon solvents such as toluene, xylene, cyclohexane and methylcyclohexane, ester solvents such as ethyl acetate and methyl isobutyrate, ketone solvents such as acetone and methyl ethyl ketone, tetrahydrofuran, Examples include ether solvents such as dioxane and alcohol solvents such as methanol and isopropanol.
- hydrocarbon solvents such as toluene, xylene, cyclohexane and methylcyclohexane
- ester solvents such as ethyl acetate and methyl isobutyrate
- ketone solvents such as acetone and methyl ethyl ketone
- tetrahydrofuran examples include ether solvents such as dioxane and alcohol solvents such as methanol and isopropanol.
- the solvent used in the hydrogenation reaction after polymerizing the (meth) acrylic acid ester monomer and the aromatic vinyl monomer may be the same as or different from the polymerization solvent described above.
- hydrocarbon solvents such as cyclohexane and methylcyclohexane
- ester solvents such as ethyl acetate and methyl isobutyrate
- ketone solvents such as acetone and methyl ethyl ketone
- ether solvents such as tetrahydrofuran and dioxane
- alcohol solvents such as methanol and isopropanol A solvent etc.
- the vinyl copolymer used in the present invention is obtained by polymerizing the (meth) acrylic acid ester monomer and the aromatic vinyl monomer as described above, and then hydrogenating the aromatic double bond derived from the aromatic vinyl monomer. Resin (A) is obtained.
- the method for hydrogenation is not particularly limited, and a known method can be used. For example, it can be carried out batchwise or continuously with a hydrogen pressure of 3 to 30 MPa and a reaction temperature of 60 to 250 ° C. By setting the temperature to 60 ° C. or higher, the reaction time does not take too long, and by setting the temperature to 250 ° C. or lower, there is little occurrence of molecular chain cleavage or ester site hydrogenation.
- Examples of the catalyst used in the hydrogenation reaction include metals such as nickel, palladium, platinum, cobalt, ruthenium, and rhodium or oxides or salts or complex compounds of these metals, carbon, alumina, silica, silica / alumina, and diatomaceous earth. And a solid catalyst supported on a porous carrier.
- the vinyl copolymer resin (A) is preferably one in which 70% or more of the aromatic double bond derived from the aromatic vinyl monomer is hydrogenated. That is, the ratio of the unhydrogenated site of the aromatic double bond in the structural unit derived from the aromatic vinyl monomer is preferably 30% or less. If the content exceeds 30%, the transparency of the vinyl copolymer resin (A) may be lowered. More preferably, it is the range of less than 10%, More preferably, it is the range of less than 5%.
- the weight average molecular weight of the vinyl copolymer resin (A) is not particularly limited, but is preferably 50,000 to 400,000, and preferably 70,000 to 300,000 from the viewpoint of strength and moldability. It is more preferable.
- the said weight average molecular weight is a weight average molecular weight of standard polystyrene conversion measured by gel permeation chromatography (GPC).
- the vinyl copolymer resin (A) can be blended with other resins as long as the transparency is not impaired.
- examples include methyl methacrylate-styrene copolymer resin, polymethyl methacrylate, polystyrene, polycarbonate, cycloolefin (co) polymer resin, acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, and various elastomers. .
- the glass transition temperature of the vinyl copolymer resin (A) is preferably in the range of 110 to 140 ° C.
- the laminate provided by the present invention is less likely to be deformed or cracked in a thermal environment or a moist heat environment, and is 140 ° C. or lower due to a mirror roll or a shaping roll.
- Excellent workability such as continuous heat forming or batch-type heat forming using mirror molds or forming molds.
- the glass transition temperature in this invention is a temperature when using a differential scanning calorimetry apparatus and measuring by 10 mg of samples and the temperature increase rate of 10 degree-C / min, and calculating by the midpoint method.
- the polycarbonate resin (B) used in the present invention is not particularly limited, and a polymer produced from a bisphenol compound by a known method can be used. Examples thereof include a carbonate polymer obtained by transesterification from 2,2-bis (4-hydroxyphenyl) propane and a carbonic acid diester.
- the vinyl copolymer resin (A) and / or the polycarbonate resin (B) may contain an ultraviolet absorber.
- the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy -4-octadecyloxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, etc.
- Benzophenone UV absorber 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole, 2- (2-hydroxy-3 -T-Butyl-5-methylphenyl) benzotriazo , Benzotriazole ultraviolet absorbers such as (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, phenyl salicylate, 2,4-di-t-butyl Benzoate UV absorbers such as phenyl-3,5-di-t-butyl-4-hydroxybenzoate, and hindered amine UV absorbers such as bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-ethoxy
- the method of mixing the ultraviolet absorber with the vinyl copolymer resin (A) and / or the polycarbonate resin (B) is not particularly limited, and a method of compounding the whole amount, a method of dry blending the master batch, a method of dry blending the whole amount, etc. are used. be able to.
- various additives can be mixed and used in the vinyl copolymer resin (A) and the polycarbonate resin (B) in the present invention as long as the transparency is not impaired.
- the additive include an antioxidant, an anticolorant, an antistatic agent, a release agent, a lubricant, a dye, and a pigment.
- the method of mixing is not particularly limited, and a method of compounding the whole amount, a method of dry blending the master batch, a method of dry blending the whole amount, and the like can be used.
- a method by coextrusion can be used as a method for producing the synthetic resin laminate of the present invention.
- the method of coextrusion is not particularly limited.
- a vinyl copolymer resin (A) layer is laminated on one side of a polycarbonate resin (B) layer with a feed block and extruded into a sheet shape with a T die. Then, it is cooled while passing through a forming roll to form a desired synthetic resin laminate.
- a vinyl copolymer resin (A) layer is laminated on one side of a polycarbonate resin (B) layer in a multi-manifold die, extruded into a sheet, and then cooled while passing through a forming roll to obtain a desired one.
- a synthetic resin laminate is formed.
- the thickness of the synthetic resin laminate of the present invention is preferably in the range of 0.1 to 10.0 mm. When it is 0.1 mm or more, transfer defects and thickness accuracy defects are less likely to occur, and when it is 10.0 mm or less, thickness accuracy defects and appearance defects due to uneven cooling after molding are less likely to occur.
- the range is more preferably 0.2 to 5.0 mm, and still more preferably 0.3 to 3.0 mm.
- the thickness of the vinyl copolymer resin (A) layer in the synthetic resin laminate of the present invention is preferably in the range of 10 to 500 ⁇ m. If it is less than 10 ⁇ m, the surface hardness, scratch resistance and weather resistance may be insufficient. If it exceeds 500 ⁇ m, the impact resistance may be insufficient. Preferably it is in the range of 30-100 ⁇ m.
- the synthetic resin laminate of the present invention may be subjected to a hard coat treatment on the vinyl copolymer resin (A) layer, or on the vinyl copolymer resin (A) layer and the polycarbonate resin (B) layer.
- a hard coat treatment include those in which a hard coat layer is formed by using a hard coat paint that is cured using thermal energy and / or light energy.
- the hard coat paint that is cured using thermal energy include polyorganosiloxane-based and cross-linked acrylic-based thermosetting resin compositions.
- a photocurable resin in which a photopolymerization initiator is added to a resin composition composed of monofunctional and / or polyfunctional acrylate monomers and / or oligomers Examples thereof include a composition.
- the hard coat coating applied on the vinyl copolymer resin (A) layer and cured using thermal energy includes, for example, 100 parts by mass of organotrialkoxysilane (a1) and a particle size of 4 to 100 parts by mass of a resin composition comprising 50 to 200 parts by mass of a colloidal silica solution (a2) containing 10 to 50% by mass of 20 nm colloidal silica contains 1 part of amine carboxylate and / or quaternary ammonium carboxylate (a3).
- a1 100 parts by mass of organotrialkoxysilane
- a2 colloidal silica solution
- a3 containing 10 to 50% by mass of 20 nm colloidal silica contains 1 part of amine carboxylate and / or quaternary ammonium carboxylate
- thermosetting resin composition to which 5 parts by mass is added.
- the hard coat coating applied on the vinyl copolymer resin (A) layer and cured using light energy includes, for example, tris (acryloxyethyl) isocyanurate (b1) of 40 to 80% by mass.
- (B1) is a bifunctional and / or trifunctional (meth) acrylate compound (b2) 20 to 40% by mass of a resin composition comprising 100 parts by mass of a photopolymerization initiator (b3). Examples thereof include a photocurable resin composition to which 10 parts by mass is added.
- the hard coat coating applied on the polycarbonate resin (B) layer and cured using light energy is, for example, 20 to 60% by mass of 1,9-nonanediol diacrylate (c1) ( a bifunctional or higher polyfunctional (meth) acrylate monomer copolymerizable with c1) and a bifunctional or higher polyfunctional urethane (meth) acrylate oligomer and / or a bifunctional or higher polyfunctional polyester (meth) acrylate oligomer and / or 2
- a curable resin composition include a curable resin composition.
- the method for applying the hard coat paint is not particularly limited, and a known method can be used. Examples thereof include brush, gravure roll, dipping, flow coating, spray, ink jet, and the method described in Japanese Patent No. 4161182.
- the synthetic resin laminate of the present invention can be subjected to one or more of antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment and antiglare treatment on one side or both sides.
- the methods of antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment and antiglare treatment are not particularly limited, and known methods can be used. For example, a method of applying a reflection reducing coating, a method of depositing a dielectric thin film, a method of applying an antistatic coating, and the like can be mentioned.
- the synthetic resin laminate of the present invention has transparency, and the total light transmittance is 80% or more, preferably 88% or more, more preferably 90% or more.
- a test piece of a synthetic resin laminate was cut out in a 10 cm square, left in an environment at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours or more, adjusted for condition, and then set at a temperature of 85 ° C. and a relative humidity of 85%.
- the test piece was suspended from the corner as a fulcrum and held in that state for 72 hours.
- the taken-out test piece was left still on a horizontal surface in a convex state, and the amount of change in the gap length between the four corners of the test piece and the horizontal surface was added together and evaluated as shape stability.
- For a test piece with a thickness of 1.2 mm a variation of 1.5 mm or less was accepted, and for a test piece with a thickness of 0.5 mm, a variation of 3.0 mm or less was accepted.
- ⁇ Pencil scratch hardness test> In accordance with JIS K 5600-5-4, the hardness that gradually increased the hardness to the surface of the vinyl copolymer resin (A) layer with an angle of 45 degrees with respect to the surface and a load of 750 g and pressed the pencil, and it was the hardest that did not produce a scratch The pencil hardness was evaluated as the pencil hardness. About the test piece which has not been hard-coated, the pencil hardness of 2H or higher was accepted, and for the hard-coated test piece, the pencil hardness of 3H or higher was accepted.
- ⁇ Impact resistance test> A test piece of a synthetic resin laminate was cut into a square of 80 mm, and left in an environment of a temperature of 23 ° C. and a relative humidity of 50% for 24 hours or more to adjust the condition. Then, a vinyl copolymer resin (A) layer was placed on a circular flange having a diameter of 50 mm. The metal weight with a mass of 40 g or 80 g and a tip radius of 2.5 mm is dropped on the vinyl copolymer resin (A) layer so that the tip of the weight collides, and then destroyed. The highest drop height at which no occurrence occurred was evaluated as impact resistance.
- test piece of hard coat untreated and hard coat single-sided treatment with a thickness of 1.2 mm a test piece with a weight of 80 g and a drop height of less than 50 cm is accepted, and a hard coat double-sided treatment with a thickness of 1.2 mm.
- a test piece with a weight of 40 g and a drop height of less than 50 cm that does not cause breakage is accepted, and the thickness is 0.5 mm. Used a weight with a mass of 40 g and a drop height of less than 20 cm and no breakage was accepted.
- Total light transmittance measurement> The total light transmittance of the test piece was measured using a color / turbidity simultaneous measuring device COH400 (manufactured by Nippon Denshoku Industries Co., Ltd.). A sample having a total light transmittance of 90% or more was regarded as acceptable.
- Synthesis Example 1 [Production of vinyl copolymer resin (A1)] Purified methyl methacrylate (Mitsubishi Gas Chemical Co., Ltd.) 77.000 mol%, purified styrene (Wako Pure Chemical Industries, Ltd.) 22.998 mol%, and t-amylperoxy-2-ethyl as a polymerization initiator A monomer composition consisting of 0.002 mol% of hexanoate (Arkema Yoshitomi Co., Ltd., trade name: Luperox 575) is continuously supplied at 1 kg / h to a 10 L complete mixing tank with a helical ribbon blade, and an average residence time of 2 Continuous polymerization was carried out at a polymerization temperature of 150 ° C.
- the obtained vinyl copolymer resin (A1 ′) was dissolved in methyl isobutyrate (manufactured by Kanto Chemical Co., Inc.) to prepare a 10 mass% methyl isobutyrate solution.
- a 1000 mL autoclave apparatus was charged with 500 parts by weight of a 10% by weight methyl isobutyrate solution (A1 ′) and 1 part by weight of 10% by weight Pd / C (manufactured by NE Chemcat), and maintained at a hydrogen pressure of 9 MPa and 200 ° C.
- the aromatic double bond site of the vinyl copolymer resin (A1 ′) was hydrogenated.
- the catalyst was removed by a filter and introduced into a solvent removal apparatus to obtain a pellet-like vinyl copolymer resin (A1).
- the proportion of the methyl methacrylate structural unit in the vinyl copolymer resin (A1) is 75 mol%, and as a result of the absorbance measurement at a wavelength of 260 nm, the hydrogenation reaction of the aromatic double bond site.
- the rate was 99%.
- the weight average molecular weight (standard polystyrene conversion) measured by gel permeation chromatography was 125,000.
- Synthesis Example 2 [Production of vinyl copolymer resin (A2)] A vinyl copolymer resin (A2) was prepared in the same manner as in Synthesis Example 1 except that the amount of methyl methacrylate used in Synthesis Example 1 was changed to 50.000 mol% and the amount of styrene used was changed to 49.998 mol%. Obtained. As a result of measurement by 1 H-NMR, the proportion of the methyl methacrylate structural unit in the vinyl copolymer resin (A2) is 48 mol%, and as a result of the absorbance measurement at a wavelength of 260 nm, the hydrogenation reaction of the aromatic double bond site. The rate was 99%. The weight average molecular weight (standard polystyrene conversion) measured by gel permeation chromatography was 170,000.
- Synthesis Example 3 [Production of vinyl copolymer resin (A3)] A vinyl copolymer resin (A3) was prepared in the same manner as in Synthesis Example 1 except that the amount of methyl methacrylate used in Synthesis Example 1 was 60.19 mol% and that of styrene was 39.979 mol%. Obtained. As a result of measurement by 1 H-NMR, the proportion of the methyl methacrylate structural unit in the vinyl copolymer resin (A3) was 58 mol%, and as a result of the absorbance measurement at a wavelength of 260 nm, the hydrogenation reaction of the aromatic double bond site. The rate was 99%. The weight average molecular weight (standard polystyrene conversion) measured by gel permeation chromatography was 155,000.
- Synthesis Example 4 [Production of vinyl copolymer resin (A4)] A vinyl copolymer resin (A4) was prepared in the same manner as in Synthesis Example 1 except that the amount of methyl methacrylate used in Synthesis Example 1 was 92.000 mol% and that of styrene was 7.998 mol%. Obtained. As a result of measurement by 1 H-NMR, the proportion of the methyl methacrylate structural unit in the vinyl copolymer resin (A4) is 90 mol%, and as a result of the absorbance measurement at a wavelength of 260 nm, the hydrogenation reaction of the aromatic double bond site. The rate was 99%. The weight average molecular weight (standard polystyrene conversion) measured by gel permeation chromatography was 120,000.
- Synthesis Example 6 [Production of photocurable resin composition for hard coat (b) coated on vinyl copolymer resin (A) layer]
- a mixing vessel equipped with a stirring blade 60 parts by mass of tris (2-acryloxyethyl) isocyanurate (manufactured by Aldrich) and 40 parts by mass of neopentyl glycol oligoacrylate (manufactured by Osaka Organic Chemical Industry, trade name: 215D) 1 part by mass of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by Ciba Japan, trade name: DAROCUR TPO), 0.3 part by mass of 1-hydroxycyclohexyl phenyl ketone (manufactured by Aldrich), A mixture of 1 part by mass of 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (manufactured by Ciba Japan, trade name: TIN
- Synthesis Example 7 [Production of photocurable resin composition for hard coat (c) coated on polycarbonate resin (B) layer]
- a mixing tank equipped with a stirring blade 40 parts by mass of 1,9-nonanediol diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: Biscote # 260) and a hexafunctional urethane acrylate oligomer (manufactured by Shin-Nakamura Chemical Co., Ltd., Product name: U-6HA) 40 parts by mass, succinic acid / trimethylolethane / acrylic acid molar ratio 1/2/4 condensate 20 parts by mass, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Ciba -Japan Co., Ltd., trade name: DAROCUR TPO) 2.8 parts by mass, benzophenone (manufactured by Aldrich) 1 part by mass, 2- (2H-benzotriazol-2-
- Example 1 Synthetic resin using a multi-layer extrusion apparatus having a single-screw extruder with a shaft diameter of 35 mm, a single-screw extruder with a shaft diameter of 65 mm, a feed block connected to all the extruders, and a T-die connected to the feed block A laminate was formed.
- the vinyl copolymer resin (A1) obtained in Synthesis Example 1 was continuously introduced into a single-screw extruder having a shaft diameter of 35 mm and extruded under the conditions of a cylinder temperature of 240 ° C. and a discharge speed of 2.6 kg / h.
- polycarbonate resin (B) (trade name: Iupilon S-1000, manufactured by Mitsubishi Engineering Plastics Co., Ltd.) was continuously introduced into a single screw extruder with a shaft diameter of 65 mm, the cylinder temperature was 280 ° C., and the discharge speed was 50.0 kg / h. Extruded with The feed block connected to the entire extruder was provided with two types and two layers of distribution pins, and the vinyl copolymer resin (A1) and the polycarbonate resin (B) were introduced and laminated at a temperature of 270 ° C.
- Example 2 Vinyl copolymerization was carried out in the same manner as in Example 1 except that the discharge rate of the vinyl copolymer resin (A1) used in Example 1 was 4.8 kg / h and the discharge rate of the polycarbonate resin (B) was 35 kg / h. A laminate (D2) of the resin (A1) layer and the polycarbonate resin (B) layer was obtained. The thickness of the obtained laminate was 0.5 mm, and the thickness of the vinyl copolymer resin (A1) layer was 60 ⁇ m near the center. The result of the R25mm bending test is passed without change, the result of the high temperature and high humidity exposure test is passed at 0.5 mm, the result of the pencil scratch hardness test is passed at 2H, and the result of the impact resistance test is 30 cm. And the total light transmittance was 91%, and the overall judgment was acceptable.
- Example 3 The coating thickness after curing the thermosetting resin composition for hard coat (a) obtained in Synthesis Example 5 on the vinyl copolymer resin (A1) layer of the laminate (D1) obtained in Example 1 is as follows. It was applied using a bar coater to a thickness of 3 to 8 ⁇ m, dried at 25 ° C. for 15 minutes, then cured with a hot air circulating dryer set at 130 ° C. for 1 hour, and hard on the vinyl copolymer resin (A1) layer. A laminate (E1) provided with a coat was obtained. R25mm bending test result passed without change, high temperature and high humidity exposure test result passed 1.2mm, pencil scratch hardness test passed 3H, impact resistance test result 60cm And the total light transmittance was 91%, and the overall judgment was acceptable.
- Example 4 The coating thickness after curing the photocurable resin composition for hard coat (b) obtained in Synthesis Example 6 on the vinyl copolymer resin (A1) layer of the laminate (D1) obtained in Example 1 is as follows. Coating was performed using a bar coater so as to have a thickness of 3 to 8 ⁇ m. After covering with a PET film and press-bonding, ultraviolet rays are irradiated on a conveyor equipped with a high-pressure mercury lamp with a light source distance of 12 cm and an output of 80 W / cm at a line speed of 1.5 m / min. b) was cured. The PET film was peeled off to obtain a laminate (E2) having a hard coat on the vinyl copolymer resin (A1) layer. R25mm bending test result passed without change, high temperature and high humidity exposure test result passed 1.3mm, pencil scratch hardness test passed 4H, impact resistance test result 60cm And the total light transmittance was 91%, and the overall judgment was acceptable.
- Example 5 The coating thickness after curing the photocurable resin composition for hard coat (b) obtained in Synthesis Example 6 on the vinyl copolymer resin (A1) layer of the laminate (D1) obtained in Example 1 is as follows. Coating was performed using a bar coater so as to have a thickness of 3 to 8 ⁇ m. Coating thickness after curing the photocurable resin composition for hard coat (c) obtained in Synthesis Example 7 on the polycarbonate resin (B) layer of the laminate (D1) after covering with PET film and press-bonding was applied using a bar coater so as to be 3 to 8 ⁇ m, covered with a PET film and pressure-bonded.
- the photocurable resin composition for hard coat (b) and (c) is cured by irradiating with ultraviolet rays on a conveyor equipped with a high pressure mercury lamp with a light source distance of 12 cm and an output of 80 W / cm at a line speed of 1.5 m / min. I let you.
- the PET film was peeled off to obtain a laminate (E3) having a hard coat on the vinyl copolymer resin (A1) layer and the polycarbonate resin (B) layer.
- the result of the R25mm bending test is acceptable without change, the result of the high temperature and high humidity exposure test is acceptable at 1.0 mm, the result of the pencil scratch hardness test is acceptable at 4H, and the result of the impact resistance test is 60 cm. And the total light transmittance was 91%, and the overall judgment was acceptable.
- Example 6 In the same manner as in Example 3, except that the laminate (D2) obtained in Example 2 was used instead of the laminate (D1) used in Example 3, a hard layer was formed on the vinyl copolymer resin (A1) layer. A laminate (E4) provided with a coat was obtained. R25mm bending test result passed without change, high temperature and high humidity exposure test result passed at 2.2mm, pencil scratch hardness test result passed at 3H, impact resistance test result 30cm And the total light transmittance was 91%, and the overall judgment was acceptable.
- Example 7 In the same manner as in Example 4 except that the laminate (D2) obtained in Example 2 was used instead of the laminate (D1) used in Example 4, a hard layer was formed on the vinyl copolymer resin (A1) layer. A laminate (E5) provided with a coat was obtained. R25mm bending test result passed without change, high temperature and high humidity exposure test result passed 2.2mm, pencil scratch hardness test result passed 4H, impact resistance test result 30cm And the total light transmittance was 91%, and the overall judgment was acceptable.
- Example 8 Except for using the laminate (D2) obtained in Example 2 instead of the laminate (D1) used in Example 5, the same procedure as in Example 5 was performed on the vinyl copolymer resin (A) layer and the polycarbonate. A laminate (E6) having a hard coat on the resin (B) layer was obtained. R25mm bending test result passed without change, high temperature and high humidity exposure test result passed 2.1mm, pencil scratch hardness test result passed 4H, impact resistance test result 30cm And the total light transmittance was 91%, and the overall judgment was acceptable.
- a vinyl copolymer resin (A2) was obtained in the same manner as in Example 1 except that the vinyl copolymer resin (A2) obtained in Synthesis Example 2 was used instead of the vinyl copolymer resin (A1) used in Example 1.
- a laminate (D3) of the layer and the polycarbonate resin (B) layer was obtained.
- the thickness of the obtained laminate was 1.2 mm, and the thickness of the vinyl copolymer resin (A2) layer was 60 ⁇ m near the center.
- the result of the high-temperature and high-humidity exposure test was 0.5 mm, the impact resistance test was 60 cm, and the total light transmittance was 91%. Peeling occurred and it was rejected, and the result of the pencil scratch hardness test was H and rejected, and the comprehensive judgment was rejected.
- a vinyl copolymer resin (A2) was obtained in the same manner as in Example 2 except that the vinyl copolymer resin (A2) obtained in Synthesis Example 2 was used instead of the vinyl copolymer resin (A1) used in Example 2.
- a laminate (D4) of the layer and the polycarbonate resin (B) layer was obtained.
- the thickness of the obtained laminate was 0.5 mm
- the thickness of the vinyl copolymer resin (A2) layer was 60 ⁇ m near the center.
- the result of the high-temperature and high-humidity exposure test was 1.2 mm
- the impact test was 30 cm
- the total light transmittance was 91%
- the R25 mm bending test was cracked.
- the result of the pencil scratch hardness test was H, and the comprehensive judgment was rejected.
- Comparative Example 3 Except for using the laminate (D3) obtained in Comparative Example 1 instead of the laminate (D1) used in Example 5, the same procedure as in Example 5 was performed on the vinyl copolymer resin (A2) layer and the polycarbonate. A laminate (E7) having a hard coat on the resin (B) layer was obtained.
- the result of the high temperature and high humidity exposure test is 0.5 mm
- the pencil scratch hardness test is 3H
- the impact resistance test is 60 cm
- the total light transmittance 91%.
- the result of the R25 mm bending test was a failure due to cracking and peeling, and the overall judgment was a failure.
- a vinyl copolymer resin (A3) was obtained in the same manner as in Example 1 except that the vinyl copolymer resin (A3) obtained in Synthesis Example 3 was used instead of the vinyl copolymer resin (A1) used in Example 1.
- a laminate (D5) of the layer and the polycarbonate resin (B) layer was obtained.
- the thickness of the obtained laminate was 1.2 mm, and the thickness of the vinyl copolymer resin (A3) layer was 60 ⁇ m near the center.
- the result of the high-temperature and high-humidity exposure test was 0.4 mm, the impact resistance test was 60 cm, and the total light transmittance was 91%, but the R25 mm bending test was cracked.
- the result of the pencil scratch hardness test was H, and the comprehensive judgment was rejected.
- a vinyl copolymer resin (A3) was obtained in the same manner as in Example 2 except that the vinyl copolymer resin (A3) obtained in Synthesis Example 3 was used instead of the vinyl copolymer resin (A1) used in Example 2.
- a laminate (D6) of the layer and the polycarbonate resin (B) layer was obtained.
- the thickness of the obtained laminate was 0.5 mm, and the thickness of the (A3) layer was 60 ⁇ m near the center.
- the result of the high-temperature and high-humidity exposure test was 1.4 mm, the impact resistance test was 30 cm, and the total light transmittance was 91%, but the R25 mm bending test was cracked.
- the result of the pencil scratch hardness test was H, and the comprehensive judgment was rejected.
- Comparative Example 6 Except for using the laminate (D5) obtained in Comparative Example 4 instead of the laminate (D1) used in Example 5, the same procedure as in Example 5 was performed on the vinyl copolymer resin (A3) layer and the polycarbonate. A laminate (E8) having a hard coat on the resin (B) layer was obtained.
- the result of the high-temperature and high-humidity exposure test was 0.6 mm
- the pencil scratch hardness test was 3H
- the impact test was 60 cm
- the total light transmittance was 91%.
- the result of the R25 mm bending test was a failure due to cracking and peeling, and the overall judgment was a failure.
- a vinyl copolymer resin (A4) was obtained in the same manner as in Example 1 except that the vinyl copolymer resin (A4) obtained in Synthesis Example 4 was used instead of the vinyl copolymer resin (A1) used in Example 1.
- a laminate (D7) of the layer and the polycarbonate resin (B) layer was obtained.
- the thickness of the obtained laminate was 1.2 mm, and the thickness of the vinyl copolymer resin (A4) layer was 60 ⁇ m near the center.
- the result of the R25mm bending test was passed without change, the result of the pencil scratch hardness test was passed at 2H, the result of the impact resistance test was passed at 90cm, and the total light transmittance was passed at 91%.
- the result of the high-temperature and high-humidity exposure test was 2.0 mm, which was unacceptable, and the comprehensive judgment was unacceptable.
- a vinyl copolymer resin (A4) was obtained in the same manner as in Example 2 except that the vinyl copolymer resin (A4) obtained in Synthesis Example 4 was used instead of the vinyl copolymer resin (A1) used in Example 2.
- a laminate (D8) of the layer and the polycarbonate resin (B) layer was obtained.
- the thickness of the obtained laminate was 0.5 mm
- the thickness of the vinyl copolymer resin (A4) layer was 60 ⁇ m near the center.
- the result of the R25mm bending test was accepted without change, the result of the pencil scratch hardness test was 2H, the result of the impact resistance test was 30cm, and the total light transmittance was 91%.
- the result of the high-temperature and high-humidity exposure test was 6.0 mm, which was unacceptable, and the comprehensive judgment was unacceptable.
- Comparative Example 9 In the same manner as in Example 4 except that the laminate (D7) obtained in Comparative Example 7 was used instead of the laminate (D1) used in Example 4, a hard layer was formed on the vinyl copolymer resin (A4) layer. A laminate (E9) provided with a coat was obtained. The result of the R25mm bending test was passed without change, the result of the pencil scratch hardness test was passed at 4H, the result of the impact resistance test was passed at 80cm, and the total light transmittance was passed at 91%. However, the result of the high-temperature and high-humidity exposure test was 3.4 mm, which was unacceptable, and the comprehensive judgment was unacceptable.
- Comparative Example 10 Except for using the laminate (D7) obtained in Comparative Example 7 instead of the laminate (D1) used in Example 5, the same procedure as in Example 5 was performed on the vinyl copolymer resin (A4) layer and the polycarbonate. A laminate (E10) having a hard coat on the resin (B) layer was obtained. The result of the R25mm bending test was passed without change, the result of the pencil scratch hardness test was passed at 4H, the result of the impact resistance test was passed at 60cm, and the total light transmittance was passed at 91%. However, the result of the high-temperature and high-humidity exposure test was 3.0 mm, which was unacceptable, and the comprehensive judgment was unacceptable.
- Comparative Example 11 In the same manner as in Example 4 except that the laminate (D8) obtained in Comparative Example 8 was used instead of the laminate (D1) used in Example 4, a hard layer was formed on the vinyl copolymer resin (A4) layer. A laminate (E11) provided with a coat was obtained. The result of the R25mm bending test was passed without change, the result of the pencil scratch hardness test was passed at 4H, the result of the impact resistance test was passed at 30cm, and the total light transmittance was passed at 91%. However, the result of the high-temperature and high-humidity exposure test was 7.8 mm, which was unacceptable, and the comprehensive judgment was unacceptable.
- Comparative Example 12 Except for using the laminate (D8) obtained in Comparative Example 8 instead of the laminate (D1) used in Example 5, the same procedure as in Example 5 was performed on the vinyl copolymer resin (A4) layer and the polycarbonate. A laminate (E12) provided with a hard coat on the resin (B) layer was obtained. The result of the R25mm bending test was passed without change, the result of the pencil scratch hardness test was passed at 4H, the result of the impact resistance test was passed at 30cm, and the total light transmittance was passed at 91%. However, the result of the high-temperature and high-humidity exposure test was 7.5 mm, which was rejected, and the comprehensive judgment was rejected.
- Comparative Example 13 A polymethyl methacrylate resin (A5) (manufactured by ARKEMA, trade name: ALTUGLAS V020) was used in place of the vinyl copolymer resin (A1) used in Example 1 in the same manner as in Example 1, except that A laminate (D9) of a methyl methacrylate resin (A5) layer and a polycarbonate resin (B) layer was obtained. The thickness of the obtained laminate was 1.2 mm, and the thickness of the polymethyl methacrylate resin (A5) layer was 60 ⁇ m near the center.
- the result of the R25mm bending test was passed without change, the result of the pencil scratch hardness test was passed at 3H, the result of the impact resistance test was passed at 120cm, and the total light transmittance was passed at 91%.
- the result of the high-temperature and high-humidity exposure test was 3.9 mm, which was unacceptable, and the comprehensive judgment was unacceptable.
- Comparative Example 15 On the polymethyl methacrylate resin (A5) layer in the same manner as in Example 4 except that the laminate (D9) obtained in Comparative Example 13 was used instead of the laminate (D1) used in Example 4. A laminate (E13) provided with a hard coat was obtained.
- the result of the R25mm bending test was passed without change, the result of the pencil scratch hardness test was passed at 4H, the result of the impact resistance test was passed at 100cm, and the total light transmittance was passed at 91%.
- the result of the high-temperature and high-humidity exposure test was 6.0 mm, which was unacceptable, and the comprehensive judgment was unacceptable.
- Comparative Example 16 In the same manner as in Example 5, except that the laminate (D9) obtained in Comparative Example 13 was used instead of the laminate (D1) used in Example 5, and on the polymethyl methacrylate resin (A5) layer and A laminate (E14) having a hard coat on the polycarbonate resin (B) layer was obtained.
- the result of the R25mm bending test was passed without change, the result of the pencil scratch hardness test was passed at 4H, the result of the impact resistance test was passed at 60cm, and the total light transmittance was passed at 91%.
- the result of the high-temperature and high-humidity exposure test was 5.3 mm, which was unacceptable, and the comprehensive judgment was unacceptable.
- Comparative Example 17 On the polymethyl methacrylate resin (A5) layer in the same manner as in Example 4 except that the laminate (D10) obtained in Comparative Example 14 was used instead of the laminate (D1) used in Example 4. A laminate (E15) provided with a hard coat was obtained.
- the result of the R25mm bending test was passed without change, the result of the pencil scratch hardness test was passed with 4H, the result of the impact resistance test was passed with 30cm, and the total light transmittance was passed with 92%.
- the result of the high-temperature and high-humidity exposure test was 19.2 mm, which was unacceptable, and the comprehensive judgment was unacceptable.
- Comparative Example 18 A polymethyl methacrylate resin (A5) layer and a polycarbonate were obtained in the same manner as in Example 5 except that the laminate (D10) obtained in Comparative Example 14 was used instead of the laminate (D1) used in Example 5. A laminate (E16) having a hard coat on the resin (B) layer was obtained. The result of the R25mm bending test was passed without change, the result of the pencil scratch hardness test was passed with 4H, the result of the impact resistance test was passed with 30cm, and the total light transmittance was passed with 92%. However, the result of the high-temperature and high-humidity exposure test was 18.1 mm, which was unacceptable, and the comprehensive judgment was unacceptable.
- the thickness of the obtained laminate was 1.2 mm, and the thickness of the polymethyl methacrylate resin (A5) layer was 60 ⁇ m near the center.
- the result of the R25 mm bending test is acceptable without any change, the result of the high temperature and high humidity exposure test is acceptable at 0.5 mm, the result of the pencil scratch hardness test is acceptable at 3H, and the total light transmittance is 91%. Although it passed, the result of the impact resistance test was 40 cm, it was rejected, and the comprehensive judgment was rejected.
- Comparative Example 21 Coating film after curing the photocurable resin composition for hard coat (b) obtained in Synthesis Example 6 on one polymethyl methacrylate resin (A5) layer of the laminate (D11) obtained in Comparative Example 19 Coating was performed using a bar coater so that the thickness was 3 to 8 ⁇ m. Covered with a PET film and pressure-bonded, irradiated with ultraviolet rays on a conveyor equipped with a high-pressure mercury lamp with a light source distance of 12 cm and an output of 80 W / cm at a line speed of 1.5 m / min. ) Was cured. The PET film was peeled off to obtain a laminate (E17) having a hard coat on one polymethyl methacrylate resin (A5) layer.
- the synthetic resin laminate of the present invention is excellent in interlayer adhesion, shape stability in a high temperature and high humidity environment, surface hardness and impact resistance.
- thermoplastic resin laminate of the present invention is characterized by excellent interlayer adhesion, shape stability in a high temperature and high humidity environment, surface hardness and impact resistance, and is suitable as a transparent substrate material, a transparent protective material, etc. Especially, it is suitably used as a display unit front plate of OA equipment / portable electronic equipment.
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Abstract
Description
特許文献2には、積層体の反りを抑えるために、吸水率の低い樹脂をポリカーボネート樹脂上に積層した積層体が開示されている。しかしながら、温度85℃、相対湿度85%といった高温高湿環境では、該積層体はポリカーボネート樹脂の吸湿により大きな反りを生じることがある。また、吸水率の低い樹脂は親水性が乏しいため、ハードコート処理や反射防止処理、防汚処理、あるいは防眩処理といった表面コートとの層間剥離や、表面硬度の不足が生じることもあり、使用方法によっては問題となることがある。
特許文献3には、特定の(メタ)アクリル酸エステル構成単位を含有するビニル共重合樹脂とポリカーボネート樹脂とを積層した、耐衝撃性、耐熱性、耐候性、耐擦傷性に優れた積層体が開示されているが、使用条件によっては積層体の界面で剥離を生じることがある。
また、ポリカーボネート樹脂層の両面にアクリル系樹脂層を積層した積層体が知られているが、その積層体の片面に面衝撃を与えた際に、その反対面のアクリル系樹脂層においてクラックを生じ易く、使用方法によっては問題となることがある。
すなわち、本発明は、以下の合成樹脂積層体及び該合成樹脂積層体を用いた透明性材料を提供するものである。
前記ビニル共重合樹脂(A)が、下記一般式(1)で表される(メタ)アクリル酸エステル構成単位(a)と、下記一般式(2)で表される脂肪族ビニル構成単位(b)とを含み、前記(メタ)アクリル酸エステル構成単位(a)と前記脂肪族ビニル構成単位(b)との合計割合が前記ビニル共重合樹脂(A)中の全構成単位の合計に対して90~100モル%であり、前記(メタ)アクリル酸エステル構成単位(a)の割合が前記ビニル共重合樹脂(A)中の全構成単位の合計に対して65~80モル%であることを特徴とする合成樹脂積層体。
3.前記一般式(1)において、R1及びR2がメチル基である上記1又は2に記載の合成樹脂積層体。
4.前記一般式(2)において、R3が水素原子であり、R4がシクロヘキシル基である上記1~3のいずれかに記載の合成樹脂積層体。
5.ビニル共重合樹脂(A)及び/又はポリカーボネート樹脂(B)が紫外線吸収剤を含有する上記1~4のいずれかに記載の合成樹脂積層体。
6.ビニル共重合樹脂(A)層上にハードコート処理を施した上記1~5のいずれかに記載の合成樹脂積層体。
7.ビニル共重合樹脂(A)層上及びポリカーボネート樹脂(B)層上にハードコート処理を施した上記1~5のいずれかに記載の合成樹脂積層体。
8.片面又は両面に反射防止処理、防汚処理、帯電防止処理、耐候性処理及び防眩処理から選択されるいずれか一つ以上の処理を施した上記1~7のいずれかに記載の合成樹脂積層体。
9.上記1~8のいずれかに記載の合成樹脂積層体からなる透明性基板材料。
10.上記1~8のいずれかに記載の合成樹脂積層体からなる透明性保護材料。
前記ビニル共重合樹脂(A)が、下記一般式(1)で表される(メタ)アクリル酸エステル構成単位(a)と、下記一般式(2)で表される脂肪族ビニル構成単位(b)とを含み、前記(メタ)アクリル酸エステル構成単位(a)と前記脂肪族ビニル構成単位(b)との合計割合が前記ビニル共重合樹脂(A)中の全構成単位の合計に対して90~100モル%であり、前記(メタ)アクリル酸エステル構成単位(a)の割合が前記ビニル共重合樹脂(A)中の全構成単位の合計に対して65~80モル%であることを特徴とするものである。
該(メタ)アクリル酸エステル構成単位のうち、好ましいのはR2がメチル基及び/又はエチル基である(メタ)アクリル酸エステル構成単位であり、更に好ましいのはR1がメチル基であり、R2がメチル基であるメタクリル酸メチル構成単位である。
該脂肪族ビニル構成単位のうち、好ましいのはR3が水素原子であり、R4がシクロヘキシル基である脂肪族ビニル構成単位である。
前記(メタ)アクリル酸エステル構成単位(a)と前記脂肪族ビニル構成単位(b)との合計割合は、前記ビニル共重合樹脂(A)中の全構成単位の合計に対して90~100モル%であり、好ましくは95~100モル%であり、より好ましくは98~100モル%である。
すなわち、前記ビニル共重合樹脂(A)は、全構成単位の合計に対して10モル%以下の範囲で、前記(メタ)アクリル酸エステル構成単位(a)及び前記脂肪族ビニル構成単位(b)以外の構成単位を含有していてもよい。
前記(メタ)アクリル酸エステル構成単位(a)及び前記脂肪族ビニル構成単位(b)以外の構成単位としては、例えば、(メタ)アクリル酸エステルモノマーと芳香族ビニルモノマーとを重合した後に該芳香族ビニルモノマー由来の芳香族二重結合を水素化して得られたビニル共重合樹脂(A)における、水素化されていない芳香族二重結合を含む芳香族ビニルモノマー由来の構成単位などが挙げられる。
また、前記一般式(1)で表される(メタ)アクリル酸エステル構成単位(a)の割合は、前記ビニル共重合樹脂(A)中の全構成単位の合計に対して65~80モル%であり、好ましくは70~80モル%である。
ビニル共重合樹脂(A)中の全構成単位の合計に対する(メタ)アクリル酸エステル構成単位(a)の割合が65モル%未満であると、ポリカーボネート樹脂(B)との密着性や表面硬度が低下し、実用的でない場合がある。また80モル%を超えると、積層体の吸水による反りが発生し、実用的でない場合がある。
この際に使用される芳香族ビニルモノマーとしては、具体的にはスチレン、α-メチルスチレン、p-ヒドロキシスチレン、アルコキシスチレン、クロロスチレン、及びそれらの誘導体などが挙げられる。これらの中で好ましいのはスチレンである。
塊状重合法は、上記モノマー、重合開始剤を含むモノマー組成物を完全混合槽に連続的に供給し、100~180℃で連続重合する方法などにより行われる。上記モノマー組成物は、必要に応じて連鎖移動剤を含んでもよい。
水素化の方法は特に限定されず、公知の方法を用いることができる。例えば、水素圧力3~30MPa、反応温度60~250℃でバッチ式あるいは連続流通式で行うことができる。温度を60℃以上とすることにより反応時間がかかり過ぎることがなく、また250℃以下とすることにより分子鎖の切断やエステル部位の水素化を起こすことが少ない。
上記重量平均分子量は、ゲル浸透クロマトグラフィー(GPC)により測定される、標準ポリスチレン換算の重量平均分子量である。
共押出の方法は特に限定されず、例えば、フィードブロック方式では、フィードブロックでポリカーボネート樹脂(B)層の片面にビニル共重合樹脂(A)層を積層し、Tダイでシート状に押し出した後、成形ロールを通過させながら冷却し所望の合成樹脂積層体を形成する。また、マルチマニホールド方式では、マルチマニホールドダイ内でポリカーボネート樹脂(B)層の片面にビニル共重合樹脂(A)層を積層し、シート状に押し出した後、成形ロールを通過させながら冷却し所望の合成樹脂積層体を形成する。
該ハードコート処理としては、熱エネルギー及び/又は光エネルギーを用いて硬化させるハードコート塗料を用いることによりハードコート層を形成するものが挙げられる。熱エネルギーを用いて硬化させるハードコート塗料としては、例えば、ポリオルガノシロキサン系、架橋型アクリル系などの熱硬化性樹脂組成物が挙げられる。また、光エネルギーを用いて硬化させるハードコート塗料としては、例えば、単官能及び/又は多官能であるアクリレートモノマー及び/又はオリゴマーからなる樹脂組成物に光重合開始剤が加えられた光硬化性樹脂組成物などが挙げられる。
実施例及び比較例で得られた合成樹脂積層体の評価は以下のように行った。
合成樹脂積層体の試験片を10cm四方に切り出し、温度23℃、相対湿度50%の環境に24時間以上放置して状態調整した後、ビニル共重合樹脂(A)層側が外側になるように半径25mmの円筒にその側面に沿うように押し付け、外観に変化のないものを合格とした。
合成樹脂積層体の試験片を10cm四方に切り出し、温度23℃、相対湿度50%の環境に24時間以上放置して状態調整した後、温度85℃、相対湿度85%に設定した環境試験機の中に角を支点として試験片を吊り下げ、その状態で72時間保持した。取り出した試験片を、下に凸の状態で水平面上に静置し、試験片の四隅と水平面との隙間長さの変化量を合算し、形状安定性として評価した。
厚み1.2mmの試験片については変化量1.5mm以下を合格とし、厚み0.5mmの試験片については変化量3.0mm以下を合格とした。
JIS K 5600-5-4に準拠し、表面に対して角度45度、荷重750gでビニル共重合樹脂(A)層の表面に次第に硬度を増して鉛筆を押し付け、きず跡を生じなかった最も硬い鉛筆の硬度を鉛筆硬度として評価した。ハードコート未処理の試験片については鉛筆硬度2H以上を合格とし、ハードコート処理した試験片については鉛筆硬度3H以上を合格とした。
合成樹脂積層体の試験片を80mm四方に切り出し、温度23℃、相対湿度50%の環境に24時間以上放置して状態調整した後、直径50mmの円形フランジにビニル共重合樹脂(A)層を上にして固定し、ビニル共重合樹脂(A)層上に次第に高さを増して質量40gあるいは80g、先端半径2.5mmの金属製錘を錘の先端部分が衝突するように落下させ、破壊の生じなかった最も高い落下高さを耐衝撃性として評価した。
厚み1.2mmでハードコート未処理及びハードコート片面処理の試験片については、質量80gの錘を用い落下高さ50cm未満で破壊の生じないものを合格とし、厚み1.2mmでハードコート両面処理の試験片については、質量40gの錘を用い落下高さ50cm未満で破壊の生じないものを合格とし、厚み0.5mmでハードコート未処理、ハードコート片面処理及びハードコート両面処理の試験片については、質量40gの錘を用い落下高さ20cm未満で破壊の生じないものを合格とした。
色彩・濁度同時測定器COH400(日本電色工業社製)を用いて試験片の全光線透過率を測定した。全光線透過率が90%以上のものを合格とした。
精製したメタクリル酸メチル(三菱ガス化学社製)77.000モル%と、精製したスチレン(和光純薬工業社製)22.998モル%と、重合開始剤としてt-アミルパーオキシ-2-エチルヘキサノエート(アルケマ吉富社製、商品名:ルペロックス575)0.002モル%からなるモノマー組成物を、ヘリカルリボン翼付き10L完全混合槽に1kg/hで連続的に供給し、平均滞留時間2.5時間、重合温度150℃で連続重合を行った。重合槽の液面が一定となるよう底部から連続的に抜き出し、脱溶剤装置に導入してペレット状のビニル共重合樹脂(A1’)を得た。
得られたビニル共重合樹脂(A1’)をイソ酪酸メチル(関東化学社製)に溶解し、10質量%イソ酪酸メチル溶液を調製した。1000mLオートクレーブ装置に(A1’)の10質量%イソ酪酸メチル溶液を500質量部、10質量%Pd/C(NEケムキャット社製)を1質量部仕込み、水素圧9MPa、200℃で15時間保持して、ビニル共重合樹脂(A1’)の芳香族二重結合部位を水素化した。フィルターにより触媒を除去し、脱溶剤装置に導入してペレット状のビニル共重合樹脂(A1)を得た。1H-NMRによる測定の結果、ビニル共重合樹脂(A1)におけるメタクリル酸メチル構成単位の割合は75モル%であり、また波長260nmにおける吸光度測定の結果、芳香族二重結合部位の水素化反応率は99%であった。ゲル浸透クロマトグラフィーにより測定した重量平均分子量(標準ポリスチレン換算)は125,000であった。
合成例1で使用したメタクリル酸メチルの使用量を50.000モル%とし、またスチレンの使用量を49.998モル%とした以外は合成例1と同様にしてビニル共重合樹脂(A2)を得た。1H-NMRによる測定の結果、ビニル共重合樹脂(A2)におけるメタクリル酸メチル構成単位の割合は48モル%であり、また波長260nmにおける吸光度測定の結果、芳香族二重結合部位の水素化反応率は99%であった。ゲル浸透クロマトグラフィーにより測定した重量平均分子量(標準ポリスチレン換算)は170,000であった。
合成例1で使用したメタクリル酸メチルの使用量を60.019モル%とし、またスチレンの使用量を39.979モル%とした以外は合成例1と同様にしてビニル共重合樹脂(A3)を得た。1H-NMRによる測定の結果、ビニル共重合樹脂(A3)におけるメタクリル酸メチル構成単位の割合は58モル%であり、また波長260nmにおける吸光度測定の結果、芳香族二重結合部位の水素化反応率は99%であった。ゲル浸透クロマトグラフィーにより測定した重量平均分子量(標準ポリスチレン換算)は155,000であった。
合成例1で使用したメタクリル酸メチルの使用量を92.000モル%とし、またスチレンの使用量を7.998モル%とした以外は合成例1と同様にしてビニル共重合樹脂(A4)を得た。1H-NMRによる測定の結果、ビニル共重合樹脂(A4)におけるメタクリル酸メチル構成単位の割合は90モル%であり、また波長260nmにおける吸光度測定の結果、芳香族二重結合部位の水素化反応率は99%であった。ゲル浸透クロマトグラフィーにより測定した重量平均分子量(標準ポリスチレン換算)は120,000であった。
撹拌翼と滴下装置を備えた混合槽に、メチルトリメトキシシラン100質量部と酢酸1質量部を加えて混合し、氷水浴で冷却して0~10℃に保持しながら撹拌した。次いで平均粒径10~20nmのコロイダルシリカ30質量%溶液(日産化学工業社製、商品名:スノーテックス30)84質量部を滴下し10℃に保持しながら4時間撹拌した。更に平均粒径10~20nmのコロイダルシリカ25~26質量%溶液(日産化学社製、商品名:スノーテックスIBA-ST)84質量部を滴下し20℃に保持しながら50時間撹拌した。酢酸セロソルブ45質量部と、イソブチルアルコール50質量部と、ポリオキシアルキレングリコールジメチルシロキサン共重合体(信越化学工業社製、商品名:KP-341)0.02質量部とからなる混合物を25℃に保持しながら1時間かけて滴下混合し、2,4-ジヒドロキシベンゾフェエノンを樹脂分100質量部に対して10質量部添加し、ハードコート用熱硬化性樹脂組成物(a)を得た。
撹拌翼を備えた混合槽に、トリス(2-アクロキシエチル)イソシアヌレート(Aldrich社製)60質量部と、ネオペンチルグリコールオリゴアクリレート(大阪有機化学工業社製、商品名:215D)40質量部と、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(チバ・ジャパン社製、商品名:DAROCUR TPO)1質量部と、1-ヒドロキシシクロヘキシルフェニルケトン(Aldrich社製)0.3質量部と、2-(2H-ベンゾトリアゾール-2-イル)-4,6-ビス(1-メチル-1-フェニルエチル)フェノール(チバ・ジャパン社製、商品名:TINUVIN234)1質量部からなる混合物を導入し、40℃に保持しながら1時間撹拌して、ハードコート用光硬化性樹脂組成物(b)を得た。
撹拌翼を備えた混合槽に、1,9-ノナンジオールジアクリレート(大阪有機化学工業社製、商品名:ビスコート#260)40質量部と、6官能ウレタンアクリレートオリゴマー(新中村化学工業社製、商品名:U-6HA)40質量部と、コハク酸/トリメチロールエタン/アクリル酸のモル比1/2/4縮合物20質量部と、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(チバ・ジャパン社製、商品名:DAROCUR TPO)2.8質量部と、ベンゾフェノン(Aldrich社製)1質量部と、2-(2H-ベンゾトリアゾール-2-イル)-4,6-ビス(1-メチル-1-フェニルエチル)フェノール(チバ・ジャパン社製、商品名:TINUVIN234)1質量部からなる混合物を導入し、40℃に保持しながら1時間撹拌して、ハードコート用光硬化性樹脂組成物(c)を得た。
軸径35mmの単軸押出機と、軸径65mmの単軸押出機と、全押出機に連結されたフィードブロックと、フィードブロックに連結されたTダイとを有する多層押出装置を用いて合成樹脂積層体を成形した。軸径35mmの単軸押出機に合成例1で得たビニル共重合樹脂(A1)を連続的に導入し、シリンダ温度240℃、吐出速度2.6kg/hの条件で押し出した。また軸径65mmの単軸押出機にポリカーボネート樹脂(B)(三菱エンジニアリングプラスチックス社製、商品名:ユーピロンS-1000)を連続的に導入し、シリンダ温度280℃、吐出速度50.0kg/hで押し出した。全押出機に連結されたフィードブロックは2種2層の分配ピンを備え、温度270℃としてビニル共重合樹脂(A1)とポリカーボネート樹脂(B)を導入し積層した。その先に連結された温度270℃のTダイでシート状に押し出し、上流側から温度120℃、130℃、190℃とした3本の鏡面仕上げロールで鏡面を転写しながら冷却し、ビニル共重合樹脂(A1)層とポリカーボネート樹脂(B)層との積層体(D1)を得た。得られた積層体の厚みは1.2mm、ビニル共重合樹脂(A1)層の厚みは中央付近で60μmであった。
R25mm曲げ試験の結果は変化なしで合格であり、高温高湿暴露試験の結果は0.9mmで合格であり、鉛筆引っかき硬度試験の結果は2Hで合格であり、耐衝撃性試験の結果は70cmで合格であり、全光線透過率は91%で合格であり、総合判定は合格であった。
実施例1で使用したビニル共重合樹脂(A1)の吐出速度を4.8kg/hとし、ポリカーボネート樹脂(B)の吐出速度を35kg/hとした以外は実施例1と同様にしてビニル共重合樹脂(A1)層とポリカーボネート樹脂(B)層との積層体(D2)を得た。得られた積層体の厚みは0.5mm、ビニル共重合樹脂(A1)層の厚みは中央付近で60μmであった。
R25mm曲げ試験の結果は変化なしで合格であり、高温高湿暴露試験の結果は0.5mmで合格であり、鉛筆引っかき硬度試験の結果は2Hで合格であり、耐衝撃性試験の結果は30cmで合格であり、全光線透過率は91%で合格であり、総合判定は合格であった。
実施例1で得た積層体(D1)のビニル共重合樹脂(A1)層上に、合成例5で得たハードコート用熱硬化性樹脂組成物(a)を硬化後の塗膜厚さが3~8μmとなるようバーコーターを用いて塗布し、25℃で15分間乾燥した後、130℃に設定した熱風循環乾燥機で1時間硬化して、ビニル共重合樹脂(A1)層上にハードコートを備えた積層体(E1)を得た。
R25mm曲げ試験の結果は変化なしで合格であり、高温高湿暴露試験の結果は1.2mmで合格であり、鉛筆引っかき硬度試験の結果は3Hで合格であり、耐衝撃性試験の結果は60cmで合格であり、全光線透過率は91%で合格であり、総合判定は合格であった。
実施例1で得た積層体(D1)のビニル共重合樹脂(A1)層上に、合成例6で得たハードコート用光硬化性樹脂組成物(b)を硬化後の塗膜厚さが3~8μmとなるようバーコーターを用いて塗布した。PETフィルムで覆って圧着した後、光源距離12cm、出力80W/cmの高圧水銀灯を備えたコンベアでラインスピード1.5m/分の条件で紫外線を照射し、ハードコート用光硬化性樹脂組成物(b)を硬化させた。PETフィルムを剥離して、ビニル共重合樹脂(A1)層上にハードコートを備えた積層体(E2)を得た。
R25mm曲げ試験の結果は変化なしで合格であり、高温高湿暴露試験の結果は1.3mmで合格であり、鉛筆引っかき硬度試験の結果は4Hで合格であり、耐衝撃性試験の結果は60cmで合格であり、全光線透過率は91%で合格であり、総合判定は合格であった。
実施例1で得た積層体(D1)のビニル共重合樹脂(A1)層上に、合成例6で得たハードコート用光硬化性樹脂組成物(b)を硬化後の塗膜厚さが3~8μmとなるようバーコーターを用いて塗布した。PETフィルムで覆って圧着した後、積層体(D1)のポリカーボネート樹脂(B)層上に、合成例7で得たハードコート用光硬化性樹脂組成物(c)を硬化後の塗膜厚さが3~8μmとなるようバーコーターを用いて塗布し、PETフィルムで覆って圧着した。光源距離12cm、出力80W/cmの高圧水銀灯を備えたコンベアでラインスピード1.5m/分の条件で紫外線を照射し、上記ハードコート用光硬化性樹脂組成物(b)及び(c)を硬化させた。PETフィルムを剥離して、ビニル共重合樹脂(A1)層上及びポリカーボネート樹脂(B)層上にハードコートを備えた積層体(E3)を得た。
R25mm曲げ試験の結果は変化なしで合格であり、高温高湿暴露試験の結果は1.0mmで合格であり、鉛筆引っかき硬度試験の結果は4Hで合格であり、耐衝撃性試験の結果は60cmで合格であり、全光線透過率は91%で合格であり、総合判定は合格であった。
実施例3で使用した積層体(D1)の代わりに実施例2で得た積層体(D2)を使用した以外は、実施例3と同様にして、ビニル共重合樹脂(A1)層上にハードコートを備えた積層体(E4)を得た。
R25mm曲げ試験の結果は変化なしで合格であり、高温高湿暴露試験の結果は2.2mmで合格であり、鉛筆引っかき硬度試験の結果は3Hで合格であり、耐衝撃性試験の結果は30cmで合格であり、全光線透過率は91%で合格であり、総合判定は合格であった。
実施例4で使用した積層体(D1)の代わりに実施例2で得た積層体(D2)を使用した以外は、実施例4と同様にして、ビニル共重合樹脂(A1)層上にハードコートを備えた積層体(E5)を得た。
R25mm曲げ試験の結果は変化なしで合格であり、高温高湿暴露試験の結果は2.2mmで合格であり、鉛筆引っかき硬度試験の結果は4Hで合格であり、耐衝撃性試験の結果は30cmで合格であり、全光線透過率は91%で合格であり、総合判定は合格であった。
実施例5で使用した積層体(D1)の代わりに実施例2で得た積層体(D2)を使用した以外は、実施例5と同様にして、ビニル共重合樹脂(A)層上及びポリカーボネート樹脂(B)層上にハードコートを備えた積層体(E6)を得た。
R25mm曲げ試験の結果は変化なしで合格であり、高温高湿暴露試験の結果は2.1mmで合格であり、鉛筆引っかき硬度試験の結果は4Hで合格であり、耐衝撃性試験の結果は30cmで合格であり、全光線透過率は91%で合格であり、総合判定は合格であった。
実施例1で使用したビニル共重合樹脂(A1)の代わりに合成例2で得たビニル共重合樹脂(A2)を使用した以外は、実施例1と同様にして、ビニル共重合樹脂(A2)層とポリカーボネート樹脂(B)層との積層体(D3)を得た。得られた積層体の厚みは1.2mm、ビニル共重合樹脂(A2)層の厚みは中央付近で60μmであった。
高温高湿暴露試験の結果は0.5mmで合格であり、耐衝撃性試験の結果は60cmで合格であり、全光線透過率は91%で合格であったが、R25mm曲げ試験の結果割れ及び剥離を生じて不合格であり、また鉛筆引っかき硬度試験の結果はHで不合格であり、総合判定は不合格であった。
実施例2で使用したビニル共重合樹脂(A1)の代わりに合成例2で得たビニル共重合樹脂(A2)を使用した以外は、実施例2と同様にして、ビニル共重合樹脂(A2)層とポリカーボネート樹脂(B)層との積層体(D4)を得た。得られた積層体の厚みは0.5mm、ビニル共重合樹脂(A2)層の厚みは中央付近で60μmであった。
高温高湿暴露試験の結果は1.2mmで合格であり、耐衝撃性試験の結果は30cmで合格であり、全光線透過率は91%で合格であったが、R25mm曲げ試験の結果は割れ及び剥離を生じて不合格であり、また鉛筆引っかき硬度試験の結果はHで不合格であり、総合判定は不合格であった。
実施例5で使用した積層体(D1)の代わりに比較例1で得た積層体(D3)を使用した以外は、実施例5と同様にして、ビニル共重合樹脂(A2)層上及びポリカーボネート樹脂(B)層上にハードコートを備えた積層体(E7)を得た。
高温高湿暴露試験の結果は0.5mmで合格であり、鉛筆引っかき硬度試験の結果は3Hで合格であり、耐衝撃性試験の結果は60cmで合格であり、全光線透過率は91%で合格であったが、R25mm曲げ試験の結果は割れ及び剥離を生じて不合格であり、総合判定は不合格であった。
実施例1で使用したビニル共重合樹脂(A1)の代わりに合成例3で得たビニル共重合樹脂(A3)を使用した以外は、実施例1と同様にして、ビニル共重合樹脂(A3)層とポリカーボネート樹脂(B)層との積層体(D5)を得た。得られた積層体の厚みは1.2mm、ビニル共重合樹脂(A3)層の厚みは中央付近で60μmであった。
高温高湿暴露試験の結果は0.4mmで合格であり、耐衝撃性試験の結果は60cmで合格であり、全光線透過率は91%で合格であったが、R25mm曲げ試験の結果は割れ及び剥離を生じて不合格であり、また鉛筆引っかき硬度試験の結果はHで不合格であり、総合判定は不合格であった。
実施例2で使用したビニル共重合樹脂(A1)の代わりに合成例3で得たビニル共重合樹脂(A3)を使用した以外は、実施例2と同様にして、ビニル共重合樹脂(A3)層とポリカーボネート樹脂(B)層との積層体(D6)を得た。得られた積層体の厚みは0.5mm、(A3)層の厚みは中央付近で60μmであった。
高温高湿暴露試験の結果は1.4mmで合格であり、耐衝撃性試験の結果は30cmで合格であり、全光線透過率は91%で合格であったが、R25mm曲げ試験の結果は割れ及び剥離を生じて不合格であり、また鉛筆引っかき硬度試験の結果はHで不合格であり、総合判定は不合格であった。
実施例5で使用した積層体(D1)の代わりに比較例4で得た積層体(D5)を使用した以外は、実施例5と同様にして、ビニル共重合樹脂(A3)層上及びポリカーボネート樹脂(B)層上にハードコートを備えた積層体(E8)を得た。
高温高湿暴露試験の結果は0.6mmで合格であり、鉛筆引っかき硬度試験の結果は3Hで合格であり、耐衝撃性試験の結果は60cmで合格であり、全光線透過率は91%で合格であったが、R25mm曲げ試験の結果は割れ及び剥離を生じて不合格であり、総合判定は不合格であった。
実施例1で使用したビニル共重合樹脂(A1)の代わりに合成例4で得たビニル共重合樹脂(A4)を使用した以外は、実施例1と同様にして、ビニル共重合樹脂(A4)層とポリカーボネート樹脂(B)層との積層体(D7)を得た。得られた積層体の厚みは1.2mm、ビニル共重合樹脂(A4)層の厚みは中央付近で60μmであった。
R25mm曲げ試験の結果は変化なしで合格であり、鉛筆引っかき硬度試験の結果は2Hで合格であり、耐衝撃性試験の結果は90cmで合格であり、全光線透過率は91%で合格であったが、高温高湿暴露試験の結果は2.0mmで不合格であり、総合判定は不合格であった。
実施例2で使用したビニル共重合樹脂(A1)の代わりに合成例4で得たビニル共重合樹脂(A4)を使用した以外は、実施例2と同様にして、ビニル共重合樹脂(A4)層とポリカーボネート樹脂(B)層との積層体(D8)を得た。得られた積層体の厚みは0.5mm、ビニル共重合樹脂(A4)層の厚みは中央付近で60μmであった。
R25mm曲げ試験の結果は変化なしで合格であり、鉛筆引っかき硬度試験の結果は2Hで合格であり、耐衝撃性試験の結果は30cmで合格であり、全光線透過率は91%で合格であったが、高温高湿暴露試験の結果は6.0mmで不合格であり、総合判定は不合格であった。
実施例4で使用した積層体(D1)の代わりに比較例7で得た積層体(D7)を使用した以外は、実施例4と同様にして、ビニル共重合樹脂(A4)層上にハードコートを備えた積層体(E9)を得た。
R25mm曲げ試験の結果は変化なしで合格であり、鉛筆引っかき硬度試験の結果は4Hで合格であり、耐衝撃性試験の結果は80cmで合格であり、全光線透過率は91%で合格であったが、高温高湿暴露試験の結果は3.4mmで不合格であり、総合判定は不合格であった。
実施例5で使用した積層体(D1)の代わりに比較例7で得た積層体(D7)を使用した以外は、実施例5と同様にして、ビニル共重合樹脂(A4)層上及びポリカーボネート樹脂(B)層上にハードコートを備えた積層体(E10)を得た。
R25mm曲げ試験の結果は変化なしで合格であり、鉛筆引っかき硬度試験の結果は4Hで合格であり、耐衝撃性試験の結果は60cmで合格であり、全光線透過率は91%で合格であったが、高温高湿暴露試験の結果は3.0mmで不合格であり、総合判定は不合格であった。
実施例4で使用した積層体(D1)の代わりに比較例8で得た積層体(D8)を使用した以外は、実施例4と同様にして、ビニル共重合樹脂(A4)層上にハードコートを備えた積層体(E11)を得た。
R25mm曲げ試験の結果は変化なしで合格であり、鉛筆引っかき硬度試験の結果は4Hで合格であり、耐衝撃性試験の結果は30cmで合格であり、全光線透過率は91%で合格であったが、高温高湿暴露試験の結果は7.8mmで不合格であり、総合判定は不合格であった。
実施例5で使用した積層体(D1)の代わりに比較例8で得た積層体(D8)を使用した以外は、実施例5と同様にして、ビニル共重合樹脂(A4)層上
及びポリカーボネート樹脂(B)層上にハードコートを備えた積層体(E12)を得た。
R25mm曲げ試験の結果は変化なしで合格であり、鉛筆引っかき硬度試験の結果は4Hで合格であり、耐衝撃性試験の結果は30cmで合格であり、全光線透過率は91%で合格であったが、高温高湿暴露試験の結果は7.5mmで不合格であり、総合判定は不合格であった。
実施例1で使用したビニル共重合樹脂(A1)の代わりにポリメタクリル酸メチル樹脂(A5)(ARKEMA社製、商品名:ALTUGLAS V020)を使用した以外は、実施例1と同様にして、ポリメタクリル酸メチル樹脂(A5)層とポリカーボネート樹脂(B)層との積層体(D9)を得た。得られた積層体の厚みは1.2mm、ポリメタクリル酸メチル樹脂(A5)層の厚みは中央付近で60μmであった。
R25mm曲げ試験の結果は変化なしで合格であり、鉛筆引っかき硬度試験の結果は3Hで合格であり、耐衝撃性試験の結果は120cmで合格であり、全光線透過率は91%で合格であったが、高温高湿暴露試験の結果は3.9mmで不合格であり、総合判定は不合格であった。
実施例2で使用したビニル共重合樹脂(A1)の代わりにポリメタクリル酸メチル樹脂(A5)(ARKEMA社製、商品名:ALTUGLAS V020)を使用した以外は、実施例2と同様にして、ポリメタクリル酸メチル樹脂(A5)層とポリカーボネート樹脂(B)層との積層体(D10)を得た。得られた積層体の厚みは0.5mm、ポリメタクリル酸メチル樹脂(A5)層の厚みは中央付近で60μmであった。
R25mm曲げ試験の結果は変化なしで合格であり、鉛筆引っかき硬度試験の結果は3Hで合格であり、耐衝撃性試験の結果は30cmで合格であり、全光線透過率は92%で合格であったが、高温高湿暴露試験の結果は12.3mmで不合格であり、総合判定は不合格であった。
実施例4で使用した積層体(D1)の代わりに比較例13で得た積層体(D9)を使用した以外は、実施例4と同様にして、ポリメタクリル酸メチル樹脂(A5)層上にハードコートを備えた積層体(E13)を得た。
R25mm曲げ試験の結果は変化なしで合格であり、鉛筆引っかき硬度試験の結果は4Hで合格であり、耐衝撃性試験の結果は100cmで合格であり、全光線透過率は91%で合格であったが、高温高湿暴露試験の結果は6.0mmで不合格であり、総合判定は不合格であった。
実施例5で使用した積層体(D1)の代わりに比較例13で得た積層体(D9)を使用した以外は、実施例5と同様にして、ポリメタクリル酸メチル樹脂(A5)層上及びポリカーボネート樹脂(B)層上にハードコートを備えた積層体(E14)を得た。
R25mm曲げ試験の結果は変化なしで合格であり、鉛筆引っかき硬度試験の結果は4Hで合格であり、耐衝撃性試験の結果は60cmで合格であり、全光線透過率は91%で合格であったが、高温高湿暴露試験の結果は5.3mmで不合格であり、総合判定は不合格であった。
実施例4で使用した積層体(D1)の代わりに比較例14で得た積層体(D10)を使用した以外は、実施例4と同様にして、ポリメタクリル酸メチル樹脂(A5)層上にハードコートを備えた積層体(E15)を得た。
R25mm曲げ試験の結果は変化なしで合格であり、鉛筆引っかき硬度試験の結果は4Hで合格であり、耐衝撃性試験の結果は30cmで合格であり、全光線透過率は92%で合格であったが、高温高湿暴露試験の結果は19.2mmで不合格であり、総合判定は不合格であった。
実施例5で使用した積層体(D1)の代わりに比較例14で得た積層体(D10)を使用した以外は、実施例5と同様にして、ポリメタクリル酸メチル樹脂(A5)層及びポリカーボネート樹脂(B)層上にハードコートを備えた積層体(E16)を得た。
R25mm曲げ試験の結果は変化なしで合格であり、鉛筆引っかき硬度試験の結果は4Hで合格であり、耐衝撃性試験の結果は30cmで合格であり、全光線透過率は92%で合格であったが、高温高湿暴露試験の結果は18.1mmで不合格であり、総合判定は不合格であった。
実施例1で使用したビニル共重合樹脂(A1)の代わりにポリメタクリル酸メチル樹脂(A5)(ARKEMA社製、商品名:ALTUGLAS V020)を使用し、ポリメタクリル酸メチル樹脂(A5)の吐出速度を5.2kg/hとし、ポリカーボネート樹脂(B)の吐出速度を46.8kg/hとし、フィードブロックの分配ピンを2種3層とした以外は、実施例1と同様にして、ポリカーボネート樹脂(B)層の両面にポリメタクリル酸メチル樹脂(A5)層が積層された積層体(D11)を得た。得られた積層体の厚みは1.2mm、ポリメタクリル酸メチル樹脂(A5)層の厚みは中央付近でそれぞれ60μmであった。
R25mm曲げ試験の結果は変化なしで合格であり、高温高湿暴露試験の結果は0.5mmで合格であり、鉛筆引っかき硬度試験の結果は3Hで合格であり、全光線透過率は91%で合格であったが、耐衝撃性試験の結果は40cmで不合格であり、総合判定は不合格であった。
実施例1で使用したビニル共重合樹脂(A1)の代わりにポリメタクリル酸メチル樹脂(A5)(ARKEMA社製、商品名:ALTUGLAS V020)を使用し、ポリメタクリル酸メチル樹脂(A5)の吐出速度を9.6kg/hとし、ポリカーボネート樹脂(B)の吐出速度を30.4kg/hとし、フィードブロックの分配ピンを2種3層とした以外は、実施例1と同様にして、ポリカーボネート樹脂(B)層の両面にポリメタクリル酸メチル樹脂(A5)層が積層された積層体(D12)を得た。得られた積層体の厚みは0.5mm、ポリメタクリル酸メチル樹脂(A5)層の厚みは中央付近でそれぞれ60μmであった。
R25mm曲げ試験の結果は変化なしで合格であり、高温高湿暴露試験の結果は1.1mmで合格であり、鉛筆引っかき硬度試験の結果は3Hで合格であり、全光線透過率は92%で合格であったが、耐衝撃性試験の結果は10cmで不合格であり、総合判定は不合格であった。
比較例19で得た積層体(D11)の片方のポリメタクリル酸メチル樹脂(A5)層上に、合成例6で得たハードコート用光硬化性樹脂組成物(b)を硬化後の塗膜厚さが3~8μmとなるようバーコーターを用いて塗布した。PETフィルムで覆って圧着し、光源距離12cm、出力80W/cmの高圧水銀灯を備えたコンベアでラインスピード1.5m/分の条件で紫外線を照射し、ハードコート用光硬化性樹脂組成物(b)を硬化させた。PETフィルムを剥離し、片方のポリメタクリル酸メチル樹脂(A5)層上にハードコートを備えた積層体(E17)を得た。
R25mm曲げ試験の結果は変化なしで合格であり、高温高湿暴露試験の結果は0.7mmで合格であり、鉛筆引っかき硬度試験の結果は4Hで合格であり、全光線透過率は91%で合格であったが、耐衝撃性試験の結果は10cmで不合格であり、総合判定は不合格であった。
表1より、本発明の合成樹脂積層体は、層間密着性、高温高湿環境における形状安定性、表面硬度及び耐衝撃性に優れる。
Claims (10)
- ビニル共重合樹脂(A)層、及びポリカーボネート樹脂(B)層を有し、(B)層の片面に(A)層が直接に積層された合成樹脂積層体であって、
前記ビニル共重合樹脂(A)が、下記一般式(1)で表される(メタ)アクリル酸エステル構成単位(a)と、下記一般式(2)で表される脂肪族ビニル構成単位(b)とを含み、前記(メタ)アクリル酸エステル構成単位(a)と前記脂肪族ビニル構成単位(b)との合計割合が前記(A)の全構成単位の合計に対して90~100モル%であり、前記(メタ)アクリル酸エステル構成単位(a)の割合が前記(A)の全構成単位の合計に対して65~80モル%であることを特徴とする合成樹脂積層体。
- ビニル共重合樹脂(A)が、少なくとも1種の(メタ)アクリル酸エステルモノマーと少なくとも1種の芳香族ビニルモノマーを重合した後、該芳香族ビニルモノマー由来の芳香族二重結合の70%以上を水素化して得られたものである請求項1に記載の合成樹脂積層体。
- 前記一般式(1)において、R1及びR2がメチル基である請求項1又は2に記載の合成樹脂積層体。
- 前記一般式(2)において、R3が水素原子であり、R4がシクロヘキシル基である請求項1~3のいずれかに記載の合成樹脂積層体。
- ビニル共重合樹脂(A)及び/又はポリカーボネート樹脂(B)が紫外線吸収剤を含有する請求項1~4のいずれかに記載の合成樹脂積層体。
- ビニル共重合樹脂(A)層上にハードコート処理を施した請求項1~5のいずれかに記載の合成樹脂積層体。
- ビニル共重合樹脂(A)層上及びポリカーボネート樹脂(B)層上にハードコート処理を施した請求項1~5のいずれかに記載の合成樹脂積層体。
- 片面又は両面に反射防止処理、防汚処理、帯電防止処理、耐候性処理及び防眩処理から選択されるいずれか一つ以上の処理を施した請求項1~7のいずれかに記載の合成樹脂積層体。
- 請求項1~8のいずれかに記載の合成樹脂積層体からなる透明性基板材料。
- 請求項1~8のいずれかに記載の合成樹脂積層体からなる透明性保護材料。
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JP2012515899A JP5712208B2 (ja) | 2010-05-21 | 2011-05-17 | 合成樹脂積層体 |
ES11783564.5T ES2688282T3 (es) | 2010-05-21 | 2011-05-17 | Laminado de resina sintética |
US13/697,882 US9731481B2 (en) | 2010-05-21 | 2011-05-17 | Synthetic resin laminate |
KR1020127030365A KR101885386B1 (ko) | 2010-05-21 | 2011-05-17 | 합성 수지 적층체 |
CN201180025016.2A CN102905894B (zh) | 2010-05-21 | 2011-05-17 | 合成树脂叠层体 |
EP11783564.5A EP2572879B1 (en) | 2010-05-21 | 2011-05-17 | Synthetic resin laminate |
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JPWO2020261783A1 (ja) * | 2019-06-26 | 2020-12-30 | ||
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KR101885386B1 (ko) | 2018-09-11 |
EP2572879A1 (en) | 2013-03-27 |
JP5712208B2 (ja) | 2015-05-07 |
EP2572879B1 (en) | 2018-08-01 |
JPWO2011145630A1 (ja) | 2013-07-22 |
KR20130093512A (ko) | 2013-08-22 |
US20130059158A1 (en) | 2013-03-07 |
TW201213119A (en) | 2012-04-01 |
US9731481B2 (en) | 2017-08-15 |
TWI548518B (zh) | 2016-09-11 |
CN102905894B (zh) | 2016-03-02 |
CN102905894A (zh) | 2013-01-30 |
EP2572879A4 (en) | 2014-08-13 |
ES2688282T3 (es) | 2018-10-31 |
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