JP2022029793A - Transparent resin laminate and transparent substrate material and transparent protective material using the same - Google Patents

Abstract

To provide a resin laminate having excellent thermal moldability at low temperature and having good appearance with suppressed formation of interference fringes.SOLUTION: The above-mentioned problems are solved by a resin laminate having a layer containing a thermoplastic resin (B) at least on one surface of a layer containing a polycarbonate-based resin (A) including a polycarbonate resin as a main component, and a hard coat layer at least on one side surface of the layer containing the thermoplastic resin (B). The thermoplastic resin (B) contains a vinyl copolymer (C) and a styrene copolymer (D). Based on a total content amount of 100 pts.mass of the vinyl copolymer (C) and the styrene copolymer (D), the content of the vinyl copolymer (C) is 20-45 pts.mass and the content of the styrene copolymer (D) is 80-55 pts.mass. The vinyl copolymer (C) is a copolymer containing 60-80 mol% of a (meth)acrylic acid ester monomer unit (c1) represented by the following general formula (1) and 40-20 mol% of an aliphatic vinyl monomer unit (c2) represented by the following general formula (2). The styrene copolymer (D) is a copolymer containing 80-90 mol% of a vinyl aromatic monomer unit (d1) and 10-20 mol% of a cyclic acid anhydride monomer unit (d2).SELECTED DRAWING: None

Description

The present invention relates to a resin laminate used as a transparent substrate material or a protective material. More specifically, the present invention relates to a resin laminate having excellent thermoformability at a low temperature and having a good appearance that suppresses the generation of interference fringes.

Acrylic resin is excellent in surface hardness, transparency, scratch resistance and weather resistance. On the other hand, the polycarbonate resin has excellent impact resistance and the like. For this reason, the laminate having the acrylic resin layer and the polycarbonate resin layer is excellent in surface hardness, transparency, scratch resistance, weather resistance, impact resistance, etc., and is excellent in automobile parts, home appliances, electronic devices, and portable information terminals. It is used for the display window of.

In recent years, with the diversification of design needs, there is a demand for products with improved design by thermoforming such as vacuum forming and compressed air forming on the front plate of a display device. A laminate having an acrylic resin layer and a polycarbonate resin layer has been attempted to be applied to a front plate from the above-mentioned excellent performance aspects. However, when the laminate having the acrylic resin layer and the polycarbonate resin layer is heat-molded, it is necessary to heat the sheet to a temperature at which the polycarbonate resin is sufficiently stretched, which causes excessive heat to be applied to the acrylic resin. Peeling may occur at the interface between the acrylic resin layer and the polycarbonate resin layer, and the surface may be whitened or cracks may occur.

Patent Document 1 discloses a laminate of a styrene-maleic anhydride copolymer, an alloy layer of a methacrylic resin, and a polycarbonate resin layer for thermoforming at a temperature of 160 ° C. Such a laminate does not cause any problems when thermoformed at a temperature of 160 ° C. However, when the resin laminate having the styrene-maleic anhydride copolymer and the hard coat layer on the surface of the alloy layer of the methacrylic resin is thermoformed at a temperature of 160 ° C., cracks are formed in the bent portion of the resin laminate. There was a problem that it occurred.

International Publication No. 2015/133530

An object of the present invention is to provide a resin laminate having excellent thermoformability at a low temperature and having a good appearance that suppresses the generation of interference fringes.

The present inventors have completed the present invention as a result of repeated diligent studies to solve the above problems. Specifically, the present invention is as follows.

（式中、Ｒ１は水素原子又はメチル基を表し、Ｒ２は炭素数１～１８のアルキル基を表す 。）

（式中、Ｒ３は水素原子又はメチル基を表し、Ｒ４は炭素数１～４の炭化水素置換基を有することのあるシクロヘキシル基を表す。）
［２］熱プレス機で５０ｍｍＲの熱成形した後に、クラックが発生しない、上記[１]に記載の樹脂積層体である。
［３］前記熱可塑性樹脂（Ｂ）が、前記ビニル共重合体（Ｃ）と前記スチレン共重合体（Ｄ）とのポリマーアロイである、上記[１]または[２]に記載の樹脂積層体である。
［４］前記ビニル共重合体（Ｃ）が、少なくとも１種の（メタ）アクリル酸エステル単量体と少なくとも１種の芳香族ビニル単量体とを重合した後、芳香族ビニル単量体由来の芳香族二重結合の７０％以上を水素化して得られたものである、上記［１］～[３]のいずれかに記載の樹脂積層体である。
［５］前記スチレン共重合体（Ｄ）に含まれるビニル芳香族単量体単位（ｄ１）が、スチレンである、上記［１］～[４]のいずれかに記載の樹脂積層体である。
［６］前記スチレン共重合体（Ｄ）に含まれる環状酸無水物単量体単位（ｄ２）が、無水マレイン酸である、上記［１］～[５]のいずれかに記載の樹脂積層体である。
［７］前記熱可塑性樹脂（Ｂ）を含む層の厚さが１０～２５０μｍであり、樹脂積層体の全体厚みが０．４～４．０ｍｍの範囲である、上記［１］～[６]のいずれかに記載の樹脂積層体である。
［８］前記ポリカーボネート系樹脂（Ａ）を含む層、前記熱可塑性樹脂（Ｂ）を含む層、および、前記ハードコート層の少なくとも一層が紫外線吸収剤を含有する、上記［１］～[７]のいずれかに記載の樹脂積層体である。
［９］前記ハードコート層がアクリル系ハードコートである、上記［１］～[８]のいずれかに記載の樹脂積層体である。
［１０］前記樹脂積層体の片面または両面に、耐指紋処理、反射防止処理、防眩処理、耐候性処理、帯電防止処理および防汚処理の少なくとも一つが施されてなる、上記［１］～[９]のいずれかに記載の樹脂積層体である。
［１１］上記［１］～[１０]のいずれかに記載の樹脂積層体を熱曲げ加工された熱成形体である。
［１２］上記［１］～[１０]のいずれかに記載の樹脂積層体、または上記［１１]に記載の熱成形体を含む、透明基板材料である。
［１３］上記［１］～[１０]のいずれかに記載の樹脂積層体、または上記［１１]に記載の熱成形体を含む、透明保護材料である。
［１４］上記［１］～[１０]のいずれかに記載の樹脂積層体、または上記［１１]に記載の熱成形体を含む、タッチパネル前面保護板である。
［１５］上記［１］～[１０]のいずれかに記載の樹脂積層体、または上記［１１]に記載の熱成形体を含む、カーナビ用、ＯＡ機器用または携帯電子機器用の前面板である。 [1] A layer containing a thermoplastic resin (B) on at least one surface of a layer containing a polycarbonate resin (A) containing a polycarbonate resin as a main component, and the layer containing the thermoplastic resin (B). A resin laminate having a hard coat layer on at least one side surface,
The thermoplastic resin (B) contains a vinyl copolymer (C) and a styrene copolymer (D), and the total content of the vinyl copolymer (C) and the styrene copolymer (D) is 100. Based on the mass part, the content of the vinyl copolymer (C) is 20 to 45 parts by mass, and the content of the styrene copolymer (D) is 80 to 55 parts by mass.
The vinyl copolymer (C) has a (meth) acrylic acid ester monomer unit (c1) represented by the following general formula (1) in an amount of 60 to 80 mol% and is represented by the following general formula (2). It is a copolymer containing 40 to 20 mol% of an aliphatic vinyl monomer unit (c2).
The styrene copolymer (D) contains 80 to 90 mol% of a vinyl aromatic monomer unit (d1) and 10 to 20 mol% of a cyclic acid anhydride monomer unit (d2). It is a coalescence,
The resin laminate.

(In the formula, R1 represents a hydrogen atom or a methyl group, and R2 represents an alkyl group having 1 to 18 carbon atoms.)

(In the formula, R3 represents a hydrogen atom or a methyl group, and R4 represents a cyclohexyl group which may have a hydrocarbon substituent having 1 to 4 carbon atoms.)
[2] The resin laminate according to the above [1], wherein cracks do not occur after thermoforming at 50 mmR with a hot press machine.
[3] The resin laminate according to the above [1] or [2], wherein the thermoplastic resin (B) is a polymer alloy of the vinyl copolymer (C) and the styrene copolymer (D). Is.
[4] The vinyl copolymer (C) is derived from the aromatic vinyl monomer after polymerizing at least one (meth) acrylic acid ester monomer and at least one aromatic vinyl monomer. The resin laminate according to any one of the above [1] to [3], which is obtained by hydrogenating 70% or more of the aromatic double bonds of the above.
[5] The resin laminate according to any one of the above [1] to [4], wherein the vinyl aromatic monomer unit (d1) contained in the styrene copolymer (D) is styrene.
[6] The resin laminate according to any one of [1] to [5] above, wherein the cyclic acid anhydride monomer unit (d2) contained in the styrene copolymer (D) is maleic anhydride. Is.
[7] The thickness of the layer containing the thermoplastic resin (B) is 10 to 250 μm, and the total thickness of the resin laminate is in the range of 0.4 to 4.0 mm. The resin laminate according to any one of.
[8] The above [1] to [7], wherein at least one layer of the polycarbonate resin (A), the layer containing the thermoplastic resin (B), and the hard coat layer contains an ultraviolet absorber. The resin laminate according to any one of.
[9] The resin laminate according to any one of [1] to [8] above, wherein the hard coat layer is an acrylic hard coat.
[10] The above [1] to the above-mentioned [1] to which at least one of fingerprint resistance treatment, antireflection treatment, antiglare treatment, weather resistance treatment, antistatic treatment and antifouling treatment is applied to one side or both sides of the resin laminate. [9] The resin laminate according to any one of [9].
[11] The resin laminate according to any one of the above [1] to [10] is a thermoformed body obtained by thermoforming.
[12] A transparent substrate material containing the resin laminate according to any one of the above [1] to [10] or the thermoformed body according to the above [11].
[13] A transparent protective material containing the resin laminate according to any one of the above [1] to [10] or the thermoformed body according to the above [11].
[14] A touch panel front surface protective plate including the resin laminate according to any one of the above [1] to [10] or the thermoformed body according to the above [11].
[15] A front plate for a car navigation system, an OA device, or a portable electronic device, which comprises the resin laminate according to any one of the above [1] to [10] or the thermoformed body according to the above [11]. be.

INDUSTRIAL APPLICABILITY According to the present invention, there is provided a resin laminate that is excellent in thermoforming at a low temperature and can form a thermoformed product in which the generation of interference fringes is suppressed. That is, according to the resin laminate of the present invention, whitening and generation of cracks during thermoforming are suppressed, and a molded product having a good appearance can be obtained. The resin laminate can be used as a transparent substrate material or a transparent protective material. Specifically, portable display devices such as mobile phone terminals, portable electronic play equipment, mobile information terminals, and mobile PCs, and stationary display devices such as notebook PCs, desktop PC LCD monitors, car navigation LCD monitors, and LCD TVs. In, for example, it can be suitably used as a front plate for protecting these devices.

Hereinafter, the present invention will be described in detail by exemplifying manufacturing examples, examples, etc., but the present invention is not limited to the exemplified manufacturing examples, examples, etc., and does not significantly deviate from the contents of the present invention. If so, it can be changed to any method.

具体的には、ポリカーボネート系樹脂（Ａ）として、芳香族ポリカーボネート樹脂（例えば、三菱エンジニアリングプラスチックス株式会社から市販されている、ユーピロンＳ－２０００、ユーピロンＳ－１０００、ユーピロンＥ－２０００）等が使用可能である。
本発明に使用されるポリカーボネート系樹脂（Ａ）のガラス転移温度は、１２０～１６０℃が好ましく、１２５～１５５℃がより好ましく、１３０℃～１５０℃が特に好ましい。
近年、前面板にも曲げ加工を行うような要望が増えていることから、ポリカーボネート系樹脂（Ａ）は、下記一般式（４）で表わされる１価フェノールを末端停止剤として用いて合成することが好ましい。

（式中、Ｒ_１は、炭素数８～３６のアルキル基、又は炭素数８～３６のアルケニル基を表し、
Ｒ_２～Ｒ_５はそれぞれ水素、ハロゲン、又は置換基を有してもよい炭素数１～２０のアルキル基若しくは炭素数６～１２のアリール基を表し、置換基は、ハロゲン、炭素数１～２０のアルキル基、又は炭素数６～１２のアリール基である。） <Polycarbonate resin (A)>
The polycarbonate-based resin (A) used in the present invention is a polycarbonate-based resin (A) containing a polycarbonate resin as a main component. Here, "having a polycarbonate resin as a main component" means that the content of the polycarbonate resin exceeds 50% by mass. The polycarbonate resin (A) preferably contains 75% by mass or more of the polycarbonate resin, more preferably 90% by mass or more of the polycarbonate resin, and further preferably substantially composed of the polycarbonate resin. .. The polycarbonate resin (A) contains a carbonic acid ester bond in the molecular main chain. That is,-[OR-OCO] -unit (in the formula, R contains an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group, and further has a linear structure or a branched structure. Is not particularly limited as long as it contains), but it is particularly preferable to use a polycarbonate containing the structural unit of the following formula (3). By using such polycarbonate, a resin laminate having excellent impact resistance can be obtained.

Specifically, as the polycarbonate resin (A), an aromatic polycarbonate resin (for example, Iupiron S-2000, Iupiron S-1000, Iupiron E-2000, which is commercially available from Mitsubishi Engineering Plastics Co., Ltd.) is used. It is possible.
The glass transition temperature of the polycarbonate resin (A) used in the present invention is preferably 120 to 160 ° C, more preferably 125 to 155 ° C, and particularly preferably 130 ° C to 150 ° C.
In recent years, since there has been an increasing demand for bending the front plate as well, the polycarbonate resin (A) should be synthesized by using a monohydric phenol represented by the following general formula (4) as a terminal terminator. Is preferable.

(In the formula, R ₁ represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms.
_R2 to R5 represent an alkyl group having 1 to 20 carbon atoms or an aryl group having ₆ to 12 carbon atoms, which may have hydrogen, halogen, or a substituent, respectively, and the substituents are halogen and 1 to 1 to carbon atoms, respectively. It is an alkyl group of 20 or an aryl group having 6 to 12 carbon atoms. )

（式中、Ｒ_１は、炭素数８～３６のアルキル基、又は、炭素数８～３６のアルケニル基を表す。） The monohydric phenol of the general formula (4) is more preferably a monohydric phenol represented by the following general formula (5).

(In the formula, R ₁ represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms.)

It is more preferable that the carbon number of R ₁ in the general formula (4) or the general formula (5) is within a specific numerical range. Specifically, as the upper limit of the number of carbon atoms of R ₁ , 36 is preferable, 22 is more preferable, and 18 is particularly preferable. Further, as the lower limit of the number of carbon atoms of R ₁ , 8 is preferable, and 12 is more preferable.

Among the monovalent phenols (termination agents) represented by the general formula (4) or the general formula (5), one or both of the parahydroxybenzoic acid hexadecyl ester and the parahydroxybenzoic acid 2-hexyldecyl ester are terminated. It is particularly preferable to use it as an agent.

When, for example, a monohydric phenol (terminal terminator) having an alkyl group having 16 carbon atoms is used as R ₁ in the general formula (4) or the general formula (5), the glass transition temperature, melt fluidity, moldability, and the like. It has excellent draw-down resistance and solvent solubility of monohydric phenol during production of a polycarbonate resin, and is particularly preferable as a terminal terminator used in the polycarbonate resin used in the present invention.

On the other hand, if the carbon number of _R1 in the general formula (4) or the general formula (5) is increased too much, the organic solvent solubility of the monohydric phenol (terminal terminator) tends to decrease, and the polycarbonate resin is manufactured. Productivity may decrease.
As an example, when the carbon number of R ₁ is 36 or less, the productivity is high and the economy is good in producing the polycarbonate resin. When the number of carbon atoms of R ₁ is 22 or less, the monohydric phenol is particularly excellent in organic solvent solubility, and can greatly increase the productivity in producing the polycarbonate resin and also improve the economic efficiency.
If the carbon number of R ₁ in the general formula (4) or the general formula (5) is too small, the glass transition temperature of the polycarbonate resin does not become a sufficiently low value, and the thermoformability may deteriorate.

As another resin contained in the polycarbonate resin (A), there is a polyester resin. The polyester resin may contain terephthalic acid as a main component as the dicarboxylic acid component, and may contain a dicarboxylic acid component other than terephthalic acid. For example, a glycol component containing 20 to 40 (molar ratio, 100 in total) of 1,4-cyclohexanedimethanol with ethylene glycol 80 to 60 (molar ratio) as the main component and a dicarboxylic acid component are polycondensed. A polyester resin, so-called "PETG", is preferable. Further, the polycarbonate-based resin (A) may contain a polyester carbonate-based resin having an ester bond and a carbonate bond in the polymer skeleton.

In the present invention, the weight average molecular weight of the polycarbonate resin (A) affects the impact resistance and molding conditions of the resin laminate. That is, if the weight average molecular weight is too small, the impact resistance of the resin laminate is lowered, which is not preferable. If the weight average molecular weight is too high, an excessive heat source may be required when laminating the layer containing the polycarbonate resin (A), which is not preferable. Further, since a high temperature is required depending on the molding method, the polycarbonate resin (A) is exposed to a high temperature, which may adversely affect its thermal stability. The weight average molecular weight of the polycarbonate resin (A) is preferably 15,000 to 75,000, more preferably 20,000 to 70,000. More preferably, it is 25,000 to 65,000.

<Measurement method of weight average molecular weight of polycarbonate resin (A)>
The weight average molecular weight of the polycarbonate resin (A) can be measured based on the description in paragraphs 0061 to 0064 of JP-A-2007-179018. The details of the measurement method are shown below.

After measuring using polystyrene (PS) as a standard polymer, the relationship between the elution time and the molecular weight of polycarbonate (PC) is obtained by a universal calibration method and used as a calibration curve. Then, the elution curve (chromatogram) of PC is measured under the same conditions as in the case of the calibration curve, and each average molecular weight is obtained from the elution time (molecular weight) and the peak area (molecular number) of the elution time. Assuming that the number of molecules of the molecular weight Mi is Ni, the weight average molecular weight is expressed as follows. The following formula was used as the conversion formula.
(Weight average molecular weight)
Mw = Σ (NiMi ² ) / Σ (NiMi)
(Conversion formula)
MPC = 0.47822MPS ^1.01470
MPC indicates the molecular weight of PC, and MPS indicates the molecular weight of PS.

The method for producing the polycarbonate resin (A) used in the present invention can be appropriately selected depending on the monomer used, such as a known phosgene method (interfacial polymerization method) or transesterification method (melting method).

<Thermoplastic resin (B)>
The thermoplastic resin (B) used in the present invention contains a vinyl copolymer (C) and a styrene copolymer (D), which will be described later. Each component will be described below.

<Vinyl copolymer (C)>
The vinyl copolymer (C) contained in the thermoplastic resin (B) according to the present invention has a (meth) acrylic acid ester monomer unit (c1) represented by the following general formula (1) and the following general formula (c1). The total ratio of the (meth) acrylic acid ester monomer unit (c1) and the aliphatic vinyl monomer unit (c2) including the aliphatic vinyl monomer unit (c2) represented by 2). Is 90 to 100 mol% with respect to the total of all the monomer units in the vinyl copolymer (C), and the ratio of the (meth) acrylic acid ester monomer unit (c1) is the vinyl co-weight. The ratio of the aliphatic vinyl monomer unit (c2) represented by the following general formula (2) is 60 to 80 mol% with respect to the total of all the monomer units in the coalescence (C). It is characterized in that it is 40 to 20 mol% with respect to the total of all the monomer units in the polymer (C).

（式中、Ｒ１は水素原子又はメチル基を表し、Ｒ２は炭素数１～１８のアルキル基を表す 。）

(In the formula, R1 represents a hydrogen atom or a methyl group, and R2 represents an alkyl group having 1 to 18 carbon atoms.)

（式中、Ｒ３は水素原子又はメチル基を表し、Ｒ４は炭素数１～４の炭化水素置換基を有することのあるシクロヘキシル基を表す。）

(In the formula, R3 represents a hydrogen atom or a methyl group, and R4 represents a cyclohexyl group which may have a hydrocarbon substituent having 1 to 4 carbon atoms.)

In the (meth) acrylic acid ester monomer unit (c1) represented by the general formula (1), R2 is an alkyl group having 1 to 18 carbon atoms, preferably an alkyl group having 1 to 12 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a butyl group, a lauryl group, a stearyl group, a cyclohexyl group and an isobornyl group. Among the (meth) acrylic acid ester monomer units (c1), the (meth) acrylic acid ester monomer unit in which R2 is a methyl group and / or an ethyl group is preferable, and R1 is more preferable. It is a methyl group and R2 is a methyl methacrylate monomer unit.

As the aliphatic vinyl monomer unit (c2) represented by the general formula (2), R3 is a hydrogen atom or a methyl group, and R4 has a cyclohexyl group or a hydrocarbon substituent having 1 to 4 carbon atoms. Examples thereof include those having a cyclohexyl group. Among the aliphatic vinyl monomer units (c2), an aliphatic vinyl monomer unit in which R3 is a hydrogen atom and R4 is a cyclohexyl group is preferable.

The vinyl copolymer (C) used in the present invention mainly contains the (meth) acrylic acid ester monomer unit (c1) represented by the general formula (1) and the fat represented by the general formula (2). It is composed of a group vinyl monomer unit (c2). The vinyl copolymer (C) may contain one or more of the (meth) acrylic acid ester monomer unit (c1), and the aliphatic vinyl monomer unit (c2) is 1 It may contain seeds or two or more kinds. The total ratio of the (meth) acrylic acid ester monomer unit (c1) and the aliphatic vinyl monomer unit (c2) is the total of all the monomer units in the vinyl copolymer (C). On the other hand, it is 90 to 100 mol%, preferably 95 to 100 mol%, and more preferably 98 to 100 mol%. That is, the vinyl copolymer (C) contains the (meth) acrylic acid ester monomer unit (c1) and the aliphatic vinyl monomer in a range of 10 mol% or less with respect to the total of all the monomer units. It may contain a monomer unit other than the polymer unit (c2).
Examples of the monomer unit other than the (meth) acrylic acid ester monomer unit (c1) and the aliphatic vinyl monomer unit (c2) include a (meth) acrylic acid ester monomer and an aromatic vinyl monomer. In the vinyl copolymer (C) obtained by hydrogenating the aromatic double bond derived from the aromatic vinyl monomer after polymerizing the above, a simple substance derived from the aromatic vinyl monomer containing the non-hydrogenated aromatic double bond. Quantitative units and the like can be mentioned. The ratio of the (meth) acrylic acid ester monomer unit (c1) represented by the general formula (1) is 60 with respect to the total of all the monomer units in the vinyl copolymer (C). It is about 80 mol%, preferably 70 to 80 mol%, and the ratio of the aliphatic vinyl monomer unit (c2) represented by the general formula (2) is in the vinyl copolymer (C). It is 40 to 20 mol%, preferably 30 to 20 mol% with respect to the total of all the monomer units of. When the ratio of the (meth) acrylic acid ester monomer unit (c1) to the total of all the monomer units in the vinyl copolymer (C) is less than 60 mol%, the adhesion with the polycarbonate resin (A) is achieved. It may be impractical due to reduced properties and surface hardness. On the other hand, if it exceeds 80 mol%, warpage occurs due to water absorption of the laminated body, which may not be practical. Further, when the ratio of the aliphatic vinyl monomer unit (c2) to the total of all the monomer units in the vinyl copolymer (C) is less than 20 mol%, the glass transition temperature is low and the heat resistance dimensional stability is low. It may be inferior and impractical. On the other hand, if it exceeds 40 mol%, the solvent resistance is poor and it may not be practical.

The method for producing the vinyl copolymer (C) is not particularly limited, but after polymerizing at least one (meth) acrylic acid ester monomer and at least one aromatic vinyl monomer, the fragrance derived from the aromatic vinyl monomer is used. The one obtained by hydrogenating the group double bond is preferable. The (meth) acrylic acid means methacrylic acid and / or acrylic acid. Specific examples of the aromatic vinyl monomer used in this case include styrene, α-methylstyrene, p-hydroxystyrene, alkoxystyrene, chlorostyrene, and derivatives thereof. Of these, styrene is preferred.

A known method can be used for the polymerization of the (meth) acrylic acid ester monomer and the aromatic vinyl monomer, and for example, it can be produced by a bulk polymerization method, a solution polymerization method, or the like. The bulk polymerization method is carried out by a method in which a monomer composition containing the above-mentioned monomer and a polymerization initiator is continuously supplied to a complete mixing tank and continuously polymerized at 100 to 180 ° C. The monomer composition may contain a chain transfer agent, if necessary.

The polymerization initiator is not particularly limited, but t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, 1,1-di (t-hexylperoxy). -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, t-hexylpropoxyisopropyl monocarbonate, t-amylperoxynormal Organic peroxides such as octoate, t-butylperoxyisopropyl monocarbonate, di-t-butyl peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile) ), 2,2'-Azobis (2,4-dimethylvaleronitrile) and other azo compounds. These can be used alone or in combination of two or more.

Chain transfer agents are used as needed and include, for example, α-methylstyrene dimer.

Examples of the solvent used in the solution polymerization method include hydrocarbon solvents such as toluene, xylene, cyclohexane and methylcyclohexane, ester solvents such as ethyl acetate and methyl isobutyrate, ketone solvents such as acetone and methyl ethyl ketone, and tetrahydrofuran, and the like. Examples thereof include ether solvents such as dioxane and alcohol solvents such as methanol and isopropanol.

The solvent used for the hydrogenation reaction after polymerizing the (meth) acrylic acid ester monomer and the aromatic vinyl monomer may be the same as or different from the above-mentioned polymerization solvent. For example, hydrocarbon solvents such as cyclohexane and methylcyclohexane, ester solvents such as ethyl acetate and methyl isobutyrate, ketone solvents such as acetone and methyl ethyl ketone, ether solvents such as tetrahydrofuran and dioxane, alcohol solvents such as methanol and isopropanol. Examples include solvents.

The vinyl copolymer used in the present invention is obtained by polymerizing the (meth) acrylic acid ester monomer and the aromatic vinyl monomer as described above, and then hydrogenating the aromatic double bond derived from the aromatic vinyl monomer. (C) is obtained. The method of hydrogenation is not particularly limited, and a known method can be used. For example, it can be carried out by a batch method or a continuous flow method at a hydrogen pressure of 3 to 30 MPa and a reaction temperature of 60 to 250 ° C. When the temperature is 60 ° C. or higher, the reaction time does not take too long, and when the temperature is 250 ° C. or lower, the molecular chain is less likely to be cleaved or the ester site is hydrogenated.

Examples of the catalyst used in the hydride reaction include metals such as nickel, palladium, platinum, cobalt, ruthenium, and rhodium, or oxides, salts, or complex compounds of these metals, and carbon, alumina, silica, silica-alumina, and diatomaceous earth. Examples thereof include a solid catalyst carried on a porous carrier such as.

The vinyl copolymer (C) is preferably one in which 70% or more of the aromatic double bonds derived from the aromatic vinyl monomer are hydrogenated. That is, the ratio of the unhydrogenated portion of the aromatic double bond in the monomer unit derived from the aromatic vinyl monomer is preferably 30% or less. If it exceeds 30%, the transparency of the vinyl copolymer resin (C) may decrease. It is more preferably in the range of less than 10%, and even more preferably in the range of less than 5%.

The weight average molecular weight of the vinyl copolymer (C) is not particularly limited, but is preferably 50,000 to 400,000, preferably 70,000 to 300,000 from the viewpoint of strength and moldability. Is more preferable. The weight average molecular weight is a standard polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

The vinyl copolymer (C) can be blended with other resins as long as the transparency is not impaired. Examples thereof include methyl methacrylate-styrene copolymer resin, polymethyl methacrylate, polystyrene, polycarbonate, cycloolefin (co) polymer resin, acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, various elastomers and the like. ..

The glass transition temperature of the vinyl copolymer (C) is preferably in the range of 110 to 190 ° C, more preferably in the range of 110 to 160 ° C. When the glass transition temperature is 110 ° C. or higher, the laminate provided in the present invention is less likely to be deformed or cracked in a thermal environment or a moist heat environment, and when the temperature is 190 ° C. or lower, it depends on a mirror surface roll or a shaping roll. It has excellent workability such as continuous heat shaping, or batch type heat shaping using a mirror surface mold or a shaping die. The glass transition temperature in the present invention is a temperature measured by a differential scanning calorimetry device at a heating rate of 10 ° C./min and calculated by the midpoint method.

<Styrene copolymer (D)>
The styrene copolymer (D) contained in the thermoplastic resin (B) according to the present invention contains a vinyl aromatic monomer unit (d1) and a cyclic acid anhydride monomer unit (d2), and has a vinyl fragrance. The total ratio of the group monomer unit (d1) and the cyclic acid anhydride monomer unit (d2) is 90 to 100 mol% with respect to the total of all the monomer units in the styrene copolymer (D). The ratio of the vinyl aromatic monomer unit (d1) is 80 to 90 mol% with respect to the total of all the monomer units in the styrene copolymer (D), and the cyclic acid anhydride is used. It is characterized in that the ratio of the monomer unit (d2) is 10 to 20 mol% with respect to the total of all the monomer units in the styrene copolymer (D).

The vinyl aromatic monomer unit (d1) of the styrene copolymer (D) is not particularly limited, and any known aromatic vinyl monomer can be used, but it is easy to obtain. From the viewpoint, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene and the like can be mentioned. Of these, styrene is particularly preferable from the viewpoint of compatibility. Two or more kinds of these aromatic vinyl monomers may be mixed.

Examples of the cyclic acid anhydride monomer unit (d2) of the styrene copolymer (D) include acid anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid, which are compatible with acrylic resins. Maleic anhydride is preferable from the viewpoint of. Two or more kinds of these unsaturated dicarboxylic acid anhydride monomers may be mixed.

In the styrene copolymer (D) used in the present invention, the total ratio of the vinyl aromatic monomer unit (d1) and the cyclic acid anhydride monomer unit (d2) is the styrene copolymer (d). It is 90 to 100 mol%, preferably 95 to 100 mol%, and more preferably 98 to 100 mol% with respect to the total of all the monomer units in D).
That is, the styrene copolymer (D) contains the vinyl aromatic monomer unit (d1) and the cyclic acid anhydride monomer in a range of 10 mol% or less with respect to the total of all the monomer units. It may contain a monomer unit other than the unit (d2). Examples of the monomer unit other than the vinyl aromatic monomer unit (d1) and the cyclic acid anhydride monomer unit (d2) include a methacrylic acid ester monomer unit and an N-substituted maleimide unit. The body etc. can be mentioned. Examples of the methacrylic acid ester monomer unit include acrylonitrile, metaacrylonitrile, acrylic acid, methacrylic acid, and (meth) acrylic acid ester. Examples of the (meth) acrylic acid ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and 2-ethylhexyl methacrylate. Be done. Among them, methyl methacrylate (MMA) is preferable from the viewpoint of compatibility with acrylic resin. Two or more kinds of these acrylic compound monomers may be mixed. Examples of the N-substituted maleimide monomer include N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-naphthylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, and N-carboxyphenyl. Examples thereof include N-arylmaleimide such as maleimide, N-nitrophenylmaleimide, and N-tribromophenylmaleimide, and N-phenylmaleimide is preferable from the viewpoint of compatibility with acrylic resin. Two or more kinds of these N-substituted maleimide monomers may be mixed.

The ratio of the vinyl aromatic monomer unit (d1) is 80 to 90 mol%, preferably 81 to 89 mol% with respect to the total of all the monomer units in the styrene copolymer (D). It is more preferably 82 to 88 mol%, still more preferably 83 to 87 mol%. The ratio of the cyclic acid anhydride monomer unit (d2) is 10 to 20 mol%, preferably 11 to 19 mol%, based on the total of all the monomer units in the styrene copolymer (D). %, More preferably 12-18 mol%, still more preferably 13-17 mol%.
When the ratio of the vinyl aromatic monomer unit (d1) to the total of all the monomer units in the styrene copolymer (D) is less than 80 mol% or more than 90 mol%, the vinyl copolymer The compatibility with (C) deteriorates. When the ratio of the cyclic acid anhydride monomer unit (d2) to the total of all the monomer units in the styrene copolymer (D) is less than 10 mol% or more than 20 mol%, the vinyl copolymer Poor compatibility with (C)

The method for producing the styrene copolymer (D) is not particularly limited, but a known solution polymerization method, bulk polymerization method, or the like can be appropriately selected.

The weight average molecular weight of the styrene copolymer (D) is not particularly limited, but is preferably 50,000 to 400,000 from the viewpoint of compatibility with the vinyl copolymer (C), 70. More preferably, it is 000 to 300,000. The weight average molecular weight is a standard polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

The glass transition temperature of the styrene copolymer (D) is preferably higher than the glass transition temperature of the vinyl copolymer (C), preferably in the range of 120 to 190 ° C, and preferably in the range of 125 to 185 ° C. Is more preferable. When the glass transition temperature is 120 ° C. or higher, the laminate provided by the present invention is less likely to be deformed or cracked in a thermal environment or a moist thermal environment. Further, when the temperature is 190 ° C. or lower, it is excellent in workability such as continuous heat shaping by a mirror surface roll or a shaping roll, or batch type heat shaping by a mirror surface mold or a shaping die. The glass transition temperature in the present invention is a temperature measured by a differential scanning calorimetry device at a heating rate of 10 ° C./min and calculated by the midpoint method.

The styrene copolymer (D) is a binary copolymer containing a vinyl aromatic monomer unit (d1) and a cyclic acid anhydride monomer unit (d2), but is a vinyl copolymer (C). ) In combination, the hardness is higher than when only the styrene copolymer (D) is used, and the shape stability under high temperature and high humidity is higher than when only the vinyl copolymer (C) is used. An excellent resin laminate can be obtained.

In the present invention, the mass ratio of the vinyl copolymer (C) to the styrene copolymer (D) is 100 parts by mass in total of the contents of the vinyl copolymer (C) and the styrene copolymer (D). The vinyl copolymer (C) is 20 to 45 parts by mass, and the styrene copolymer (D) is 80 to 55 parts by mass. Preferably, the vinyl copolymer (C) is 25 to 45 parts by mass, the styrene copolymer (D) is 75 to 55 parts by mass, and more preferably, the vinyl copolymer (C) is. It is 25 to 40 parts by mass, and the styrene copolymer (D) is 75 to 60 parts by mass. By keeping the mass ratio within this range, the thermoplastic resin (B) has excellent thermoformability at low temperature and has a good appearance to suppress the generation of interference fringes while maintaining transparency.

The temperature at which the vinyl copolymer (C) and the styrene copolymer (D) are alloyed is preferably in the range of 230 to 320 ° C, more preferably in the range of 240 to 300 ° C. If the alloy temperature is less than 230 ° C., the compatibility tends to be poor and the haze tends to be high. Further, if the temperature exceeds 320 ° C., the vinyl copolymer (C) and / or the styrene copolymer (D) may be thermally decomposed.

In the present invention, the method for producing the thermoplastic resin (B) is not particularly limited, and necessary components are mixed in advance using a mixer such as a tumbler, a Henschel mixer, or a super mixer, and then a Banbury mixer. , A known method such as melt-kneading with a machine such as a roll, a brabender, a single-screw extruder, a twin-screw extruder, or a pressure kneader can be applied.
One of the characteristics of the thermoplastic resin (B) used in the present invention is that the glass transition temperature is relatively high, preferably in the range of 120 to 185 ° C, and preferably in the range of 123 to 160 ° C. It is more preferable, and it is particularly preferable that the temperature is in the range of 125 to 140 ° C. Since the glass transition temperature of the thermoplastic resin (B) used in the present invention is relatively high and the difference from the glass transition temperature of the polycarbonate resin (A) is small, the polycarbonate resin is used during hot press molding or hot bending. Even when the temperature approaches the glass transition temperature of (A), there is an advantage that there is little problem that the layer containing the thermoplastic resin (B) has an appearance defect. The difference between the glass transition temperature of the polycarbonate resin (A) and the glass transition temperature of the thermoplastic resin (B) is preferably in the range of 0 to 25 ° C, more preferably in the range of 0 to 20 ° C. It is particularly preferably in the range of 10 to 20 ° C.

<Hard coat layer>
A further layer may be present between the hardcourt layer according to the present invention and the layer containing the thermoplastic resin (B), but preferably the hardcourt layer is one side surface of the layer containing the thermoplastic resin (B). Or it is laminated on both sides. The hard coat layer is preferably an acrylic hard coat. As used herein, the term "acrylic hardcoat" means a coating film formed by polymerizing a monomer or oligomer or prepolymer containing a (meth) acryloyl group as a polymerization group to form a crosslinked structure. The composition of the acrylic hard coat preferably contains 2 to 98% by mass of the (meth) acrylic monomer, 2 to 98% by mass of the (meth) acrylic oligomer, and 0 to 15% by mass of the surface modifier. It is preferable to contain 0.001 to 7 parts by mass of the photopolymerization initiator with respect to 100 parts by mass of the total of the (meth) acrylic monomer, the (meth) acrylic oligomer and the surface modifier.

The hard coat layer more preferably contains 5 to 50% by mass of the (meth) acrylic monomer, 50 to 95% by mass of the (meth) acrylic oligomer, and 1 to 10% by mass of the surface modifier, and is particularly preferable. , 20-40% by mass of (meth) acrylic monomer, 60-80% by mass of (meth) acrylic oligomer and 2-5% by mass of surface modifier.
The amount of the photopolymerization initiator is more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the total of the (meth) acrylic monomer, the (meth) acrylic oligomer and the surface modifier. It is particularly preferably 0.1 to 3 parts by mass.

The (meth) acrylic monomer can be used as long as the (meth) acryloyl group is present as a functional group in the molecule, and may be a monofunctional monomer, a bifunctional monomer, or a trifunctional or higher functional monomer.
Examples of the monofunctional monomer include (meth) acrylic acid and (meth) acrylic acid ester, and specific examples of bifunctional and / or trifunctional or higher (meth) acrylic monomers include diethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate. Propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, tetraethylene glycol di (meth) acrylate, hydroxy Neopentyl glycol diacrylate, neopentyl glycol di (meth) acrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol di (meth) acrylate, dicyclopentanyldi (meth) acrylate, polyethylene glycol Diacrylate, 1,4-butanediol oligo acrylate, neopentyl glycol oligo acrylate, 1,6-hexanediol oligo acrylate, trimethylol propanetri (meth) acrylate, trimethylol propaneethoxytri (meth) acrylate, trimethylol propanepropoxy Tri (meth) acrylate, pentaerythritol tri (meth) acrylate, glyceryl propoxytri (meth) acrylate, trimethylolpropane trimethacrylate, trimethylolpropaneethylene oxide adduct triacrylate, glycerin propylene oxide adduct triacrylate, pentaerythritol tetraacrylate, etc. Can be exemplified.
The hard coat layer may contain one or more (meth) acrylic monomers.

As the (meth) acrylic oligomer, a bifunctional or higher polyfunctional urethane (meth) acrylate oligomer [hereinafter, also referred to as a polyfunctional urethane (meth) acrylate oligomer], a bifunctional or higher polyfunctional polyester (meth) acrylate oligomer [hereinafter, , Also referred to as polyfunctional polyester (meth) acrylate oligomer], bifunctional or higher functional epoxy (meth) acrylate oligomer [hereinafter, also referred to as polyfunctional epoxy (meth) acrylate oligomer] and the like. The hardcoat layer may contain one or more (meth) acrylic oligomers.
As the polyfunctional urethane (meth) acrylate oligomer, a urethanization reaction product of a (meth) acrylate monomer having at least one (meth) acryloyloxy group and a hydroxyl group in one molecule and a polyisocyanate; polyols are polyisocyanates. Examples thereof include a urethanization reaction product of an isocyanate compound obtained by reacting with and a (meth) acrylate monomer having at least one (meth) acryloyloxy group and a hydroxyl group in one molecule.

Examples of the (meth) acrylate monomer having at least one (meth) acryloyloxy group and a hydroxyl group in one molecule used in the urethanization reaction include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. 2-Hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerindi (meth) acrylate, trimerol propandi (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta Examples include (meth) acrylate.

The polyisocyanate used in the urethanization reaction includes hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and diisocyanate obtained by hydrogenating aromatic isocyanates among these diisocyanates. (For example, diisocyanate such as hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate), di or tri polyisocyanate such as triphenylmethane triisocyanate, dimethylene triphenyl triisocyanate, or polyisocyanate obtained by increasing the amount of diisocyanate. Can be mentioned.

As the polyols used in the urethanization reaction, in addition to aromatic, aliphatic and alicyclic polyols, polyester polyols, polyether polyols and the like are generally used. Usually, aliphatic and alicyclic polyols include 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, ethylene glycol, propylene glycol, trimethylolethane, trimethylolpropane, dimethylolheptan, and di. Examples thereof include trimethylolpropionic acid, dimethylolbutyrian acid, glycerin, hydrogenated bisphenol A and the like.

Examples of the polyester polyol include those obtained by a dehydration condensation reaction between the above-mentioned polyols and a polycarboxylic acid. Specific examples of the polycarboxylic acid include succinic acid, adipic acid, maleic acid, trimellitic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, and terephthalic acid. These polycarboxylic acids may be anhydrous. In addition to polyalkylene glycols, examples of the polyether polyols include the above-mentioned polyols or polyoxyalkylene-modified polyols obtained by reacting phenols with alkylene oxides.

Further, the polyfunctional polyester (meth) acrylate oligomer is obtained by a dehydration condensation reaction using (meth) acrylic acid, a polycarboxylic acid and a polyol. Examples of the polycarboxylic acid used in the dehydration condensation reaction include succinic acid, adipic acid, maleic acid, itaconic acid, trimellitic acid, pyromellitic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, and terephthalic acid. These polycarboxylic acids may be anhydrous. The polyols used in the dehydration condensation reaction include 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, dimethylolheptan, dimethylolpropionic acid, and dimethylol. Examples thereof include butyionic acid, trimethylolpropane, trimethylolpropane, pentaerythritol, and dipentaerythritol.

The polyfunctional epoxy (meth) acrylate oligomer is obtained by an addition reaction between polyglycidyl ether and (meth) acrylic acid. Examples of the polyglycidyl ether include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and bisphenol A diglycidyl ether.

The surface modifier used in the present invention changes the surface performance of a hard coat layer such as a leveling agent, an antistatic agent, a surfactant, a water-repellent oil-repellent agent, inorganic particles, and organic particles.
Examples of the leveling agent include polyether-modified polyalkylsiloxane, polyether-modified siloxane, polyester-modified hydroxyl group-containing polyalkylsiloxane, polyether-modified polydimethylsiloxane having an alkyl group, modified polyether, silicon-modified acrylic and the like.

Examples of the antistatic agent include glycerin fatty acid ester monoglyceride, glycerin fatty acid ester organic acid monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid ester, cationic surfactant, anionic surfactant and the like.
Examples of the inorganic particles include silica particles, alumina particles, zirconia particles, silicon particles, silver particles, and glass particles.
Examples of the organic particles include acrylic particles and silicon particles.
Examples of the surfactant and the water- and oil-repellent agent include a fluorine-containing surfactant such as a fluorine-containing group / lipophilic group-containing oligomer and a fluorine-containing group / hydrophilic group / lipophilic group / UV-reactive group-containing oligomer. And water and oil repellents.

The hardcourt layer may contain a photopolymerization initiator. As used herein, the photopolymerization initiator refers to a photoradical generator.

Examples of the monofunctional photopolymerization initiator that can be used in the present invention include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone [Darocure 2959: manufactured by Merck]; α-hydroxy. -Α, α'-Dimethylacetophenone [Darocure 1173: manufactured by Merck]; Acetphenone-based initiators such as methoxyacetophenone, 2,2'-dimethoxy-2-phenylacetophenone [Irgacure-651], 1-hydroxy-cyclohexylphenylketone. Benzoin ether-based initiators such as benzoin ethyl ether and benzoin isopropyl ether; other examples include halogenated ketones, acylphosphinoxides, and acylphosphonates.

The method for forming the hard coat layer is not particularly limited, but for example, it can be formed by applying a hard coat liquid on a layer located under the hard coat layer and then photopolymerizing the hard coat layer.

The method of applying the hard coat liquid (polymerizable composition) is not particularly limited, and a known method can be used. For example, spin coating method, dip method, spray method, slide coating method, bar coating method, roll coating method, gravure coating method, meniscus coating method, flexographic printing method, screen printing method, beat coating method, handling method and the like can be mentioned. ..

As the lamp used for light irradiation in photopolymerization, a lamp having a light emission distribution with a light wavelength of 420 nm or less is used, and examples thereof include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, and a black light lamp. , Microwave-excited mercury lamp, metal halide lamp, etc. Among these, high-pressure mercury lamps or metal halide lamps efficiently emit light in the active wavelength region of the initiator, and heat short-wavelength light or reaction compositions that reduce the viscoelastic properties of the obtained polymer by cross-linking. It is preferable because it does not emit a large amount of long-wavelength light that causes evaporation.

The irradiation intensity of the lamp is a factor that influences the degree of polymerization of the obtained polymer, and is appropriately controlled for each performance of the target product. When a cleavage-type initiator having a normal acetophenone group is blended, the illuminance is preferably in the range of 0.1 to 300 mW / cm ² . In particular, it is preferable to use a metal halide lamp and set the illuminance to 10 to 40 mW / cm ² .

The photopolymerization reaction is inhibited by oxygen in the air or oxygen dissolved in the reactive composition. Therefore, it is desirable to carry out light irradiation using a method that can eliminate the reaction inhibition due to oxygen. One such method is to cover the reactive composition with a film made of polyethylene terephthalate or Teflon to cut off contact with oxygen and irradiate the reactive composition with light through the film. Further, the composition may be irradiated with light through a light-transmitting window in an inert atmosphere in which oxygen is replaced with an inert gas such as nitrogen gas or carbon dioxide gas.

When light irradiation is performed in an inert atmosphere, a constant amount of inert gas is always introduced in order to keep the atmospheric oxygen concentration at a low level. Due to the introduction of this inert gas, an air flow is generated on the surface of the reactive composition, and monomer evaporation occurs. In order to suppress the level of monomer evaporation, the air velocity of the inert gas is preferably 1 m / sec or less as a relative velocity with respect to the laminate coated with the hard coat liquid moving under the atmosphere of the inert gas. It is more preferably 0.1 m / sec or less. By setting the airflow velocity in the above range, the monomer evaporation due to the airflow is substantially suppressed.

The coated surface may be pretreated for the purpose of improving the adhesion of the hardcoat layer. Known treatment examples include sandblasting, solvent treatment, corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone treatment, ultraviolet treatment, and primer treatment with a resin composition. Can be mentioned.

The hard coat layer preferably has a pencil hardness of 2H or more when irradiated with ultraviolet rays using a metal halide lamp having an irradiation output of UV light (254 nm) of 20 mW / cm ² .

The film thickness of the hard coat layer is preferably 1 μm or more and 40 μm or less, and more preferably 2 μm or more and 10 μm or less. Sufficient hardness can be obtained when the film thickness is 1 μm or more. Further, when the film thickness is 40 μm or less, it is possible to suppress the occurrence of cracks during bending. The film thickness of the hard coat layer can be measured by observing the cross section with a microscope or the like and actually measuring the film thickness from the coating film interface to the surface.

<Haze>
The resin laminate of the present invention preferably has Haze ≦ 1.0%, more preferably Haze ≦ 0.8%, further preferably Haze ≦ 0.7%, and particularly preferably Haze ≦ 0.5%. If Haze exceeds 1.0%, the resin laminate may appear whitish visually. In the present invention, as the method for measuring Haze, the method described in Examples described later can be adopted.

<Resin laminate>
In the present invention, the thickness of the layer containing the thermoplastic resin (B) affects the surface hardness and impact resistance of the resin laminate. That is, if the thickness of the layer containing the thermoplastic resin (B) is too thin, the surface hardness becomes low, which is not preferable. If the thickness of the layer containing the thermoplastic resin (B) is too large, the impact resistance deteriorates, which is not preferable. The thickness of the layer containing the thermoplastic resin (B) is preferably 10 to 250 μm, more preferably 20 to 200 μm. More preferably, it is 30 to 150 μm.

In the present invention, if the total thickness of the layer containing the polycarbonate resin (A), the layer containing the thermoplastic resin (B), and the hard coat layer is too thin or too thick, molding is difficult. The total thickness of the resin laminate is preferably 0.4 to 4.0 mm, more preferably 0.5 to 3.5 mm, and even more preferably 0.5 to 3.0 mm.

In the present invention, the difference in refractive index between the polycarbonate resin (A) and the thermoplastic resin (B) is preferably in the range of 0 to 0.07, more preferably in the range of 0 to 0.06. It is more preferably in the range of 0 to 0.05. When the difference in refractive index between the polycarbonate resin (A) and the thermoplastic resin (B) is larger than 0.07, the reflected light intensity at the interface between the layer containing the polycarbonate resin (A) and the layer containing the thermoplastic resin (B). Is large, and problems such as interference fringes may occur.

The resin laminate of the present invention may be subjected to any one or more of anti-fingerprint treatment, anti-reflection treatment, anti-fouling treatment, anti-static treatment, weather resistance treatment and anti-glare treatment on one or both sides thereof. The methods of antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment and antiglare treatment are not particularly limited, and known methods can be used. For example, a method of applying a reflection-reducing paint, a method of depositing a dielectric thin film, a method of applying an antistatic paint, and the like can be mentioned.

<Any additive>
In the present invention, the layer containing the polycarbonate resin (A) forming the base material layer and / or the layer containing the thermoplastic resin (B) forming the surface layer may contain components other than the above-mentioned main components. ..

For example, an ultraviolet absorber can be mixed and used in the layer containing the polycarbonate resin (A) and / or the layer containing the thermoplastic resin (B). In the present invention, the hard coat layer may contain an ultraviolet absorber. If the content of the UV absorber is too high, depending on the molding method, the excess UV absorber may be scattered due to the high temperature, which may contaminate the molding environment and cause a problem. From this, the content ratio of the ultraviolet absorber is preferably 0 to 5% by mass, more preferably 0 to 3% by mass, still more preferably 0 to 1% by mass. Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, and 2-hydroxy. -4-octadecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, etc. Benzophenone UV absorber, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole, 2- (2-hydroxy-3) -T-butyl-5-Methylphenyl) benzotriazole, (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol and other benzotriazole-based ultraviolet absorbers, salicylic acid Phenyl, benzoate-based UV absorbers such as 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, bis (2,2,6,6-tetramethylpiperidine-4) -Il) Hinderdamine-based ultraviolet absorbers such as sebacate, 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-) Hydroxy-4-ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-) Hydroxy-4-butoxyphenyl) 1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-Hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2, 4-Diphenyl-6- (2-hydroxy-4-dodecyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-benzyloxyphenyl) -1,3, Triazine-based ultraviolet absorbers such as 5-triazine, 2- [2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazole-5 -Il] ethyl methacrylate, 2- [2- (6-hydroxybenzo [1,3] dioxotol-5-yl) -2H-benzotriazole-5-yl] ethyl acrylate, 3- [2- (6-hydroxybenzo [1,3] Dioxotol-5-yl) -2H-benzotriazole-5-yl] propylmethacrylate, 3- [2- (6-hydroxybenzo [1,3] dioxotri-5-yl) -2H-benzotriazole -5-yl] propyl acrylate, 4- [2- (6-hydroxybenzo [1,3] dioxotol-5-yl) -2H-benzotriazole-5-yl] butyl methacrylate, 4- [2- (6--) Hydroxybenzo [1,3] dioxotri-5-yl) -2H-benzotriazole-5-yl] butyl acrylate, 2- [2- (6-hydroxybenzo [1,3] dioxotri-5-yl) -2H- Benzotriazole-5-yloxy] ethyl methacrylate, 2- [2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazole-5-yloxy] ethyl acrylate, 2- [3- { 2- (6-Hydroxybenzo [1,3] dioxotri-5-yl) -2H-benzotriazole-5-yl} propanoyloxy] ethyl methacrylate, 2- [3- {2- (6-hydroxybenzo [1] , 3] Dioxotol-5-yl) -2H-benzotriazole-5-yl} propanoyloxy] ethyl acrylate, 4- [3- {2- (6-hydroxybenzo [1,3] dioxotri-5-yl) -2H-benzotriazole-5-yl} propanoyloxy] butyl methacrylate, 4- [3- {2- (6-hydroxybenzo [1,3] dioxotol-5-yl) -2H-benzotriazole-5-yl) } Propanoyloxy] butyl acrylate, 2- [3- {2- (6-hydroxybenzo [1,3] dioxotol-5-yl) -2H-benzotriazole-5-yl} propanoyloxy] ethyl methacrylate, 2 -[3- {2- (6-Hydroxybenzo [1,3] dioxotri-5-yl) -2H-benzotriazole-5-yl} propanoyloxy] ethyl acrylate, 2- (methacryloyloxy) ethyl 2- ( 6-Hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazole-5 carboxylate, 2- (acryloyloxy) ethyl 2- (6-Hydroxybenzo [1,3] dioxotol-5-yl) -2H-benzotriazole-5-carboxylate, 4- (methacryloyloxy) butyl 2- (6-hydroxybenzo [1,3] dioxotol- 5-yl) -2H-benzotriazole-5-carboxylate, 4- (acryloyloxy) butyl 2- (6-hydroxybenzo [1,3] dioxotol-5-yl) -2H-benzotriazole-5-carboxylate Examples thereof include sesamole-type benzotriazole-based ultraviolet absorbers. The mixing method is not particularly limited, and a method of total compounding, a method of dry blending the masterbatch, a method of total dry blending, and the like can be used.

In the present invention, various additives other than the above-mentioned ultraviolet absorber are added to the layer containing the polycarbonate resin (A) forming the base material layer and / or the layer containing the thermoplastic resin (B) forming the surface layer. Can be mixed and used. Such additives include, for example, antioxidants, anticolorants, antistatic agents, mold release agents, lubricants, dyes, pigments, plasticizers, flame retardants, resin modifiers, compatibilizers, organic fillers and the like. Reinforcing materials such as inorganic fillers can be mentioned. The mixing method is not particularly limited, and a method of total compounding, a method of dry blending the masterbatch, a method of total dry blending, and the like can be used.

The materials of the layer containing the polycarbonate resin (A), the layer containing the thermoplastic resin (B), and the hard coat layer in the present invention, for example, the polycarbonate resin (A) and the thermoplastic resin (B), are filtered. It is preferable that the plastic is filtered and purified by. By purifying or laminating through a filter, it is possible to obtain a resin laminate having few appearance defects such as foreign substances and defects. The filtration method is not particularly limited, and melt filtration, solution filtration, or a combination thereof can be used.

The filter to be used is not particularly limited, and known ones can be used, and are appropriately selected depending on the operating temperature, viscosity and filtration accuracy of each material. The filter medium of the filter is not particularly limited, but is a non-woven fabric of polypropylene, cotton, polyester, viscose rayon or glass fiber or roving yarn roll, phenol resin impregnated cellulose, metal fiber non-woven fabric sintered body, metal powder sintered body, breaker plate, etc. Alternatively, any combination of these can be used. In particular, considering heat resistance, durability, and pressure resistance, a type obtained by sintering a metal fiber non-woven fabric is preferable.

The filtration accuracy of the polycarbonate resin (A) and the thermoplastic resin (B) is 50 μm or less, preferably 30 μm or less, and more preferably 10 μm or less. Further, the filtration accuracy of the hard coat agent is 20 μm or less, preferably 10 μm or less, and more preferably 2 μm or less because it is applied to the outermost surface layer of the resin laminate.

For the filtration of the polycarbonate resin (A) and the thermoplastic resin (B), for example, it is preferable to use the polymer filter used for the thermoplastic resin melt filtration. The polymer filter is classified into a leaf disc filter, a candle filter, a pack disc filter, a cylindrical filter and the like according to its structure, and a leaf disc filter having a large effective filtration area is particularly suitable.

<Thermal bending>
The thermal bending process of the resin laminate of the present invention is not particularly limited. For example, "heat press forming" in which a convex (male type) and concave (female type) molds are attached to a press machine and the heat-softened laminated sheet is sandwiched between the two molds, and the heat-softened laminated sheet and convex type "Vacuum forming" that makes the laminated sheet adhere to the mold by putting the (male type) mold in a vacuum state and finishes it in the desired shape. There is "vacuum forming" in which a laminated sheet is brought into close contact with a mold by applying a large pressure to finish it in a desired shape.

<Thermoformed body>
A resin laminate having a layer containing a thermoplastic resin on a layer containing a polycarbonate resin and having a hard coat layer on the surface of the layer containing the thermoplastic resin is heat-press molded at a low temperature of 120 ° C to 130 ° C. If this is done, cracks may occur in the bent portion of the resin laminate.

On the other hand, since the resin laminate of the embodiment of the present invention uses a specific thermoplastic resin (B), the resin laminate is bent when it is thermoformed at a low temperature (for example, 120 to 130 ° C.). It is possible to obtain a thermoformed body having excellent designability at a low temperature without cracking in the portion.

<Use>
The molded product of the embodiment (for example, a thermoformed product) is a molded product containing the resin laminate of the present invention containing various preferable forms and configurations described above. There are no restrictions on the shape, pattern, color, dimensions, etc. of the molded product, and it may be set arbitrarily according to the intended use.
The resin laminate and the thermoformed body of the embodiment are excellent in thermoforming property at a low temperature (for example, 120 to 130 ° C.), and can suppress the generation of interference fringes. Therefore, it is suitably used as a transparent substrate material, a transparent protective material, and the like. Specifically, portable display devices such as mobile phone terminals, portable electronic play equipment, mobile information terminals, and mobile PCs, and stationary display devices such as notebook PCs, desktop PC LCD monitors, car navigation LCD monitors, and LCD TVs. It can be used as a transparent substrate material such as, and a transparent protective material (for example, a front plate). Among them, a touch panel front protective plate that requires high design, a front for a car navigation system, an OA device, or a portable electronic device. It is suitably used as a face plate.

Hereinafter, the present invention will be specifically described with reference to Examples. However, the present invention is not limited to these examples.

The physical properties of the resin laminates obtained in Examples and Comparative Examples were evaluated as follows.

<Measurement of total light transmittance>
The total light transmittance was measured using a reflection / transmittance meter HR-100 manufactured by Murakami Color Technology Laboratory Co., Ltd.

<Haze measurement>
Haze was measured using COH-400 manufactured by Nippon Denshoku Kogyo Co., Ltd.

<Mole ratio of monomer unit in copolymer>
It was calculated from the measured values of ¹ H-NMR and ¹³ C-NMR (400 MHz: solvent is CDCl ₃ ) using JNM-AL400 manufactured by JEOL Ltd.

<Hydrogenation rate of copolymer>
It was determined by the reduction rate of absorption at 260 nm in the UV spectrum measurement before and after the hydrogenation reaction. Various copolymers were dissolved in tetrahydrofuran at an arbitrary ratio, and the absorbance A1 at the resin concentration C1 before the hydrogenation reaction and the absorbance A2 at the resin concentration C2 after the hydrogenation reaction were calculated from the following formulas. Hydrogenation rate = 100 x [1- (A2 x C1) / (A1 x C2)]

<Glass transition temperature>
A differential scanning calorimetry device DSC6200 manufactured by Seiko Instruments Inc. was used. Nitrogen 30 ml / min. Under circulation, 10 ° C./min. The temperature was raised from 30 ° C to 200 ° C, and then 50 ° C / min. The temperature was lowered from 200 ° C to 30 ° C, and the temperature was changed to 10 ° C / min. The temperature was raised from 30 ° C to 200 ° C. The midpoint glass transition temperature (Tmg) in the second temperature rise was used as the glass transition temperature.

<Pellet appearance>
At the time of pellet preparation, the appearance of the pellet was visually evaluated. The pass / fail judgment of the appearance of the pellet was made according to the following criteria, and 〇 was judged as a pass.
○: Transparent ×: Translucent or cloudy

<Measurement of refractive index>
The measurement was performed with a multi-wavelength Abbe refractometer DR-M2 manufactured by Atago Co., Ltd. The measurement temperature was 20 ° C., the measurement wavelength was 589 nm, and monobromonaphthalene was used as the intermediate solution.

<Pencil scratch hardness test>
In accordance with JIS K 5600-5-4, the hardness of the surface of the hard coat layer on the layer containing the thermoplastic resin (B) near the center of the resin laminate is gradually increased at an angle of 45 degrees and a load of 750 g. The hardness of the hardest pencil that did not cause scars was evaluated as the pencil hardness.

<Interference fringes>
A black tape (black vinyl tape model number 117BLA manufactured by 3M Japan Co., Ltd.) is attached to the layer side of the resin laminate containing the polycarbonate resin (A), and three-wavelength fluorescent light is applied from the surface of the layer containing the thermoplastic resin (B). The interference fringes were evaluated by illuminating with a lamp (Technica Inverter Light 60 AL-60231). The pass / fail judgment of the interference fringes was made according to the following criteria, and 〇 was judged as a pass.
○: Interference fringes are not visible or interference fringes appear weak ×: Interference fringes appear strong

<Hot press molding processability>
A convex type (male type) and a concave type (female type) in which a 1 mmt resin laminate bends to 50 mmR were produced. The resin laminate is preheated at 90 ° C. for 1 minute before molding so that the surface of the thermoplastic resin (B) becomes convex before the hard coat coating and the hard coat surface becomes convex after the hard coat coating. A hot press molded product was produced by placing it in a mold, pressing it at a mold temperature of 120 ° C. for 3 minutes, and naturally cooling it.

<Crack in the bent part>
The cracks in the bent portion of the hot press molded product were visually evaluated. The pass / fail judgment of the crack in the bent part was made according to the following criteria, and 〇 was judged as a pass.
◯: No cracks can be seen in the bent part of the hot press molded body ×: Cracks can be seen in the bent part of the hot press molded body

Polycarbonate resins (A-1)-(A-2), thermoplastic resins (B-1)-(B-2), vinyl copolymers (C-1), and styrene copolymers for the examples. The materials shown below were used as the coalescing (D-1), but are not limited thereto. On the other hand, the styrene copolymers (E-1) to (E-3) shown below were used for comparative production examples, respectively.

<Polycarbonate resin (A-1), styrene copolymer (D-1) and styrene copolymer (E-1) to (E-3)>
Polycarbonate resin (A-1): Iupiron S-1000 manufactured by Mitsubishi Engineering Plastics Co., Ltd. (weight average molecular weight: 33,000, glass transition temperature: 147 ° C, temperature 300 ° C, melt flow rate under 1.2 kg load: 7.5 g / 10 minutes, refractive index 1.59)
Styrene copolymer (D-1): XIBOND140 manufactured by Polyscope (weight average molecular weight: 114,000, glass transition temperature: 134 ° C., (d1) / (d2) = styrene / maleic anhydride = 85 mol% / 15 mol %)
Styrene copolymer (E-1): XIBOND120 manufactured by Polyscoppe (weight average molecular weight: 163,000, glass transition temperature: 116 ° C., (d1) / (d2) = styrene / maleic anhydride = 93 mol% / 7 mol %)
Styrene copolymer (E-2): XIBOND160 manufactured by Polyscoppe (weight average molecular weight: 69,500, glass transition temperature: 147 ° C., (d1) / (d2) = styrene / maleic anhydride = 77 mol% / 23 mol %)
Styrene copolymer (E-3): XIBOND180 manufactured by Polyscope (weight average molecular weight: 50,100, glass transition temperature: 165 ° C., (d1) / (d2) = styrene / maleic anhydride = 66 mol% / 34 mol %)

<Synthesis of polycarbonate resin (A-2)>
Synthesis Example 1 [Synthesis of Polycarbonate Resin Terminator]
Based on the Organic Chemistry Handbook P143-150, esterification by dehydration reaction was performed using 4-hydroxybenzoic acid manufactured by Tokyo Chemical Industry Co., Ltd. and 1-hexadecanol manufactured by Tokyo Chemical Industry Co., Ltd., and hexahydroxybenzoate parahydroxybenzoate. Decylester (CEBP) was obtained.

Synthesis Example 2 [Manufacturing of Polycarbonate Resin (A-2) Pellet]
To 57.2 kg of 9 w / w% sodium hydroxide aqueous solution, 7.1 kg (31.14 mol) of bisphenol A (hereinafter referred to as BPA) manufactured by Nippon Steel Sumitomo Chemical Co., Ltd. and 30 g of hydrosulfite are added and dissolved. did. 40 kg of dichloromethane was added thereto, and 4.33 kg of phosgene was blown over 30 minutes while keeping the solution temperature in the range of 15 ° C. to 25 ° C. with stirring. After the injection of phosgene was completed, 6 kg of 9 w / w% sodium hydroxide aqueous solution, 11 kg of dichloromethane, and 443 g (1.22 mol) of parahydroxybenzoic acid hexadecyl ester (CEBP) as a terminal terminator were dissolved in 10 kg of methylene chloride. The solution was added and vigorously stirred to emulsify. After that, 10 ml of triethylamine was added to the solution as a polymerization catalyst, and the mixture was polymerized for about 40 minutes.
The polymerization solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing with pure water was repeated until the pH of the washing solution became neutral. A polycarbonate resin powder was obtained by evaporating and distilling off an organic solvent from this purified polycarbonate resin solution.
The obtained polycarbonate resin powder was melt-kneaded at a cylinder temperature of 260 ° C. using a twin-screw extruder having a screw diameter of 35 mm, extruded into strands, and pelletized with a pelletizer.
Weight average molecular weight of polycarbonate resin (A-2): 29,000, glass transition temperature: 127 ° C, temperature 300 ° C, melt flow rate under 1.2 kg load: 12.1 g / 10 minutes, refractive index 1.59 Met.

Synthesis Example 3 [Production of Vinyl Copolymer (C-1)]
Purified methyl methacrylate (manufactured by Mitsubishi Gas Chemical Industries, Ltd.) 75,000 mol% and purified styrene (manufactured by Wako Pure Chemical Industries, Ltd.) 24.998 mol% as monomer components, and t-amylperoxy as a polymerization initiator. -2-Ethylhexanoate (manufactured by Alchema Yoshitomi, trade name: Luperox 575) A monomer composition consisting of 0.002 mol% was continuously supplied to a 10 L complete mixing tank with helical ribbon wings at 1 kg / h. Continuous polymerization was carried out at an average residence time of 2.5 hours and a polymerization temperature of 150 ° C. The liquid level in the polymerization tank was continuously withdrawn from the bottom so as to be constant, and introduced into a solvent removing device to obtain a pellet-shaped copolymer. The ratio of the (meth) acrylic acid ester monomer unit (c1) derived from methyl methacrylate in the obtained copolymer was 73 mol%. The weight average molecular weight (standard polystyrene equivalent) measured by gel permeation chromatography was 124,000. This copolymer was dissolved in methyl isobutyrate (manufactured by Kanto Chemical Co., Inc.) to prepare a 10% by mass methyl isobutyrate solution. In a 1000 mL autoclave device, 500 parts by mass of a 10% by mass methyl isobutyrate solution of this polymer and 1 part by mass of 10% by mass Pd / C (manufactured by NE Chemcat) as a hydrogenation catalyst were charged, and the hydrogen pressure was 9 MPa, 200 ° C. The aromatic double bond at the styrene moiety of the copolymer was hydrogenated. The hydrogenation reaction rate of the styrene moiety was 99%. Further, in the obtained vinyl copolymer (C-1), the proportion of the structural unit derived from methyl methacrylate was 73 mol%, and the vinyl copolymer (C-1) had a glass transition temperature of 121 ° C. rice field.

Production Example 1 [Manufacturing of pellets of thermoplastic resin (B-1)]
A phosphorus-based additive PEP-36 (manufactured by ADEKA Co., Ltd.) with respect to 25 parts by mass of the vinyl copolymer (C-1) and 75 parts by mass of the styrene copolymer (D-1) for a total of 100 parts by mass. Add 500 ppm and 0.2% by mass of stearate monoglyceride (product name: H-100, manufactured by RIKEN Vitamin Co., Ltd.), mix for 20 minutes with a blender, and then attach a polymer filter with a mesh opening of 10 μm to a two-screw shaft with a screw diameter of 26 mm. Using an extruder (manufactured by Toshiba Machinery Co., Ltd., TEM-26SS, L / D≈40), the mixture was melt-kneaded at a cylinder temperature of 240 ° C., extruded into strands, and pelletized with a pelletizer. The pellets could be produced stably.
The pellets of the thermoplastic resin (B-1) had an appearance: 〇 (transparent), a glass transition temperature of 131 ° C., and a refractive index of 1.57.

Production Example 2 [Manufacturing of pellets of thermoplastic resin (B-2)]
Phosphorus additive PEP-36 (manufactured by ADEKA Co., Ltd.) for a total of 100 parts by mass of vinyl copolymer (C-1) and 60 parts by mass of styrene copolymer (D-1). 500 ppm and 0.2% by mass of stearate monoglyceride (product name: H-100, manufactured by RIKEN Vitamin Co., Ltd.) were added, and the mixture was mixed and pelletized in the same manner as in Production Example 1. The pellets could be produced stably.
The pellets of the thermoplastic resin (B-2) had an appearance: 〇 (transparent), a glass transition temperature of 129 ° C., and a refractive index of 1.55.

Production Comparative Example 1 [Manufacturing of Pellet of Thermoplastic Resin (F-1)]
A phosphorus-based additive PEP-36 (manufactured by ADEKA Co., Ltd.) with respect to 50 parts by mass of the vinyl copolymer (C-1) and 50 parts by mass of the styrene copolymer (D-1) for a total of 100 parts by mass. 500 ppm and 0.2% by mass of stearate monoglyceride (product name: H-100, manufactured by RIKEN Vitamin Co., Ltd.) were added, and the mixture was mixed and pelletized in the same manner as in Production Example 1. The pellets could be produced stably.
The pellets of the thermoplastic resin (F-1) had an appearance: 〇 (transparent), a glass transition temperature of 128 ° C., and a refractive index of 1.54.

Production Comparative Example 2 [Manufacturing of Pellet of Thermoplastic Resin (F-2)]
A phosphorus-based additive PEP-36 (manufactured by ADEKA Co., Ltd.) with respect to 60 parts by mass of the vinyl copolymer (C-1) and 40 parts by mass of the styrene copolymer (D-1) for a total of 100 parts by mass. 500 ppm and 0.2% by mass of stearate monoglyceride (product name: H-100, manufactured by RIKEN Vitamin Co., Ltd.) were added, and the mixture was mixed and pelletized in the same manner as in Production Example 1. The pellets could be produced stably.
The pellets of the thermoplastic resin (F-2) had an appearance: 〇 (transparent), a glass transition temperature of 127 ° C., and a refractive index of 1.52.

Production Comparative Example 3 [Manufacturing of Pellet of Thermoplastic Resin (F-3)]
A phosphorus-based additive PEP-36 (manufactured by ADEKA Co., Ltd.) with respect to 75 parts by mass of the vinyl copolymer (C-1) and 25 parts by mass of the styrene copolymer (D-1) for a total of 100 parts by mass. 500 ppm and 0.2% by mass of stearate monoglyceride (product name: H-100, manufactured by RIKEN Vitamin Co., Ltd.) were added, and the mixture was mixed and pelletized in the same manner as in Production Example 1. The pellets could be produced stably.
The pellets of the thermoplastic resin (F-3) had an appearance: 〇 (transparent), a glass transition temperature of 125 ° C., and a refractive index of 1.52.

Production Comparative Example 4 [Manufacturing of Pellet of Thermoplastic Resin (F-4)]
Phosphorus additive PEP-36 (manufactured by ADEKA Co., Ltd.) 500 ppm and stearic acid monoglyceride (product name: H-100, manufactured by Riken Vitamin Co., Ltd.) with respect to 100 parts by mass of the vinyl copolymer (C-1). 0.2% by mass was added, and the mixture and pelletization were carried out in the same manner as in Production Example 1. The pellets could be produced stably.
The pellets of the thermoplastic resin (F-4) had an appearance: 〇 (transparent), a glass transition temperature of 121 ° C., and a refractive index of 1.49.

Production Comparative Example 5 [Manufacturing of Pellet of Thermoplastic Resin (F-5)]
Phosphorus additive PEP-36 (manufactured by ADEKA Co., Ltd.) 500 ppm and stearic acid monoglyceride (product name: H-100, manufactured by Riken Vitamin Co., Ltd.) with respect to 100 parts by mass of the styrene copolymer (D-1). 0.2% by mass was added, and the mixture and pelletization were carried out in the same manner as in Production Example 1. The pellets could be produced stably.
The pellets of the thermoplastic resin (F-5) had an appearance: 〇 (transparent), a glass transition temperature: 134 ° C., and a refractive index of 1.59.

Production Comparative Example 6 [Manufacturing of Pellet of Thermoplastic Resin (F-6)]
A phosphorus-based additive PEP-36 (manufactured by ADEKA Co., Ltd.) with respect to 25 parts by mass of the vinyl copolymer (C-1) and 75 parts by mass of the styrene copolymer (E-1) for a total of 100 parts by mass. 500 ppm and 0.2% by mass of stearate monoglyceride (product name: H-100, manufactured by RIKEN Vitamin Co., Ltd.) were added, and the mixture was mixed and pelletized in the same manner as in Production Example 1. The pellets could be produced stably.
The pellets of the thermoplastic resin (F-6) had an appearance: × (white turbidity), a glass transition temperature: two peaks were generated due to incompatibility, and a refractive index: incompatibility was not measurable.

Production Comparative Example 7 [Manufacturing of Pellet of Thermoplastic Resin (F-7)]
A phosphorus-based additive PEP-36 (manufactured by ADEKA Co., Ltd.) with respect to 40 parts by mass of the vinyl copolymer (C-1) and 60 parts by mass of the styrene copolymer (E-1) for a total of 100 parts by mass. 500 ppm and 0.2% by mass of stearate monoglyceride (product name: H-100, manufactured by RIKEN Vitamin Co., Ltd.) were added, and the mixture was mixed and pelletized in the same manner as in Production Example 1. The pellets could be produced stably.
The pellets of the thermoplastic resin (F-7) had an appearance: × (white turbidity), a glass transition temperature: two peaks were generated due to incompatibility, and a refractive index: incompatibility was not measurable.

Production Comparative Example 8 [Manufacturing of pellets of thermoplastic resin (F-8)]
A phosphorus-based additive PEP-36 (manufactured by ADEKA Co., Ltd.) with respect to 25 parts by mass of the vinyl copolymer (C-1) and 75 parts by mass of the styrene copolymer (E-2) for a total of 100 parts by mass. 500 ppm and 0.2% by mass of stearate monoglyceride (product name: H-100, manufactured by RIKEN Vitamin Co., Ltd.) were added, and the mixture was mixed and pelletized in the same manner as in Production Example 1. The pellets could be produced stably.
The pellets of the thermoplastic resin (F-8) had an appearance: × (white turbidity), a glass transition temperature: two peaks were generated due to incompatibility, and a refractive index: incompatibility was not measurable.

Production Comparative Example 9 [Manufacturing of Pellet of Thermoplastic Resin (F-9)]
Phosphorus additive PEP-36 (manufactured by ADEKA Co., Ltd.) for a total of 100 parts by mass of vinyl copolymer (C-1) and 60 parts by mass of styrene copolymer (E-2). 500 ppm and 0.2% by mass of stearate monoglyceride (product name: H-100, manufactured by RIKEN Vitamin Co., Ltd.) were added, and the mixture was mixed and pelletized in the same manner as in Production Example 1. The pellets could be produced stably.
The pellets of the thermoplastic resin (F-9) had an appearance: × (white turbidity), a glass transition temperature: two peaks were generated due to incompatibility, and a refractive index: incompatibility was not measurable.

Production Comparative Example 10 [Manufacturing of Pellet of Thermoplastic Resin (F-10)]
A phosphorus-based additive PEP-36 (manufactured by ADEKA Co., Ltd.) with respect to 25 parts by mass of the vinyl copolymer (C-1) and 75 parts by mass of the styrene copolymer (E-3) for a total of 100 parts by mass. 500 ppm and 0.2% by mass of stearate monoglyceride (product name: H-100, manufactured by RIKEN Vitamin Co., Ltd.) were added, and the mixture was mixed and pelletized in the same manner as in Production Example 1. The pellets could be produced stably.
The pellets of the thermoplastic resin (F-10) had an appearance: × (white turbidity), a glass transition temperature: two peaks were generated due to incompatibility, and a refractive index: incompatibility was not measurable.

Production Comparative Example 11 [Manufacturing of Pellet of Thermoplastic Resin (F-11)]
A phosphorus-based additive PEP-36 (manufactured by ADEKA Co., Ltd.) with respect to 40 parts by mass of the vinyl copolymer (C-1) and 60 parts by mass of the styrene copolymer (E-3) for a total of 100 parts by mass. 500 ppm and 0.2% by mass of stearate monoglyceride (product name: H-100, manufactured by RIKEN Vitamin Co., Ltd.) were added, and the mixture was mixed and pelletized in the same manner as in Production Example 1. The pellets could be produced stably.
The pellets of the thermoplastic resin (F-11) had an appearance: × (white turbidity), a glass transition temperature: two peaks were generated due to incompatibility, and a refractive index: incompatibility was not measurable.

Example 1 [Manufacturing of resin laminate (G-1)]
Each is a multi-layer 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 all extruders, and a 650 mm wide T-die connected to the feed block. A resin laminate was molded using a multi-layer extruder with a multi-manifold die coupled to the extruder. The thermoplastic resin (B-1) obtained in Production Example 1 was continuously introduced into a single-screw extruder having a shaft diameter of 32 mm, and extruded under the conditions of a cylinder temperature of 240 ° C. and a discharge rate of 2.7 kg / h. Further, the polycarbonate resin (A-1) was continuously introduced into a single-screw extruder having a shaft diameter of 65 mm, and the cylinder temperature was 280 ° C. and the discharge amount was 31.8 kg / h. The feed block connected to all extruders was equipped with two types and two layers of distribution pins, and a thermoplastic resin (B-1) and a polycarbonate resin (A-1) were introduced and laminated at a temperature of 270 ° C.
A T-die with a temperature of 270 ° C connected to the tip extrudes it into a sheet, and three mirror-finishing rolls with temperatures of 130 ° C, 140 ° C, and 185 ° C are used to cool the resin while transferring the mirror surface. A resin laminate of (B-1) and a polycarbonate resin (A-1) was obtained. The total thickness of the central portion of the obtained resin laminate was 1000 μm, and the thickness of the surface layer (layer containing the thermoplastic resin (B)) was 80 μm.
Further, on the surface of the thermoplastic resin (B-1) of the resin laminate obtained above, 60 parts by mass of a hexafunctional urethane acrylate oligomer (product name: U6HA, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), PEG200 # diacrylate. (Product name: 4EG-A, manufactured by Kyoeisha Chemical Co., Ltd.) 35 parts by mass, and oligomer containing fluorine-containing group, hydrophilic group, lipophilic group, UV reactive group (product name: RS-90, manufactured by DIC Co., Ltd.) A paint obtained by adding 1% by mass of a photopolymerization initiator (product name: I-184 [compound name: 1-hydroxy-cyclohexylphenylketone] manufactured by BASF Corporation) to a total of 100 parts by mass of 5 parts is added to the bar. The resin laminate (G-1) was prepared by applying with a coater and applying a metal halide lamp (20 mW / cm ² ) for 5 seconds to cure the hard coat. The thickness of the hard coat layer (H-1) was 6 μm.
This resin laminate (G-1) has total light transmittance: 90.9%, Haze: 0.4%, pencil hardness: 2H, interference fringes: 〇, cracks in the bent portion of heat press formability: 〇. there were.

Example 2 [Manufacturing of resin laminate (G-2)]
Instead of the polycarbonate resin (A-1), the polycarbonate resin (A-2) obtained in Synthesis Example 2 was used, and three mirror-finished rolls having temperatures of 110 ° C, 105 ° C, and 110 ° C from the upstream side were used. The hard coat layer (H-1), the thermoplastic resin (B-1), and the polycarbonate resin (B-1) are the same as those of the resin laminate (G-1) of Example 1, except that the mirror surface is transferred and changed to cooling. A resin laminate (G-2) with A-2) was obtained. The total thickness of the central portion of the obtained resin laminate (G-2) was 1006 μm, the surface layer (B-1) thickness was 80 μm, and the hard coat layer (H-1) thickness was 6 μm.
This resin laminate (G-2) has total light transmittance: 90.9%, Haze: 0.4%, pencil hardness: 2H, interference fringes: 〇, cracks in the bent portion of heat press formability: 〇. there were.

Example 3 [Manufacturing of resin laminate (G-3)]
With the hard coat layer (H-1) in the same manner as the resin laminate (G-1) of Example 1 except that the thermoplastic resin (B-2) was used instead of the thermoplastic resin (B-1). A resin laminate (G-3) of a thermoplastic resin (B-2) and a polycarbonate resin (A-1) was obtained. The total thickness of the central portion of the obtained resin laminate (G-3) was 1006 μm, the thickness of the surface layer (B-2) was 80 μm, and the thickness of the hard coat layer (H-1) was 6 μm.
This resin laminate (G-3) has total light transmittance: 90.9%, Haze: 0.3%, pencil hardness: 3H, interference fringes: 〇, cracks in the bent portion of heat press formability: 〇. there were.

Example 4 [Manufacturing of resin laminate (G-4)]
With the hard coat layer (H-1) in the same manner as the resin laminate (G-2) of Example 2 except that the thermoplastic resin (B-2) was used instead of the thermoplastic resin (B-1). A resin laminate (G-4) of a thermoplastic resin (B-2) and a polycarbonate resin (A-2) was obtained. The total thickness of the central portion of the obtained resin laminate (G-4) was 1006 μm, the surface layer (B-2) thickness was 80 μm, and the hard coat layer (H-1) thickness was 6 μm.
This resin laminate (G-4) has total light transmittance: 90.9%, Haze: 0.3%, pencil hardness: 3H, interference fringes: 〇, cracks in the bent portion of heat press formability: 〇. there were.

Comparative Example 1 [Manufacturing of Resin Laminated Body (I-1)]
With the hard coat layer (H-1) in the same manner as the resin laminate (G-1) of Example 1 except that the thermoplastic resin (F-1) was used instead of the thermoplastic resin (B-1). A resin laminate (I-1) of a thermoplastic resin (F-1) and a polycarbonate resin (A-1) was obtained. The total thickness of the central portion of the obtained resin laminate (I-1) was 1006 μm, the surface layer (F-1) thickness was 80 μm, and the hard coat layer (H-1) thickness was 6 μm.
This resin laminate (I-1) has total light transmittance: 91.1%, Haze: 0.3%, pencil hardness: 3H, interference fringes: 〇, cracks in the bent portion of heat press formability: ×. there were.

Comparative Example 2 [Manufacturing of Resin Laminated Body (I-2)]
With the hard coat layer (H-1) in the same manner as the resin laminate (G-2) of Example 2 except that the thermoplastic resin (F-1) was used instead of the thermoplastic resin (B-1). A resin laminate (I-2) of a thermoplastic resin (F-1) and a polycarbonate resin (A-2) was obtained. The total thickness of the central portion of the obtained resin laminate (I-2) was 1006 μm, the surface layer (F-1) thickness was 80 μm, and the hard coat layer (H-1) thickness was 6 μm.
This resin laminate (I-2) has total light transmittance: 91.1%, Haze: 0.3%, pencil hardness: 3H, interference fringes: 〇, cracks in the bent portion of heat press formability: ×. there were.

Comparative Example 3 [Manufacturing of Resin Laminated Body (I-3)]
With the hard coat layer (H-1) in the same manner as the resin laminate (G-1) of Example 1 except that the thermoplastic resin (F-2) was used instead of the thermoplastic resin (B-1). A resin laminate (I-3) of a thermoplastic resin (F-2) and a polycarbonate resin (A-1) was obtained. The total thickness of the central portion of the obtained resin laminate (I-3) was 1006 μm, the surface layer (F-2) thickness was 80 μm, and the hard coat layer (H-1) thickness was 6 μm.
This resin laminate (I-3) has total light transmittance: 91.3%, Haze: 0.3%, pencil hardness: 3H, interference fringes: 〇, cracks in the bent portion of heat press formability: ×. there were.

Comparative Example 4 [Manufacturing of Resin Laminated Body (I-4)]
With the hard coat layer (H-1) in the same manner as the resin laminate (G-2) of Example 2 except that the thermoplastic resin (F-2) was used instead of the thermoplastic resin (B-1). A resin laminate (I-4) of a thermoplastic resin (F-2) and a polycarbonate resin (A-2) was obtained. The total thickness of the central portion of the obtained resin laminate (I-4) was 1006 μm, the surface layer (F-2) thickness was 80 μm, and the hard coat layer (H-1) thickness was 6 μm.
This resin laminate (I-4) has total light transmittance: 91.3%, Haze: 0.3%, pencil hardness: 3H, interference fringes: 〇, cracks in the bent portion of heat press formability: ×. there were.

Comparative Example 5 [Manufacturing of Resin Laminated Body (I-5)]
With the hard coat layer (H-1) in the same manner as the resin laminate (G-1) of Example 1 except that the thermoplastic resin (F-3) was used instead of the thermoplastic resin (B-1). A resin laminate (I-5) of a thermoplastic resin (F-3) and a polycarbonate resin (A-1) was obtained. The total thickness of the central portion of the obtained resin laminate (I-5) was 1006 μm, the surface layer (F-3) thickness was 80 μm, and the hard coat layer (H-1) thickness was 6 μm.
This resin laminate (I-5) has total light transmittance: 91.3%, Haze: 0.3%, pencil hardness: 3H, interference fringes: 〇, cracks in the bent portion of heat press formability: ×. there were.

Comparative Example 6 [Manufacturing of Resin Laminated Body (I-6)]
With the hard coat layer (H-1) in the same manner as the resin laminate (G-2) of Example 2 except that the thermoplastic resin (F-3) was used instead of the thermoplastic resin (B-1). A resin laminate (I-6) of a thermoplastic resin (F-3) and a polycarbonate resin (A-2) was obtained. The total thickness of the central portion of the obtained resin laminate (I-6) was 1006 μm, the surface layer (F-3) thickness was 80 μm, and the hard coat layer (H-1) thickness was 6 μm.
This resin laminate (I-6) has total light transmittance: 91.3%, Haze: 0.3%, pencil hardness: 3H, interference fringes: 〇, cracks in the bent portion of heat press formability: ×. there were.

Comparative Example 7 [Manufacturing of resin laminate (I-7)]
With the hard coat layer (H-1) in the same manner as the resin laminate (G-1) of Example 1 except that the thermoplastic resin (F-4) was used instead of the thermoplastic resin (B-1). A resin laminate (I-7) of a thermoplastic resin (F-4) and a polycarbonate resin (A-1) was obtained. The total thickness of the central portion of the obtained resin laminate (I-7) was 1006 μm, the surface layer (F-4) thickness was 80 μm, and the hard coat layer (H-1) thickness was 6 μm.
This resin laminate (I-7) has total light transmittance: 91.4%, Haze: 0.3%, pencil hardness: 3H, interference fringes: ×, and cracks in the bent portion of heat press formability: ×. there were.

Comparative Example 8 [Manufacturing of resin laminate (I-8)]
With the hard coat layer (H-1) in the same manner as the resin laminate (G-2) of Example 2 except that the thermoplastic resin (F-4) was used instead of the thermoplastic resin (B-1). A resin laminate (I-8) of a thermoplastic resin (F-4) and a polycarbonate resin (A-2) was obtained. The total thickness of the central portion of the obtained resin laminate (I-8) was 1006 μm, the surface layer (F-4) thickness was 80 μm, and the hard coat layer (H-1) thickness was 6 μm.
This resin laminate (I-8) has total light transmittance: 91.4%, Haze: 0.3%, pencil hardness: 3H, interference fringes: ×, and cracks in the bent portion of heat press formability: ×. there were.

Comparative Example 9 [Manufacturing of Resin Laminated Body (I-9)]
With the hard coat layer (H-1) in the same manner as the resin laminate (G-1) of Example 1 except that the thermoplastic resin (F-5) was used instead of the thermoplastic resin (B-1). A resin laminate (I-9) of a thermoplastic resin (F-5) and a polycarbonate resin (A-1) was obtained. The total thickness of the central portion of the obtained resin laminate (I-9) was 1006 μm, the surface layer (F-5) thickness was 80 μm, and the hard coat layer (H-1) thickness was 6 μm.
This resin laminate (I-9) has total light transmittance: 90.7%, Haze: 0.4%, pencil hardness: H, interference fringes: 〇, cracks in the bent portion of heat press formability: ×. there were.

Comparative Example 10 [Manufacturing of Resin Laminated Body (I-10)]
With the hard coat layer (H-1) in the same manner as the resin laminate (G-2) of Example 2 except that the thermoplastic resin (F-5) was used instead of the thermoplastic resin (B-1). A resin laminate (I-10) of a thermoplastic resin (F-5) and a polycarbonate resin (A-2) was obtained. The total thickness of the central portion of the obtained resin laminate (I-10) was 1006 μm, the surface layer (F-5) thickness was 80 μm, and the hard coat layer (H-1) thickness was 6 μm.
This resin laminate (I-10) has a total light transmittance of 90.7%, Haze: 0.4%, pencil hardness: H, interference fringes: 〇, and cracks in the bent portion of heat press formability: ×. there were.

As described above, by satisfying the conditions of the present invention, it is possible to obtain an advantageous effect that a resin laminate having excellent thermoformability at low temperature and having a good appearance suppressing the generation of interference fringes can be obtained.

That is, as shown in Table 2, Production Examples 1 and 2 in which a specific vinyl copolymer (C) and a specific styrene copolymer (D) were blended with respect to the pelletized thermoplastic resin (B). Comparing with Production Comparative Example 4 of the specific vinyl copolymer (C) alone, Production Examples 1 and 2 had a higher refractive index.
Further, Production Comparative Example 6 in which Production Examples 1 and 2 and a specific vinyl copolymer (C) and a styrene copolymer (E) other than the specific styrene copolymer (D) are blended in a specific mass ratio. Comparing with No. 11, Production Examples 1 and 2 were more transparent and had a better appearance.

As shown in Table 3, in the resin laminate after hard coat coating, a specific vinyl copolymer (C) and a specific styrene copolymer (D) are blended in a specific ratio and pelletized with a refractive index. Examples 1 to 4 in which a thermoplastic resin (B) having a high content and a polycarbonate resin (A) are laminated and a hard coat is provided on one side of the thermoplastic resin (B), and a specific vinyl copolymer (C). ) And the specific styrene copolymer (D) are blended at a ratio other than the specific ratio, and the pelletized thermoplastic resin (F) and the polycarbonate resin (A) are laminated to form the thermoplastic resin (F). Comparing with Comparative Examples 1 to 6 having a hard coat on one side surface, the resin laminates of Examples 1 to 4 suppressed cracks in the bent portion during the hot press molding process.
Further, Examples 1 to 4 are laminated with a thermoplastic resin (F) obtained by pelletizing a specific vinyl copolymer (C) alone and a specific polycarbonate resin (A) to obtain a thermoplastic resin (F). Comparing with Comparative Examples 7 to 8 having a hard coat on one side surface, the resin laminates of Examples 1 to 4 have better interference fringes and suppress cracks in the bent portion during hot press molding. rice field.
Further, Examples 1 to 4 are laminated with a thermoplastic resin (F) obtained by pelletizing a specific styrene copolymer (D) alone and a specific polycarbonate resin (A) to obtain a thermoplastic resin (F). Comparing with Comparative Examples 9 to 10 having a hard coat on one side surface, the resin laminates of Examples 1 to 4 had higher pencil hardness and suppressed cracks in the bent portion during hot press molding. ..

Claims (15)

A layer containing a thermoplastic resin (B) is provided on at least one surface of a layer containing a polycarbonate resin (A) containing a polycarbonate resin as a main component, and at least one side surface of the layer containing the thermoplastic resin (B). It is a resin laminate having a hard coat layer in polycarbonate.
The thermoplastic resin (B) contains a vinyl copolymer (C) and a styrene copolymer (D), and the total content of the vinyl copolymer (C) and the styrene copolymer (D) is 100. Based on the mass part, the content of the vinyl copolymer (C) is 20 to 45 parts by mass, and the content of the styrene copolymer (D) is 80 to 55 parts by mass.
The vinyl copolymer (C) has a (meth) acrylic acid ester monomer unit (c1) represented by the following general formula (1) in an amount of 60 to 80 mol% and is represented by the following general formula (2). It is a copolymer containing 40 to 20 mol% of an aliphatic vinyl monomer unit (c2).
The styrene copolymer (D) contains 80 to 90 mol% of a vinyl aromatic monomer unit (d1) and 10 to 20 mol% of a cyclic acid anhydride monomer unit (d2). It is a coalescence,
The resin laminate.

(In the formula, R1 represents a hydrogen atom or a methyl group, and R2 represents an alkyl group having 1 to 18 carbon atoms.)

(In the formula, R3 represents a hydrogen atom or a methyl group, and R4 represents a cyclohexyl group which may have a hydrocarbon substituent having 1 to 4 carbon atoms.) The resin laminate according to claim 1, wherein cracks do not occur after thermoforming to 50 mmR with a hot press machine. The resin laminate according to claim 1 or 2, wherein the thermoplastic resin (B) is a polymer alloy of the vinyl copolymer (C) and the styrene copolymer (D). The vinyl copolymer (C) polymerizes at least one (meth) acrylic acid ester monomer and at least one aromatic vinyl monomer, and then the aromatic vinyl monomer-derived aromatic. The resin laminate according to any one of claims 1 to 3, which is obtained by hydrogenating 70% or more of the double bonds. The resin laminate according to any one of claims 1 to 4, wherein the vinyl aromatic monomer unit (d1) contained in the styrene copolymer (D) is styrene. The resin laminate according to any one of claims 1 to 5, wherein the cyclic acid anhydride monomer unit (d2) contained in the styrene copolymer (D) is maleic anhydride. The invention according to any one of claims 1 to 6, wherein the thickness of the layer containing the thermoplastic resin (B) is 10 to 250 μm, and the total thickness of the resin laminate is in the range of 0.4 to 4.0 mm. Resin laminate. The layer according to any one of claims 1 to 7, wherein at least one layer of the polycarbonate resin (A), the layer containing the thermoplastic resin (B), and the hard coat layer contains an ultraviolet absorber. Resin laminate. The resin laminate according to any one of claims 1 to 8, wherein the hard coat layer is an acrylic hard coat. Any one of claims 1 to 9, wherein one or both sides of the resin laminate is subjected to at least one of fingerprint resistance treatment, antireflection treatment, antiglare treatment, weather resistance treatment, antistatic treatment and antifouling treatment. The resin laminate according to the above. A thermoformed body obtained by thermoforming the resin laminate according to any one of claims 1 to 10. A transparent substrate material comprising the resin laminate according to any one of claims 1 to 10 or the thermoformed body according to claim 11. A transparent protective material comprising the resin laminate according to any one of claims 1 to 10 or the thermoformed body according to claim 11. A touch panel front surface protective plate comprising the resin laminate according to any one of claims 1 to 10 or the thermoformed body according to claim 11. A front plate for a car navigation system, an OA device, or a portable electronic device, comprising the resin laminate according to any one of claims 1 to 10 or the thermoformed body according to claim 11.