JPWO2015108064A1 - Thermoplastic resin laminate - Google Patents

Abstract

According to the present invention, a thermoplastic resin 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 a diol derived from a diol having a cyclic acetal skeleton in which 10 to 60 mol% of all diol constituent units are represented by the above formula (1) or formula (2). Polyester resin (a) containing a structural unit and a dicarboxylic acid structural unit and a polycarbonate resin (b) The ratio of b) is 5 to 50% by weight, and the acrylic resin composition comprises an acrylic resin (c) and a methyl methacrylate-styrene copolymer (d). At least one selected from the group, styrene - containing maleic anhydride copolymer (e), it is possible to provide a thermoplastic resin laminate.

Description

  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-made transparent plates are used in a wide variety of applications, such as exterior signs for outdoor signage and carports, and optical uses for display unit front plates of OA devices and portable electronic devices. In recent years, 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. However, 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.

または一般式（２）：

（式（１）、（２）中、Ｒ¹、Ｒ²およびＲ³ はそれぞれ独立して、炭素数が１〜１０の脂肪族基、炭素数が３〜１０の脂環式基、及び炭素数が６〜１０の芳香族基からなる群から選ばれる有機基を表す。）
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）：

または一般式（４）：

（式（３）、（４）中、Ｒ⁴ およびＲ⁵ はそれぞれ独立して炭素数が１〜１０の脂肪族基、炭素数が３〜１０の脂環式基、及び炭素数が６〜１０の芳香族基からなる群から選ばれる有機基を表し、Ｒ⁶ およびＲ⁷ はそれぞれ独立して水素原子、メチル基、エチル基、又はイソプロピル基を表す。）
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。In Patent Document 1, 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. Represents an organic group selected from the group consisting of aromatic groups having a number of 6 to 10.)
The diol unit having a cyclic acetal skeleton represented by the formula: 10 to 60 mol% of the diol constituent unit, or the general formula (3):

Or general formula (4):

(In 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. 10 represents an organic group selected from the group consisting of 10 aromatic groups, and R ⁶ and R ⁷ each independently represents a hydrogen atom, a methyl group, an ethyl group, or an isopropyl group.)
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 is used as a core layer, and an acrylic resin is used for the skin layer. It is described that a multilayer sheet excellent in heat resistance, heat resistance, scratch resistance and impact resistance can be obtained.

  However, although 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.

JP 2003-182014 A

  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.

（式（１）及び（２）において、Ｒ¹ 、Ｒ² 、およびＲ³はそれぞれ独立して、炭素数が１〜１０の脂肪族基、炭素数が３〜１０の脂環式基、及び炭素数が６〜１０の芳香族基からなる群から選ばれる有機基を表す。）
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。As a result of intensive studies, the present inventors have found that the following problems can be solved by the following present invention.
That is, the present invention is as follows.
<1> A 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
10-60 mol% in all diol structural units is the following formula (1) or the following formula (2)

(In 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 This represents an organic group selected from the group consisting of aromatic groups having 6 to 10 carbon atoms.)
A polyester resin (a) containing a diol structural unit derived from a diol having a cyclic acetal skeleton represented by formula (1) and a dicarboxylic acid structural unit, and a polycarbonate resin (b), and a polyester resin in the thermoplastic resin composition ( 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 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 in the acrylic resin composition is 70 to 95 mol%. The thermoplastic resin laminate is characterized in that the proportion of structural units derived from maleic anhydride is 1 to 5 mol%.
<2> In the styrene-maleic anhydride copolymer (e), 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>.
<3> The diol having a cyclic acetal skeleton is 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane. The thermoplastic resin laminate according to <1> or <2>.
<4> The thermoplastic resin according to any one of <1> to <3>, wherein the proportion of structural units derived from terephthalic acid in all structural units of dicarboxylic acid in the polyester resin (a) is 70 mol% or more. It is a resin laminate.
<5> The thermoplastic resin laminate according to any one of <1> to <4>, wherein one side or both sides are hard-coated.
<6> The above <1> to <5, wherein one or both surfaces are subjected to at least one treatment selected from antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment and antiglare treatment. > Is a thermoplastic resin laminate according to any one of the above.
<7> A transparent substrate material comprising the thermoplastic resin laminate according to any one of <1> to <6>.
<8> A transparent protective material comprising the thermoplastic resin laminate according to any one of <1> to <6>.

  According to a preferred embodiment of the present invention, there is provided a thermoplastic resin laminate excellent in transparency, heat resistance, scratch resistance, impact resistance, and dimensional stability in a high-temperature and high-humidity environment, and the 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.

DETAILED DESCRIPTION OF THE INVENTION

  The present invention is described in detail below. 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). (B), wherein 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. A diol constituent unit derived from a diol having a skeleton, wherein the acrylic resin composition is at least one selected from the group consisting of an acrylic resin (c) and a methyl methacrylate-styrene copolymer (d), and styrene- And maleic anhydride copolymer (e).

（式（１）及び（２）において、Ｒ¹ 、Ｒ² 、およびＲ³はそれぞれ独立して、炭素数が１〜１０の脂肪族基、炭素数が３〜１０の脂環式基、及び炭素数が６〜１０の芳香族基からなる群から選ばれる有機基を表す。）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 which 10 to 60 mol% of all diol constituent units are represented. And a dicarboxylic acid structural unit.

(In 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 This represents an organic group selected from the group consisting of aromatic groups having 6 to 10 carbon atoms.)

In the diol having a cyclic acetal skeleton represented by the formula (1) or the formula (2), 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. Among them, as the diol having the cyclic acetal skeleton, 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, and 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, 1 Fats such as 5-decahydronaphthalene diethanol, 1,6-decahydronaphthalene diethanol, 2,7-decahydronaphthalene diethanol, tetralin dimethanol, norbornene dimethanol, tricyclodecane dimethanol, pentacyclododecane dimethanol Cyclic diols; 4,4 ′-(1-methylethylidene) bisphenol, methylene bisphenol (bisphenol F), 4,4′-cyclohexylidene bisphenol (bisphenol Z), 4,4′-sulfonylbisphenol (bisphenol S) Bisphenols such as alkylene oxide adducts of the bisphenols; hydroquinone, resorcin, 4,4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydi Aromatic dihydroxy compounds such as E sulfonyl benzophenone; and said aromatic diol constitutional units derived from the alkylene oxide adducts of dihydroxy compounds can be exemplified. Among these, as the diol structural unit other than the diol structural unit derived from the diol having a cyclic acetal skeleton, 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, Examples include dicarboxylic acid structural units derived from aromatic dicarboxylic acids such as naphthalenedicarboxylic acid, biphenyldicarboxylic acid, tetralindicarboxylic acid, and ester-forming derivatives thereof. Among these, a dicarboxylic acid structural unit derived from terephthalic acid and 3-naphthalenedicarboxylic acid is more preferable, and terephthalic acid is particularly preferable.

  In the polyester resin (a) used in the present invention, the ratio of the diol structural unit derived from the diol having a cyclic acetal skeleton in all the diol structural units is preferably 10 to 60 mol%, more preferably 15 to 50 mol%. is there. When the ratio is less than 10 mol%, the polyester resin (a) may not exhibit sufficient heat resistance, which is not preferable. On the other hand, if it is more than 60 mol%, the impact resistance may decrease, which is not preferable.

  In the polyester resin (a), 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%. . When the polyester resin (a) has the diol structural unit and the dicarboxylic acid structural unit, 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 conventionally known methods 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. Within the range of the 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. Various kinds of commonly used additives may be added to the polycarbonate resin (b). Examples of the 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.

  As a ratio of the polyester resin (a) and the polycarbonate resin (b) in the thermoplastic resin composition, 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. By making the ratio of the polyester resin (a) and the polycarbonate resin (b) in the thermoplastic resin composition within the above range, 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 include a resin other than the polyester resin (a) and the polycarbonate resin (b). Examples of 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 comprises 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. Preferably, it is a copolymer composed of 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 of structural units derived from styrene and 40% by weight derived from styrene. When the structural unit derived from methyl methacrylate is less than 5% by weight and the structural unit derived from styrene exceeds 95% by weight, the transparency is lowered and the appearance is degraded. The methyl methacrylate-styrene copolymer (d) preferably has a polystyrene-equivalent weight average molecular weight of 10,000 to 30,000.

  From the point of being transparently compatible with the styrene-maleic anhydride copolymer (e) and scratch resistance, 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. Preferably, 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, more preferably 80 to 90% by weight of structural units derived from styrene and maleic anhydride. It is 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. By setting it as the said composition, 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), methyl methacrylate-styrene copolymer (d), and styrene-maleic anhydride copolymer (e). Other resin components include polyesters other than the 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 methacrylate-acrylic acid copolymer, styrene-methyl methacrylate-acrylonitrile copolymer, styrene-methyl methacrylate-methacrylonitrile copolymer Coalescence, a copolymer of styrene and methyl methacrylate and N- phenylmaleimide, copolymer of styrene and methyl methacrylate and N- cyclohexylmaleimide, vinyl chloride resins, alicyclic polyolefin resins. Specific examples of the 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. Examples of the organic peroxide 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 addition amount of the organic peroxide 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. Further, 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 relative 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. -It is preferable that the ratio of maleic anhydride copolymer (e) is 1-35 weight%. When 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. By setting it as the said composition, heat resistance and moisture absorption are improved, without deteriorating the abrasion resistance of the layer (B) containing an acrylic resin composition, The 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. More preferably, the styrene-maleic anhydride copolymer 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). 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 in the acrylic resin composition is 70 to 95 mol%. It is preferable that the ratio of the structural unit derived from maleic anhydride is 1 to 5 mol%. When the proportion of these structural units in the acrylic resin composition is in the above range, the thermoplastic resin laminate of the present invention is excellent in dimensional stability and scratch resistance in a high temperature and high humidity environment. More preferably, 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. Examples of 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.

  The thermoplastic resin composition is produced 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.

  The 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.

  As a method for producing the thermoplastic resin laminate of the present invention, known laminating techniques such as a coextrusion method, a coextrusion laminating method, an extrusion laminating method, and a dry laminating method can be used. Moreover, you may use the adhesive agent suitable between resin for these lamination | stacking, or adhesive resin.

  What is necessary is just to select the kind and layer structure (lamination order, the number of layers) of the layer (A) containing a thermoplastic resin composition, and the layer (B) containing the multilayered acrylic resin composition according to a use. For example, in an application that requires both surface hardness and dimensional stability in a high-temperature and high-humidity environment, the layer (B) containing the acrylic resin composition is used as the skin layer, and the layer (A) containing the thermoplastic resin composition is used. 2 types and 2 layers used for the core layer (layer containing acrylic resin composition (B) / layer containing thermoplastic resin composition (A)) and 2 types and 3 layers (acrylic resin composition) Layer (B) containing a product / layer (A) containing a thermoplastic resin composition / layer (B) containing an acrylic resin composition), transparency, heat resistance, scratch resistance, impact resistance In addition, a 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 the range of 0.3-5.0 mm, More preferably, it is the range of 0.3-3.0 mm.

  The thickness (one side) of the layer (B) containing the acrylic resin composition of the thermoplastic resin laminate in the present invention is preferably 25% or less of the total thickness of the thermoplastic resin laminate, and is in the range of 10 to 500 μm. 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 μm, the scratch resistance and weather resistance may be insufficient, and if it exceeds 500 μm, warping may occur in a high-temperature and high-humidity environment. More preferably, it is the range of 30-200 micrometers.

  One side or both sides of the thermoplastic resin laminate of the present invention can be subjected to a hard coat treatment. For example, the hard coat layer is formed by using a photosensitive hard coat paint that is cured using light energy. As 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. For example, 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) Examples thereof include a photocurable resin composition in which 1 to 10 parts by weight of the 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. For example, 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 or both sides. The methods of antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment and antiglare treatment are not particularly limited, and known methods can be used. For example, a method of applying a reflection reducing coating, a method of depositing a dielectric thin film, a method of applying an antistatic coating, and the like can be mentioned.

  The thermoplastic resin laminate of the present invention preferably has a total light transmittance of 90% or more at a thickness of 1.0 mm.

  The 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.

Hereinafter, the present invention will be described specifically by way of examples. However, the scope of the present invention is not limited by these examples.
Evaluation of 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.

<Structural analysis of resin components>
The structure of the polyester resin (a), methyl methacrylate-styrene copolymer (d), and styrene-maleic anhydride copolymer (e) was determined by dissolving 20 mg of the resin in 1 g of deuterated chloroform, 1H-NMR measurement, peak It was calculated from the area ratio. The measuring apparatus used JNM-AL400 by JEOL Co., Ltd., and measured it at 400 MHz.

<Measurement of average molecular weight>
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 at a column temperature of 40 ° C. by connecting two Tosoh Co., Ltd. TOSOH 8020 with two Tosoh Co., Ltd. columns GMHHR-L and one TSK G5000HR. As an eluent, chloroform was flowed at a flow rate of 1.0 ml / min, and measurement was performed with a UV detector.

<Evaluation of component molar ratio of acrylic resin composition>
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 molar ratio of structural units derived from styrene (hereinafter abbreviated as St units) and structural units derived from maleic anhydride (hereinafter abbreviated as MAH units) was analyzed.
The component molar ratio was 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 heavy 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.

<Transparency evaluation>
For the thermoplastic resin laminates obtained in the following examples and comparative examples, 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.

<Heat resistance evaluation>
About the 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 φ38 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.

<Abrasion resistance evaluation>
For the thermoplastic resin laminates obtained in the following examples and comparative examples, the pencil hardness is acrylic using pencils of various hardness (Uni, manufactured by Mitsubishi Pencil Co., Ltd.) according to JIS K 5600-5-4. The pencil hardness of the layer (B) containing the resin composition was measured. Those having a pencil hardness of 3H or more were accepted.

<Impact resistance test>
For the thermoplastic resin laminates obtained in the following Examples and Comparative Examples, 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. As a side, it was evaluated by a falling ball test. The falling ball test is performed by fixing the sample between φ50 flanges, dropping a φ25, 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 | rupture of 100 cm or more was set as the pass.

<Dimensional stability evaluation in high temperature and high humidity environment>
About the 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, suspended so that the test piece was vertical, and heated in a constant temperature and humidity chamber set at a temperature of 85 ° C. and a humidity of 85% for 120 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 φ38 mm and a weight of 300 g on the center of the test piece, and the amount of deformation of the gap length between the four corners of the test piece and the horizontal surface Was measured, and the sum of the deformation amounts did not exceed 0.5 mm.

<Formability evaluation>
About the 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 φ38 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.

[Synthesis Example 1]
Dimethylterephthalic acid as the dicarboxylic acid component, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane and ethylene glycol as the diol component In the presence of 0.03 mol of manganese acetate tetrahydrate with respect to 100 mol of the dicarboxylic acid component, the raw material monomers of 45 mol% and 55 mol%, respectively, were heated to 200 ° C. in a nitrogen atmosphere to conduct a transesterification reaction. went. After the amount of distilled methanol reached 90% or more of the theoretical amount, 0.01 mol of antimony (III) oxide and 0.06 mol of triphenyl phosphate were added to 100 mol of the dicarboxylic acid component, The pressure was gradually reduced, and polymerization was finally performed at 280 ° C. and 0.1 MPa or less. The reaction was terminated when an appropriate melt viscosity was reached, and a polyester resin (a) was obtained. The proportion of the diol unit having a cyclic acetal skeleton in the obtained polyester resin (a) was 45 mol%, Mn was 16500, and Mw / Mn was 3.6.

[Synthesis Example 2]
A complete mixing type reactor having a capacity of about 20 liters equipped with a stirrer, a tower type plug flow type reactor having a capacity of about 40 liters, and a devolatilization tank equipped with a preheater were connected in series. A monomer mixture composed of 11 parts by mass of styrene, 89 parts by mass of methyl methacrylate, and 8 parts by mass of ethylbenzene was prepared, and 1,1-bis (t-butylperoxy) -cyclohexane (Perhexa manufactured by NOF Corporation) was prepared. C) 0.02 part by mass and 0.02 part by mass of n-dodecyl mercaptan (Taocalcol 20 manufactured by Kao Corporation) were mixed to obtain a raw material solution. This raw material solution was introduced into a fully mixed reactor controlled at a temperature of 130 ° C. at 6 kg per hour. In addition, the stirring number of the complete mixing type reactor was 180 rpm. Next, the reaction liquid was continuously withdrawn from the complete mixing type reactor and introduced into a column type plug flow type reactor adjusted so as to have a gradient of 130 ° C. to 160 ° C. in the flow direction. While this reaction solution was heated with a preheater, it was introduced into a devolatilization tank controlled at a temperature of 235 ° C. and a pressure of 1.0 kPa to remove volatile components such as unreacted monomers. This resin liquid was extracted with a gear pump to obtain a methyl methacrylate-styrene copolymer (d). In the obtained 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.

[Synthesis Example 3]
Styrene-maleic anhydride was prepared in the same manner as in Synthesis Example 2 except that the monomer mixture was 84 parts by mass of styrene, 16 parts by mass of maleic anhydride, and 0.2 parts by mass of n-dodecyl mercaptan added to the raw material solution. An acid copolymer (e) was obtained. The resulting styrene-maleic anhydride copolymer (e) had 84% by weight of styrene units, 16% by weight of maleic anhydride units, Mn = 17000, and Mw / Mn = 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 (trade name: Delpet 80NH manufactured by Asahi Kasei Chemicals Corporation) (c), methyl methacrylate-styrene copolymer (d) obtained in Synthesis Example 2 and 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. Moreover, the polyester resin (a) obtained by the synthesis example 1 and the polycarbonate resin [Mitsubishi Gas Chemical Co., Ltd. make, brand name: Iupilon S-3000] (b) are respectively weighted to the single screw extruder with a shaft diameter of 65 mm. 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. . Extruded into a sheet with a T-die with a temperature of 260 ° C. connected to the tip, cooled while transferring the mirror surface with three mirror finish rolls, and the acrylic resin composition on one side of the thermoplastic resin composition (A1) layer (B1) A thermoplastic resin laminate in which layers were laminated was obtained. At this time, 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 μm 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), The thermoplastic resin composition (A1) 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) at 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 μm 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 μm 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 μm 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 5]
Instead of the 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 μm 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 6]
Instead of the 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 μm 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 7]
Instead of the 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 μm 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 8]
Instead of the 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 μm 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.

[Comparative Example 1]
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) was used in the same manner as in Example 1. Thus, a thermoplastic resin laminate in which an acrylic resin (c) layer was laminated on one surface 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 μm 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.

[Comparative 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 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 μm 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.

[Comparative Example 3]
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), Thermoplastic resin 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 μm 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.

[Comparative Example 4]
An acrylic resin composition on one side of the polyester resin (a) layer in the same manner as in Example 1 except that the polyester resin (a) was used instead of the thermoplastic resin composition (A1) used in Example 2. (B2) 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 (B2) layer was 70 μm 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.

[Comparative Example 5]
Example 1 except that polycarbonate resin [Mitsubishi Gas Chemical Co., Ltd., trade name: Iupilon S-3000] (b) was used instead of the thermoplastic resin composition (A1) used in Example 2. 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 μm 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.

[Comparative Example 6]
A 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.

[Comparative Example 7]
Instead of the polyester resin (a) used in Comparative Example 6, polycarbonate resin [manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: Iupilon S-3000] (b) was used, and the same procedure as in Comparative Example 6 was performed. A 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.

[Comparative Example 8]
An acrylic resin was used in the same manner as in Comparative Example 6 except that an acrylic resin [manufactured by Asahi Kasei Chemicals Corporation, trade name: Delpet 80NH] (c) was used instead of the polyester resin (a) used in Comparative Example 6. A 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.

[Comparative Example 9]
The heat of the methyl methacrylate-styrene copolymer (d) was the same as in Comparative Example 6 except that methyl methacrylate-styrene copolymer (d) was used instead of the polyester resin (a) used in Comparative Example 6. A plastic 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 transparency evaluation, heat resistance evaluation, and moldability evaluation were good, respectively, but the results of scratch resistance evaluation, impact resistance evaluation, and dimensional stability evaluation in a high temperature and high humidity environment were poor. It was a failure.

[Comparative Example 10]
A styrene-maleic anhydride copolymer (e) was used in the same manner as in Comparative Example 6 except that a styrene-maleic anhydride copolymer (e) was used instead of the polyester resin (a) used in Comparative Example 6. A 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.

Claims (8)

A thermoplastic resin laminate comprising 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
10-60 mol% in all diol structural units is the following formula (1) or the following 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. Represents an organic group selected from the group consisting of aromatic groups having a number of 6 to 10.)
A polyester resin (a) containing a diol structural unit derived from a diol having a cyclic acetal skeleton represented by formula (1) and a dicarboxylic acid structural unit, and a polycarbonate resin (b), and a polyester resin in the thermoplastic resin composition ( 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 includes 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 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 in the acrylic resin composition is 70 to 95 mol%. The ratio of the structural unit derived from maleic anhydride is 1-5 mol%, The thermoplastic resin laminated body characterized by the above-mentioned.   In the styrene-maleic anhydride copolymer (e), 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. Item 2. The thermoplastic resin laminate according to Item 1.   The diol having the cyclic acetal skeleton is 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane. Or the thermoplastic resin laminated body of 2.   The thermoplastic resin laminate according to any one of claims 1 to 3, wherein the proportion of structural units derived from terephthalic acid in all the dicarboxylic acid structural units in the polyester resin (a) is 70 mol% or more.   The thermoplastic resin laminate according to any one of claims 1 to 4, wherein one or both sides are subjected to a hard coat treatment.   6. One or more treatments selected from antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment and antiglare treatment are applied to one side or both sides. Thermoplastic resin laminate.   The transparent substrate material containing the thermoplastic resin laminated body in any one of Claims 1-6.   The transparency protective material containing the thermoplastic resin laminated body in any one of Claims 1-6.