WO2015108064A1 - 熱可塑性樹脂積層体 - Google Patents
熱可塑性樹脂積層体 Download PDFInfo
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- WO2015108064A1 WO2015108064A1 PCT/JP2015/050773 JP2015050773W WO2015108064A1 WO 2015108064 A1 WO2015108064 A1 WO 2015108064A1 JP 2015050773 W JP2015050773 W JP 2015050773W WO 2015108064 A1 WO2015108064 A1 WO 2015108064A1
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- WIPO (PCT)
- Prior art keywords
- thermoplastic resin
- resin composition
- styrene
- structural unit
- evaluation
- Prior art date
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- 0 CN(OC)O** Chemical compound CN(OC)O** 0.000 description 1
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
-
- 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
- B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- 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
Definitions
- the present invention relates to a thermoplastic resin laminate, and more particularly to a thermoplastic resin laminate excellent in transparency, heat resistance, scratch resistance, impact resistance, and dimensional stability in a high temperature and high humidity environment.
- Resin transparent plates are used in a wide variety of applications, including outdoor signboard and carport exterior applications, and optical applications for display unit front plates in office automation equipment and portable electronic devices.
- front panels of portable display devices such as mobile phone terminals, portable electronic playground equipment, and portable information terminals are required to have higher dimensional stability when used in harsh environments in addition to transparency, visibility, and scratch resistance. It has been.
- As a transparent resin used for the front panel an acrylic resin excellent in transparency, weather resistance, and scratch resistance is widely used.
- acrylic resins have poor impact resistance, and there is a problem that cracks are likely to occur in the front panel in applications where impacts such as touch panel displays are likely to be applied.
- the general formula (1) Or general formula (2): (In the formulas (1) and (2), R 1 , R 2 and R 3 are each independently an aliphatic group having 1 to 10 carbon atoms, an alicyclic group having 3 to 10 carbon atoms, and carbon. This represents an organic group selected from the group consisting of aromatic groups having a number of 6 to 10.) Or a diol unit having a cyclic acetal skeleton represented by the formula: Or general formula (4): (In the formulas (3) and (4), R 4 and R 5 are each independently an aliphatic group having 1 to 10 carbon atoms, an alicyclic group having 3 to 10 carbon atoms, and 6 to 6 carbon atoms.
- a polyester resin (a) having a dicarboxylic acid unit having a cyclic acetal skeleton represented by 10 to 60 mol% of the dicarboxylic acid structural unit as a core layer and an acrylic resin in the skin layer is used to make the transparent It is described that a multilayer sheet excellent in heat resistance, heat resistance, scratch resistance and impact resistance can be obtained.
- the multilayer sheet disclosed in the publication is excellent in heat resistance in a low humidity environment, the dimensional stability in a high temperature and high humidity environment such as a temperature of 85 ° C. and a humidity of 85% is not sufficient.
- an object of the present invention is to solve at least one of the above conventional problems. Furthermore, an object of the present invention is to provide a thermoplastic resin laminate excellent in transparency, heat resistance, scratch resistance, impact resistance, and dimensional stability in a high temperature and high humidity environment.
- thermoplastic resin laminate having a layer (A) containing a thermoplastic resin composition and a layer (B) containing an acrylic resin composition provided on at least one surface of the layer (A).
- the thermoplastic resin composition is 10 to 60 mol% of all diol constitutional units is represented by the following formula (1) or the following formula (2).
- R 1 , R 2 and R 3 are each independently an aliphatic group having 1 to 10 carbon atoms, an alicyclic group having 3 to 10 carbon atoms, and Represents an organic group selected from the group consisting of aromatic groups having 6 to 10 carbon atoms.
- the ratio of the polycarbonate resin (b) to the total of a) and the polycarbonate resin (b) is 5 to 50% by weight
- the acrylic resin composition comprises at least one selected from the group consisting of an acrylic resin (c) and a methyl methacrylate-styrene copolymer (d) and a styrene-maleic anhydride copolymer (e), The proportion of the structural unit
- thermoplastic resin laminate is characterized in that the proportion of structural units derived from maleic anhydride is 1 to 5 mol%.
- the ratio of the structural unit derived from styrene to the total of the structural unit derived from styrene and the structural unit derived from maleic anhydride is 75 to 95% by weight. It is a thermoplastic resin laminate according to the above ⁇ 1>.
- the diol having a cyclic acetal skeleton is 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane.
- thermoplastic resin laminate according to any one of the above.
- a transparent substrate material comprising the thermoplastic resin laminate according to any one of ⁇ 1> to ⁇ 6>.
- transparent protective material comprising the thermoplastic resin laminate according to any one of ⁇ 1> to ⁇ 6>.
- thermoplastic resin laminate excellent in transparency, heat resistance, scratch resistance, impact resistance, and dimensional stability in a high-temperature and high-humidity environment
- thermoplastic resin laminate excellent in transparency, heat resistance, scratch resistance, impact resistance, and dimensional stability in a high-temperature and high-humidity environment
- thermoplastic resin laminate The body is used as a transparent substrate material, a transparent protective material, and the like, and is suitably used for a front panel of a portable display device that requires high dimensional stability particularly in a high temperature and high humidity environment.
- the thermoplastic resin laminate of the present invention has a layer (A) containing a thermoplastic resin composition and a layer (B) containing an acrylic resin composition, and the layer is provided on at least one surface of the layer (A).
- the thermoplastic resin composition includes a polyester resin (a) and a polycarbonate resin (b), and the polyester resin (a) is a cyclic acetal in a diol constituent unit.
- the polyester resin (a) used in the present invention is a diol constituent unit derived from a diol having a cyclic acetal skeleton represented by the following formula (1) or the following formula (2) in 10 to 60 mol% of all diol constituent units: And a dicarboxylic acid structural unit.
- R 1 , R 2 and R 3 are each independently an aliphatic group having 1 to 10 carbon atoms, an alicyclic group having 3 to 10 carbon atoms, and Represents an organic group selected from the group consisting of aromatic groups having 6 to 10 carbon atoms.
- R 1 and R 2 are preferably methylene group, ethylene group, propylene group, butylene group or structural isomers thereof, for example, , Isopropylene group, isobutylene group and the like.
- R 3 preferably represents a methyl group, an ethyl group, a propyl group, a butyl group, or a structural isomer thereof such as an isopropyl group or an isobutyl group.
- examples of the diol having a cyclic acetal skeleton include 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, 5-methylol. More preferred is -5-ethyl-2- (1,1-dimethyl-2-hydroxyethyl) -1,3-dioxane, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4 , 8,10-Tetraoxaspiro [5.5] undecane is particularly preferred.
- the diol constituent unit other than the diol constituent unit derived from the diol having a cyclic acetal skeleton in the polyester resin (a) used in the present invention is not particularly limited, but ethylene glycol, trimethylene glycol, 1,4-butanediol.
- Aliphatic diols such as 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, propylene glycol and neopentyl glycol; polyether compounds such as polyethylene glycol, polypropylene glycol and polybutylene glycol; Cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,2-decahydronaphthalenediethanol, 1,3-decahydronaphthalenediethanol, 1,4-decahydronaphthalenediethanol, , 5-decahydronaphthalene diethanol, 1,6-decahydronaphthalene diethanol, 2,7-decahydronaphthalene diethanol, tetralin dimethanol, norbornene dimethanol, tricyclodecane dimethanol, pentacyclododecane dimethanol, etc.
- polyether compounds such as polyethylene glycol, polypropylene glycol and polybutylene glycol
- Cycloaliphatic diols 4,4 ′-(1-methylethylidene) bisphenol, methylene bisphenol (bisphenol F), 4,4′-cyclohexylidene bisphenol (bisphenol Z), 4,4′-sulfonyl bisphenol (bisphenol S) ) Bisphenols; alkylene oxide adducts of the above bisphenols; hydroquinone, resorcin, 4,4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy Aromatic dihydroxy compounds such as phenyl benzophenone; and diol constituent units derived from the alkylene oxide adducts of the aromatic dihydroxy compound can be exemplified.
- a structural unit derived from ethylene glycol is particularly preferable.
- the dicarboxylic acid structural unit of the polyester resin (a) used in the present invention is not particularly limited, but succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid.
- Acid decanedicarboxylic acid, norbornane dicarboxylic acid, tricyclodecanedicarboxylic acid, aliphatic dicarboxylic acid such as pentacyclododecanedicarboxylic acid and ester-forming derivatives thereof; terephthalic acid, isophthalic acid, phthalic acid, 2-methylterephthalic acid,
- dicarboxylic acid structural units derived from aromatic dicarboxylic acids such as naphthalenedicarboxylic acid, biphenyldicarboxylic acid, tetralindicarboxylic acid, and ester-forming derivatives thereof.
- a dicarboxylic acid structural unit derived from terephthalic acid and 3-naphthalenedicarboxylic acid is more preferable, and terephthalic acid is particularly preferable.
- the ratio of the diol constituent unit derived from the diol having a cyclic acetal skeleton in all the diol constituent units is preferably 10 to 60 mol%, more preferably 15 to 50 mol%. is there.
- the polyester resin (a) may not exhibit sufficient heat resistance, which is not preferable.
- the impact resistance may decrease, which is not preferable.
- the proportion of structural units derived from terephthalic acid in all the dicarboxylic acid structural units is preferably 70 mol% to 100 mol%, more preferably 90 mol% to 100 mol%.
- the thermoplastic resin laminate of the present invention is more excellent in heat resistance, mechanical performance, and economy.
- the method for producing the polyester resin (a) used in the present invention is not particularly limited, and a conventionally known method can be applied. Examples thereof include a melt polymerization method such as a transesterification method and a direct esterification method, or a solution polymerization method. Various kinds of commonly used additives may be added to the polyester resin (a). Examples of the additives include transesterification catalysts, esterification catalysts, etherification inhibitors, heat stabilizers, light stabilizers, and the like. Stabilizers, polymerization regulators and the like can be mentioned.
- the polycarbonate resin (b) used in the present invention is obtained by an interfacial polymerization method of an aromatic dihydroxy compound or a small amount thereof and a polyhydroxy compound and phosgene, or an ester of the above aromatic dihydroxy compound and a diester of carbonic acid.
- a thermoplastic polycarbonate polymer which may be branched by an exchange reaction, for example, a carbonate polymer containing bisphenol A as a main raw material is used.
- the molecular weight of the polycarbonate resin (b) to be used is preferably such that a sheet can be produced by ordinary extrusion molding, and is preferably 45,000 to 70,000 in terms of polystyrene equivalent weight average molecular weight.
- the linear expansion coefficient of the polycarbonate resin substrate is in the range of 6 ⁇ 10 ⁇ 5 / ° C. to 8 ⁇ 10 ⁇ 5 / ° C.
- additives include an antioxidant, an anti-coloring agent, an ultraviolet absorber, a light diffusing agent, a flame retardant, and a release agent. Agents, lubricants, antistatic agents, dyes and pigments, and the like.
- the ratio of the polyester resin (a) and the polycarbonate resin (b) in the thermoplastic resin composition is such that the ratio of the polycarbonate resin (b) to the total of the polyester resin (a) and the polycarbonate resin (b) is 5 to 50 wt. % Is preferred. If the polycarbonate resin (b) is less than 5% by weight, the dimensional stability in a high-temperature and high-humidity environment will be poor, and if it exceeds 50% by weight, the Tg of the thermoplastic resin composition will be high, and the acrylic resin composition Since the difference in Tg from the layer (B) containing, increases, it becomes difficult to form a flat molded product.
- the thermoplastic resin laminate of the present invention has impact resistance and dimensional stability in a high temperature and high humidity environment. The characteristic that it is excellent in property is obtained.
- the ratio of the polycarbonate resin (b) to the total of the polyester resin (a) and the polycarbonate resin (b) is more preferably in the range of 10 to 50% by weight, and further preferably in the range of 20 to 50% by weight.
- the thermoplastic resin composition may contain a resin other than the polyester resin (a) and the polycarbonate resin (b).
- resins other than the polyester resin (a) and the polycarbonate resin (b) include polyester resins such as polyethylene terephthalate, polyethylene naphthalate, isophthalic acid-modified polyethylene terephthalate, 1,4-cyclohexanedimethanol-modified polyethylene terephthalate, and polyarylate (a ) Other than polyester resins.
- the acrylic resin (c) used in the present invention is made of a methyl methacrylate polymer.
- the acrylic resin (c) preferably has a polystyrene equivalent weight average molecular weight of 10,000 to 30,000.
- the methyl methacrylate-styrene copolymer (d) used in the present invention is a copolymer comprising 5 to 99% by weight of structural units derived from methyl methacrylate and 95 to 1% by weight of structural units derived from styrene.
- it is a copolymer comprising 50 to 95% by weight of structural units derived from methyl methacrylate and 50 to 5% by weight of structural units derived from styrene, and more preferably 60 to 90 structural units derived from methyl methacrylate.
- It is a copolymer composed of 40% by weight and 10 to 10% by weight of structural units derived from styrene.
- the methyl methacrylate-styrene copolymer (d) preferably has a polystyrene equivalent weight average molecular weight of 10,000 to 30,000.
- the acrylic resin (c) and / or methyl methacrylate-styrene copolymer (d) is preferably used.
- the thermoplastic resin laminate of the invention has the advantage of being excellent in transparency and scratch resistance.
- the styrene-maleic anhydride copolymer (e) used in the present invention is a copolymer comprising 75 to 95% by weight of structural units derived from styrene and 25 to 5% by weight of maleic anhydride.
- it is a copolymer comprising 78 to 92% by weight of structural units derived from styrene and 22 to 8% by weight of maleic anhydride, and more preferably 80 to 90% by weight of structural units derived from styrene and maleic anhydride.
- a copolymer comprising 20 to 10% by weight of an acid.
- the styrene-maleic anhydride copolymer (e) preferably has a polystyrene equivalent weight average molecular weight of 10,000 to 30,000. If the structural unit derived from styrene is less than 75% by weight and exceeds 25% by weight of maleic anhydride, the transparency may be lowered and the appearance may be lowered. On the other hand, if it exceeds 95% by weight of the structural unit derived from styrene and is less than 5% by weight of maleic anhydride, the transparency is lowered and the effect of improving heat resistance and moisture absorption is small.
- the thermoplastic resin laminated body of this invention has the characteristic that it is excellent in the dimensional stability in a high temperature, high humidity environment.
- the acrylic resin composition may contain other resin components in addition to the acrylic resin (c), the methyl methacrylate-styrene copolymer (d), and the styrene-maleic anhydride copolymer (e).
- Other resin components include polyesters other than polyester resin (a), polycarbonate, polystyrene, acrylonitrile-butadiene-styrene copolymer, methyl methacrylate-methacrylic acid copolymer, methyl methacrylate-acrylic acid copolymer, methyl methacrylate- Acrylonitrile copolymer, methyl methacrylate-methacrylonitrile copolymer, copolymer of methyl methacrylate and N-phenylmaleimide, copolymer of methyl methacrylate and N-cyclohexylmaleimide, styrene-methyl methacrylate-methacrylic acid copolymer, styrene -Methyl me
- polyester resin other than the polyester resin (a) include polyethylene terephthalate, polyethylene naphthalate, isophthalic acid-modified polyethylene terephthalate, 1,4-cyclohexanedimethanol-modified polyethylene terephthalate, and polyarylate.
- Said other resin component may be used independently and may be used in combination of 2 or more type.
- the proportion of the other resin components in the acrylic resin composition is less than 10% by weight.
- the method for polymerizing the methyl methacrylate-styrene copolymer (d) and the styrene-maleic anhydride copolymer (e) used in the present invention is not particularly limited, but radical polymerization using an organic peroxide is preferable.
- the production process is preferably a bulk continuous polymerization process using a small amount of solvent. In a method obtained by a suspension polymerization or emulsion polymerization process, sufficient transparency may not be obtained.
- Organic peroxides added during polymerization include t-butyl peroxybenzoate, t-butyl peroxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) -3,3,5- Trimethylcyclohexane, 1,1-bis (t-butylperoxy) -cyclohexane, 2,2-bis (4,4-di-butylperoxycyclohexyl) propane, t-butylperoxyisopropyl monocarbonate, di-t- Known materials such as butyl peroxide, dicumyl peroxide, ethyl-3,3-di- (t-butylperoxy) butyrate can be used.
- the amount of organic peroxide added is preferably 0.001 to 5 parts by weight with respect to 100 parts by weight of the total amount of monomers.
- Solvents include aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, octane and isooctane, alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane and ethylcyclohexane, or benzene and toluene.
- Aromatic hydrocarbons such as ethylbenzene and xylene can be used, and the amount of solvent added is preferably 5 to 20 parts by weight with respect to 100 parts by weight of the total amount of monomers.
- a known molecular weight modifier such as 4-methyl-2,4-diphenylpentene-1, t-dodecyl mercaptan, n-dodecyl mercaptan may be added during the polymerization.
- the polymerization temperature is preferably 80 to 170 ° C, more preferably 100 to 160 ° C.
- Styrene with respect to the total of at least one selected from the group consisting of acrylic resin (c) and methyl methacrylate-styrene copolymer (d) and styrene-maleic anhydride copolymer (e) in the acrylic resin composition
- the proportion of maleic anhydride copolymer (e) is preferably 1 to 35% by weight.
- the styrene-maleic anhydride copolymer (e) is less than 1% by weight, the dimensional stability in a high-temperature and high-humidity environment decreases, and when it exceeds 35% by weight, the scratch resistance decreases.
- thermoplastic resin laminated body of this invention is abrasion resistance,
- the feature is that it has excellent dimensional stability in a high temperature and high humidity environment.
- the styrene-maleic anhydride copolymer with respect to the total of the styrene-maleic anhydride copolymer (e) and at least one selected from the group consisting of acrylic resin (c) and methyl methacrylate-styrene copolymer (d).
- the proportion of the polymer (e) is in the range of 5 to 30% by weight.
- the ratio of the structural unit derived from methyl methacrylate to the total of the structural unit derived from methyl methacrylate, the structural unit derived from styrene, and the structural unit derived from maleic anhydride is 70 to 95 mol%.
- the proportion of structural units derived from maleic anhydride is preferably 1 to 5 mol%.
- the ratio of the structural unit derived from methyl methacrylate to the total of the structural unit derived from methyl methacrylate, the structural unit derived from styrene, and the structural unit derived from maleic anhydride is 70 to 90 mol%.
- the ratio of the structural unit derived from styrene to the total of the structural unit derived from methyl methacrylate, the structural unit derived from styrene, and the structural unit derived from maleic anhydride in the acrylic resin composition is 4 to 29.
- the mol% is preferable, and 5 to 25 mol% is more preferable.
- the thermoplastic resin composition and / or the acrylic resin composition may contain various additives.
- the various additives include an antioxidant, an ultraviolet absorber, an anti-colorant, an antistatic agent, a release agent, a lubricant, a dye, a pigment, an inorganic filler, and a resin filler.
- 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.
- thermoplastic resin composition is manufactured by a known technique. Although it does not specifically limit, For example, it obtains by melt-kneading, after dry-mixing the component containing polyester resin (a) and polycarbonate resin (b).
- the acrylic resin composition can also be obtained by the same method.
- thermoplastic resin laminate of the present invention comprises a layer (A) containing a thermoplastic resin composition and a layer (B) containing an acrylic resin composition provided on at least one surface of the layer (A). Comprising.
- thermoplastic resin laminate of the present invention As a method for producing the thermoplastic resin laminate of the present invention, known lamination techniques such as a co-extrusion method, a co-extrusion lamination method, an extrusion lamination method, and a dry lamination method can be used. Moreover, you may use the adhesive agent suitable between resin for these lamination
- the layer (B) containing the acrylic resin composition is used as the skin layer
- the layer (A) containing the thermoplastic resin composition is used as the skin layer.
- thermoplastic resin laminate excellent in dimensional stability in a high temperature and high humidity environment can be obtained.
- the thickness of the thermoplastic resin laminate in the present invention is preferably in the range of 0.1 to 10.0 mm. If the thickness is less than 0.1 mm, transfer failure or thickness accuracy failure may occur due to bank omission. In addition, when the thickness exceeds 10.0 mm, a thickness accuracy defect or an appearance defect due to uneven cooling after molding may occur. More preferably, it is in the range of 0.3 to 5.0 mm, and still more preferably in the range of 0.3 to 3.0 mm.
- the thickness (one side) of the layer (B) containing the acrylic resin composition is preferably 25% or less of the total thickness of the thermoplastic resin laminate, and is in the range of 10 to 500 ⁇ m. It is preferable that When the thickness (one side) of the layer (B) exceeds 25% of the total thickness of the thermoplastic resin laminate, warping may occur in a high temperature and high humidity environment. If the thickness is less than 10 ⁇ m, the scratch resistance and weather resistance may be insufficient, and if it exceeds 500 ⁇ m, warping may occur in a high-temperature and high-humidity environment. More preferably, it is in the range of 30 to 200 ⁇ m.
- a hard coat treatment can be applied to one or both sides of the thermoplastic resin laminate of the present invention.
- the hard coat layer is formed by using a photosensitive hard coat paint that is cured using light energy.
- a photosensitive hard coat paint to be cured using light energy a photocurable resin composition in which a photopolymerization initiator is added to a resin composition composed of monofunctional and / or polyfunctional acrylate monomers and / or oligomers Etc.
- a resin comprising 40 to 80% by weight of tris (acryloxyethyl) isocyanurate (f1) and 20 to 40% by weight of a bifunctional and / or trifunctional methacrylate compound (f2) copolymerizable with (f1)
- a photocurable resin composition in which 1 to 10 parts by weight of a photopolymerization initiator (f3) is added to 100 parts by weight of the composition.
- the method for applying the hard coat paint in the present invention is not particularly limited, and a known method can be used.
- a brush, a gravure roll, dipping, a flow coating, a spray, an inkjet, etc. are mentioned.
- the thermoplastic 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 thereof.
- 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.
- thermoplastic resin laminate of the present invention preferably has a total light transmittance of 90% or more at a thickness of 1.0 mm.
- thermoplastic resin laminate of a preferred embodiment of the present invention is characterized by being excellent in transparency, heat resistance, scratch resistance, and dimensional stability in a high-temperature and high-humidity environment, and the thermoplastic resin laminate is transparent. It is used as a conductive substrate material, a transparent protective material, and the like, and is suitably used for a front panel of a display device that requires high dimensional stability particularly in a high temperature and high humidity environment.
- polyester resin (a) methyl methacrylate-styrene copolymer (d), styrene-maleic anhydride copolymer (e), acrylic resin composition, thermoplastic resin laminate obtained in Examples and Comparative Examples
- the body was evaluated as follows.
- the molecular weight (number average molecular weight Mn, weight average molecular weight Mw, molecular weight distribution Mw / Mn) is obtained by dissolving 2 mg of resin in 20 g of chloroform, measuring it with gel permeation chromatography (GPC), and calibrating with standard polystyrene. Mn, Mw, and Mw / Mn were set. GPC was measured by connecting TOSOH 8020 manufactured by Tosoh Corporation with two columns GMHHR-L and one TSK G5000HR manufactured by Tosoh Corporation at a column temperature of 40 ° C. As an eluent, chloroform was flowed at a flow rate of 1.0 ml / min, and measurement was performed with a UV detector.
- GPC gel permeation chromatography
- MMA units Structural units derived from methyl methacrylate (hereinafter referred to as MMA units) in the acrylic resin composition in the layer (B) containing the acrylic resin composition of the thermoplastic resin laminate obtained in the following examples and comparative examples.
- the component molar ratio is calculated from 13C-NMR (ig) measurement and peak area ratio after scraping 20 mg of the acrylic resin composition from the layer (B) of the thermoplastic resin laminate and dissolving it in 1 g of deuterated chloroform. did.
- the measurement device was an AVANCE II manufactured by Bruker BioSpin Co., Ltd., and the measurement was performed at 600 MHz.
- the molar ratios of MMA units, St units, and MAH units in the acrylic resin compositions of the thermoplastic resin laminates obtained in Examples and Comparative Examples are shown in Table 1, respectively.
- the total light transmittance is a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd .: COH-400) in accordance with JIS K 7105 and ASTM D1003. Measured with Those having a total light transmittance of 90% or more at a thickness of 1.0 mm were regarded as acceptable.
- thermoplastic resin laminates obtained in the following Examples and Comparative Examples from a 1.0 mm thick thermoplastic resin laminate, a rectangular test of 90 mm in length and 60 mm in width with the extrusion direction as the length and the width direction as the width. The piece was cut out, fastened to a short side central portion of 5 mm with a clip having a width of 13 mm, hung so that the test piece was vertical, and heated in an oven set at a temperature of 90 ° C. for 48 hours. The test piece after the test is placed on a horizontal surface so as to be concave upward, and is fixed by placing a weight of ⁇ 38 mm and a weight of 300 g on the center of the test piece. Was measured, and the sum of the deformation amounts did not exceed 0.5 mm.
- the pencil hardness is acrylic in accordance with JIS K 5600-5-4 using pencils of various hardness (Uni, manufactured by Mitsubishi Pencil Co., Ltd.).
- the pencil hardness of the layer (B) containing the resin composition was measured. Those having a pencil hardness of 3H or more were accepted.
- the impact resistance is such that the layer (B) containing the acrylic resin composition is on the upper side and the layer (A) containing the thermoplastic resin composition is on the lower side.
- a side it was evaluated by a falling ball test.
- the falling ball test is performed by fixing the sample between ⁇ 50 flanges, dropping a ⁇ 25, 63.7 g metal ball, and measuring the height when the test piece mounted on the bottom breaks at 10 cm intervals. The value up to a maximum height of 150 cm at the time of breaking was measured. The thing with the height at the time of a fracture
- thermoplastic resin laminates obtained in the following Examples and Comparative Examples, from a 1.0 mm thick thermoplastic resin laminate, a rectangular test of 90 mm in length and 60 mm in width with the extrusion direction as the length and the width direction as the width. A piece was cut out, and a short side central portion up to 5 mm was fastened with a clip having a width of 13 mm. The test piece after the test is placed on a horizontal surface so as to be concave upward, and is fixed by placing a weight of ⁇ 38 mm and a weight of 300 g on the center of the test piece. Was measured, and the sum of the deformation amounts did not exceed 0.5 mm.
- thermoplastic resin laminates obtained in the following Examples and Comparative Examples from a 1.0 mm thick thermoplastic resin laminate, a rectangular test of 90 mm in length and 60 mm in width with the extrusion direction as the length and the width direction as the width. A piece was cut out and conditioned at a temperature of 23 ° C. and a humidity of 50%. The test piece after the test is placed on a horizontal surface so as to be concave upward, and is fixed by placing a weight of ⁇ 38 mm and a weight of 300 g on the center of the test piece. Was measured, and the sum of the deformation amounts did not exceed 0.3 mm.
- methyl methacrylate-styrene copolymer (d) a methyl methacrylate-styrene copolymer (d).
- methyl methacrylate-styrene copolymer (d) the proportion of methyl methacrylate units was 89% by weight, the proportion of styrene units was 11% by weight, Mn was 17000, and Mw / Mn was 2.4.
- Example 1 Thermoplastic using a multilayer extruder having a single screw extruder with a shaft diameter of 32 mm, a single screw extruder with a shaft diameter of 65 mm, a feed block connected to the full extruder, and a T-die connected to the feed block. A resin laminate was molded.
- Acrylic resin manufactured by Asahi Kasei Chemicals Corporation, trade name: Delpet 80NH
- methyl methacrylate-styrene copolymer obtained in Synthesis Example 2
- Synthesis Example Acrylic resin mixture obtained by dry-mixing the styrene-maleic anhydride copolymer (e) obtained in 3 to a weight ratio of 90: 2.5: 7.5 was continuously introduced, and the cylinder temperature was 250 ° C. And extruded at a discharge speed of 4.8 kg / h.
- each of the single-screw extruder having a shaft diameter of 65 mm weighs the polyester resin (a) obtained in Synthesis Example 1 and the polycarbonate resin [Mitsubishi Gas Chemical Co., Ltd., trade name: Iupilon S-3000] (b).
- a thermoplastic resin mixture dry-mixed to a ratio of 60:40 was continuously introduced and extruded at a cylinder temperature of 260 ° C. and a discharge speed of 67 kg / h.
- the feed block connected to the entire extruder has two types and two layers of distribution pins, and the acrylic resin composition (B1) layer was introduced and laminated on one side of the thermoplastic resin composition (A1) layer at a temperature of 260 ° C. .
- thermoplastic resin composition (A1) layer (B1) A thermoplastic resin laminate in which layers were laminated was obtained.
- the set temperature of the roll was set to 85 ° C., 85 ° C., and 107 ° C. in order from the upstream side.
- the thickness of the obtained thermoplastic resin laminate was 1.0 mm, and the thickness of the acrylic resin composition (B1) layer was 70 ⁇ m near the center.
- the evaluation results are shown in Table 1. The results of transparency evaluation, heat resistance evaluation, scratch resistance evaluation, impact resistance evaluation, dimensional stability in a high-temperature and high-humidity environment, and moldability evaluation were good, and the overall judgment was acceptable.
- Example 2 instead of the acrylic resin composition (B1) used in Example 1, an acrylic resin [manufactured by Asahi Kasei Chemicals Corporation, trade name: Delpet 80NH] (c), methyl methacrylate-styrene copolymer (d), A thermoplastic resin composition (A1) was prepared in the same manner as in Example 1 except that an acrylic resin mixture obtained by dry mixing the styrene-maleic anhydride copolymer (e) in a weight ratio of 80: 5: 15 was used. ) A thermoplastic resin laminate in which an acrylic resin composition (B2) layer was laminated on one side of the layer was obtained.
- the thickness of the obtained thermoplastic resin laminate was 1.0 mm, and the thickness of the acrylic resin composition (B2) layer was 70 ⁇ m near the center.
- the evaluation results are shown in Table 1. The results of transparency evaluation, heat resistance evaluation, scratch resistance evaluation, impact resistance evaluation, dimensional stability evaluation in a high-temperature and high-humidity environment, and moldability evaluation were satisfactory, and the overall judgment was acceptable.
- Example 3 instead of the acrylic resin composition (B1) used in Example 1, an acrylic resin [manufactured by Asahi Kasei Chemicals Corporation, trade name: Delpet 80NH] (c), methyl methacrylate-styrene copolymer (d), A thermoplastic resin was used in the same manner as in Example 1 except that an acrylic resin mixture obtained by dry mixing the styrene-maleic anhydride copolymer (e) to a weight ratio of 70: 7.5: 22.5 was used. A thermoplastic resin laminate was obtained in which the acrylic resin composition (B3) layer was laminated on one side of the composition (A1) layer.
- the thickness of the obtained thermoplastic resin laminate was 1.0 mm, and the thickness of the acrylic resin composition (B3) layer was 70 ⁇ m near the center.
- the evaluation results are shown in Table 1. The results of transparency evaluation, heat resistance evaluation, scratch resistance evaluation, impact resistance evaluation, dimensional stability evaluation in a high-temperature and high-humidity environment, and moldability evaluation were satisfactory, and the overall judgment was acceptable.
- Example 4 instead of the acrylic resin composition (B1) used in Example 1, an acrylic resin [manufactured by Asahi Kasei Chemicals Corporation, trade name: Delpet 80NH] (c), styrene-maleic anhydride copolymer (e) Acrylic resin composition (B4) on one side of the thermoplastic resin composition (A1) layer in the same manner as in Example 1 except that an acrylic resin mixture obtained by dry mixing so as to have a weight ratio of 90:10 was used. A thermoplastic resin laminate in which layers were laminated was obtained. The thickness of the obtained thermoplastic resin laminate was 1.0 mm, and the thickness of the acrylic resin composition (B4) layer was 70 ⁇ m near the center. The evaluation results are shown in Table 1. The results of transparency evaluation, heat resistance evaluation, scratch resistance evaluation, impact resistance evaluation, dimensional stability evaluation in a high-temperature and high-humidity environment, and moldability evaluation were satisfactory, and the overall judgment was acceptable.
- thermoplastic resin composition (A1) used in Example 2 a polyester resin (a) and a polycarbonate resin [manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: Iupilon S-3000] (b) are respectively weight ratios.
- the acrylic resin composition (B2) layer was laminated on one side of the thermoplastic resin composition (A2) layer in the same manner as in Example 2 except that a thermoplastic resin mixture dry-mixed to 90:10 was used.
- a thermoplastic resin laminate was obtained.
- the thickness of the obtained thermoplastic resin laminate was 1.0 mm, and the thickness of the acrylic resin composition (B2) layer was 70 ⁇ m near the center.
- the evaluation results are shown in Table 1. The results of transparency evaluation, heat resistance evaluation, scratch resistance evaluation, impact resistance evaluation, dimensional stability evaluation in a high-temperature and high-humidity environment, and moldability evaluation were satisfactory, and the overall judgment was acceptable.
- thermoplastic resin composition (A1) used in Example 2 a polyester resin (a) and a polycarbonate resin [manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: Iupilon S-3000] (b) are respectively weight ratios.
- the acrylic resin composition (B2) layer was laminated on one side of the thermoplastic resin composition (A3) layer in the same manner as in Example 2 except that a thermoplastic resin mixture dry-mixed to 75:25 was used.
- a thermoplastic resin laminate was obtained.
- the thickness of the obtained thermoplastic resin laminate was 1.0 mm, and the thickness of the acrylic resin composition (B2) layer was 70 ⁇ m near the center.
- the evaluation results are shown in Table 1. The results of transparency evaluation, heat resistance evaluation, scratch resistance evaluation, impact resistance evaluation, dimensional stability evaluation in a high-temperature and high-humidity environment, and moldability evaluation were satisfactory, and the overall judgment was acceptable.
- thermoplastic resin composition (A1) used in Example 2 a polyester resin (a) and a polycarbonate resin [manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: Iupilon S-3000] (b) are respectively weight ratios.
- the acrylic resin composition (B2) layer was laminated on one side of the thermoplastic resin composition (A4) layer in the same manner as in Example 2 except that a thermoplastic resin mixture that was dry-mixed to 50:50 was used.
- a thermoplastic resin laminate was obtained.
- the thickness of the obtained thermoplastic resin laminate was 1.0 mm, and the thickness of the acrylic resin composition (B2) layer was 70 ⁇ m near the center.
- the evaluation results are shown in Table 1. The results of transparency evaluation, heat resistance evaluation, scratch resistance evaluation, impact resistance evaluation, dimensional stability evaluation in a high-temperature and high-humidity environment, and moldability evaluation were satisfactory, and the overall judgment was acceptable.
- thermoplastic resin composition (A1) used in Example 3 a polyester resin (a) and a polycarbonate resin [manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: Iupilon S-3000] (b) are respectively weight ratios.
- the acrylic resin composition (B3) layer was laminated on one side of the thermoplastic resin composition (A2) layer in the same manner as in Example 3 except that a thermoplastic resin mixture that was dry-mixed to 90:10 was used.
- a thermoplastic resin laminate was obtained.
- the thickness of the obtained thermoplastic resin laminate was 1.0 mm, and the thickness of the acrylic resin composition (B3) layer was 70 ⁇ m near the center.
- the evaluation results are shown in Table 1. The results of transparency evaluation, heat resistance evaluation, scratch resistance evaluation, impact resistance evaluation, dimensional stability evaluation in a high-temperature and high-humidity environment, and moldability evaluation were satisfactory, and the overall judgment was acceptable.
- thermoplastic resin laminate in which the acrylic resin (c) layer was laminated on one side of the thermoplastic resin composition (A1) layer was obtained.
- the thickness of the obtained thermoplastic resin laminate was 1.0 mm, and the thickness of the acrylic resin layer was 70 ⁇ m near the center.
- the evaluation results are shown in Table 1. The results of transparency evaluation, heat resistance evaluation, scratch resistance evaluation, impact resistance evaluation, and moldability evaluation were good, respectively, but the results of dimensional stability evaluation in high temperature and high humidity environment were poor, and comprehensive judgment Was rejected.
- thermoplastic resin instead of the acrylic resin composition (B1) used in Example 1, an acrylic resin [manufactured by Asahi Kasei Chemicals Corporation, trade name: Delpet 80NH] (c), methyl methacrylate-styrene copolymer (d), A thermoplastic resin was used in the same manner as in Example 1 except that an acrylic resin mixture obtained by dry mixing the styrene-maleic anhydride copolymer (e) to a weight ratio of 50: 12.5: 37.5 was used. A thermoplastic resin laminate was obtained in which the acrylic resin composition (B5) layer was laminated on one side of the composition (A1) layer.
- the thickness of the obtained thermoplastic resin laminate was 1.0 mm, and the thickness of the acrylic resin composition (B5) layer was 70 ⁇ m near the center.
- the evaluation results are shown in Table 1. The results of heat resistance evaluation, impact resistance evaluation, dimensional stability evaluation in high-temperature and high-humidity environment, and formability evaluation were good, respectively, but the results of transparency evaluation and scratch resistance evaluation were poor, and comprehensive judgment Was rejected.
- thermoplastic resin instead of the acrylic resin composition (B2) used in Example 5, an acrylic resin [manufactured by Asahi Kasei Chemicals Corporation, trade name: Delpet 80NH] (c), methyl methacrylate-styrene copolymer (d), A thermoplastic resin was used in the same manner as in Example 5 except that an acrylic resin mixture obtained by dry mixing the styrene-maleic anhydride copolymer (e) to a weight ratio of 50: 12.5: 37.5 was used. A thermoplastic resin laminate was obtained in which the acrylic resin composition (B5) layer was laminated on one side of the composition (A2) layer.
- the thickness of the obtained thermoplastic resin laminate was 1.0 mm, and the thickness of the acrylic resin composition (B5) layer was 70 ⁇ m near the center.
- the evaluation results are shown in Table 1. The results of heat resistance evaluation, impact resistance evaluation, and moldability evaluation were good, respectively, but the results of transparency evaluation, scratch resistance evaluation, and dimensional stability evaluation under high-temperature and high-humidity environment were poor, and comprehensive judgment Was rejected.
- Example 1 is the same as Example 1 except that instead of the thermoplastic resin composition (A1) used in Example 2, a polycarbonate resin [Mitsubishi Gas Chemical Co., Ltd., trade name: Iupilon S-3000] (b) was used. Similarly, a thermoplastic resin laminate in which an acrylic resin composition (B2) layer was laminated on one side of a polycarbonate resin (b) layer was obtained. The thickness of the obtained thermoplastic resin laminate was 1.0 mm, and the thickness of the acrylic resin composition (B2) layer was 70 ⁇ m near the center. The evaluation results are shown in Table 1. The results of transparency evaluation, heat resistance evaluation, impact resistance evaluation, and dimensional stability evaluation under high-temperature and high-humidity environments were good, but the results of scratch resistance evaluation and moldability evaluation were poor. Was rejected.
- thermoplastic resin plate was formed using a single-layer extruder having a shaft diameter of 65 mm and a T-die.
- Polyester resin (a) was continuously introduced into a single screw extruder having a shaft diameter of 65 mm and extruded at a cylinder temperature of 250 ° C. and a discharge speed of 70 kg / h. It was extruded in a sheet form with a T-die having a temperature of 250 ° C. connected to the tip, and cooled while transferring the mirror surface with three mirror finish rolls to obtain a thermoplastic resin plate of polyester resin (a).
- the thickness of the obtained thermoplastic resin plate was 1.0 mm.
- the evaluation results are shown in Table 1. The results of transparency evaluation, heat resistance evaluation, impact resistance evaluation, and moldability evaluation were good, but the results of scratch resistance evaluation and dimensional stability evaluation in a high temperature and high humidity environment were poor, and comprehensive judgment Was rejected.
- thermoplastic resin plate of polycarbonate resin (b) was obtained.
- the thickness of the obtained thermoplastic resin plate was 1.0 mm.
- the evaluation results are shown in Table 1. The results of heat resistance evaluation, impact resistance evaluation, and dimensional stability evaluation in a high temperature and high humidity environment were satisfactory, but the results of transparency evaluation, scratch resistance evaluation, and moldability evaluation were poor. Was rejected.
- thermoplastic resin plate (c) was obtained.
- the thickness of the obtained thermoplastic resin plate was 1.0 mm.
- the evaluation results are shown in Table 1. The results of transparency evaluation, heat resistance evaluation, scratch resistance evaluation, and moldability evaluation were good, but the results of impact resistance evaluation and dimensional stability evaluation in a high temperature and high humidity environment were poor. It was a failure.
- thermoplastic resin plate was obtained. The thickness of the obtained thermoplastic resin plate was 1.0 mm.
- the evaluation results are shown in Table 1. The results of heat resistance evaluation, dimensional stability evaluation in high temperature and high humidity environment, and moldability evaluation were good, but the results of transparency evaluation, scratch resistance evaluation, and impact resistance evaluation were poor. It was a failure.
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Abstract
Description
で表される環状アセタール骨格を有するジオール単位をジオール構成単位の10~60モル%有するか、又は一般式(3):
で表される環状アセタール骨格を有するジカルボン酸単位をジカルボン酸構成単位の10~60モル%有するポリエステル樹脂(a)をコア層として用い、スキン層にアクリル樹脂を用いた構成とすることにより、透明性、耐熱性、耐擦傷性、耐衝撃性に優れた多層シートが得られるとの記載がなされている。
すなわち、本発明は、以下の通りである。
<1> 熱可塑性樹脂組成物を含む層(A)と、前記層(A)の少なくとも一方の面に設けられたアクリル系樹脂組成物を含む層(B)を有する熱可塑性樹脂積層体であって、前記熱可塑性樹脂組成物が、
全ジオール構成単位中の10~60モル%が下記式(1)または下記式(2)
で表される環状アセタール骨格を有するジオールに由来するジオール構成単位とジカルボン酸構成単位を含むポリエステル樹脂(a)と、ポリカーボネート樹脂(b)とを含み、前記熱可塑性樹脂組成物中のポリエステル樹脂(a)とポリカーボネート樹脂(b)の合計に対するポリカーボネート樹脂(b)の割合が5~50重量%であり、
前記アクリル系樹脂組成物が、アクリル樹脂(c)及びメチルメタクリレート-スチレン共重合体(d)から成る群から選ばれた少なくとも1種とスチレン-無水マレイン酸共重合体(e)とを含み、前記アクリル系樹脂組成物中のメチルメタクリレートに由来する構成単位とスチレンに由来する構成単位と無水マレイン酸に由来する構成単位の合計に対するメチルメタクリレートに由来する構成単位の割合が70~95モル%であり、無水マレイン酸に由来する構成単位の割合が1~5モル%であることを特徴とする、熱可塑性樹脂積層体である。
<2> スチレン-無水マレイン酸共重合体(e)中の、スチレンに由来する構成単位と無水マレイン酸に由来する構成単位の合計に対するスチレンに由来する構成単位の割合が75~95重量%である、上記<1>に記載の熱可塑性樹脂積層体である。
<3> 前記環状アセタール骨格を有するジオールが、3,9-ビス(1,1-ジメチル-2-ヒドロキシエチル)-2,4,8,10-テトラオキサスピロ〔5.5〕ウンデカンである、上記<1>または<2>に記載の熱可塑性樹脂積層体である。
<4> ポリエステル樹脂(a)における、全ジカルボン酸構成単位中のテレフタル酸に由来する構成単位の割合が70モル%以上である、上記<1>~<3>のいずれかに記載の熱可塑性樹脂積層体である。
<5> 片面または両面にハードコート処理を施したものである上記<1>~<4>のいずれかに記載の熱可塑性樹脂積層体である。
<6> 片面または両面に反射防止処理、防汚処理、帯電防止処理、耐候性処理およ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ものである上記<1>~<5>のいずれかに記載の熱可塑性樹脂積層体である。
<7> 上記<1>~<6>のいずれかに記載の熱可塑性樹脂積層体を含む透明性基板材料である。
<8> 上記<1>~<6>のいずれかに記載の熱可塑性樹脂積層体を含む透明性保護材料である。
ポリエステル樹脂(a)、メチルメタクリレート-スチレン共重合体(d)、スチレン-無水マレイン酸共重合体(e)、アクリル系樹脂組成物の評価、実施例および比較例で得られた熱可塑性樹脂積層体の評価は以下のように行った。
ポリエステル樹脂(a)、メチルメタクリレート-スチレン共重合体(d)、スチレン-無水マレイン酸共重合体(e)の構造決定は、樹脂20mgを1gの重クロロホルムに溶解し、1H-NMR測定、ピーク面積比から算出して行った。測定装置は日本電子(株)製JNM-AL400を用い、400MHzで測定した。
分子量(数平均分子量Mn、重量平均分子量Mw、分子量分布Mw/Mn)は、樹脂2mgを20gのクロロホルムに溶解し、ゲルパーミエイションクロマトグラフィー(GPC)で測定し、標準ポリスチレンで検量したものをMn、Mw、Mw/Mnとした。GPCは東ソー(株)製TOSOH 8020に東ソー(株)製カラムGMHHR-Lを2本、TSK G5000HRを1本接続し、カラム温度40℃で測定した。溶離液はクロロホルムを1.0ml/minの流速で流し、UV検出器で測定した。
以下の実施例、比較例にて得られた熱可塑性樹脂積層体のアクリル系樹脂組成物を含む層(B)におけるアクリル系樹脂組成物中の、メチルメタクリレートに由来する構成単位(以下、MMA単位と略す)、スチレンに由来する構成単位(以下、St単位と略す)、無水マレイン酸に由来する構成単位(以下、MAH単位と略す)のモル比を分析した。
成分モル比は、熱可塑性樹脂積層体の層(B)からアクリル系樹脂組成物のみを20mg削り取り、1gの重クロロホルムに溶解し、13C-NMR(i.g.)測定、ピーク面積比から算出した。測定装置はブルカー・バイオスピン(株)製AVANCEIIを用い、600MHzで測定した。実施例、比較例にて得られた熱可塑性樹脂積層体のアクリル系樹脂組成物中のMMA単位、St単位、MAH単位のモル比は、それぞれ表1に記載した。
以下の実施例、比較例にて得られた熱可塑性樹脂積層体について、全光線透過率はJIS K 7105、ASTM D1003に準じて、色差計(日本電色工業(株)製:COH―400)にて測定した。厚さ1.0mmにおける全光線透過率90%以上のものを合格とした。
以下の実施例、比較例にて得られた熱可塑性樹脂積層体について、1.0mm厚の熱可塑性樹脂積層体から、押出方向を縦、幅方向を横として、縦90mm、横60mmの長方形試験片を切り出し、短辺中央部5mm部分までを幅13mmのクリップで留め、試験片が垂直になるよう吊るし、温度90℃に設定したオーブン内で48時間加熱した。試験後の試験片を上に凹となるよう水平面に静置し、試験片中央部にφ38mm、重さ300gの重りを乗せて固定し、試験片の四隅と水平面との隙間長さの変形量を測定し、その変形量の合算値が0.5mmを超えないものを合格とした。
以下の実施例、比較例にて得られた熱可塑性樹脂積層体について、鉛筆硬度はJIS K 5600-5-4に準じて、各種硬度の鉛筆(三菱鉛筆(株)製 ユニ)を用いてアクリル系樹脂組成物を含む層(B)の鉛筆硬度を測定した。鉛筆硬度3H以上のものを合格とした。
以下の実施例、比較例にて得られた熱可塑性樹脂積層体について、耐衝撃性はアクリル系樹脂組成物を含む層(B)を上側、熱可塑性樹脂組成物を含む層(A)を下側として、落球試験にて評価した。落球試験は、φ50のフランジの間にサンプルを固定し、φ25、63.7gの金属球を落とし、底部に装着した試験片が破断したときの高さを10cm間隔で計測する方法で行い、その破断時点の高さが最高150cmまでの値を測定した。破断時点での高さが100cm以上のものを合格とした。
以下の実施例、比較例にて得られた熱可塑性樹脂積層体について、1.0mm厚の熱可塑性樹脂積層体から、押出方向を縦、幅方向を横として、縦90mm、横60mmの長方形試験片を切り出し、短辺中央部5mm部分までを幅13mmのクリップで留め、試験片が垂直になるよう吊るし、温度85℃、湿度85%に設定した恒温恒湿機内で120時間加熱した。試験後の試験片を上に凹となるよう水平面に静置し、試験片中央部にφ38mm、重さ300gの重りを乗せて固定し、試験片の四隅と水平面との隙間長さの変形量を測定し、その変形量の合算値が0.5mmを超えないものを合格とした。
以下の実施例、比較例にて得られた熱可塑性樹脂積層体について、1.0mm厚の熱可塑性樹脂積層体から、押出方向を縦、幅方向を横として、縦90mm、横60mmの長方形試験片を切り出し、温度23℃、湿度50%に調湿した。試験後の試験片を上に凹となるよう水平面に静置し、試験片中央部にφ38mm、重さ300gの重りを乗せて固定し、試験片の四隅と水平面との隙間長さの変形量を測定し、その変形量の合算値が0.3mmを超えないものを合格とした。
ジカルボン酸成分としてジメチルテレフタル酸、ジオール成分として3,9-ビス(1,1-ジメチル-2-ヒドロキシエチル)-2,4,8,10-テトラオキサスピロ〔5.5〕ウンデカンとエチレングリコールをそれぞれ45モル%、55モル%とした原料モノマーを、ジカルボン酸成分100モルに対し酢酸マンガン四水和物0.03モルの存在下、窒素雰囲気下で200℃まで昇温してエステル交換反応を行った。メタノールの留出量が理論量に対して90%以上に達した後、ジカルボン酸成分100モルに対し、酸化アンチモン(III)0.01モルとトリフェニルホスフェート0.06モルを加え、昇温と減圧を徐々に行い、最終的に280℃、0.1MPa以下で重合を行った。適度な溶融粘度になった時点で反応を終了し、ポリエステル樹脂(a)を得た。得られたポリエステル樹脂(a)中の環状アセタール骨格を有するジオール単位の割合は45モル%、Mnは16500、Mw/Mnは3.6であった。
撹拌機を付した容積約20リットルの完全混合型反応器、容積約40リットルの塔式プラグフロー型反応器、予熱器を付した脱揮槽を直列に接続して構成した。スチレン11質量部、メタクリル酸メチル89質量部、エチルベンゼン8質量部で構成される単量体混合液を調製し、さらに1,1-ビス(t-ブチルパーオキシ)-シクロヘキサン(日本油脂社製パーヘキサC)0.02質量部とn-ドデシルメルカプタン(花王社製チオカルコール20)0.02質量部を混合し原料溶液とした。この原料溶液を毎時6kgで温度130℃に制御した完全混合型反応器に導入した。なお、完全混合型反応器の撹拌数は180rpmで実施した。次いで完全混合型反応器より反応液を連続的に抜き出し、流れの方向に向かって温度130℃から160℃の勾配がつくように調整した塔式プラグフロー型反応器に導入した。この反応液を予熱器で加温しながら、温度235℃で圧力1.0kPaに制御した脱揮槽に導入し、未反応単量体等の揮発分を除去した。この樹脂液をギアポンプで抜き出し、メチルメタクリレート-スチレン共重合体(d)を得た。得られたメチルメタクリレート-スチレン共重合体(d)のメチルメタクリレート単位の割合は89重量%、スチレン単位の割合は11重量%、Mnは17000、Mw/Mnは2.4であった。
単量体混合液を、スチレン84質量部、無水マレイン酸を16質量部とし、原料溶液に加えるn-ドデシルメルカプタンを0.2質量部とした以外は合成例2と同様にし、スチレン-無水マレイン酸系共重合体(e)を得た。得られたスチレン-無水マレイン酸共重合体(e)のスチレン単位は84重量%、無水マレイン酸単位は16重量%、Mn=17000、Mw/Mn=2.4であった。
軸径32mm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熱可塑性樹脂積層板を成形した。軸径32mmの単軸押出機にアクリル樹脂〔旭化成ケミカルズ(株)製、商品名:デルペット 80NH〕(c)、合成例2で得られたメチルメタクリレート-スチレン共重合体(d)、合成例3で得られたスチレン-無水マレイン酸共重合体(e)をそれぞれ重量比90:2.5:7.5になるよう乾式混合したアクリル系樹脂混合物を連続的に導入し、シリンダ温度250℃、吐出速度4.8kg/hの条件で押し出した。また、軸径65mmの単軸押出機には合成例1で得られたポリエステル樹脂(a)とポリカーボネート樹脂〔三菱ガス化学(株)製、商品名:ユーピロン S-3000〕(b)をそれぞれ重量比60:40となるよう乾式混合した熱可塑性樹脂混合物を連続的に導入し、シリンダ温度260℃、吐出速度67kg/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260℃として熱可塑性樹脂組成物(A1)層の片面にアクリル系樹脂組成物(B1)層を導入し積層した。その先に連結された温度260℃のTダイでシート状に押し出し、3本の鏡面仕上げロールで鏡面を転写しながら冷却し、熱可塑性樹脂組成物(A1)層の片面にアクリル系樹脂組成物(B1)層が積層した熱可塑性樹脂積層体を得た。このときロールの設定温度は上流側から順に85℃、85℃、107℃とした。得られた熱可塑性樹脂積層体の厚みは1.0mm、アクリル系樹脂組成物(B1)層の厚みは中央付近で70μmであった。
評価結果を表1に示す。透明性評価、耐熱性評価、耐擦傷性評価、耐衝撃性評価、高温高湿環境での寸法安定性、成形性評価の結果はそれぞれ良好であり、総合判定は合格であった。
実施例1で使用したアクリル系樹脂組成物(B1)の代わりに、アクリル樹脂〔旭化成ケミカルズ(株)製、商品名:デルペット 80NH〕(c)、メチルメタクリレート-スチレン共重合体(d)、スチレン-無水マレイン酸共重合体(e)をそれぞれ重量比80:5:15になるよう乾式混合したアクリル系樹脂混合物を使用した以外は、実施例1と同様にして熱可塑性樹脂組成物(A1)層の片面にアクリル系樹脂組成物(B2)層が積層した熱可塑性樹脂積層体を得た。得られた熱可塑性樹脂積層体の厚みは1.0mm、アクリル系樹脂組成物(B2)層の厚みは中央付近で70μmであった。
評価結果を表1に示す。透明性評価、耐熱性評価、耐擦傷性評価、耐衝撃性評価、高温高湿環境での寸法安定性評価、成形性評価の結果はそれぞれ良好であり、総合判定は合格であった。
実施例1で使用したアクリル系樹脂組成物(B1)の代わりに、アクリル樹脂〔旭化成ケミカルズ(株)製、商品名:デルペット 80NH〕(c)、メチルメタクリレート-スチレン共重合体(d)、スチレン-無水マレイン酸共重合体(e)をそれぞれ重量比70:7.5:22.5になるよう乾式混合したアクリル系樹脂混合物を使用した以外は、実施例1と同様にして熱可塑性樹脂組成物(A1)層の片面にアクリル系樹脂組成物(B3)層が積層した熱可塑性樹脂積層体を得た。得られた熱可塑性樹脂積層体の厚みは1.0mm、アクリル系樹脂組成物(B3)層の厚みは中央付近で70μmであった。
評価結果を表1に示す。透明性評価、耐熱性評価、耐擦傷性評価、耐衝撃性評価、高温高湿環境での寸法安定性評価、成形性評価の結果はそれぞれ良好であり、総合判定は合格であった。
実施例1で使用したアクリル系樹脂組成物(B1)の代わりに、アクリル樹脂〔旭化成ケミカルズ(株)製、商品名:デルペット 80NH〕(c)、スチレン-無水マレイン酸共重合体(e)をそれぞれ重量比90:10になるよう乾式混合したアクリル系樹脂混合物を使用した以外は、実施例1と同様にして熱可塑性樹脂組成物(A1)層の片面にアクリル系樹脂組成物(B4)層が積層した熱可塑性樹脂積層体を得た。得られた熱可塑性樹脂積層体の厚みは1.0mm、アクリル系樹脂組成物(B4)層の厚みは中央付近で70μmであった。
評価結果を表1に示す。透明性評価、耐熱性評価、耐擦傷性評価、耐衝撃性評価、高温高湿環境での寸法安定性評価、成形性評価の結果はそれぞれ良好であり、総合判定は合格であった。
実施例2で使用した熱可塑性樹脂組成物(A1)の代わりに、ポリエステル樹脂(a)、ポリカーボネート樹脂〔三菱ガス化学(株)製、商品名:ユーピロン S-3000〕(b)をそれぞれ重量比90:10になるよう乾式混合した熱可塑性樹脂混合物を使用した以外は、実施例2と同様にして熱可塑性樹脂組成物(A2)層の片面にアクリル系樹脂組成物(B2)層が積層した熱可塑性樹脂積層体を得た。得られた熱可塑性樹脂積層体の厚みは1.0mm、アクリル系樹脂組成物(B2)層の厚みは中央付近で70μmであった。
評価結果を表1に示す。透明性評価、耐熱性評価、耐擦傷性評価、耐衝撃性評価、高温高湿環境での寸法安定性評価、成形性評価の結果はそれぞれ良好であり、総合判定は合格であった。
実施例2で使用した熱可塑性樹脂組成物(A1)の代わりに、ポリエステル樹脂(a)、ポリカーボネート樹脂〔三菱ガス化学(株)製、商品名:ユーピロン S-3000〕(b)をそれぞれ重量比75:25になるよう乾式混合した熱可塑性樹脂混合物を使用した以外は、実施例2と同様にして熱可塑性樹脂組成物(A3)層の片面にアクリル系樹脂組成物(B2)層が積層した熱可塑性樹脂積層体を得た。得られた熱可塑性樹脂積層体の厚みは1.0mm、アクリル系樹脂組成物(B2)層の厚みは中央付近で70μmであった。
評価結果を表1に示す。透明性評価、耐熱性評価、耐擦傷性評価、耐衝撃性評価、高温高湿環境での寸法安定性評価、成形性評価の結果はそれぞれ良好であり、総合判定は合格であった。
実施例2で使用した熱可塑性樹脂組成物(A1)の代わりに、ポリエステル樹脂(a)、ポリカーボネート樹脂〔三菱ガス化学(株)製、商品名:ユーピロン S-3000〕(b)をそれぞれ重量比50:50になるよう乾式混合した熱可塑性樹脂混合物を使用した以外は、実施例2と同様にして熱可塑性樹脂組成物(A4)層の片面にアクリル系樹脂組成物(B2)層が積層した熱可塑性樹脂積層体を得た。得られた熱可塑性樹脂積層体の厚みは1.0mm、アクリル系樹脂組成物(B2)層の厚みは中央付近で70μmであった。
評価結果を表1に示す。透明性評価、耐熱性評価、耐擦傷性評価、耐衝撃性評価、高温高湿環境での寸法安定性評価、成形性評価の結果はそれぞれ良好であり、総合判定は合格であった。
実施例3で使用した熱可塑性樹脂組成物(A1)の代わりに、ポリエステル樹脂(a)、ポリカーボネート樹脂〔三菱ガス化学(株)製、商品名:ユーピロン S-3000〕(b)をそれぞれ重量比90:10になるよう乾式混合した熱可塑性樹脂混合物を使用した以外は、実施例3と同様にして熱可塑性樹脂組成物(A2)層の片面にアクリル系樹脂組成物(B3)層が積層した熱可塑性樹脂積層体を得た。得られた熱可塑性樹脂積層体の厚みは1.0mm、アクリル系樹脂組成物(B3)層の厚みは中央付近で70μmであった。
評価結果を表1に示す。透明性評価、耐熱性評価、耐擦傷性評価、耐衝撃性評価、高温高湿環境での寸法安定性評価、成形性評価の結果はそれぞれ良好であり、総合判定は合格であった。
実施例1で使用したアクリル系樹脂組成物(B1)の代わりに、アクリル樹脂〔旭化成ケミカルズ(株)製、商品名:デルペット 80NH〕(c)を使用した以外は、実施例1と同様にして熱可塑性樹脂組成物(A1)層の片面にアクリル樹脂(c)層が積層した熱可塑性樹脂積層体を得た。得られた熱可塑性樹脂積層体の厚みは1.0mm、アクリル樹脂層の厚みは中央付近で70μmであった。
評価結果を表1に示す。透明性評価、耐熱性評価、耐擦傷性評価、耐衝撃性評価、成形性評価の結果はそれぞれ良好であったが、高温高湿環境での寸法安定性評価の結果は不良であり、総合判定は不合格であった。
実施例1で使用したアクリル系樹脂組成物(B1)の代わりに、アクリル樹脂〔旭化成ケミカルズ(株)製、商品名:デルペット 80NH〕(c)、メチルメタクリレート-スチレン共重合体(d)、スチレン-無水マレイン酸共重合体(e)をそれぞれ重量比50:12.5:37.5になるよう乾式混合したアクリル系樹脂混合物を使用した以外は、実施例1と同様にして熱可塑性樹脂組成物(A1)層の片面にアクリル系樹脂組成物(B5)層が積層した熱可塑性樹脂積層体を得た。得られた熱可塑性樹脂積層体の厚みは1.0mm、アクリル系樹脂組成物(B5)層の厚みは中央付近で70μmであった。
評価結果を表1に示す。耐熱性評価、耐衝撃性評価、高温高湿環境での寸法安定性評価、成形性評価の結果はそれぞれ良好であったが、透明性評価、耐擦傷性評価の結果は不良であり、総合判定は不合格であった。
実施例5で使用したアクリル系樹脂組成物(B2)の代わりに、アクリル樹脂〔旭化成ケミカルズ(株)製、商品名:デルペット 80NH〕(c)、メチルメタクリレート-スチレン共重合体(d)、スチレン-無水マレイン酸共重合体(e)をそれぞれ重量比50:12.5:37.5になるよう乾式混合したアクリル系樹脂混合物を使用した以外は、実施例5と同様にして熱可塑性樹脂組成物(A2)層の片面にアクリル系樹脂組成物(B5)層が積層した熱可塑性樹脂積層体を得た。得られた熱可塑性樹脂積層体の厚みは1.0mm、アクリル系樹脂組成物(B5)層の厚みは中央付近で70μmであった。
評価結果を表1に示す。耐熱性評価、耐衝撃性評価、成形性評価の結果はそれぞれ良好であったが、透明性評価、耐擦傷性評価、高温高湿環境での寸法安定性評価の結果は不良であり、総合判定は不合格であった。
実施例2で使用した熱可塑性樹脂組成物(A1)の代わりに、ポリエステル樹脂(a)を使用した以外は、実施例1と同様にしてポリエステル樹脂(a)層の片面にアクリル系樹脂組成物(B2)層が積層した熱可塑性樹脂積層体を得た。得られた熱可塑性樹脂積層体の厚みは1.0mm、アクリル系樹脂組成物(B2)層の厚みは中央付近で70μmであった。
評価結果を表1に示す。透明性評価、耐熱性評価、耐擦傷性評価、耐衝撃性評価、成形性評価の結果はそれぞれ良好であったが、高温高湿環境での寸法安定性評価の結果は不良であり、総合判定は不合格であった。
実施例2で使用した熱可塑性樹脂組成物(A1)の代わりに、ポリカーボネート樹脂〔三菱ガス化学(株)製、商品名:ユーピロン S-3000〕(b)を使用した以外は、実施例1と同様にしてポリカーボネート樹脂(b)層の片面にアクリル系樹脂組成物(B2)層が積層した熱可塑性樹脂積層体を得た。得られた熱可塑性樹脂積層体の厚みは1.0mm、アクリル系樹脂組成物(B2)層の厚みは中央付近で70μmであった。
評価結果を表1に示す。透明性評価、耐熱性評価、耐衝撃性評価、高温高湿環境での寸法安定性評価の結果はそれぞれ良好であったが、耐擦傷性評価、成形性評価の結果は不良であり、総合判定は不合格であった。
軸径65mmの単軸押出機とTダイとを有する単層押出装置を用いて熱可塑性樹脂板を成形した。軸径65mmの単軸押出機にポリエステル樹脂(a)を連続的に導入し、シリンダ温度250℃、吐出速度70kg/hで押し出した。その先に連結された温度250℃のTダイでシート状に押し出し、3本の鏡面仕上げロールで鏡面を転写しながら冷却し、ポリエステル樹脂(a)の熱可塑性樹脂板を得た。得られた熱可塑性樹脂板の厚みは1.0mmであった。
評価結果を表1に示す。透明性評価、耐熱性評価、耐衝撃性評価、成形性評価の結果はそれぞれ良好であったが、耐擦傷性評価、高温高湿環境での寸法安定性評価の結果は不良であり、総合判定は不合格であった。
比較例6で使用したポリエステル樹脂(a)の代わりに、ポリカーボネート樹脂〔三菱ガス化学(株)製、商品名:ユーピロン S-3000〕(b)を使用した以外は、比較例6と同様にしてポリカーボネート樹脂(b)の熱可塑性樹脂板を得た。得られた熱可塑性樹脂板の厚みは1.0mmであった。
評価結果を表1に示す。耐熱性評価、耐衝撃性評価、高温高湿環境での寸法安定性評価の結果はそれぞれ良好であったが、透明性評価、耐擦傷性評価、成形性評価の結果は不良であり、総合判定は不合格であった。
比較例6で使用したポリエステル樹脂(a)の代わりに、アクリル樹脂〔旭化成ケミカルズ(株)製、商品名:デルペット 80NH〕(c)を使用した以外は、比較例6と同様にしてアクリル樹脂(c)の熱可塑性樹脂板を得た。得られた熱可塑性樹脂板の厚みは1.0mmであった。
評価結果を表1に示す。透明性評価、耐熱性評価、耐擦傷性評価、成形性評価の結果はそれぞれ良好であったが耐衝撃性評価、高温高湿環境での寸法安定性評価の結果は不良であり、総合判定は不合格であった。
比較例6で使用したポリエステル樹脂(a)の代わりに、メチルメタクリレート-スチレン共重合体(d)を使用した以外は、比較例6と同様にしてメチルメタクリレート-スチレン共重合体(d)の熱可塑性樹脂板を得た。得られた熱可塑性樹脂板の厚みは1.0mmであった。
評価結果を表1に示す。透明性評価、耐熱性評価、成形性評価の結果はそれぞれ良好であったが耐擦傷性評価、耐衝撃性評価、高温高湿環境での寸法安定性評価の結果は不良であり、総合判定は不合格であった。
比較例6で使用したポリエステル樹脂(a)の代わりに、スチレン-無水マレイン酸共重合体(e)を使用した以外は、比較例6と同様にしてスチレン-無水マレイン酸共重合体(e)の熱可塑性樹脂板を得た。得られた熱可塑性樹脂板の厚みは1.0mmであった。
評価結果を表1に示す。耐熱性評価、高温高湿環境での寸法安定性評価、成形性評価の結果はそれぞれ良好であったが透明性評価、耐擦傷性評価、耐衝撃性評価の結果は不良であり、総合判定は不合格であった。
Claims (8)
- 熱可塑性樹脂組成物を含む層(A)と、前記層(A)の少なくとも一方の面に設けられた、アクリル系樹脂組成物を含む層(B)とを有する熱可塑性樹脂積層体であって、前記熱可塑性樹脂組成物が、
全ジオール構成単位中の10~60モル%が下記式(1)または下記式(2)
で表される環状アセタール骨格を有するジオールに由来するジオール構成単位とジカルボン酸構成単位を含むポリエステル樹脂(a)と、ポリカーボネート樹脂(b)とを含み、前記熱可塑性樹脂組成物中のポリエステル樹脂(a)とポリカーボネート樹脂(b)の合計に対するポリカーボネート樹脂(b)の割合が5~50重量%であり、
前記アクリル系樹脂組成物が、アクリル樹脂(c)及びメチルメタクリレート-スチレン共重合体(d)から成る群から選ばれた少なくとも1種と、スチレン-無水マレイン酸共重合体(e)とを含み、前記アクリル系樹脂組成物中のメチルメタクリレートに由来する構成単位とスチレンに由来する構成単位と無水マレイン酸に由来する構成単位の合計に対するメチルメタクリレートに由来する構成単位の割合が70~95モル%であり、無水マレイン酸に由来する構成単位の割合が1~5モル%であることを特徴とする、熱可塑性樹脂積層体。 - スチレン-無水マレイン酸共重合体(e)中の、スチレンに由来する構成単位と無水マレイン酸に由来する構成単位の合計に対するスチレンに由来する構成単位の割合が75~95重量%である、請求項1に記載の熱可塑性樹脂積層体。
- 前記環状アセタール骨格を有するジオールが、3,9-ビス(1,1-ジメチル-2-ヒドロキシエチル)-2,4,8,10-テトラオキサスピロ〔5.5〕ウンデカンである、請求項1または2に記載の熱可塑性樹脂積層体。
- ポリエステル樹脂(a)における、全ジカルボン酸構成単位中のテレフタル酸に由来する構成単位の割合が70モル%以上である、請求項1~3のいずれかに記載の熱可塑性樹脂積層体。
- 片面または両面にハードコート処理を施したものである請求項1~4のいずれかに記載の熱可塑性樹脂積層体。
- 片面または両面に反射防止処理、防汚処理、帯電防止処理、耐候性処理およ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ものである請求項1~5のいずれかに記載の熱可塑性樹脂積層体。
- 請求項1~6のいずれかに記載の熱可塑性樹脂積層体を含む透明性基板材料。
- 請求項1~6のいずれかに記載の熱可塑性樹脂積層体を含む透明性保護材料。
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CN115038586A (zh) * | 2020-12-18 | 2022-09-09 | 三菱瓦斯化学株式会社 | 多层体和成型品 |
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