JP5292257B2 - Polycarbonate resin laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polycarbonate resin laminate which has a layer comprising a polycarbonate resin layer and an acrylic resin composition, and is not whitened when stretched, bent, shocked, or exposed to a wet heat condition for a long period of time. <P>SOLUTION: The acrylic resin composition is prepared by a process in which a methacrylic resin (A) and a polyvinyl acetal resin (B) produced by acetalizing a polyvinyl alcohol resin by aldehydes are melt/kneaded under conditions of a mass ratio (A)/(B) of 99/1-51/49 and a shear rate of at least 100 sec<SP>-1</SP>to form the continuous phase of the methacrylic resin (A). The polyvinyl acetal resin (B) contains 65-85 mol% of repeating units acetalized by the aldehydes of the total mol% of repeating units. The molar ratio of repeating units acetalized by &ge;4C aldehydes/repeating units acetalized by &le;3C aldehydes is 90/10-0/100. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

The present invention relates to a polycarbonate resin laminate. More specifically, the present invention is a laminate having a polycarbonate resin layer and an acrylic resin composition layer, having high transparency, excellent surface smoothness, surface hardness and toughness or impact resistance. The present invention relates to a polycarbonate resin laminate that is excellent in balance, and that does not whiten an acrylic resin composition layer when stretched, bent, subjected to an impact, and / or placed under a wet and heat condition for a long time.
Moreover, this invention is a laminated body which has a polycarbonate resin layer and the layer of the acrylic resin composition containing the ultraviolet absorber, and relates to the polycarbonate resin laminated body which was excellent in the weather resistance in addition to the said characteristic.

Polycarbonate resin has excellent transparency and impact resistance, high heat distortion temperature, excellent dimensional stability, workability and self-extinguishing properties, so it can be used in many fields as window glass materials and optical materials. It is used. However, since the polycarbonate resin is inferior in surface hardness, it is easily damaged, and since it is inferior in weather resistance, the impact strength may be lowered or discolored when used outdoors exposed to direct sunlight.
As a laminate that attempts to improve these points, for example, Patent Document 1 discloses a laminate in which a polycarbonate resin layer is covered with a layer made of a (meth) acrylate polymer. Patent Document 2 discloses an acrylic resin layer containing an ultraviolet absorber having a glass transition temperature of 40 to 90 ° C. and a molecular weight of 400 or more at 0.5 to 5.0 g / m ² on one side or both sides of a polycarbonate resin sheet. The provided laminate is disclosed.
However, in the laminate described in the above-mentioned patent document, the (meth) acrylic resin layer is easily broken when stretched, bent and / or subjected to an impact, for example, for a thin plate such as a front plate of a mobile phone. The impact strength, bending strength, or surface hardness required in the above was not fully satisfied.

  Patent Document 3 discloses a two-phase mixed polymer comprising, on an aromatic polycarbonate layer, a polymer (I) having a glass transition temperature of 10 ° C. or lower and a methyl methacrylate copolymer (II) having a glass transition temperature of 30 ° C. or higher. A laminate formed by coating these layers is described. As the polymer (I), a terpolymer composed of ethylene-propylene-diene and an acrylate elastic rubber based on butyl acrylate are disclosed. Further, as a two-phase mixed polymer, a core-shell type particle structure having a core made of copolymer (II) and a shell made of polymer (I) is disclosed. The laminate obtained by the method of Patent Document 3 is less likely to crack in the two-phase mixed polymer layer even when stretched, bent and / or impacted, but is easily whitened and has transparency. There was a decline. In addition, when core-shell type particles are used in the laminate, surface smoothness may be reduced or haze may be increased due to the particles.

JP 55-59929 A JP-A-4-270652 JP-A-2-175245

  It is an object of the present invention to have high transparency, excellent surface smoothness, excellent balance between surface hardness and toughness or impact resistance, and when stretched, bent, subjected to impact and / or An object of the present invention is to provide a polycarbonate resin laminate in which an acrylic resin composition layer does not whiten when placed under a wet heat condition for a long time.

  As a result of intensive investigations in order to achieve the above object, the present inventor conducted strong shearing of a specific methacrylic resin (A) and a specific polyvinyl acetal resin (B) on at least one surface of the polycarbonate resin layer. By laminating a layer having a thickness of 5 to 200 μm made of an acrylic resin composition obtained by melting and kneading, it has high transparency, excellent surface smoothness, surface hardness and toughness or impact resistance It is possible to obtain a polycarbonate resin laminate in which the acrylic resin composition layer is not whitened when it is stretched, bent, subjected to an impact, and / or when subjected to a long-time wet heat condition. I found it. The present invention has been further studied and completed based on this finding.

That is, the present invention is a polycarbonate resin laminate having a polycarbonate resin layer and an acrylic resin composition having a thickness of 5 to 200 μm,
The acrylic resin composition comprises a methacrylic resin (A) having a weight average molecular weight of 40000 or more and a polyvinyl acetal resin (B) obtained by acetalizing a polyvinyl alcohol resin having a viscosity average polymerization degree of 200 to 4000 with an aldehyde. A methacrylic resin (A) is formed by melting and kneading under conditions of a mass ratio (A) / (B) of from ^{1 to} 51/49 and a shear rate of 100 sec ^-1 or more, and The polyvinyl acetal resin (B) contains 65 to 85 mol% of a repeating unit acetalized with an aldehyde and a repeating unit acetalized with an aldehyde having 4 or more carbon atoms / 3 carbon atoms. A polycarbonate tree having a molar ratio of the repeating unit acetalized with the following aldehyde of 90/10 to 0/100 It is a fat laminate.

The polycarbonate resin laminate according to the present invention has high transparency, excellent surface smoothness, excellent balance between surface hardness and toughness (low-speed tensile toughness) or impact resistance, and when stretched or bent. The acrylic resin composition layer does not whiten when subjected to an impact and / or when it is placed under wet heat conditions for a long time. In addition to the above features, a laminate having excellent weather resistance can be obtained by including an ultraviolet absorber in the layer of the acrylic resin composition laminated on the polycarbonate resin.
The polycarbonate resin laminate according to the present invention is suitably used in the fields of various glazing materials, optical members, LCD and EL display protective sheets, signboards, automobile window materials, soundproof walls, vending machine front plates, carports, and the like. Can be used.

Hereinafter, the present invention will be described in detail.
The laminate of the present invention comprises a layer made of a polycarbonate resin and a layer made of an acrylic resin composition.
The polycarbonate resin used in the present invention is not particularly limited. The polycarbonate resin is a polymer obtained by a reaction between a polyfunctional hydroxy compound and a carbonate ester-forming compound.

  Examples of the polyfunctional hydroxy compound include 4,4′-dihydroxybiphenyls which may have a substituent; bis (hydroxyphenyl) alkanes which may have a substituent; Good bis (4-hydroxyphenyl) ethers; optionally substituted bis (4-hydroxyphenyl) sulfides; optionally substituted bis (4-hydroxyphenyl) sulfoxides; substituted Bis (4-hydroxyphenyl) sulfones optionally having a group; bis (4-hydroxyphenyl) ketones optionally having a substituent; bis (hydroxyphenyl) optionally having a substituent ) Fluorenes; optionally substituted dihydroxy-p-terphenyls; optionally substituted dihydroxy-p-quarterpheny Bis (hydroxyphenyl) pyrazines optionally having a substituent; bis (hydroxyphenyl) menthanes optionally having a substituent; bis [2- (4-hydroxyphenyl) -2-propyl] benzenes; dihydroxynaphthalenes optionally having substituents; dihydroxybenzenes optionally having substituents; poly optionally having substituents Siloxanes; dihydroperfluoroalkanes which may have a substituent, and the like.

  Among these polyfunctional hydroxy compounds, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 1,1-bis ( 4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-phenylphenyl) propane, 4,4′- Dihydroxybiphenyl, bis (4-hydroxyphenyl) sulfone, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 3,3-bis (4-hydroxyphenyl) pentane, 9,9-bis ( 4-hydroxy-3-methylphenyl) fluorene, bis (4-hydroxyphenyl) ether, 4,4 '-Dihydroxybenzophenone, 2,2-bis (4-hydroxy-3-methoxyphenyl) 1,1,1,3,3,3-hexafluoropropane, α, ω-bis [3- (2-hydroxyphenyl) Propyl] polydimethylsiloxane, resorcin, and 2,7-dihydroxynaphthalene are preferable, and 2,2-bis (4-hydroxyphenyl) propane is particularly preferable.

  Examples of the carbonate ester-forming compound include various dihalogenated carbonyls such as phosgene, haloformates such as chloroformate, and carbonate ester compounds such as bisaryl carbonate. The amount of the carbonate ester-forming compound may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction.

  The reaction between the polyfunctional hydroxy compound and the carbonate ester-forming compound is usually performed in a solvent in the presence of an acid binder. Examples of acid binders include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and cesium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, trimethylamine, triethylamine, tributylamine, Tertiary amines such as N, N-dimethylcyclohexylamine, pyridine, dimethylaniline, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tributylbenzylammonium chloride, trioctylmethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide Quaternary ammonium salts, quaternary phosphonium salts such as tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, etc. And the like. Furthermore, if desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added to this reaction system. The amount of the acid binder may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. Specifically, 1 equivalent or an excess amount, preferably 1 to 5 equivalents of acid binder may be used per 1 mol of hydroxyl group of the starting polyfunctional hydroxy compound.

  Moreover, a well-known terminal stopper and a branching agent can be used for reaction. As the terminator, p-tert-butyl-phenol, p-phenylphenol, p-cumylphenol, p-perfluorononylphenol, p- (perfluorononylphenyl) phenol, p- (perfluoroxylphenyl) phenol , P-tert-perfluorobutylphenol, 1- (p-hydroxybenzyl) perfluorodecane, p- [2- (1H, 1H-perfluorotridodecyloxy) -1,1,1,3,3,3- Hexafluoropropyl] phenol, 3,5-bis (perfluorohexyloxycarbonyl) phenol, perfluorododecyl p-hydroxybenzoate, p- (1H, 1H-perfluorooctyloxy) phenol, 2H, 2H, 9H-par Fluorononanoic acid, 1,1,1,3,3,3 Such Tetorafuroro 2-propanol.

  Examples of branching agents include phloroglysin, pyrogallol, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) -2-heptene, 2,6-dimethyl-2,4,6-tris (4- Hydroxyphenyl) -3-heptene, 2,4-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (2-hydroxyphenyl) benzene, 1,3,5- Tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, tris (4-hydroxyphenyl) phenylmethane, 2,2-bis [4,4-bis (4-hydroxyphenyl) ) Cyclohexyl] propane, 2,4-bis [2-bis (4-hydroxyphenyl) -2-propyl] phenol, 2,6-bis (2-hydroxy-) -Methylbenzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane, tetrakis (4-hydroxyphenyl) methane, tetrakis [4- (4-hydroxyphenylisopropyl) ) Phenoxy] methane, 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric acid, 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole, 3,3- Bis (4-hydroxyaryl) oxindole, 5-chloroisatin, 5,7-dichloroisatin, 5-bromoisatin and the like can be mentioned.

The polycarbonate resin may contain a unit having a polyester, polyurethane, polyether or polysiloxane structure in addition to the polycarbonate unit.
The polycarbonate resin suitably used in the present invention is not particularly limited by its molecular weight, but has a viscosity average molecular weight of about 13,000 to 30,000 or a melt at 250 ° C. and 100 sec ⁻¹ from the viewpoint of ease of production by extrusion molding. A thing with a viscosity of about 13,000-60000 poise is preferable. The molecular weight can be adjusted by adjusting the amount of the terminal terminator or branching agent.
The polycarbonate resin used in the present invention has various additives as necessary, for example, an antioxidant, a stabilizer, an ultraviolet absorber, a lubricant, a processing aid, an antistatic agent, a colorant, an impact resistance aid, A foaming agent, a filler, a matting agent, etc. may be blended.
In view of the mechanical properties and surface hardness of the polycarbonate resin laminate of the present invention, the polycarbonate resin preferably does not contain a large amount of softener or plasticizer.

The shape of the polycarbonate resin layer is not particularly limited, but is preferably a thin, wide area such as a film, sheet or plate.
Although there is no restriction | limiting in particular in the thickness of a polycarbonate resin layer, Usually, 0.05-20 mm, Preferably it is 0.1-10 mm, More preferably, it is 0.2-10 mm.
The surface of the polycarbonate resin layer on the side in contact with the layer made of the acrylic resin composition may be subjected to a surface treatment in order to improve adhesion. Examples of the surface treatment include corona discharge treatment and plasma treatment.

  The acrylic resin composition used in the present invention is obtained by melt-kneading a methacrylic resin (A) and a polyvinyl acetal resin (B).

  The methacrylic resin (A) used in the present invention is obtained by polymerizing a monomer mixture containing a methacrylic acid ester.

  Methacrylic acid esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, Examples include myristyl methacrylate, palmityl methacrylate, stearyl methacrylate, behenyl methacrylate, cyclohexyl methacrylate, and phenyl methacrylate. These methacrylic acid esters may be used alone or in combination of two or more. Of these, alkyl methacrylates having 1 to 4 carbon atoms in the alkyl group are preferred, and methyl methacrylate is particularly preferred.

Examples of monomers other than methacrylic acid esters include acrylic acid esters.
Examples of acrylic esters include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, pentyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, Examples include myristyl acrylate, palmityl acrylate, stearyl acrylate, behenyl acrylate, cyclohexyl acrylate, and phenyl acrylate. Of these, alkyl acrylates having 1 to 8 carbon atoms in the alkyl group are preferred. These acrylic acid esters may be used alone or in combination of two or more.

Further, the methacrylic resin (A) may be obtained by copolymerizing other ethylenically unsaturated monomers copolymerizable with methacrylic acid esters and acrylic acid esters. Examples of ethylenically unsaturated monomers copolymerizable with methacrylic acid esters and acrylic acid esters include diene compounds such as 1,3-butadiene and isoprene; styrene, α-methylstyrene, vinyltoluene, 2,4-dimethyl Styrene, halogen-substituted styrene, 1-vinylnaphthalene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) Vinyl aromatic compounds such as styrene; ethylenically unsaturated nitriles such as acrylonitrile and methacrylonitrile; acrylic acid, methacrylic acid, acrylamide, methacrylamide, maleic anhydride, maleic imide, monomethyl maleate, dimethyl maleate, etc. To mention Can.
These ethylenically unsaturated monomers may be used alone or in combination of two or more.

In the methacrylic resin (A) used in the present invention, the proportion of methacrylic acid ester units is preferably 50 to 100% by mass and more preferably 80 to 99.9% by mass from the viewpoint of weather resistance. preferable.
Moreover, it is preferable that methacrylic resin (A) contains an acrylate ester unit in the range of 0.1-20 mass% from a heat resistant viewpoint.

  The methacrylic resin (A) used in the present invention has a weight average molecular weight of 40,000 or more, preferably 40,000 to 1,000,000, more preferably 80 from the viewpoint of strength characteristics and meltability. , 000 to 500,000. The methacrylic resin (A) used in the present invention may have a linear molecular chain, a branched molecular chain, or a cyclic structure in the molecular chain. There may be.

  The methacrylic resin (A) used in the present invention is not particularly limited as long as it is a method capable of polymerizing an α, β-unsaturated compound, but is preferably produced by radical polymerization. Examples of the polymerization method include bulk polymerization, suspension polymerization, solution polymerization, and emulsion polymerization.

  Examples of radical polymerization initiators used during polymerization include azo compounds such as azobisisobutyronitrile and azobisγ-dimethylvaleronitrile; benzoyl peroxide, cumyl peroxide, oxyneodecanoate, diisopropyl peroxydicarbonate, t Examples thereof include peroxides such as -butyl cumyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, and lauroyl peroxide. The polymerization initiator is usually used in an amount of 0.05 to 0.5 parts by mass with respect to 100 parts by mass of all monomers. The polymerization is usually performed at a temperature of 50 to 140 ° C. for 2 to 20 hours.

  In order to control the molecular weight of the methacrylic resin (A), a chain transfer agent can be used. Examples of chain transfer agents include methyl mercaptan, ethyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, t-butyl mercaptan, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, ethylthioglycoate, mercaptoethanol, thio- β-naphthol, thiophenol and the like can be mentioned. The chain transfer agent is usually used in the range of 0.005 to 0.5 mass% with respect to the total monomers.

  The polyvinyl acetal resin (B) is usually a resin having a repeating unit represented by Chemical Formula 1.

In Chemical Formula 1, R ³ is an alkyl residue or hydrogen atom derived from an aldehyde having 3 or less carbon atoms used in the acetalization reaction, and R ⁴ is an alkyl residue derived from an aldehyde having 4 or more carbon atoms used in the acetalization reaction (note that The carbon number of the alkyl residues R ³ and R ⁴ is an integer i obtained by subtracting 1 from the carbon number of the aldehyde used in the acetalization reaction. When i is zero, R ³ is a hydrogen atom. k ₃ is the molar ratio of vinyl alcohol units acetalized with an aldehyde having 3 or less carbon atoms, k ₄ is the molar ratio of vinyl alcohol units acetalized with an aldehyde having 4 or more carbon atoms, and l is the molar ratio of vinyl alcohol units. , M is the molar ratio of vinyl acetate units. However, l and / or m may be zero.
The repeating units are not particularly limited by the arrangement order shown in Chemical Formula 1, and may be arranged at random, may be arranged in a block shape, or may be arranged in a taper shape.

In addition, the mol% of the repeating unit refers to a unit consisting of two main chain carbons (for example, a polyvinyl alcohol unit, a vinyl acetate unit, an ethylene unit, etc.) in the polyvinyl alcohol resin that is a raw material for producing the polyvinyl acetal resin. It is calculated. For example, in the polyvinyl acetal resin shown in Chemical Formula 1, the mol% (k _(AA) ) of the repeating unit acetalized with an aldehyde having 3 or less carbon atoms with respect to all repeating units (= k ₃ + k ₄ + l + m) is represented by the formula: (K ₃ / (k ₃ + k ₄ + l + m)) × 100 The mol% (k _(BA) ) of the repeating unit acetalized with an aldehyde having 4 or more carbon atoms is expressed by the formula: (k ₄ / (k ₃ + k ₄ + l + m)) × 100, and the mole percent of vinyl alcohol repeating units (k _(VA) ) is determined by the formula: (l / (k ₃ + k ₄ + l + m)) × 100 The mole% of repeating units (k _(AV) ) is determined by the formula: (m / (k ₃ + k ₄ + l + m)) × 100

  The polyvinyl acetal resin (B) used in the present invention can be obtained by acetalizing a polyvinyl alcohol resin with an aldehyde.

  The polyvinyl alcohol resin used for the production of the polyvinyl acetal resin (B) has a viscosity average polymerization degree of 200 to 4,000, preferably 300 to 3,000, more preferably 500 to 2,000. If the polyvinyl alcohol resin has a viscosity average polymerization degree of less than 200, the resulting polyvinyl acetal resin has insufficient mechanical properties, and the polycarbonate resin laminate of the present invention tends to have insufficient mechanical properties, particularly toughness. On the other hand, when the viscosity average polymerization degree of the polyvinyl alcohol resin exceeds 4,000, the melt viscosity at the time of melt kneading the acrylic resin composition tends to be high, and the production tends to be difficult.

A polyvinyl alcohol resin is not specifically limited by the manufacturing method, For example, what was manufactured by saponifying polyvinyl acetate etc. using an alkali, an acid, ammonia water, etc. can be used.
The polyvinyl alcohol resin may be completely saponified, or may be partially saponified, that is, partially saponified polyvinyl alcohol resin. The saponification degree is preferably 80 mol% or more, more preferably 97 mol% or more, and particularly preferably 99.5 mol% or more.

Further, as the polyvinyl alcohol resin, a copolymer composed of a vinyl alcohol unit and a monomer unit copolymerizable therewith, such as an ethylene-vinyl alcohol copolymer resin and a partially saponified ethylene-vinyl alcohol copolymer resin, is used. be able to. Furthermore, a modified polyvinyl alcohol resin into which carboxylic acid or the like is partially introduced can be used.
These polyvinyl alcohol resins may be used individually by 1 type, and may be used in combination of 2 or more types.

  Examples of the aldehyde having 3 or less carbon atoms used in the production of the polyvinyl acetal resin (B) include formaldehyde (including paraformaldehyde), acetaldehyde (including paraacetaldehyde), propionaldehyde, and the like. These aldehydes having 3 or less carbon atoms can be used singly or in combination of two or more. Of these aldehydes having 3 or less carbon atoms, those mainly composed of acetaldehyde (including paraacetaldehyde) and formaldehyde (including paraformaldehyde) are preferable, and acetaldehyde is particularly preferable.

  Examples of the aldehyde having 4 or more carbon atoms used for producing the polyvinyl acetal resin (B) include butyraldehyde, n-octylaldehyde, amylaldehyde, hexylaldehyde, heptylaldehyde, 2-ethylhexylaldehyde, cyclohexylaldehyde, furfural, glyoxal, glutar Examples include aldehyde, benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, phenylacetaldehyde, β-phenylpropionaldehyde and the like. These aldehydes having 4 or more carbon atoms may be used alone or in combination of two or more. Of these aldehydes, those mainly composed of butyraldehyde are preferred from the viewpoint of ease of production, and butyraldehyde is particularly preferred.

When the acetalization of the polyvinyl alcohol resin is performed with butyraldehyde, the molar ratio of the repeating unit of the acetalized vinyl alcohol is called the degree of butyralization. The molar ratio of the repeating unit of vinyl alcohol acetalized with acetaldehyde is called the degree of acetoacetalization, and the molar ratio of the repeating unit of vinyl alcohol acetalized with formaldehyde is called the degree of formalization.
For example, in a polyvinyl acetal resin obtained by acetalization with butyraldehyde, acetaldehyde, and formaldehyde, the molar ratio of vinyl acetal units obtained by acetalization with butyraldehyde is k _(BA) , vinyl obtained by acetalization with acetaldehyde. The mole fraction of acetal units is k _(AA) , the mole fraction of vinyl acetal units obtained by acetalization with formaldehyde is k _(FA) , the mole fraction of vinyl alcohol units is l, and the mole fraction of vinyl acetate units is m. If there is, the degree of butyralization is determined by the formula: (k _(BA) / {k _(BA) + k _(AA) + k _(FA) + l + m}) × 100. The degree of acetoacetalization is determined by the formula: (k _(AA) / {k _(BA) + k _(AA) + k _(FA) + l + m}) × 100. The degree of formalization is determined by the formula: (k _(FA) / {k _(BA) + k _(AA) + k _(FA) + l + m}) × 100.

The acetalization reaction of the polyvinyl alcohol resin can be performed by a known method. For example, an aqueous medium method in which an aqueous solution of polyvinyl alcohol resin and an aldehyde are subjected to an acetalization reaction in the presence of an acid catalyst to precipitate resin particles; a polyvinyl alcohol resin is dispersed in an organic solvent, and an aldehyde is added in the presence of an acid catalyst. Examples thereof include a solvent method in which an acetalization reaction is performed and the reaction solution is precipitated with water or the like which is a poor solvent for the polyvinyl acetal resin. Of these methods, the aqueous medium method is preferable.
The aldehydes used for acetalization may be charged all at the same time or may be charged separately one by one. In addition, the acid catalyst may be added all at the same time, or one type may be charged separately. Furthermore, the order of addition of the aldehyde and the acid catalyst is not particularly limited.

  The acid catalyst used in the acetalization reaction is not particularly limited, and examples thereof include organic acids such as acetic acid and p-toluenesulfonic acid; inorganic acids such as nitric acid, sulfuric acid and hydrochloric acid; and gas which shows acidity when an aqueous solution such as carbon dioxide gas is used. A solid acid catalyst such as a cation exchanger or a metal oxide.

The total of the repeating units acetalized with the aldehyde having 4 or more carbon atoms and the aldehyde having 3 or less carbon atoms (total degree of acetalization) of the polyvinyl acetal resin (B) is in accordance with the method described in JIS K6728 (1977). The mass ratio (l ₀ ) of vinyl alcohol units and the ratio (m ₀ ) of vinyl acetate units were determined by titration, and the mass ratio (k ₀ ) of acetalized vinyl alcohol units was calculated as k ₀ = 1−l ₀ -m. determined by _0, from which to calculate the molar ratio of the molar proportion (l) and vinyl acetate units of vinyl alcohol units (m), the molar ratio of k = 1-l-m acetalized vinyl alcohol unit by a calculation formula of ( k) may be calculated, and the total degree of acetalization (mol%) = k / (k + 1 + m) × 100 may be obtained, or polyvinyl acetal tree Was dissolved in deuterated dimethyl sulfoxide, it may be calculated by measuring the ^{1 H-NMR, 13 C-} NMR.

The polyvinyl acetal resin (B) used in the present invention has a total of repeating units acetalized with an aldehyde having 4 or more carbon atoms and an aldehyde having 3 or less carbon atoms (total degree of acetalization) of 65% with respect to all repeating units. It is -85 mol%, Preferably it is 70-85 mol%, More preferably, it is 80-85 mol%. When the total of the acetalized repeating units is less than 65 mol% with respect to all repeating units, the mechanical properties, particularly toughness and impact resistance, of the acrylic resin molding according to the present invention are insufficient. On the other hand, when a polyvinyl acetal resin exceeding 85 mol% is produced, it takes a very long time, which is economically disadvantageous.
When a polyvinyl acetal resin having a total degree of acetalization within the above range is used, a polycarbonate resin laminate excellent in mechanical properties, particularly toughness, can be obtained easily and inexpensively. In addition, when a polyvinyl acetal resin having a total degree of acetalization within the above range is used, the difference between the refractive index of the methacrylic resin (A) and the refractive index of polyvinyl butyral is reduced, which is a feature of the methacrylic resin (A). Transparency (high visible light transmittance / low haze) is easily maintained. Furthermore, when stretched, bent, subjected to an impact, and / or placed in a wet and heat condition for a long time, the feature of hardly whitening is likely to appear.

  Moreover, suitable polyvinyl acetal resin (B) contains 17-45 mol% of vinyl alcohol units normally, and contains 0-5 mol% of vinyl acetate units normally, Preferably it contains 0-3 mol%.

The slurry of the polyvinyl acetal resin (B) produced in the water medium method, the solvent method, or the like is usually acidic by an acid catalyst. As a method for removing the acid catalyst, the slurry is repeatedly washed with water, and the pH is usually adjusted to 5 to 9, preferably 6 to 9, more preferably 6 to 8; a neutralizing agent is added to the slurry, The method of adjusting pH to 5-9 normally, Preferably 6-9, More preferably, 6-8; The method of adding alkylene oxides etc. are mentioned.
Examples of the compound used for removing the acid catalyst include alkali metal compounds such as sodium hydroxide, potassium hydroxide, sodium acetate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, ammonia, and an aqueous ammonia solution. Examples of alkylene oxides include ethylene oxide, propylene oxide; glycidyl ethers such as ethylene glycol diglycidyl ether.

Next, salts generated by neutralization, aldehyde reaction residues, and the like are removed. The removal method is not particularly limited, and methods such as repeated dehydration and water washing are usually used.
The water-containing polyvinyl acetal resin from which residues and the like have been removed is dried as necessary, and further processed into powder, granules, or pellets as necessary, and subjected to molding. When processing into a powder, granule, or pellet, it is preferable to reduce the aldehyde reaction residue, moisture, and the like by degassing under reduced pressure.

  In the acrylic resin composition used in the present invention, a continuous phase is formed by the methacrylic resin (A). When the methacrylic resin (A) forms a continuous phase, the heat resistance, surface hardness and rigidity of the laminate are improved.

Methacrylic resin used in the present invention (A) and polyvinyl acetal resin (B), methacrylic resin main dispersion peak temperature of the main dispersion peak temperature of (A) (T [alpha _A) and the polyvinyl acetal resin (B) (T [alpha _B ) between, 90 ℃ ≦ Tα _B ≦ Tα is preferably one having a relation of _a or _{90 ℃ ≦ Tα a ≦ Tα B} , 95 ℃ ≦ Tα B ≦ Tα a or 95 ℃ ≦ Tα _a ≦ Tα relationship _B It is more preferable that 110 ° C. ≦ Tα _B ≦ Tα _A or 110 ° C. ≦ Tα _A ≦ Tα _B is more preferable. When Tα _A or Tα _B is less than 90 ° C., the heat resistance of the acrylic resin composition used in the present invention tends to decrease.

The main dispersion peak temperature of the acrylic resin composition includes a main dispersion peak temperature (Tα _AP ) attributable to the methacrylic resin (A) and a main dispersion peak temperature (Tα _BP ) attributable to the polyvinyl acetal resin (B). There is.
The acrylic resin composition according to a preferred embodiment of the present invention has a main dispersion peak temperature Tα _AP attributed to the methacrylic resin (A) in the acrylic resin composition, the main dispersion peak temperature of the methacrylic resin (A) alone. It is a value between (Tα _A ) and the main dispersion peak temperature (Tα _B ) of the polyvinyl acetal resin (B) alone. That is, the relationship of Tα _B <Tα _AP <Tα _A or Tα _A <Tα _AP <Tα _B is satisfied. Such acrylic resin composition having a T [alpha _AP satisfying the relation is considered methacrylic resin (A) and the polyvinyl acetal resin (B) is partially turned compatible state.
In the present invention, when the methacrylic resin (A) is a combination of two or more methacrylic resins, and any one of the primary dispersion peak temperature of a combination thereof with T [alpha _A, polyvinyl acetal resin (B ) Is a combination of two or more polyvinyl acetal resins, the main dispersion peak temperature of any one of the combinations is Tα _B , and the above relationship, that is, Tα _B <Tα _AP <Tα _A , or Tα It is preferable that the relationship of _A <Tα _AP <Tα _B is satisfied.

The acrylic resin composition preferably has Tα _AP = Tα _BP . Furthermore, it is preferable to satisfy the relationship of Tα _B <Tα _AP = Tα _BP <Tα _A or Tα _A <Tα _AP = Tα _BP <Tα _B.
When Tα _AP = Tα _A and Tα _BP = Tα _B , it indicates that the methacrylic resin (A) and the polyvinyl acetal resin (B) in the acrylic resin composition are in a completely compatible state. ing.

Although the detailed reason is not clear, when the methacrylic resin (A) and the polyvinyl acetal resin (B) are partially compatible, the acrylic resin composition has heat resistance, surface hardness, and rigidity as compared with the methacrylic resin. It is almost the same, and it is difficult to whiten when stretched, bent, subjected to an impact, and / or placed under a wet and heat condition for a long time. In addition, it has excellent toughness and handleability.
On the other hand, when the methacrylic resin (A) and the polyvinyl acetal resin (B) are completely compatible and Tα _B <Tα _A , the heat resistance tends to decrease. When the methacrylic resin (A) and the polyvinyl acetal resin (B) are completely incompatible, the strength decreases or whitens.

In the acrylic resin composition used in the present invention, the methacrylic resin (A) forms a continuous phase. When the methacrylic resin (A) forms a continuous phase, a polycarbonate resin laminate having good heat resistance and high surface hardness derived from the methacrylic resin (A) can be obtained.
The acrylic resin composition preferably has a dyed dispersed phase that is observed with a transmission electron microscope when electron dyed with ruthenium tetroxide. The dispersed phase is preferably smaller, and the average diameter is usually 200 nm or less, preferably 100 nm or less, particularly preferably 50 nm or less. In addition, in the case of 50 nm or less, the case where two components are completely compatible with each other and no dispersed particles are observed is included.
The dyed dispersed phase is considered to contain the polyvinyl acetal resin (B). On the other hand, it is considered that the unstained continuous phase is formed by the methacrylic resin (A).
The phase structure of the acrylic resin composition is observed by first preparing an ultrathin section using a microtome, then electron-staining with ruthenium tetroxide, and using a transmission electron microscope.

In the acrylic resin composition, the mass ratio (A) / (B) of the methacrylic resin (A) to the polyvinyl acetal resin (B) is 99/1 to 51/49, preferably 95/5 to 60. / 40, more preferably 90/10 to 60/40. With such a mass ratio, the acrylic resin composition has good toughness, impact resistance, surface hardness and rigidity.
When the proportion of the polyvinyl acetal resin (B) is less than 1% by mass, the effect of improving the mechanical properties such as toughness and impact resistance of the laminate of the present invention tends to decrease. On the other hand, when the proportion of the polyvinyl acetal resin (B) exceeds 49% by mass, the surface hardness and rigidity of the laminate of the present invention tend to be insufficient.

The acrylic resin composition preferably used in the present invention has a strain rate of 1 mm / min. Using a test piece of length 80 mm × width 10 mm × thickness 4 mm in accordance with JIS K7171. In accordance with the flexural modulus at the time of the test and the JIS K7162, a strain rate of 1 mm / min. At least one of the tensile elastic moduli when tested in (1) is 2 GPa or more, preferably 2.5 GPa or more, more preferably 2.7 GPa or more.
In addition, an acrylic resin composition preferably used in the present invention has a strain rate of 1 mm / min. Using a test piece of length 80 mm × width 10 mm × thickness 4 mm in accordance with JIS K7171. It has a yield point of stress when it is subjected to a bending test. The yield point of stress is the stress limit where plastic deformation starts in a solid.

Acrylic resin composition used in the present invention, the methacrylic resin (A) and the polyvinyl acetal resin (B), a shear rate of 100 sec ^-1 or more, preferably by melt-kneading by applying shear than 200 sec ^-1 It is obtained. By applying such high shear and melt-kneading, the layer made of the acrylic resin composition has the same heat resistance, surface hardness and rigidity as those of the methacrylic resin, and when stretched, bent, It becomes difficult to whiten when subjected to an impact and / or when it is left for a long time under humid and heat conditions.
A suitable method for preparing the acrylic resin composition includes a step of applying shear at a shear rate of 100 sec ⁻¹ or more when melt-kneading the methacrylic resin (A) and the polyvinyl acetal resin (B), And a step of reducing the shear rate to 50 sec ⁻¹ or less at least twice. When the shear rate is changed as described above and melt-kneaded, the layer made of the acrylic resin composition is stretched, folded, subjected to an impact, and / or subjected to a long period of wet heat. It becomes difficult to whiten.

In the preparation of the acrylic resin composition, a methacrylic resin (A) and a polyvinyl acetal resin (B) are mixed into a known kneader such as a single screw extruder, a twin screw extruder, a Banbury mixer, a brabender, an open roll, or a kneader. It is important to knead each component in a molten state using Among these kneaders, a large shearing force is obtained, the methacrylic resin (A) is easy to form a continuous phase, is excellent in productivity, and a shear is applied at a shear rate of 100 sec ⁻¹ or more. A twin screw extruder is preferred because it can easily create a process including at least twice each step of setting the speed to 50 sec ^-1 or less.
The resin temperature at the time of melt kneading is preferably 140 ° C. or higher, more preferably 140 to 270 ° C., and particularly preferably 160 to 250 ° C.

  After melt-kneading, it is cooled to a temperature of 120 ° C. or lower. Cooling is preferably performed more rapidly than natural cooling by, for example, immersing the melted strand in a tank in which cold water is stored. By rapid cooling, the methacrylic resin (A) forms a continuous phase, and the methacrylic resin (A) and the polyvinyl acetal resin (B) are easily fixed in a partially compatible state. The size of is very small. The size of the dispersed phase is usually 200 nm or less, preferably 100 nm or less, particularly preferably 50 nm or less. In addition, in the case of 50 nm or less, the case where two components are completely compatible with each other and no dispersed particles are observed is included.

  For the acrylic resin composition, various additives as required, for example, antioxidants, stabilizers, ultraviolet absorbers, lubricants, processing aids, antistatic agents, colorants, impact resistance aids, foaming agents. Further, a filler, a matting agent, etc. may be added. In addition, it is preferable that a softener and a plasticizer are not added in a large amount from the viewpoint of mechanical properties and surface hardness of the resin composition. These additives may be blended at the stage of a) obtaining a methacrylic resin (A) by a polymerization reaction, for example, a monomer having methyl methacrylate as a main component or a partial polymer thereof, and b). You may mix | blend in the step which acetalizes polyvinyl alcohol resin and synthesize | combines polyvinyl acetal resin (B), c) A methacrylic resin (A) and a polyvinyl acetal resin (B) are a uniaxial kneader, a biaxial kneader, etc. It may be blended at the stage of melt kneading with a kneading machine, or d) after the acrylic resin composition comprising the methacrylic resin (A) and the polyvinyl acetal resin (B) is produced.

  Among these additives, the ultraviolet absorber can be preferably added for the purpose of improving the weather resistance. Although the kind of ultraviolet absorber is not specifically limited, A benzotriazole type, a benzophenone type, or a triazine type is preferable. Content of a ultraviolet absorber is 0.01-2 mass% normally with respect to an acrylic resin composition, Preferably it is 0.1-2 mass%.

  The laminate of the present invention is prepared by separately preparing a layer (thin film) made of an acrylic resin composition and a polycarbonate resin layer, and laminating them continuously between heating rolls, and thermocompression bonding with a press. , A method of laminating simultaneously with compressed air or vacuum forming, a method of laminating via an adhesive layer (wet lamination); a method of casting a molten polycarbonate resin using a thin film made of an acrylic resin composition as a base material; A method of co-extrusion molding of a polycarbonate resin and an acrylic resin composition can be used.

  A thin film made of an acrylic resin composition can be obtained by a known film forming method. For example, melt extrusion molding methods with high shearing force such as T-die method, calendar method, inflation method, melt casting method and the like can be mentioned. According to the melt extrusion molding method with high shearing force, it has excellent transparency, improved toughness, excellent handleability, excellent balance between toughness, surface hardness and rigidity, and when stretched, folded, It is possible to obtain a laminate that is less likely to be whitened when subjected to an impact and / or when placed under a wet and heat condition for a long time. Among the methods for obtaining a thin film comprising an acrylic resin composition, the above melt-kneaded product is extruded from a T-die in a molten state from the viewpoint of obtaining a thin film with good surface smoothness, good specular gloss and low haze. A method including a step of forming both surfaces of the mirror roll surface or the mirror belt surface in contact with both surfaces is preferable. The roll or belt used at this time is preferably made of metal. In the case where the both sides of the melt-kneaded product thus extruded are brought into contact with a mirror surface and molded, it is preferable that both sides of the molded body are pressed and sandwiched with a mirror roll or a mirror belt. The pinching pressure by the mirror roll or mirror belt is preferably higher, and the linear pressure is preferably 10 N / mm or more, and more preferably 30 N / mm or more.

  Further, from the viewpoint of obtaining a thin film comprising an acrylic resin composition having good surface smoothness, good specular gloss, and low haze, the surface temperature of at least one of a mirror roll or a mirror belt sandwiching the acrylic resin composition is set. It is preferable that the surface temperature of both the mirror roll or the mirror belt sandwiching the molded body is 60 ° C. or higher and 130 ° C. or lower. When the surface temperature of both the mirror surface roll and the mirror surface belt is less than 60 ° C., the surface smoothness of the resulting thin film made of the acrylic resin composition tends to be insufficient and the haze tends to increase. Since the thin film and the mirror roll or mirror belt are in close contact with each other when the temperature exceeds ℃, the surface is easily roughened when the thin film made of the acrylic resin composition is peeled off from the mirror roll or mirror belt, and the resulting acrylic resin composition There is a tendency that the surface smoothness of the thin film consisting of becomes lower or the haze becomes higher.

  The resin temperature in the melt extrusion method is preferably 140 to 270 ° C, more preferably 160 to 250 ° C. After melt molding, it is preferable to cool the thin film more rapidly than natural cooling. For example, it is preferable that the thin film immediately after being formed is brought into contact with a cooling roll for rapid cooling. By performing such rapid cooling, a thin film in which the methacrylic resin (A) forms a continuous phase and the methacrylic resin (A) and the polyvinyl acetal resin (B) are partially or completely compatible. Can be obtained.

  The roughness of at least one surface of the thin film made of the acrylic resin composition used in the present invention, preferably the surface opposite to the surface in contact with the polycarbonate resin layer, is preferably 1.5 nm or less, more preferably 0. .1 to 1.0 nm. Thereby, it is excellent in the handleability at the time of a cutting | disconnection, the time of punching, etc., and is excellent in surface glossiness and transparency. Moreover, in optical use, it is excellent in optical characteristics such as light transmittance and in shaping accuracy when performing surface shaping. In addition, the roughness of a film is the value calculated | required by the method as described in an Example.

  The haze of the thin film made of the acrylic resin composition is preferably 0.3% or less, more preferably 0.2% or less, at a thickness of 100 μm. Thereby, it is excellent in the handleability at the time of a cutting | disconnection, the time of punching, etc., and is excellent in surface glossiness and transparency. Further, in optical applications such as a liquid crystal protective film and a light guide film, the use efficiency of the light source is preferably increased. Furthermore, it is preferable because it is excellent in shaping accuracy when performing surface shaping.

The thickness of the thin film which consists of an acrylic resin composition is 5-200 micrometers, Preferably it is 50-200 micrometers, More preferably, it is 50-125 micrometers. When it is thicker than 200 μm, the laminate property, handling property, cutting property, etc. are deteriorated, it becomes difficult to use as a film, and the unit price per unit area increases, which is not preferable because it is economically disadvantageous.
The thin film made of the acrylic resin composition may be printed on at least one surface. Patterns such as pictures, characters, and figures, colors, and the like are given by printing. The pattern may be chromatic or achromatic. Printing is preferably performed on the side in contact with the polycarbonate resin layer in order to prevent discoloration of the printing layer.

  The thin film made of the acrylic resin composition has a JIS pencil hardness (thickness of 100 μm), preferably HB or harder, more preferably F or harder, more preferably H or harder. . It is preferable to use a thin film made of an acrylic resin composition having a hard surface because the surface hardness of the laminate of the present invention is also increased.

  The thin film made of the acrylic resin composition may be a single layer film made of the acrylic resin composition, or may be a laminated film made of the acrylic resin composition and another resin.

  The thin film made of the acrylic resin composition may be colored. As a coloring method, a method in which a pigment or a dye is contained in an acrylic resin composition of a methacrylic resin (A) and a polyvinyl acetal resin (B) and the resin composition itself before coloring is colored; an acrylic resin composition Although the method (dyeing method) etc. which immerse and color the thin film which consists of a thing in the liquid which disperse | distributed dye are mentioned, it does not specifically limit.

The polycarbonate resin layer can be obtained by a known molding method such as an extrusion molding method or an injection molding method.
The thermocompression bonding between the thin film made of the acrylic resin composition obtained as described above and the polycarbonate resin layer can be performed using a known means such as a hot press machine or a hot roll machine. The temperature during thermocompression bonding is usually 50 to 250 ° C.
Also, a thin film made of an acrylic resin composition is placed in a mold or the like, a molten polycarbonate resin is poured onto the thin film, and a thin film made of the acrylic resin composition is laminated simultaneously with the molding of the polycarbonate resin layer. You can also.

  In the production by the coextrusion method, the melted polycarbonate resin and the melted acrylic resin composition are poured into a die for coextrusion such as a feed block method or a multi-manifold method, and each is extruded at the same time. The temperatures of the melted polycarbonate resin and the melted acrylic resin composition are appropriately adjusted so that the disturbance of the interface between the polycarbonate resin layer and the acrylic resin composition layer is reduced. The co-extruded molten resin is preferably a method including a step of forming the co-extruded molten resin by bringing its both surfaces into contact with the mirror roll surface or the mirror belt surface in the same manner as described in the description of the preparation of the thin film comprising the acrylic resin composition. . The temperature or linear pressure of the mirror roll surface or the mirror belt surface can be selected as appropriate, but it should be in the condition range described in the description of the preparation of the thin film made of the acrylic resin composition, with good surface smoothness and good This is preferable in that a laminate having a specular gloss and a low haze can be obtained.

  In the laminate of the present invention, the number of layers made of the acrylic resin composition and the number of polycarbonate resin layers are not particularly limited, but the surface hardness, weather resistance, adhesion during hard coat treatment, and impact resistance of the laminate are not limited. The surface smoothness and transparency (haze) are excellent, and the layer made of an acrylic resin composition is difficult to whiten when the laminate is stretched, bent and / or subjected to an impact. From the viewpoint of holding, it is preferable that the layer made of the acrylic resin composition is the outermost layer.

In the laminate of the present invention, another layer may be interposed between the layer made of the acrylic resin composition and the polycarbonate resin layer, or outside the layer made of the acrylic resin composition, that is, Another layer may be laminated on the opposite side of the surface in contact with the polycarbonate resin layer.
As another layer interposed between the layer which consists of an acrylic resin composition, and a polycarbonate resin layer, the layer which consists of the thermoplastic resin which is excellent in the transparency which may be colored is mentioned, for example.

Moreover, as another layer provided in the outer side of the layer which consists of an acrylic resin composition, the layer which consists of transparent resin from a viewpoint of improving the designability of a laminated body is preferable. The resin material used for the outermost layer is preferably one having high surface hardness and weather resistance from the viewpoint that the surface of the laminate is not easily scratched and the design property lasts long. For example, even if it contains an ultraviolet absorber A good methacrylic resin is preferable.
Moreover, you may provide hard coat layers, such as an ultraviolet-ray cured film, as another layer provided in the outer side of the layer which consists of an acrylic resin composition.
In addition, in order to improve adhesiveness with other layers, surface treatment such as plasma treatment, electron beam treatment, corona discharge treatment may be performed on the surface of the layer made of the acrylic resin composition.

The thickness of the layer made of the acrylic resin composition in the laminate of the present invention is 5 to 200 μm, preferably 50 to 200 μm, and more preferably 50 to 125 μm.
When the thickness of the layer made of the acrylic resin composition in the laminate of the present invention is less than 5 μm, the surface hardness of the laminate is insufficient. In applications that require weather resistance, the acrylic resin composition cannot hold a sufficient amount of the UV absorber, and the mechanical properties of the laminate deteriorate over time. Further, when the thickness of the layer made of the acrylic resin composition in the laminate of the present invention exceeds 200 μm, the layer made of the acrylic resin composition when stretched, bent and / or subjected to impact, etc. Tends to break. Moreover, it tends to be disadvantageous in terms of economy.

  The laminate of the present invention has a haze measured according to JIS K7136, preferably 0.3% or less, more preferably 0.2% or less.

  The laminate of the present invention is excellent in surface hardness, weather resistance, impact resistance, surface smoothness, and transparency (haze), and receives an impact when the layer made of an acrylic resin composition is stretched or folded. Building materials and houses such as corrugated sheets, carports, arcades, balconies, roofing materials, wall materials, highway fences, etc. Equipment use, sound insulation wall, nameplate, liquid crystal display cover, touch panel, display dummy can, vehicle window, pachinko machine, mobile phone full board, insulator and other industrial and industrial applications, LCD TV diffuser, Fresnel lens such as PTV, lenticular It can be used in a wide range of optical applications such as lenses, LCDs, PTVs, projection TV front plates, and lens sheets.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the examples, “part” represents “part by mass” unless otherwise specified, and “%” represents “% by mass” unless otherwise specified.

The physical properties of the laminate of the present invention and its raw materials were evaluated according to the following methods.
(1) Weight average molecular weight Using tetrahydrofuran as a solvent, Shodex (trademark) GPC SYSTEM11 manufactured by Showa Denko KK was connected to Shodex (trademark) KF-806L as a column for gel permeation chromatography, and Shodex (trademark) as a detector. It measured using the differential refractive index detector RI-101. The sample solution was prepared by accurately weighing 3 mg of the polymer, dissolving the polymer in 3 ml of tetrahydrofuran, and filtering with a membrane filter having an opening of 0.45 μm. The measurement temperature was 40 ° C., and the flow rate was 1.0 ml / min. The weight average molecular weight was calculated as the molecular weight in terms of polymethyl methacrylate based on a calibration curve prepared with standard polymethyl methacrylate manufactured by Polymer Laboratories.

(2) Observation of elastic modulus, yield point elongation, elongation at break, toughness and whitening state in bending test Elastic modulus, yield point elongation and breaking elongation in bending test are in accordance with JIS K7171, manufactured by Shimadzu Corporation Using graph AG-5000B, a strain rate of 1 mm / min. Using a test piece of length 80 mm × width 10 mm × thickness 4 mm obtained by the injection molding method. Measured with
Toughness was evaluated by the energy required for the test piece to break.
The whitening state is carried out by visually observing the whitening state of the test piece at a bending strain of 20%. When the length of the whitened portion in the length direction of the test piece is 2 mm or more, x, 0.3 mm The above and less than 2 mm were evaluated as Δ, the less than 0.3 mm as ◯, and the one in which no whitening was observed was evaluated as ◎.

(3) Observation of elastic modulus, elongation at break, toughness and whitening state in tensile test The elastic modulus in the tensile test was obtained by injection molding using Autograph AG-5000B manufactured by Shimadzu Corporation according to JIS K7162. In addition, a strain rate of 1 mm / min. Measured with Observation of breaking elongation, toughness, and whitening state was performed according to JIS K7162, using an autograph AG-5000B manufactured by Shimadzu Corporation and using a 1A-type dumbbell-shaped test piece obtained by an injection molding method. min. It evaluated by measuring by. Toughness was evaluated by the energy required for the test piece to break.
The whitening state is performed by visually observing the whitening state of the test piece at a tensile strain of 10%, and the length of the whitened portion in the length direction of the test piece is 10 mm or more x 1 mm or more The case of less than 10 mm was evaluated as Δ, the case of less than 1 mm was evaluated as ◯, and the case where no whitening was observed was evaluated as ◎.

(4) Main dispersion peak temperature (Tα)
The main dispersion peak temperature (Tα) of the loss tangent (tan δ) is 60 mm long × width obtained by cutting a test piece obtained by injection molding using EXSTAR6000 DMS manufactured by SII NanoTechnology Co., Ltd. In a bending mode (both-end beam measurement), a rectangular parallelepiped test piece having a thickness of 10 mm and a thickness of 4 mm is subjected to a sinusoidal vibration of 10 Hz, a heating rate of 3 ° C./min. It was measured by.

(5) Morphological Observation by Transmission Electron Microscope An ultrathin section was prepared from a test piece obtained by injection molding using an ultramicrotome (Reichert ULTRACUT-S manufactured by RICA). The sections were exposed to ruthenium tetroxide vapor to electronically stain the polyvinyl acetal resin (B) portion. The morphology of the sample thus prepared was observed using a transmission electron microscope H-800NA manufactured by Hitachi, Ltd.
In the observed morphology, the case where the non-stained part formed a continuous phase was evaluated as ◯, and the case where the non-stained part was discontinuous was evaluated as x. The non-dyed portion is a portion mainly composed of a methacrylic resin (A).
Moreover, the average particle diameter of the dyed dispersed phase was measured. A dyeing | staining part is a part which consists of polyvinyl acetal resin (B).

(6) Visible light transmittance of film Visible light calculated according to JIS R3106 by measuring the transmittance at a wavelength of 380 nm to 780 nm of a 100 μm thick film using a spectrophotometer U-4100 manufactured by Hitachi High-Technologies Corporation. The transmittance was measured.

(7) Haze of film It measured with the film of thickness 100micrometer according to JISK7136.
(8) Surface hardness of film The pencil hardness of a film having a thickness of 100 μm was measured according to JIS K5400. (9) Elastic modulus, elongation at break, and toughness in film tensile test A plastic JIS1A type dumbbell-shaped test film is punched from a film having a thickness of 100 μm so as to be stretched in the MD direction at the time of a tensile test. Using AG-5000B, the strain rate is 5 mm / min. The test was conducted to measure the elastic modulus, elongation at break, and toughness of the test film. Toughness was evaluated by the energy required for the test film to break.

(10) Tear strength of the film Using an autograph AG-5000B manufactured by Shimadzu Corporation, an angle-less test film without cut in accordance with JIS K6252 standard was punched out, and a tensile speed of 5 mm / min. The maximum tear strength (unit: N / mm) in terms of thickness when the angle type test film with a cut was torn was evaluated. The measurement was performed with a film having a thickness of 100 μm.

(11) Observation of the whitening state of the film When a film having a thickness of 100 μm is folded 180 ° so as to be creased in the TD direction, according to a visual evaluation, the folded portion is not whitened at all, and one of the folded portions Evaluation was made with Δ for the part whitened, and × for the whole bent part whitened.

(12) DuPont-type falling ball impact test A film having a length of 25 mm, a width of 25 mm, and a thickness of 100 μm is subjected to a falling ball impact test using a weight of 0.3 to 1.0 kg. : J). The impact (unit: J) applied to the film can be calculated from the weight (unit: kg) used for the test and the falling distance (unit: m) by the following formula.
Impact on film [J] =
Weight of weight [kg] x Gravity acceleration [m / s ² ] x Distance of weight fall [m]

(13) Morphological observation of acrylic resin composition layer in film or laminate by transmission electron microscope Ultramicrotome (Reichert U manufactured by RICA)
After making an ultrathin section using LTRACUT-S), the polyvinyl acetal resin portion of the acrylic resin composition layer was electron-stained with ruthenium tetroxide vapor to prepare a sample. The morphology of the sample thus prepared was observed using a transmission electron microscope H-800NA manufactured by Hitachi, Ltd.
In the observed morphology, the case where the non-dyed portion of the acrylic resin composition layer formed a continuous phase was evaluated as ◯, and the case where the non-dyed portion was discontinuous was evaluated as x. The non-dyed portion is a portion mainly composed of a methacrylic resin (A).
Moreover, the average particle diameter of the dyed dispersed phase was measured. A dyeing | staining part is a part which consists of polyvinyl acetal resin (B).

(14) Measurement of surface roughness of film and laminate The shape of the surface was measured in the DFM mode using an atomic force microscope (SPI4000 probe station E-sweep environment control unit manufactured by SII Nanotechnology). SI-DF20 (back Al) manufactured by SII Nano Technology was used as the probe. Prior to the measurement of the sample, a reference sample having a pitch of 10 μm and a step of 100 nm is measured. The measurement error of the X axis and Y axis of the apparatus is 5% or less with respect to 10 μm, and the error of the Z axis is 5% with respect to 100 nm. It was confirmed that:
The observation area of the sample was 2 μm × 2 μm, and the measurement frequency was 1.0 Hz. The number of scan lines was 512 on the X axis and 512 on the Y axis. The measurement was performed in an atmospheric environment at 25 ° C. ± 2 ° C. and humidity 30 ± 5%. The obtained measurement data was analyzed by data processing software attached to the apparatus, and the average surface roughness Ra was obtained. In other words, after selecting the [Third-order tilt correction] command in the [Tool] menu of the measurement software of the device and correcting the entire tilt of the film and large waviness, the [Surface roughness analysis] command in the [Analysis] menu The average surface roughness Ra was selected. The average surface roughness Ra is defined as follows.
* Average surface roughness Ra: A value obtained by averaging the absolute values of deviations from the reference surface to the specified surface.

ここでＦ（Ｘ，Ｙ）は（Ｘ，Ｙ）座標での高さの値を表す。Ｚ₀は以下で定義されるＺ
データの平均値を表す。

Here, F (X, Y) represents a height value in the (X, Y) coordinates. Z ₀ is defined as
Represents the average value of the data.

また、Ｓ₀は、測定領域の面積を表す。
この平均面粗さＲａをフィルムの両面（便宜上、Ａ面およびＢ面とする）において異なる１０箇所の領域でそれぞれ測定し、１０箇所の平均面粗さＲａの平均値を成形体表面の粗度とした。また、積層体のアクリル系樹脂層において異なる１０箇所の領域で測定し、１０箇所の平均面粗さＲａの平均値を積層体表面の粗度とした。
３次傾き補正は、測定した試料表面を３次の曲面で最小２乗近似によってフィッティングすることによって行い、試料の傾きおよびうねりの影響を排除するために行った。

S ₀ represents the area of the measurement region.
The average surface roughness Ra was measured at 10 different regions on both surfaces of the film (for convenience, the A surface and the B surface), and the average value of the 10 average surface roughness Ra was determined as the roughness of the surface of the molded body. It was. Moreover, it measured in 10 area | regions different in the acrylic resin layer of a laminated body, and made the average value of 10 average surface roughness Ra the roughness of the laminated body surface.
The cubic inclination correction was performed by fitting the measured sample surface with a cubic surface by least square approximation to eliminate the influence of the inclination and waviness of the sample.

(15) Haze of laminate The haze of the laminate was measured according to JIS K7136.
(16) Elastic modulus, breaking elongation, and toughness in tensile test of laminate The plastic JIS1A type dumbbell shape test film was punched from the laminate so as to be stretched in the MD direction during the tensile test, and Autograph AG- manufactured by Shimadzu Corporation. Using 5000B, the strain rate is 5 mm / min. The test was conducted to measure the elastic modulus, elongation at break, and toughness of the test film. Toughness was evaluated by the energy required for the test film to break.

(17) DuPont falling ball impact test of laminates A laminate (length 25 mm x width 25 mm) was subjected to a falling ball impact test using a weight of 0.3 to 1.0 kg, and the maximum impact (the film was not crushed by falling balls) Unit: J) was determined. The impact (unit: J) applied to the film can be calculated from the weight (unit: kg) used for the test and the falling distance (unit: m) by the following formula.
Impact on film [J] =
Weight of weight [kg] x Gravity acceleration [m / s ² ] x Distance of weight fall [m]

(18) Surface hardness of laminate The pencil hardness was measured according to JIS K5400.
(19) Observation of the whitening state of the laminate When a strip of 6 cm in the MD direction and 1 cm in the TD direction is cut out from the laminate and folded at 90 ° so that a crease is formed in the TD direction, the bent portion is visually evaluated. Evaluation was made with ◯ indicating that the material was not whitened at all, Δ when the part of the folded portion was whitened, and Δ when the material was broken when folded. In that case, when the layer made of the acrylic resin composition of the laminate is laminated only on one side, it is folded in a mountain fold with respect to the surface of the laminate made of the acrylic resin composition And evaluated.

(20) Weather resistance of laminated body Accelerated exposure test is performed using Xenon Weatherometer (Ci4000) manufactured by Atlas Co., Ltd. according to JIS B7754 (black panel temperature 63 ° C, humidity 50%, sprayed for 120 minutes cycle 18 minutes). The test piece after 2000 hours exposure was visually observed to evaluate the weather resistance. In addition, the accelerated exposure test was performed so that only the acrylic resin composition layer side of the laminate was irradiated with ultraviolet rays. By visual evaluation, the laminated body after the test was evaluated as “◯” when the crack was not present, and “X” when the crack was present.

[Methacrylic resin (A)]
A methacrylic resin composed of methyl methacrylate units and methyl acrylate units in the ratios shown in Table 1 was prepared by bulk polymerization. Table 1 shows the weight average molecular weight and main dispersion peak temperature (Tα _A ) of the prepared methacrylic resin.

[Polyvinyl acetal resin (B)]
An aldehyde compound and an acid catalyst (hydrochloric acid) were added to an aqueous solution in which the polyvinyl alcohol resin was dissolved, and the mixture was stirred to acetalize to precipitate the resin. Wash until pH = 6 according to known methods, then suspend in alkaline aqueous medium and stir, wash again until pH = 7, dry until volatiles are below 1.0% As a result, polyvinyl acetal resins having the characteristics shown in Table 2 were obtained.

Example 1
A cylinder temperature of 220 ° C. using 75 parts of methacrylic resin (A-1) and 25 parts of polyvinyl acetal resin (B-2) using a twin screw kneading extruder TEX-44α (L / D = 40) manufactured by Nippon Steel. The mixture was kneaded at a screw speed of 200 rpm to obtain an acrylic resin composition pellet. The resin temperature measured immediately before the die of the extruder at that time was 230 ° C. Maximum shear rate of the extruder is 300 sec ^-1, shear rates in the clearance large portion of the barrel and the screw elements were 45 sec ^-1. Screw, the rotational speed of the used was a structure in which the shear shear and 45 sec ^-1 of 300 sec ^-1 is applied twice alternately.

The obtained acrylic resin composition pellets were injection-molded at a cylinder temperature of 240 ° C. using J50E2 manufactured by Nippon Steel Works, and were a plastic JIS 1A type dumbbell-shaped test piece having a length of 80 mm × width of 10 mm × thickness of 4 mm. A rectangular parallelepiped specimen was obtained. Furthermore, the rectangular parallelepiped test piece of length 60mm * width 10mm * thickness 4mm was obtained by cut | disconnecting the rectangular parallelepiped test piece of length 80mm * width 10mm * thickness 4mm.
Using these specimens, elastic modulus, yield elongation, elongation at break, toughness and whitening state in bending test; elastic modulus, elongation at break, toughness and whitening state in tensile test; methacrylic acrylic resin composition The main dispersion peak temperature (Tα _AP ) attributable to the resin (A) and the main dispersion peak temperature (Tα _BP ) attributable to the polyvinyl acetal resin (B) were measured. In addition, the morphology was observed. Table 3 shows the results.
Also, the obtained acrylic resin composition pellets were extruded from a T-die having a width of 500 mm using a GT-40 made by Plastics Engineering Laboratory under conditions of a cylinder temperature and a T-die temperature of 220 ° C. A film having a thickness of 100 μm was obtained by sandwiching with two metal mirror rolls whose temperature was adjusted to 90 ° C. at a pressing pressure of 50 N / mm. Visible light transmittance, haze, surface hardness, tensile modulus, elongation at break, toughness and whitening state of this film, DuPont falling ball impact test, surface roughness (for convenience, it was described as A and B surfaces). The same applies hereinafter)) and the like are shown in Table 4.
A film made of the acrylic resin composition having a thickness of 100 μm and a polycarbonate film having a thickness of 500 μm (Iupilon film FE-2000, manufactured by Mitsubishi Engineering Plastics Co., Ltd.) are overlapped one by one, and the two surface temperatures are 170 ° C. By passing between the metal mirror surface rolls, thermocompression bonding was performed from both sides of the film to obtain a laminate in which a film made of an acrylic resin composition was laminated on one side of the polycarbonate film.
Table 5 shows the results of evaluation of haze, morphology, tensile modulus, tensile strength, fracture elongation, and toughness of the obtained laminate; DuPont falling ball impact test, surface hardness, whitening state, surface roughness, and weather resistance. It was.

Examples 2-7
A laminate was produced in the same manner as in Example 1 except that the types and / or blending amounts of the methacrylic resin (A) and the polyvinyl acetal resin (B) were changed to the formulations shown in Table 3. Their characteristics are shown in Tables 3 to 5.

Example 8
The pellet of the acrylic resin composition obtained in Example 1 was extruded from a T-die having a width of 500 mm using a GT-40 manufactured by Plastics Engineering Laboratory under conditions of a cylinder temperature and a T-die temperature of 220 ° C. A film made of an acrylic resin composition having a thickness of 50 μm was obtained by sandwiching with two metal mirror rolls whose temperature was adjusted to 90 ° C. immediately below at a pressing pressure of 50 N / mm.
This film made of an acrylic resin composition having a thickness of 50 μm and a polycarbonate film having a thickness of 500 μm (Iupilon film FE-2000, manufactured by Mitsubishi Engineering Plastics Co., Ltd.) are converted into a film in which the polycarbonate film is made of an acrylic resin composition. A film made of an acrylic resin composition is laminated on both sides of a polycarbonate film by superimposing so as to be sandwiched from both sides and passing between two metal mirror rolls having a surface temperature of 170 ° C. A laminate was obtained. Properties such as mechanical properties are shown in Tables 3 to 5.

Example 9
The pellet of the acrylic resin composition obtained in Example 1 was extruded from a T-die having a width of 500 mm using a GT-40 manufactured by Plastics Engineering Laboratory under conditions of a cylinder temperature and a T-die temperature of 220 ° C. A film made of an acrylic resin composition having a thickness of 50 μm was obtained by sandwiching with two metal mirror rolls whose temperature was adjusted to 90 ° C. immediately below at a pressing pressure of 50 N / mm. A laminate was obtained in the same manner as in Example 1 except that this film was used. Tables 3 to 5 show mechanical properties.

Example 10
The pellet of the acrylic resin composition obtained in Example 1 was extruded from a T-die having a width of 500 mm using a GT-40 manufactured by Plastics Engineering Laboratory under conditions of a cylinder temperature and a T-die temperature of 220 ° C. A film made of an acrylic resin composition having a thickness of 20 μm was obtained by sandwiching with two metal mirror rolls adjusted to 90 ° C. at a pressing pressure of 50 N / mm. A laminate was obtained in the same manner as in Example 1 except that this film was used. The results of measuring mechanical properties and the like are shown in Tables 3 to 5.

Example 11
As a UV absorber, 75 parts of methacrylic resin (A-2), 25 parts of polyvinyl acetal resin (B-2), and a total of methacrylic resin (A-2) and polyvinyl acetal resin (B-2) are 0. A laminate was produced in the same manner as in Example 1 except that 8% by mass of Adekastab LA-31 was further added. The results are shown in Tables 3-5. Moreover, when the weather resistance of the laminated body was evaluated, the laminated body was not cracked and evaluated as ◯.

Example 12
A film made of the acrylic resin composition having a thickness of 100 μm obtained in Example 1 and a polycarbonate sheet having a thickness of 2 mm (Iupilon sheet NF-2000; manufactured by Mitsubishi Engineering Plastics Co., Ltd.) are superposed one by one. A laminated body in which a film made of an acrylic resin composition was laminated on one side of a polycarbonate film by thermocompression bonding from both sides of the film by passing between metal mirror rolls having a surface temperature of 170 ° C. was obtained. The evaluation results are shown in Tables 3 to 5.

Comparative Example 1
Table 6 shows the results of measuring the mechanical properties of a polycarbonate single layer film (Iupilon film FE-2000; manufactured by Mitsubishi Engineering Plastics Co., Ltd.) having a thickness of 500 μm. Moreover, when the weather resistance of this single layer film was evaluated, the film was cracked and evaluated as x.

Comparative Examples 2-3
Instead of the acrylic resin composition pellets used in Example 1, a laminate was prepared in the same manner as in Example 1 except that pellets consisting only of methacrylic resin (A-1) or (A-2) were used. Manufactured. The results are shown in Table 6.

Comparative Examples 4-7
Example in place of the acrylic resin composition pellets used in Example 1 except that the types and / or blending amounts of methacrylic resin (A) and polyvinyl acetal resin (B) were changed to the formulations shown in Table 6. A laminate was produced in the same manner as in Example 1. The results are shown in Table 6.

Comparative Example 8
The pellet of the acrylic resin composition obtained in Example 1 was extruded from a T-die having a width of 500 mm using a GT-40 manufactured by Plastics Engineering Laboratory under conditions of a cylinder temperature and a T-die temperature of 220 ° C. A film made of an acrylic resin composition having a thickness of 300 μm was obtained by sandwiching with two metal mirror rolls whose temperature was adjusted to 90 ° C. directly below at a pressing pressure of 50 N / mm. A laminate was obtained in the same manner as in Example 1 except that this film was used. Table 6 shows the results of measuring the mechanical properties and the like of the obtained laminate.

As is clear from Tables 5 and 6, the laminate of the present invention has high transparency, excellent surface smoothness, excellent balance between surface hardness, impact resistance, elastic modulus, and toughness, and stretched. The acrylic resin composition layer does not whiten when it is bent, bent, subjected to impact, and / or placed under wet heat conditions for a long time.
Further, compared with the laminates of Comparative Example 2 and Comparative Example 3 having a layer made of only methacrylic resin, the laminate of the present invention has the same transparency, surface smoothness, and surface hardness, toughness and resistance. It has excellent impact properties, and also has a feature that the acrylic resin composition layer does not whiten when stretched, bent, subjected to impact, and / or placed under long-term wet heat conditions.
Furthermore, the repeating unit of the polyvinyl acetal resin (B) acetalized using an aldehyde having 4 or more carbon atoms and an aldehyde having 3 or less carbon atoms deviated from the range of 65 to 85 mol% with respect to all the repeating units. A material, a material in which the molar ratio of a repeating unit acetalized with an aldehyde having 4 or more carbon atoms / a repeating unit acetalized with an aldehyde having 3 or less carbon atoms deviates from 90/10 to 0/100, or a methacrylic resin ( The polycarbonate resin laminate obtained using a material in which the mass ratio of A) and the polyvinyl acetal resin (B) is out of the range of 99/1 to 51/49 is heat resistance, toughness, impact resistance, or surface Either of the hardness is inferior. On the other hand, the laminate manufactured according to the present invention has excellent heat resistance, and has high toughness, impact resistance, and surface hardness.

Claims (9)

A polycarbonate resin laminate having a polycarbonate resin layer and a layer having a thickness of 5 to 200 μm made of an acrylic resin composition,
The acrylic resin composition comprises a methacrylic resin (A) having a weight average molecular weight of 40000 or more and a polyvinyl acetal resin (B) obtained by acetalizing a polyvinyl alcohol resin having a viscosity average polymerization degree of 200 to 4000 with an aldehyde. A methacrylic resin (A) is formed by melting and kneading under conditions of a mass ratio (A) / (B) of from ^{1 to} 51/49 and a shear rate of 100 sec ^-1 or more, and The polyvinyl acetal resin (B) contains 65 to 85 mol% of repeating units acetalized with aldehydes and is acetalized with aldehydes having 4 or more carbon atoms / 3 or less carbon atoms with respect to all repeating units. Polycarbonate resin having a molar ratio of 90/10 to 0/100 of the repeating unit acetalized with aldehyde Laminated body.   2. The polycarbonate resin laminate according to claim 1, wherein the acrylic resin composition is observed with a transmission electron microscope when it is electron-stained with ruthenium tetroxide, and the average diameter of the dyed dispersed phase is 50 nm or less. body.   The polycarbonate resin laminate according to claim 1 or 2, wherein the acrylic resin composition contains 0.1 to 2% by mass of an ultraviolet absorber.   The polycarbonate resin laminate according to any one of claims 1 to 3, wherein the layer made of the acrylic resin composition has a surface roughness of 1.5 nm or less opposite to the surface in contact with the polycarbonate resin layer. body.   The haze measured according to JIS K7136 is 0.3% or less, The polycarbonate resin laminated body of any one of Claims 1-4. The methacrylic resin (A) and the polyvinyl acetal resin (B) are the main dispersion peak temperature (Tα _A ) of the methacrylic resin (A) alone and the polyvinyl acetal resin observed in dynamic viscoelasticity measurement. and (B) alone in the main dispersion peak temperature (T [alpha _B) but, according to any one of claims 1 to 5 with the relationship 90 ℃ ≦ Tα _B ≦ Tα _a or 90 ℃ ≦ Tα _a ≦ Tα _B Polycarbonate resin laminate. In the acrylic resin composition, the main dispersion peak temperature Tα _AP attributed to the methacrylic resin (A) observed in the dynamic viscoelasticity measurement is the main dispersion peak temperature (Tα) of the methacrylic resin (A) alone. The main dispersion peak temperature (Tα _B ) of _A ) and the polyvinyl acetal resin (B) alone has a relationship of Tα _AP <Tα _A or Tα _AP <Tα _B. The polycarbonate resin laminate described. The acrylic resin composition has a main dispersion peak temperature Tα _AP attributed to the methacrylic resin (A) and a main dispersion peak temperature Tα _BP attributed to the polyvinyl acetal resin (B) observed in the dynamic viscoelasticity measurement. The polycarbonate resin laminate according to claim 1, wherein Tα _AP = Tα _BP . The acrylic resin composition has a main dispersion peak temperature Tα _AP attributed to the methacrylic resin (A) and a main dispersion peak temperature Tα _BP attributed to the polyvinyl acetal resin (B) observed in the dynamic viscoelasticity measurement. for the methacrylic resin (a) alone in the main dispersion peak temperature (T [alpha _a) and polyvinyl acetal resin (B) alone in the main dispersion peak temperature _{(Tα B), Tα B <} Tα AP = Tα BP <Tα The polycarbonate resin laminate according to claim 1, wherein _A or Tα _A <Tα _AP = Tα _BP <Tα _B is satisfied.