WO2017094282A1

WO2017094282A1 - Transparent resin laminate

Info

Publication number: WO2017094282A1
Application number: PCT/JP2016/069856
Authority: WO
Inventors: 正樹平林
Original assignee: 三菱瓦斯化学株式会社; Ｍｇｃフィルシート株式会社
Priority date: 2015-12-01
Filing date: 2016-07-05
Publication date: 2017-06-08
Also published as: CN108290404A; JPWO2017094282A1; TW201736131A; JP6787925B2; TWI740834B; KR20180088681A

Abstract

Provided is a resin laminate which exhibits excellent warping deformation resistance even if exposed to high temperature and high humidity conditions, while having excellent surface hardness. A resin laminate which is obtained by laminating a thermoplastic resin (B) on at least one surface of a polycarbonate resin sheet (A) that is mainly composed of a polycarbonate resin, and which is characterized in that the thermoplastic resin (B) contains either a copolymer (b1) that contains 50-80% by mass of an aromatic vinyl monomer unit, 10-25% by mass of an unsaturated dicarboxylic acid anhydride monomer unit and 5-24% by mass of an acrylic compound monomer unit, with the mass content of the unsaturated dicarboxylic acid anhydride monomer unit being larger than the mass content of the acrylic compound monomer unit, or the copolymer (b1) and an acrylic resin (b2) that contains an acrylic compound monomer unit as a main component.

Description

Transparent resin laminate

The present invention is used for transparent base materials and protective materials, and has a polycarbonate resin layer and a thermoplastic resin layer containing a specific copolymer and a specific acrylic resin, and has excellent surface hardness and high temperature and high temperature. The present invention relates to a resin laminate having excellent warpage and deformation resistance even when exposed to moisture.

Acrylic resin is excellent in surface hardness, transparency, scratch resistance and weather resistance. On the other hand, polycarbonate resin is excellent in impact resistance and the like. Therefore, a laminate having an acrylic resin layer and a polycarbonate resin layer is excellent in surface hardness, transparency, scratch resistance, weather resistance, impact resistance, and the like, and is used for automobile parts, home appliances, electronic devices, and portable information terminals. Used for display windows. However, a laminate having an acrylic resin layer and a polycarbonate resin layer has a problem of warping when used outdoors or in a car under high temperature and high humidity.

In order to solve the above problem, in Patent Document 1 (Japanese Patent Laid-Open No. 2014-198454) and Patent Document 2 (International Publication No. 2015/133530), a vinyl aromatic monomer unit, a methacrylic acid ester monomer unit, A laminate comprising a copolymer comprising a cyclic acid anhydride monomer unit, a layer composed of a resin composition obtained by polymer alloying an acrylic resin, and a layer composed of a polycarbonate resin has been reported. Such a laminate suppresses warpage under high temperature and high humidity of 85 ° C. and 85%, but has a lower surface hardness than an acrylic resin used for polymer alloy, and as a resin laminate used as a substitute for glass in recent years, the surface hardness is low. There may have been insufficient.

JP 2014-198454 A International Publication No. 2015/133530

The present invention provides a resin laminate that can be used as a transparent base material and a transparent protective material, has shape stability that can prevent warpage even in a high-temperature and high-humidity environment, and is excellent in surface hardness. With the goal.

As a result of intensive studies to solve the above problems, the present inventors laminated a thermoplastic resin (B) on at least one surface of a polycarbonate-based resin (A) sheet mainly composed of a polycarbonate resin, This thermoplastic resin (B) has an aromatic vinyl monomer unit of 50 to 80% by mass, an unsaturated dicarboxylic acid anhydride monomer unit of 10 to 25% by mass, and an acrylic compound monomer unit of 5 to 24% by mass. And a copolymer (b1) in which the mass% of unsaturated dicarboxylic acid anhydride monomer units is larger than the mass% of acrylic compound monomer units, or the copolymer (b1 ) And an acrylic resin (b2) containing an acrylic compound monomer unit as a main component, a resin laminate having shape stability under high temperature and high humidity and excellent surface hardness can be obtained. Heading that And it reached the present invention.

That is, the present invention has the characteristics described below.
[1] A resin laminate in which a thermoplastic resin (B) is laminated on at least one surface of a polycarbonate resin (A) sheet mainly composed of a polycarbonate resin,
The thermoplastic resin (B)
It contains 50 to 80% by weight of aromatic vinyl monomer units, 10 to 25% by weight of unsaturated dicarboxylic acid anhydride monomer units, 5 to 24% by weight of acrylic compound monomer units, and The copolymer (b1) contains a copolymer (b1) in which the mass% of the saturated dicarboxylic acid anhydride monomer unit is larger than the mass% of the acrylic compound monomer unit, or the acrylic compound monomer It is a resin laminated body characterized by including the acrylic resin (b2) which contains a unit as a main component.
[2] The copolymer (b1) is 55 to 90 parts by mass based on 100 parts by mass in total of the contents of the copolymer (b1) and the acrylic resin (b2) in the thermoplastic resin (B). The resin (b2) is 45 to 10 parts by mass, and the acrylic resin (b2) containing an acrylic compound monomer unit as a main component contains 80% by mass or more of the acrylic compound monomer unit [1] It is a resin laminated body as described in above.
[3] The copolymer (b1) is 10 to 40 parts by mass based on the total content of the copolymer (b1) and the acrylic resin (b2) in the thermoplastic resin (B) being 100 to 40 parts by mass. The resin (b2) is 90 to 60 parts by mass, and the acrylic resin (b2) containing an acrylic compound monomer unit as a main component contains an acrylic compound monomer unit of less than 80% by mass [1] It is a resin laminated body as described in above.
[4] The resin laminate according to any one of [1] to [3], wherein the thermoplastic resin (B) is a polymer alloy of the copolymer (b1) and the acrylic resin (b2).
[5] When the indentation hardness of the thermoplastic resin (B) is HIT hardness {thermoplastic resin} and the indentation hardness of the acrylic resin (b2) is HIT hardness {acrylic resin}, the HIT hardness {thermoplastic resin} Is a resin divided by HIT hardness {acrylic resin} (HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin}) of 1.01 or more. It is a laminate.
[6] The resin laminate according to any one of [1] to [5], wherein the pencil hardness of the surface of the thermoplastic resin (B) is equal to or greater than the pencil hardness of the surface of the acrylic resin (b2) alone. It is.
[7] The resin laminate according to any one of [1] to [6], wherein the aromatic vinyl monomer unit contained in the copolymer (b1) is styrene.
[8] The resin laminate according to any one of [1] to [7], wherein the unsaturated dicarboxylic acid anhydride monomer unit contained in the copolymer (b1) is maleic anhydride.
[9] The resin laminate according to any one of [1] to [8], wherein the acrylic compound monomer unit contained in the copolymer (b1) is a methacrylic acid ester.
[10] The resin laminate according to any one of [1] to [9], wherein the copolymer (b1) has a weight average molecular weight (Mw) of 50,000 to 300,000.
[11] Any of [1] to [10] above, wherein the thermoplastic resin (B) layer has a thickness of 10 to 250 μm and the total thickness of the resin laminate is in the range of 0.05 to 3.0 mm. It is a resin laminated body of a crab.
[12] The resin laminate according to any one of [1] to [11], wherein the polycarbonate resin (A) has a weight average molecular weight of 25,000 to 75,000.
[13] The resin laminate according to any one of [1] to [12], wherein the resin laminate has a total light transmittance of 75% or more and a Haze of 30% or less.
[14] The resin laminate according to any one of [1] to [13], wherein at least one of the thermoplastic resin (B) layer and the polycarbonate-based resin (A) layer contains an ultraviolet absorber. .
[15] The resin laminate according to any one of [1] to [14], further comprising a hard coat layer on the surface of the thermoplastic resin (B) layer.
[16] One or more of the anti-fingerprint treatment, antireflection treatment, antiglare treatment, weather resistance treatment, antistatic treatment and antifouling treatment are applied to one or both surfaces of the resin laminate. [1] -The resin laminate according to any one of [15].
[17] A transparent substrate material comprising the resin laminate according to any one of [1] to [16].
[18] A transparent protective material comprising the resin laminate according to any one of [1] to [17].
[19] A touch panel front protective plate including the resin laminate according to any one of [1] to [18].
[20] A front plate for an OA device or a portable electronic device, comprising the resin laminate according to any one of [1] to [16].
[21] A resin laminate in which a thermoplastic resin (B) is laminated on at least one surface of a polycarbonate-based resin (A) sheet mainly composed of a polycarbonate resin,
The thermoplastic resin (B)
It contains 50 to 80% by weight of aromatic vinyl monomer units, 10 to 30% by weight of unsaturated dicarboxylic anhydride monomer units, 5 to 25% by weight of acrylic compound monomer units, and The copolymer (b1) contains a copolymer (b1) in which the mass% of the saturated dicarboxylic acid anhydride monomer unit is larger than the mass% of the acrylic compound monomer unit, or the acrylic compound monomer It is a resin laminated body characterized by including the acrylic resin (b2) which contains a unit as a main component.

According to the present invention, there is provided a resin laminate having shape stability such as warpage prevention in a high-temperature and high-humidity environment, and a surface hardness equal to or greater than that of a single acrylic resin, and the resin laminate is a transparent substrate material. Or as a transparent protective material. Specifically, in portable display devices such as mobile phone terminals, portable electronic play equipment, portable information terminals, and mobile PCs, and stationary display devices such as notebook PCs, desktop PC liquid crystal monitors, liquid crystal televisions, etc. It can be suitably used as a front plate for protecting the device.

Hereinafter, the present invention will be described in detail with reference to production examples and examples, but the present invention is not limited to the illustrated production examples and examples, and the scope of the present invention is not greatly deviated. If so, it can be changed to any method.

The present invention relates to a resin laminate in which a thermoplastic resin (B) is laminated on at least one surface of a polycarbonate-based resin sheet (A) containing a polycarbonate resin as a main component, and this thermoplastic resin (B ) Comprises 50-80% by weight of aromatic vinyl monomer units, 10-25% by weight of unsaturated dicarboxylic acid anhydride monomer units, and 5-24% by weight of acrylic compound monomer units, In addition, the copolymer (b1), in which the mass% of the unsaturated dicarboxylic acid anhydride monomer unit is larger than the mass% of the acrylic compound monomer unit, or the copolymer (b1) and the acrylic compound The present invention relates to a resin laminate comprising an acrylic resin (b2) containing a monomer unit as a main component.

<Polycarbonate resin (A)>
The polycarbonate resin (A) used in the present invention is a polycarbonate resin (A) mainly composed of a polycarbonate resin. Here, “having a polycarbonate resin as a main component” means that the content of the polycarbonate resin exceeds 50 mass%. The polycarbonate-based resin (A) preferably contains 75% by mass or more of polycarbonate resin, more preferably 90% by mass or more of polycarbonate resin, and further preferably substantially consists of polycarbonate resin. . The polycarbonate resin (A) contains a carbonate ester bond in the molecular main chain. That is, — [O—R—OCO] — unit (wherein R includes 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) In particular, it is preferable to use a polycarbonate containing a structural unit of the following formula [1]. By using such a polycarbonate, a resin laminate excellent in impact resistance can be obtained.

Specifically, as the polycarbonate resin (A), an aromatic polycarbonate resin (for example, Iupilon S-2000, Iupilon S-1000, Iupilon E-2000 commercially available from Mitsubishi Engineering Plastics Co., Ltd.) is used. Is possible.

In recent years, since there is an increasing demand for bending the front plate, the polycarbonate resin (A) can be synthesized using a monohydric phenol represented by the following formula [2] as a terminal stopper. preferable.

(Wherein R ₁ represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms;
R ₂ to R ₅ each represent hydrogen, halogen, or an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms which may have a substituent. An alkyl group having 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms. )

The monohydric phenol of the general formula [2] is more preferably a monohydric phenol represented by the following formula [3].

(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.)

In general formula [2] or general formula [3], the carbon number of R ₁ is more preferably within a specific numerical range. Specifically, 22 is more preferable as the upper limit value of the carbon number of R ₁ , and 18 is particularly preferable. Moreover, 12 is more preferable as the lower limit of the carbon number of R ₁ .

Among the monohydric phenols (terminal terminators) represented by general formula [2] or general formula [3], either or both of parahydroxybenzoic acid hexadecyl ester and parahydroxybenzoic acid 2-hexyldecyl ester are terminated. It is particularly preferable to use it as an agent.

For example, when R ₁ is a monohydric phenol (termination terminator) having an alkyl group having 16 carbon atoms, glass transition temperature, melt fluidity, moldability, draw-down resistance, monovalent during the production of polycarbonate resin The solvent solubility of phenol is excellent, and it is particularly preferable as a terminal terminator used in the polycarbonate resin used in the present invention.

On the other hand, when the carbon number of R _{1 in} the general formula [2] or the general formula [3] is excessively increased, the solubility of the monohydric phenol (terminal stopper) in the organic solvent tends to decrease, and the polycarbonate resin is produced. Productivity may be reduced.
As an example, if the carbon number of R ₁ is 36 or less, the productivity is high and the economy is good in producing a polycarbonate resin. If the carbon number of R ₁ is 22 or less, monohydric phenol is particularly excellent in organic solvent solubility, and can be very productive in producing a polycarbonate resin, and economical efficiency is also improved.
When the carbon number of R _{1 in} the general formula [2] or the general formula [3] is too small, the glass transition temperature of the polycarbonate resin does not become a sufficiently low value, and the thermoformability may be lowered.

Another resin contained in the polycarbonate resin (A) is a polyester resin. The polyester resin only needs to 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 polyester resin obtained by polycondensation of a glycol component containing 20 to 40 (molar ratio, total 100) of 1,4-cyclohexanedimethanol with respect to ethylene glycol 80 to 60 (molar ratio) as a main component, So-called “PETG” is preferred. The polycarbonate resin (A) may contain a polyester carbonate 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, when the weight average molecular weight is too small, the impact resistance of the resin laminate is lowered, which is not preferable. When the weight average molecular weight is too high, an excessive heat source may be required when laminating the resin 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. Details of the measurement method are shown below.

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

The production method of the polycarbonate-based resin (A) used in the present invention can be appropriately selected depending on the monomers used, such as a known phosgene method (interfacial polymerization method) and transesterification method (melting method).

<Thermoplastic resin (B)>
The thermoplastic resin (B) used in the present invention contains a copolymer (b1) described later, or an acrylic resin (b2) containing the copolymer (b1) and an acrylic compound monomer unit as main components. ). Each component will be described below.

[Copolymer (b1)]
The copolymer (b1) contained in the thermoplastic resin (B) according to the present invention contains 50 to 80% by mass of an aromatic vinyl monomer unit, preferably 50 to 75% by mass, more preferably 50 to 70% by mass. The unsaturated dicarboxylic acid anhydride monomer unit is 10 to 30% by mass, preferably 10 to 25% by mass, more preferably 15 to 25% by mass, and the acrylic compound monomer unit is 5 to 25% by mass, preferably Is a copolymer comprising 5 to 24% by weight, more preferably 8 to 21% by weight, and the unsaturated dicarboxylic acid anhydride monomer unit is more than the acrylic compound monomer unit. b1).

The aromatic vinyl monomer is not particularly limited, and any known aromatic vinyl monomer can be used. From the viewpoint of availability, styrene, α-methylstyrene, o-methylstyrene. M-methylstyrene, p-methylstyrene, t-butylstyrene and the like. Among these, styrene is particularly preferable from the viewpoint of compatibility. Two or more of these aromatic vinyl monomers may be mixed.

Examples of the unsaturated dicarboxylic acid anhydride monomer include maleic acid, itaconic acid, citraconic acid, aconitic acid and other acid anhydrides, and maleic anhydride is preferred from the viewpoint of compatibility with acrylic resins. Two or more of these unsaturated dicarboxylic acid anhydride monomers may be mixed.

In the present specification, “acrylic compound monomer” includes acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid and (meth) acrylic acid ester. Examples of (meth) acrylic acid esters include methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate. It is done. Among these, methyl methacrylate (MMA) is preferable from the viewpoint of compatibility with the acrylic resin. Two or more of these acrylic compound monomers may be mixed.

The weight average molecular weight (Mw) of the copolymer (b1) is preferably 50,000 to 300,000, and more preferably 100,000 to 200,000. When the weight average molecular weight is 50,000 to 300,000, the compatibility with the acrylic resin (b2) is good. In addition, a weight average molecular weight (Mw), a number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) can be measured using the gel permeation chromatography which used THF and chloroform as a solvent.

[Acrylic resin (b2)]
The thermoplastic resin (B) used in the present invention preferably contains an acrylic resin (b2) containing an acrylic compound monomer unit as a main component in addition to the copolymer (b1). Here, “comprising an acrylic compound monomer unit as a main component” means that the content of the acrylic compound monomer unit exceeds 50 mass%. The acrylic resin (b2) preferably contains 60% by mass or more of acrylic compound monomer units, and more preferably contains 75% by mass or more of acrylic compound monomer units. Further, the acrylic resin (b2) may be a homopolymer substantially consisting of an acrylic compound monomer unit or a copolymer containing other monomer units.

Examples of the acrylic compound monomer used in the present invention include acrylonitrile, methacrylonitrile, acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, and methacrylic acid. Examples include (meth) acrylic acid ester monomer units such as ethyl, n-butyl methacrylate, and 2-ethylhexyl methacrylate, and methyl methacrylate is particularly preferable. The acrylic resin (b2) may be a polymer obtained by homopolymerizing these monomer units, but may also be a copolymer containing two or more types of monomer units.

The acrylic resin (b2) may be a copolymer containing a monomer other than the acrylic compound monomer as long as the acrylic compound monomer is the main component. The monomer other than the acrylic compound monomer is not particularly limited, but an unsaturated dicarboxylic acid anhydride monomer such as an acid anhydride such as maleic acid, itaconic acid, citraconic acid, and aconitic acid, Aromatic vinyl monomers such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide N-substituted maleimides such as N-arylmaleimide, N-naphthylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, N-tribromophenylmaleimide, etc. Examples include a polymer. Examples of the copolymer containing such a monomer include 16% by mass of an aromatic vinyl monomer unit, 8% by mass of an unsaturated dicarboxylic acid anhydride monomer unit, and an acrylic compound monomer unit. Copolymer containing 76% by mass, copolymer containing 4% by mass of aromatic vinyl monomer units, 15% by mass of N-substituted maleimide monomer units, and 81% by mass of acrylic compound monomer units. Coalescence etc. can be used.

In the present invention, the weight-average molecular weight of the acrylic resin (b2) containing an acrylic compound monomer unit as a main component is easy to mix (disperse) with the copolymer (b1), and the heat of these polymer alloys. It is determined by the ease of production of the plastic resin (B) layer. That is, if the weight average molecular weight of the acrylic resin (b2) containing the acrylic compound monomer unit as a main component is too large, the difference in melt viscosity between the acrylic resin (b2) and the copolymer (b1) becomes too large. The mixing (dispersing) of the polymer becomes worse, and the transparency of the polymer-alloyed thermoplastic resin (B) layer may be deteriorated, or a problem that stable melt-kneading cannot be continued may occur. On the contrary, if the weight average molecular weight of the acrylic resin (b2) containing the acrylic compound monomer unit as a main component is too small, the strength of the polymer-alloyed thermoplastic resin (B) layer is lowered. There is a possibility that a problem such as a decrease in impact resistance of the steel may occur. The weight average molecular weight of the acrylic resin (b2) containing an acrylic compound monomer unit as a main component is preferably in the range of 50,000 to 700,000, and more preferably in the range of 60,000 to 550,000. More preferably, it is in the range of 70,000 to 500,000.

On the basis of the total content of the copolymer (b1) and the acrylic resin (b2) being 100 parts by mass, the copolymer (b1) is 5 to 100 parts by mass and the acrylic resin (b2) is 95 to 0 parts by mass. Part. More preferably, the acrylic resin (b2) is 90 to 0 parts by mass with respect to 10 to 100 parts by mass, and still more preferably the acrylic resin (b2) with respect to 10 to 95 parts by mass of the copolymer (b1). ) Is 90 to 5 parts by mass. When the acrylic resin (b2) containing an acrylic compound monomer unit as a main component contains less than 80% by mass of an acrylic compound monomer unit, the copolymer (b1) is acrylic with respect to 10 to 40 parts by mass. More preferably, the resin (b2) is 90 to 60 parts by mass. Further, when the acrylic resin (b2) containing the acrylic compound monomer unit as a main component contains 80% by mass or more of the acrylic compound monomer unit, the copolymer (b1) is 55 to 90 parts by mass. The acrylic resin (b2) is more preferably 45 to 10 parts by mass. By making it within this weight ratio, thermoplasticity having a surface hardness equal to or higher than that of the acrylic resin (b2) alone and having shape stability such as warpage prevention in a high temperature and high humidity environment while maintaining transparency. Resin (B).

[Polymer alloy of copolymer and acrylic resin]
In the present invention, the thermoplastic resin (B) is preferably a polymer alloy of a copolymer (b1) and an acrylic resin (b2). Here, the polymer alloy refers to a composite material obtained by mixing two or more kinds of polymers. Such a polymer alloy can be obtained by mechanical mixing, melt mixing, or solution mixing of polymers. When the polymer alloy is formed, the content of the copolymer (b1) and the acrylic resin (b2) is such that the copolymer (b1) is 5 parts by mass or more and less than 100 parts by mass with respect to 100 parts by mass in total. Yes, the acrylic resin (b2) is more than 0 parts by mass and 95 parts by mass or less. Preferably, the copolymer (b1) is 10 parts by mass or more and less than 100 parts by mass, and the acrylic resin (b2) is more than 0 part by mass and 90 parts by mass or less. More preferably, the acrylic resin (b2) is 90 to 5 parts by mass with respect to the copolymer (b1) of 10 to 95 parts by mass. When the acrylic resin (b2) containing an acrylic compound monomer unit as a main component contains less than 80% by mass of an acrylic compound monomer unit, the copolymer (b1) is acrylic with respect to 10 to 40 parts by mass. More preferably, the resin (b2) is 90 to 60 parts by mass. Further, when the acrylic resin (b2) containing the acrylic compound monomer unit as a main component contains 80% by mass or more of the acrylic compound monomer unit, the copolymer (b1) is 55 to 90 parts by mass. The acrylic resin (b2) is more preferably 45 to 10 parts by mass.

The hardness of the thermoplastic resin (B) can be evaluated by indentation hardness and pencil hardness. When the indentation hardness of the thermoplastic resin (B) is HIT hardness {thermoplastic resin} and the indentation hardness of the acrylic resin (b2) is HIT hardness {acrylic resin}, the HIT hardness {thermoplastic resin} is HIT hardness. The value divided by {acrylic resin} (HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin}) is preferably 1.01 or more, and more preferably 1.04 or more. The pencil hardness of the thermoplastic resin (B) is preferably equal to or higher than the pencil hardness of the acrylic resin (b1) alone.

<Various material manufacturing methods>
The method for producing the synthetic resin laminate of the present invention is not particularly limited. For example, a method of laminating a separately formed thermoplastic resin layer (B) and a polycarbonate resin layer (A) and thermocompression bonding the two, a separately formed thermoplastic resin layer (B) and a polycarbonate resin layer A method of laminating (A) and bonding them together with an adhesive, a method of co-extrusion molding of a thermoplastic resin (B) layer and a polycarbonate-based resin (A) layer, a thermoplastic resin formed in advance There are various methods such as a method of in-mold molding and integrating the polycarbonate resin (A) using the (B) layer, but from the viewpoint of production cost and productivity, a method of co-extrusion molding is preferable. .

In the present invention, the production method of 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 by a machine such as a roll, a brabender, a single screw extruder, a twin screw extruder, or a pressure kneader can be applied.

<Resin laminate>
In the present invention, the thickness of the thermoplastic resin (B) layer affects the surface hardness and impact resistance of the resin laminate. That is, when the thickness of the thermoplastic resin (B) layer is too thin, the surface hardness is lowered, which is not preferable. If the thickness of the thermoplastic resin (B) layer is too large, the impact resistance deteriorates, which is not preferable. The thickness of the thermoplastic resin (B) layer is preferably 10 to 250 μm, more preferably 30 to 200 μm. More preferably, it is 60 to 150 μm.

In the present invention, the total thickness of the resin laminate (sheet), the thickness of the thermoplastic resin (B) layer, and the composition of the thermoplastic resin (B) layer are warped in a high temperature and high humidity environment of the resin laminate. Affect. In other words, if the overall thickness is too thin, the warpage in a high-temperature and high-humidity environment increases. Further, if the thickness of the thermoplastic resin (B) layer is too thin, warpage in a high-temperature and high-humidity environment is reduced, but the hardness is reduced. When the thermoplastic resin (B) layer is thick, Since the warpage in the environment increases, the weight ratio of the copolymer (b1) and the acrylic resin (b2) of the thermoplastic resin (B) layer matched to the total thickness of each and the thickness of the thermoplastic resin (B) layer is set. Need to find out. Specifically, the total thickness of the polycarbonate resin (A) layer and the thermoplastic resin (B) layer is preferably 0.05 to 3.0 mm, more preferably 0.1 to 2.0 mm, still more preferably 0.00. 12 to 1.5 mm.

In the present invention, from the appearance of the resin laminate (sheet), the total light transmittance is preferably 75% or more, more preferably 80% or more, and still more preferably 85% or more. The upper limit of the total light transmittance is preferably 95%. The haze of the resin laminate (sheet) is preferably 30% or less, more preferably 25% or less, and still more preferably 20% or less. The lower limit of Haze is preferably 0.1%.

<Optional additives>
In the present invention, the polycarbonate-based resin (A) that forms the base layer and / or the thermoplastic resin (B) that forms the surface layer can contain components other than the main components described above.

For example, a polycarbonate resin (A) and / or a thermoplastic resin (B) can be used by mixing an ultraviolet absorber. If the content of the UV absorber is too high, depending on the molding method, excessive UV absorber may be scattered due to the high temperature applied, which may cause problems because it contaminates the molding environment. Accordingly, the content of the ultraviolet absorber is preferably 0 to 5% by mass, more preferably 0 to 3% by mass, and 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, 2-hydroxy -4-octadecyloxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, etc. Benzophenone UV absorber, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole, 2- (2-hydroxy-3 -T-Butyl-5-methylphenyl) benzotriazo , Benzotriazole ultraviolet absorbers such as (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, phenyl salicylate, 2,4-di-t-butyl Benzoate UV absorbers such as phenyl-3,5-di-t-butyl-4-hydroxybenzoate, and hindered amine UV absorbers such as bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-ethoxyphenyl) -1,3 , 5-triazine, 2,4-diphenyl- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-dipheni -(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)- Examples include triazine-based ultraviolet absorbers such as 1,3,5-triazine. The method of mixing is not particularly limited, and a method of compounding the whole amount, a method of dry blending the master batch, a method of dry blending the whole amount, and the like can be used.

In the present invention, the polycarbonate resin (A) for forming the base material layer and / or the thermoplastic resin (B) for forming the surface layer may be used by mixing various additives in addition to the ultraviolet absorber. Can do. Examples of such additives include antioxidants and anti-coloring agents, antistatic agents, mold release agents, lubricants, dyes, pigments, plasticizers, flame retardants, resin modifiers, compatibilizers, organic fillers, Examples thereof include reinforcing materials such as inorganic fillers. The method of mixing is not particularly limited, and a method of compounding the whole amount, a method of dry blending the master batch, a method of dry blending the whole amount, and the like can be used.

<Arbitrary processing>
In the present invention, the surface of the thermoplastic resin (B) layer or the surface of the polycarbonate resin (A) layer may be subjected to a hard coat treatment. For example, the hard coat layer is formed by a hard coat process using a hard coat paint that is cured using thermal energy and / or light energy. Examples of the hard coat paint that is cured using thermal energy include polyorganosiloxane-based and cross-linked acrylic-based thermosetting resin compositions. In addition, as a hard coat paint that is cured using light energy, for example, a photocurable resin in which a photopolymerization initiator is added to a resin composition composed of monofunctional and / or polyfunctional acrylate monomers and / or oligomers. Examples thereof include a composition.

Examples of the hard coat paint to be cured using light energy applied on the surface of the thermoplastic resin (B) layer or the surface of the polycarbonate resin (A) layer in the present invention include 1,9-nonanediol diacrylate. Bifunctional or higher polyfunctional (meth) acrylate monomer and bifunctional or higher polyfunctional urethane (meth) acrylate oligomer and / or bifunctional or higher that can be copolymerized with 20 to 60% by mass and 1,9-nonanediol diacrylate The photopolymerization initiator is contained in 100 parts by mass of a resin composition comprising 40 to 80% by mass of a compound comprising a polyfunctional polyester (meth) acrylate oligomer and / or a polyfunctional epoxy (meth) acrylate oligomer having two or more functions. Examples thereof include a photocurable resin composition to which 10 parts by mass is added.

The method for applying the hard coat paint in the present invention is not particularly limited, and a known method can be used. Examples include spin coating, dipping, spraying, slide coating, bar coating, roll coating, gravure coating, meniscus coating, flexographic printing, screen printing, beat coating, and blurring. .

In order to improve the adhesion of the hard coat, pretreatment of the coated surface may be performed before the hard coat. Examples of treatment include known methods such as 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 thermoplastic resin (B) layer, the polycarbonate resin (A) layer, and the hard coat materials in the present invention, for example, the thermoplastic resin (B) and the polycarbonate resin (A) are filtered and purified by filtering. It is preferable. By producing or laminating through a filter, it is possible to obtain a synthetic resin laminate having few appearance defects such as foreign matters and defects. There is no restriction | limiting in particular in the filtration method, Melt filtration, solution filtration, or those combinations can be used.

The filter to be used is not particularly limited, and known filters can be used, and are appropriately selected depending on the use temperature, viscosity, and filtration accuracy of each material. The filter medium is not particularly limited, but polypropylene, cotton, polyester, viscose rayon or glass fiber nonwoven fabric or roving yarn roll, phenol resin impregnated cellulose, metal fiber nonwoven fabric sintered body, metal powder sintered body, breaker plate, Alternatively, any combination of these can be used. In view of heat resistance, durability, and pressure resistance, a type in which a metal fiber nonwoven fabric is sintered is preferable.

The filtration accuracy for the polycarbonate resin (A) is 50 μm or less, preferably 30 μm or less, and more preferably 10 μm or less. The filtration accuracy of the hard coat agent is 20 μm or less, preferably 10 μm or less, and more preferably 5 μm or less because it is applied to the outermost layer of the resin laminate.

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

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

Hereinafter, the present invention will be specifically described by way of examples. However, this invention is not restrict | limited at all by these Examples.

Measurement of physical properties of the laminated resin obtained in the production examples and evaluation of the synthetic resin laminated bodies obtained in the examples and comparative examples were performed as follows.

<Indentation hardness (HIT hardness)>
Using an ultra-micro hardness meter HM2000 (manufactured by Fischer Instruments Co., Ltd.), it was pressed against the thermoplastic resin (B) layer under a pressing pressure of 3 mN, and the HIT hardness (N / mm ² ) was measured. As a comparison object, the indentation hardness was similarly measured for a layer (Comparative Example 5 or Comparative Example 8 described later) formed of the acrylic resin (b2) alone. Then, the indentation hardness of the thermoplastic resin (B) was HIT hardness {thermoplastic resin}, and the indentation hardness of the acrylic resin (b2) was HIT hardness {acrylic resin}. At that time, when the thermoplastic resin (B) layer is a layer containing the copolymer (b1) and the acrylic resin (b2), the indentation hardness of the acrylic resin (B2-1 or B2-2) used is used. And evaluated. Further, when the thermoplastic resin (B) layer was composed only of the copolymer (b1), it was evaluated using the indentation hardness of the acrylic resin (B2-1).
○ (Pass): HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} ≧ 1.01
X (fail): Outside the above range

<Pencil scratch hardness test>
In accordance with JIS K 5600-5-4, a layer formed of a thermoplastic resin (B) layer or an acrylic resin (b2) alone at an angle of 45 degrees with respect to the surface and a load of 750 g (Comparative Example 5 or Comparative Example 8 described later) ) The hardness was gradually increased on the surface and the pencil was pressed, and the hardness of the hardest pencil that did not cause scars was evaluated as the pencil hardness. The pencil hardness is indicated by 2B, B, HB, F, H, 2H, 3H, and 4H in order of rank. Here, “the pencil hardness of the surface of the thermoplastic resin (B) is equal to or higher than the pencil hardness of the surface of the acrylic resin (b2) alone” means that the pencil hardness of the surface of the thermoplastic resin (B) is the surface of the acrylic resin (b2) alone. It means that it is the same rank as pencil hardness or higher than that. For example, when the pencil hardness of the surface of the acrylic resin (b2) is 2H, the pencil hardness of the surface of the thermoplastic resin (B) is 2H or 3H or more.
○ (Pass): The pencil hardness on the surface of the thermoplastic resin (B) is equal to or higher than the pencil hardness on the surface of the acrylic resin (b2) × (Fail): Other than the above range

<Warp test under high temperature and high humidity>
A test piece of the resin laminate was cut into a 10 cm × 6 cm square. The test piece was set in a two-point support type holder, placed in an environmental testing machine set at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours or more, and after adjusting the state, the warpage was measured. The value at this time was taken as the value of the amount of warp before processing. Next, the test piece was set in a holder, put into an environmental test machine set at a temperature of 85 ° C. and a relative humidity of 85%, and kept in that state for 120 hours. Further, the holder was moved into an environmental testing machine set to a temperature of 23 ° C. and a relative humidity of 50%, and the warpage was measured again after being held in that state for 4 hours. The value at this time was taken as the value of the warp amount after processing. To measure the warpage, use a 3D shape measuring machine equipped with an electric stage. Place the removed specimen horizontally in a convex state, scan it at 1 mm intervals, and measure the bulge at the center as a warp. did. The absolute value of the difference between the warpage amounts before and after the treatment, that is, | (warping amount after processing) − (warping amount before processing) || was evaluated as the amount of warpage change. At that time, if the amount of warpage change exceeds 700 μm, the warpage may be recognized even with the naked eye.
○ (Pass): Warpage change amount of resin laminate ≦ 700 μm
X (fail): Outside the above range

<Total light transmittance measurement>
The total light transmittance of the resin laminate was measured according to JIS K7361-1, using a reflection / transmittance meter HR-100 (manufactured by Murakami Color Research Laboratory Co., Ltd.), and the total light transmittance test was performed according to the following criteria. A pass / fail decision was made.
○ (Pass): Total light transmittance of the resin laminate ≧ 75%
X (fail): Outside the above range

<Haze measurement>
Using a reflection / transmittance meter HR-100 (manufactured by Murakami Color Research Laboratory Co., Ltd.), the haze of the resin laminate was measured according to JIS K7136, and the pass / fail judgment of the haze test was performed based on the following criteria.
○ (Pass): Haze ≦ 30% of resin laminate
X (fail): Outside the above range

<Examples of various materials>
Examples of the polycarbonate resin (A), the copolymer (b1), and the acrylic resin (b2) include the following materials, but are not limited thereto.
A-1: Polycarbonate resin: Iupilon E-2000 manufactured by Mitsubishi Engineering Plastics Co., Ltd.
b1-1: Copolymer: KX-406 manufactured by Denka Co., Ltd.
b1-2: Copolymer: KX-407 manufactured by Denka Co., Ltd.
b1-3: Copolymer: KX-422 manufactured by DENKA CORPORATION
b1-4: Copolymer: KX-435 manufactured by Denka Co., Ltd.
b1-5: Copolymer: R100 manufactured by DENKA CORPORATION
b1-6: Copolymer: R200 manufactured by DENKA CORPORATION
b2-1: Acrylic resin: Methyl methacrylate resin manufactured by Kuraray Co., Ltd. Parapet HR-L (HIT hardness {acrylic resin} = 269 N / mm ² )
b2-2: Acrylic resin: Acrylic resin manufactured by Asahi Kasei Chemicals Corporation Delpet PM120N (styrene: N-phenylmaleimide: MMA ratio by mass = 4: 15: 81, HIT hardness {acrylic resin} = 274 N / mm ² .)
b2-3: Acrylic resin: Acrylic resin manufactured by Asahi Kasei Chemicals Corporation Delpet 980N (mass ratio of styrene: maleic anhydride: MMA = 16: 8: 76, HIT hardness {acrylic resin} = 266 N / mm ² . )
b2-4: Acrylic resin: acrylic resin PLEXIGLAS hw55 (mass ratio of styrene: maleic anhydride: MMA = 15: 9: 76, HIT hardness {acrylic resin} = 266 N / mm ² )

Production Example 1 [Production of Resin (B11) Pellets]
25 parts by mass of KX-406 (b1-1) (weight average molecular weight: 155,000, mass ratio of styrene: maleic anhydride: MMA = 69: 22: 9) as copolymer (b1) and acrylic resin ( b2) 500 ppm of phosphorus-based additive PEP-36 (manufactured by ADEKA Corporation) and stearic acid monoglyceride (based on 75 parts by mass of parapet HR-L (b2-1) as methyl methacrylate resin) (Product name: H-100, manufactured by Riken Vitamin Co., Ltd.) After adding 0.2% by mass and mixing with a blender for 20 minutes, a twin screw extruder with a screw diameter of 26 mm (Toshiba Machine Co., Ltd., TEM-26SS, L / D) ≈40), melt kneaded at a cylinder temperature of 240 ° C., extruded into a strand, and pelletized with a pelletizer. The pellets could be manufactured stably.

Production Example 2 [Production of Resin (B12) Pellets]
100 parts by mass in total of 50 parts by mass of KX-406 (b1-1) as copolymer (b1) and 50 parts by mass of parapet HR-L (b2-1) as methyl methacrylate resin as acrylic resin (b2) The phosphorus-based additive PEP36 500 ppm and stearic acid monoglyceride 0.2% by mass were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Production Example 3 [Production of Resin (B13) Pellets]
100 parts by mass in total of 75 parts by mass of KX-406 (b1-1) as copolymer (b1) and 25 parts by mass of parapet HR-L (b2-1) as methyl methacrylate resin as acrylic resin (b2) The phosphorus-based additive PEP36 500 ppm and stearic acid monoglyceride 0.2% by mass were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Production Example 4 [Production of Resin (B14) Pellets]
Phosphoric additive PEP36 (500 ppm) and stearic acid monoglyceride (0.2 mass%) were added to 100 parts by mass of KX-406 (b1-1) as copolymer (b1), and mixed and pelleted in the same manner as in Production Example 1. Made. The pellets could be manufactured stably.

Production Example 5 [Production of Resin (B15) Pellets]
A total of 100 parts by mass of 25 parts by mass of KX-406 (b1-1) as copolymer (b1) and 75 parts by mass of Delpet 980N (b2-3) as methyl methacrylate resin as acrylic resin (b2) On the other hand, 500 ppm of phosphorus-based additive PEP36 and 0.2% by mass of stearic acid monoglyceride were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Production Example 6 [Production of Resin (B16) Pellets]
40 parts by mass of KX-406 (b1-1) as copolymer (b1) and 60 parts by mass of Delpet 980N (b2-3) as methyl methacrylate resin as acrylic resin (b2) On the other hand, 500 ppm of phosphorus-based additive PEP36 and 0.2% by mass of stearic acid monoglyceride were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Production Example 7 [Production of Resin (B17) Pellets]
A total of 100 parts by mass of 50 parts by mass of KX-406 (b1-1) as the copolymer (b1) and 50 parts by mass of Delpet 980N (b2-3) as the methyl methacrylate resin as the acrylic resin (b2) On the other hand, 500 ppm of phosphorus-based additive PEP36 and 0.2% by mass of stearic acid monoglyceride were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Production Example 8 [Production of resin (B18) pellets]
A total of 100 parts by mass of 60 parts by mass of KX-406 (b1-1) as copolymer (b1) and 40 parts by mass of Delpet 980N (b2-3) as methyl methacrylate resin as acrylic resin (b2) On the other hand, 500 ppm of phosphorus-based additive PEP36 and 0.2% by mass of stearic acid monoglyceride were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Production Example 9 [Production of Resin (B19) Pellets]
For a total of 100 parts by mass of 25 parts by mass of KX-406 (b1-1) as copolymer (b1) and 75 parts by mass of PLEXIGLAS hw55 (b2-4) as methyl methacrylate resin as acrylic resin (b2) Then, phosphorus-based additive PEP36 (500 ppm) and stearic acid monoglyceride (0.2% by mass) were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Production Example 10 [Production of Resin (B20) Pellets]
For a total of 100 parts by mass of 40 parts by mass of KX-406 (b1-1) as copolymer (b1) and 60 parts by mass of PLEXIGLAS hw55 (b2-4) as methyl methacrylate resin as acrylic resin (b2) Then, phosphorus-based additive PEP36 (500 ppm) and stearic acid monoglyceride (0.2% by mass) were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Production Example 11 [Production of Resin (B21) Pellets]
For a total of 100 parts by mass of 50 parts by mass of KX-406 (b1-1) as copolymer (b1) and 50 parts by mass of PLEXIGLAS hw55 (b2-4) as methyl methacrylate resin as acrylic resin (b2) Then, phosphorus-based additive PEP36 (500 ppm) and stearic acid monoglyceride (0.2% by mass) were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Production Example 12 [Production of resin (B22) pellets]
For a total of 100 parts by mass of 60 parts by mass of KX-406 (b1-1) as the copolymer (b1) and 40 parts by mass of PLEXIGLAS hw55 (b2-4) as the methyl methacrylate resin as the acrylic resin (b2) Then, phosphorus-based additive PEP36 (500 ppm) and stearic acid monoglyceride (0.2% by mass) were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Production Example 13 [Production of Resin (B23) Pellets]
25 parts by mass of KX-407 (b1-2) (weight average molecular weight: 165,000, mass ratio of styrene: maleic anhydride: MMA = 57: 23: 20) as copolymer (b1) and acrylic resin ( b2) To 100 parts by mass of 75 parts by mass of parapet HR-L (b2-1) as methyl methacrylate resin, 500 ppm of phosphorus-based additive PEP36 and 0.2% by mass of stearic acid monoglyceride were added to produce Mixing and pelletization were carried out in the same manner as in Example 1. The pellets could be manufactured stably.

Production Example 14 [Production of Resin (B24) Pellets]
100 parts by mass in total of 50 parts by mass of KX-407 (b1-2) as copolymer (b1) and 50 parts by mass of parapet HR-L (b2-1) as methyl methacrylate resin as acrylic resin (b2) The phosphorus-based additive PEP36 500 ppm and stearic acid monoglyceride 0.2% by mass were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Production Example 15 [Production of resin (B25) pellets]
100 parts by mass in total of 75 parts by mass of KX-407 (b1-2) as copolymer (b1) and 25 parts by mass of parapet HR-L (b2-1) as methyl methacrylate resin as acrylic resin (b2) The phosphorus-based additive PEP36 500 ppm and stearic acid monoglyceride 0.2% by mass were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Production Example 16 [Production of resin (B26) pellets]
To 100 parts by mass of KX-407 (b1-2) as copolymer (b1), 500 ppm of phosphorus-based additive PEP36 and 0.2% by mass of stearic acid monoglyceride were added and mixed in the same manner as in Production Example 1. Pelletization was performed. The pellets could be manufactured stably.

Production Example 17 [Production of Resin (B27) Pellets]
25 parts by mass of KX-422 (b1-3) (weight average molecular weight: 119,000, mass ratio of styrene: maleic anhydride: MMA = 57: 23: 20) as copolymer (b1) and acrylic resin ( b2) To 100 parts by mass of 75 parts by mass of parapet HR-L (b2-1) as methyl methacrylate resin, 500 ppm of phosphorus-based additive PEP36 and 0.2% by mass of stearic acid monoglyceride were added to produce Mixing and pelletization were carried out in the same manner as in Example 1. The pellets could be manufactured stably.

Production Example 18 [Production of resin (B28) pellets]
100 parts by mass in total of 50 parts by mass of KX-422 (b1-3) as copolymer (b1) and 50 parts by mass of parapet HR-L (b2-1) as methyl methacrylate resin as acrylic resin (b2) The phosphorus-based additive PEP36 500 ppm and stearic acid monoglyceride 0.2% by mass were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Production Example 19 [Production of resin (B29) pellets]
100 parts by mass in total of 55 parts by mass of KX-422 (b1-3) as copolymer (b1) and 45 parts by mass of parapet HR-L (b2-1) as methyl methacrylate resin as acrylic resin (b2) The phosphorus-based additive PEP36 500 ppm and stearic acid monoglyceride 0.2% by mass were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Production Example 20 [Production of resin (B30) pellets]
100 parts by mass in total of 60 parts by mass of KX-422 (b1-3) as copolymer (b1) and 40 parts by mass of parapet HR-L (b2-1) as methyl methacrylate resin as acrylic resin (b2) The phosphorus-based additive PEP36 500 ppm and stearic acid monoglyceride 0.2% by mass were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Production Example 21 [Production of Resin (B31) Pellets]
100 parts by mass in total of 65 parts by mass of KX-422 (b1-3) as copolymer (b1) and 35 parts by mass of parapet HR-L (b2-1) as methyl methacrylate resin as acrylic resin (b2) The phosphorus-based additive PEP36 500 ppm and stearic acid monoglyceride 0.2% by mass were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Production Example 22 [Production of resin (B32) pellets]
100 parts by mass in total of 75 parts by mass of KX-422 (b1-3) as copolymer (b1) and 25 parts by mass of parapet HR-L (b2-1) as methyl methacrylate resin as acrylic resin (b2) The phosphorus-based additive PEP36 500 ppm and stearic acid monoglyceride 0.2% by mass were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Production Example 23 [Production of resin (B33) pellet]
Phosphorous additive PEP36 500 ppm and stearic acid monoglyceride 0.2% to 100 parts by mass of KX-422 (b1-3) as copolymer (b1), mixed and pelletized in the same manner as in Production Example 1. Went. The pellets could be manufactured stably.

Production Example 24 [Production of Resin (B34) Pellets]
Phosphorus based on a total of 100 parts by mass of 50 parts by mass of KX-422 (b1-3) as copolymer (b1) and 50 parts by mass of Delpet PM120N (b2-2) as acrylic resin (b2) Additive PEP36 500 ppm and stearic acid monoglyceride 0.2% by mass were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Production Example 25 [Production of resin (B35) pellets]
Phosphorus based on a total of 100 parts by mass of 55 parts by mass of KX-422 (b1-3) as copolymer (b1) and 45 parts by mass of Delpet PM120N (b2-2) as acrylic resin (b2) Additive PEP36 500 ppm and stearic acid monoglyceride 0.2% by mass were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Production Example 26 [Production of resin (B36) pellets]
Phosphorus based on a total of 100 parts by mass of 60 parts by mass of KX-422 (b1-3) as copolymer (b1) and 40 parts by mass of Delpet PM120N (b2-2) as acrylic resin (b2) Additive PEP36 500 ppm and stearic acid monoglyceride 0.2% by mass were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Production Example 27 [Production of resin (B37) pellets]
Phosphorus based on a total of 100 parts by mass of 55 parts by mass of KX-422 (b1-3) as copolymer (b1) and 45 parts by mass of Delpet 980N (b2-3) being acrylic resin (b2) Additive PEP36 500 ppm and stearic acid monoglyceride 0.2% by mass were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Production Example 28 [Production of resin (B38) pellets]
For a total of 100 parts by mass of 60 parts by mass of KX-422 (b1-3) as copolymer (b1) and 40 parts by mass of Delpet 980N (b2-3) as acrylic resin (b2) Additive PEP36 500 ppm and stearic acid monoglyceride 0.2% by mass were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Production Example 29 [Production of resin (B39) pellets]
Phosphorus-based addition to 100 parts by mass in total of 60 parts by mass of KX-422 (b1-3) as copolymer (b1) and 40 parts by mass of PLEXIGLAS hw55 (b2-4) as acrylic resin (b2) Agent PEP36 500 ppm and stearic acid monoglyceride 0.2% by mass were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Production Example 30 [Production of Resin (B40) Pellets]
15 parts by mass of KX-435 (b1-4) (weight average molecular weight: 124,000, styrene: maleic anhydride: MMA mass ratio = 71: 23: 6) as a copolymer (b1) and an acrylic resin ( b2) To 100 parts by mass of Delpet 980N (b2-3) 85 parts by mass as methyl methacrylate resin, 500 ppm of phosphorus-based additive PEP36 and 0.2% by mass of stearic acid monoglyceride were added. In the same manner as in No. 1, mixing and pelletization were performed. The pellets could be manufactured stably.

Production Example 31 [Production of Resin (B41) Pellets]
A total of 100 parts by mass of 25 parts by mass of KX-435 (b1-4) as copolymer (b1) and 75 parts by mass of Delpet 980N (b2-3) as methyl methacrylate resin as acrylic resin (b2) On the other hand, 500 ppm of phosphorus-based additive PEP36 and 0.2% by mass of stearic acid monoglyceride were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Production Example 32 [Production of Resin (B42) Pellets]
30 parts by mass of KX-435 (b1-4) as copolymer (b1) and 70 parts by mass of Delpet 980N (b2-3) as methyl methacrylate resin as acrylic resin (b2) On the other hand, 500 ppm of phosphorus-based additive PEP36 and 0.2% by mass of stearic acid monoglyceride were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Production Example 33 [Production of Resin (B43) Pellets]
40 parts by mass of KX-435 (b1-4) as copolymer (b1) and 60 parts by mass of Delpet 980N (b2-3) as methyl methacrylate resin as acrylic resin (b2) On the other hand, 500 ppm of phosphorus-based additive PEP36 and 0.2% by mass of stearic acid monoglyceride were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Production Example 34 [Production of Resin (B44) Pellets]
A total of 100 parts by mass of 50 parts by mass of KX-435 (b1-4) as copolymer (b1) and 50 parts by mass of Delpet 980N (b2-3) as methyl methacrylate resin as acrylic resin (b2) On the other hand, 500 ppm of phosphorus-based additive PEP36 and 0.2% by mass of stearic acid monoglyceride were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Production Example 35 [Production of resin (B45) pellet]
A total of 100 parts by mass of 60 parts by mass of KX-435 (b1-4) as copolymer (b1) and 40 parts by mass of Delpet 980N (b2-3) as methyl methacrylate resin as acrylic resin (b2) On the other hand, 500 ppm of phosphorus-based additive PEP36 and 0.2% by mass of stearic acid monoglyceride were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Production Example 36 [Production of Resin (B46) Pellets]
For a total of 100 parts by mass of 15 parts by mass of KX-435 (b1-4) as copolymer (b1) and 85 parts by mass of Plexiglas hw55 (b2-4) as methyl methacrylate resin as acrylic resin (b2) Then, phosphorus-based additive PEP36 (500 ppm) and stearic acid monoglyceride (0.2% by mass) were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Production Example 37 [Production of Resin (B47) Pellets]
For a total of 100 parts by mass of 25 parts by mass of KX-435 (b1-4) as copolymer (b1) and 75 parts by mass of PLEXIGLAS hw55 (b2-4) as methyl methacrylate resin as acrylic resin (b2) Then, phosphorus-based additive PEP36 (500 ppm) and stearic acid monoglyceride (0.2% by mass) were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Production Example 38 [Production of resin (B48) pellets]
For a total of 100 parts by mass of 30 parts by mass of KX-435 (b1-4) as copolymer (b1) and 70 parts by mass of PLEXIGLAS hw55 (b2-4) as methyl methacrylate resin as acrylic resin (b2) Then, phosphorus-based additive PEP36 (500 ppm) and stearic acid monoglyceride (0.2% by mass) were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Production Example 39 [Production of resin (B49) pellets]
For a total of 100 parts by mass of 40 parts by mass of KX-435 (b1-4) as copolymer (b1) and 60 parts by mass of PLEXIGLAS hw55 (b2-4) as methyl methacrylate resin as acrylic resin (b2) Then, phosphorus-based additive PEP36 (500 ppm) and stearic acid monoglyceride (0.2% by mass) were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Production Example 40 [Production of Resin (B50) Pellets]
For a total of 100 parts by mass of 50 parts by mass of KX-435 (b1-4) as copolymer (b1) and 50 parts by mass of Plexiglas hw55 (b2-4) as methyl methacrylate resin as acrylic resin (b2) Then, phosphorus-based additive PEP36 (500 ppm) and stearic acid monoglyceride (0.2% by mass) were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Production Example 41 [Production of Resin (B51) Pellets]
For a total of 100 parts by mass of 60 parts by mass of KX-435 (b1-4) as copolymer (b1) and 40 parts by mass of PLEXIGLAS hw55 (b2-4) as methyl methacrylate resin as acrylic resin (b2) Then, phosphorus-based additive PEP36 (500 ppm) and stearic acid monoglyceride (0.2% by mass) were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Comparative Production Example 1 [Production of Resin (D11) Pellets]
50 parts by mass of R100 (b1-5) (weight average molecular weight: 170,000, mass ratio of styrene: maleic anhydride: MMA = 65: 15: 20) as copolymer (b1), and acrylic resin (b2) To 100 parts by mass of a total of 50 parts by mass of parapet HR-L (b2-1) as methyl methacrylate resin, 500 ppm of phosphorus-based additive PEP36 and 0.2% by mass of stearic acid monoglyceride were added. Production Example 1 In the same manner, mixing and pelletization were performed. The pellets could be manufactured stably.

Comparative Production Example 2 [Production of Resin (D12) Pellets]
For a total of 100 parts by mass of 75 parts by mass of R100 (b1-5) as copolymer (b1) and 25 parts by mass of parapet HR-L (b2-1) as methyl methacrylate resin as acrylic resin (b2) Then, phosphorus-based additive PEP36 (500 ppm) and stearic acid monoglyceride (0.2% by mass) were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Comparative Production Example 3 [Production of Resin (D13) Pellets]
Phosphorous additive for 100 parts by mass in total of 70 parts by mass of R100 (b1-5) as copolymer (b1) and 30 parts by mass of Delpet PM120N (b2-2) as acrylic resin (b2) PEP36 500 ppm and stearic acid monoglyceride 0.2% by mass were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Comparative Production Example 4 [Production of Resin (D14) Pellets]
Phosphorous additive to 100 parts by mass in total of 75 parts by mass of R100 (b1-5) as copolymer (b1) and 25 parts by mass of Delpet PM120N (b2-2) as acrylic resin (b2) PEP36 500 ppm and stearic acid monoglyceride 0.2% by mass were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Comparative Production Example 5 [Production of Resin (D15) Pellets]
Phosphorous additive for 100 parts by mass in total of 50 parts by mass of R100 (b1-5) as copolymer (b1) and 50 parts by mass of Delpet 980N (b2-3) as acrylic resin (b2) PEP36 500 ppm and stearic acid monoglyceride 0.2% by mass were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Comparative Production Example 6 [Production of Resin (D16) Pellets]
Phosphorous additive for 100 parts by mass in total of 75 parts by mass of R100 (b1-5) as copolymer (b1) and 25 parts by mass of Delpet 980N (b2-3) as acrylic resin (b2) PEP36 500 ppm and stearic acid monoglyceride 0.2% by mass were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Comparative Production Example 7 [Production of Resin (D17) Pellets]
Phosphorous additive PEP36 with respect to a total of 100 parts by mass of R100 (b1-5) as a copolymer (b1) and 50 parts by mass of Plexiglas hw55 (b2-4) as an acrylic resin (b2) 500 ppm and 0.2 mass% of stearic acid monoglyceride were added, and mixing and pelletizing were performed in the same manner as in Production Example 1. The pellets could be manufactured stably.

Comparative Production Example 8 [Production of Resin (D18) Pellets]
Phosphorous additive PEP36 with respect to a total of 100 parts by mass of 75 parts by mass of R100 (b1-5) as copolymer (b1) and 25 parts by mass of Plexiglas hw55 (b2-4) as acrylic resin (b2) 500 ppm and 0.2 mass% of stearic acid monoglyceride were added, and mixing and pelletizing were performed in the same manner as in Production Example 1. The pellets could be manufactured stably.

Comparative production example 9 [Production of resin (D19) pellets]
50 parts by mass of R200 (b1-6) (weight average molecular weight: 185,000, mass ratio of styrene: maleic anhydride: MMA = 55: 20: 25) as copolymer (b1), and acrylic resin (b2) To 100 parts by mass of 50 parts by mass of parapet HR-L (b2-1) as methyl methacrylate resin, 500 ppm of phosphorus-based additive PEP36 and 0.2% by mass of stearic acid monoglyceride were added, and Production Example 1 In the same manner, mixing and pelletization were performed. The pellets could be manufactured stably.

Comparative Production Example 10 [Production of Resin (D20) Pellets]
For a total of 100 parts by mass of 75 parts by mass of R200 (b1-6) as copolymer (b1) and 25 parts by mass of parapet HR-L (b2-1) as methyl methacrylate resin as acrylic resin (b2) Then, phosphorus-based additive PEP36 (500 ppm) and stearic acid monoglyceride (0.2% by mass) were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Comparative Production Example 11 [Production of Resin (D21) Pellets]
Based on 100 parts by mass in total of 20 parts by mass of R200 (b1-6) as copolymer (b1) and 80 parts by mass of Delpet 980N (b2-3) as methyl methacrylate resin as acrylic resin (b2) Then, phosphorus-based additive PEP36 500 ppm and stearic acid monoglyceride 0.2% by mass were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Comparative Production Example 12 [Production of Resin (D22) Pellets]
For a total of 100 parts by mass of 40 parts by mass of R200 (b1-6) as the copolymer (b1) and 60 parts by mass of Delpet 980N (b2-3) as the methyl methacrylate resin as the acrylic resin (b2) Then, phosphorus-based additive PEP36 (500 ppm) and stearic acid monoglyceride (0.2% by mass) were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Comparative Production Example 13 [Production of Resin (D23) Pellets]
100 parts by mass in total of 60 parts by mass of R200 (b1-6) as copolymer (b1) and 40 parts by mass of Delpet 980N (b2-3) as methyl methacrylate resin as acrylic resin (b2) Then, phosphorus-based additive PEP36 500 ppm and stearic acid monoglyceride 0.2% by mass were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Comparative Production Example 14 [Production of Resin (D24) Pellets]
For a total of 100 parts by mass of 20 parts by mass of R200 (b1-6) as the copolymer (b1) and 80 parts by mass of PLEXIGLAS hw55 (b2-4) as the methyl methacrylate resin as the acrylic resin (b2), Phosphorous additive PEP36 (500 ppm) and stearic acid monoglyceride (0.2% by mass) were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Comparative Production Example 15 [Production of Resin (D25) Pellets]
For a total of 100 parts by mass of 40 parts by mass of R200 (b1-6) as the copolymer (b1) and 60 parts by mass of PLEXIGLAS hw55 (b2-4) as the methyl methacrylate resin as the acrylic resin (b2), Phosphorus additive PEP36 (500 ppm) and stearic acid monoglyceride (0.2% by mass) were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Comparative Production Example 16 [Production of Resin (D26) Pellets]
For a total of 100 parts by mass of R200 (b1-6) 60 parts by mass as a copolymer (b1) and PLEXIGLAS hw55 (b2-4) 40 parts by mass as an acrylic resin (b2) methyl methacrylate resin, Phosphorous additive PEP36 (500 ppm) and stearic acid monoglyceride (0.2% by mass) were added and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Comparative Production Example 17 [Production of Resin (D27) Pellets]
To 100 parts by mass of Parapet HR-L (b2-1) as methyl methacrylate resin which is an acrylic resin (b2), 500 ppm of phosphorus-based additive PEP36 and 0.2% by mass of stearic acid monoglyceride were added, and Production Example 1 In the same manner, mixing and pelletization were performed. The pellets could be manufactured stably.

Comparative Production Example 18 [Production of Resin (D28) Pellets]
To 100 parts by mass of Delpet PM120N (b2-2), which is an acrylic resin (b2), 500 ppm of phosphorus-based additive PEP36 and 0.2% by mass of stearic acid monoglyceride are added and mixed in the same manner as in Production Example 1, pellets Made. The pellets could be manufactured stably.

Comparative Production Example 19 [Production of Resin (D29) Pellets]
To 100 parts by mass of Delpet 980N (b2-3), which is an acrylic resin (b2), 500 ppm of phosphorus-based additive PEP36 and 0.2% by mass of stearic acid monoglyceride are added and mixed in the same manner as in Production Example 1 and pellets Made. The pellets could be manufactured stably.

Comparative Production Example 20 [Production of Resin (D30) Pellets]
Phosphoric additive PEP36 500 ppm and stearic acid monoglyceride 0.2 mass% are added to 100 parts by mass of PLEXIGLAS hw55 (b2-4) which is an acrylic resin (b2), and mixed and pelletized in the same manner as in Production Example 1. Went. The pellets could be manufactured stably.

Example 1
Each extruder in 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 the extruders, and a T die connected to the feed block The resin laminate was molded using a multi-layer extrusion apparatus having connected multi-manifold dies. The resin (B11) obtained in Production Example 1 was continuously introduced into a single-screw extruder having a shaft diameter of 32 mm, and extruded under conditions of a cylinder temperature of 240 ° C. and a discharge rate of 2.1 kg / h. Polycarbonate resin (A-1) (manufactured by Mitsubishi Engineering Plastics, product name: Iupilon E-2000, weight average molecular weight: 34,000) was continuously introduced into a single screw extruder with a shaft diameter of 65 mm, and the cylinder Extrusion was performed at a temperature of 280 ° C. and a discharge rate of 30.0 kg / h. The feed block connected to the entire extruder was provided with two types and two layers of distribution pins, and the temperature was set to 270 ° C. and (B11) and (A-1) were introduced and laminated. Extruded into a sheet shape with a T-die with a temperature of 270 ° C connected to the tip, and cooled while transferring the mirror surface with three mirror finish rolls at temperatures of 130 ° C, 140 ° C and 180 ° C from the upstream side (B11) And a laminate (E11) of (A-1) was obtained. The total thickness of the obtained laminate (E11) was 1000 μm, and the thickness of the layer made of B11 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B11) layer {thermoplastic resin} = 275 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.022, which was passed, and the pencil scratch hardness test The result is 2H, the warp change amount in a high temperature and high humidity environment is 472μm, the total light transmittance is 91.3%, the haze is 0.2%, and the pass is 0.2%. It was a pass in the judgment.

Example 2
A laminate (E12) of (B12) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B12) was used instead of the resin (B11). The total thickness of the obtained laminate (E12) was 1000 μm, and the thickness of the layer made of B12 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B12) layer {thermoplastic resin} = 280 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.041 is passed, and the pencil scratch hardness test The result is 2H, the warp change amount under high temperature and high humidity environment is 34μm, the total light transmittance is 91.2%, the haze is 0.2%, and the pass is 0.2%. It was a pass in the judgment.

Example 3
A laminate (E13) of (B13) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B13) was used instead of the resin (B11). The total thickness of the obtained laminate (E13) was 1000 μm, and the thickness of the layer made of B13 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B13) layer {thermoplastic resin} = 282 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.048 is passed, and the pencil scratch hardness test The result is 2H, the warp change amount in a high temperature and high humidity environment is 307μm, the total light transmittance is 90.9%, the haze is 0.2%, and the pass is 0.2%. It was a pass in the judgment.

Example 4
A laminate (E14) of (B14) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B14) was used instead of the resin (B11). The overall thickness of the obtained laminate (E14) was 1000 μm, and the thickness of the layer made of B14 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B14) layer {thermoplastic resin} = 276 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.026 was passed, and the pencil scratch hardness test The result is 2H, the warp change amount in a high temperature and high humidity environment is 445μm, the total light transmittance is 90.7%, the haze is 0.2%, and the pass is 0.2%. It was a pass in judgment.

Example 5
A laminate (E15) of (B15) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B15) was used instead of the resin (B11). The total thickness of the obtained laminate (E15) was 1000 μm, and the thickness of the layer made of B15 was 60 μm near the center. The HIT hardness {thermoplastic resin} of the thermoplastic resin (B15) layer is 280 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.053 is passed, and the pencil scratch hardness test The result is 2H, the warp change amount in a high temperature and high humidity environment is 155 μm, the total light transmittance is 91.1%, the haze is 0.1%, and the pass is 0.1%. It was a pass in the judgment.

Example 6
A laminate (E16) of (B16) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B16) was used instead of the resin (B11). The total thickness of the obtained laminate (E16) was 1000 μm, and the thickness of the layer made of B16 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B16) layer {thermoplastic resin} = 282 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.060 was passed, and the pencil scratch hardness test The result is 2H, the warp change amount in the high temperature and high humidity environment is 352μm, the total light transmittance is 91.0%, the haze is 0.1%, and the pass is 0.1%. It was a pass in judgment.

Example 7
A laminate (E17) of (B17) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B17) was used instead of the resin (B11). The total thickness of the obtained laminate (E17) was 1000 μm, and the thickness of the layer composed of B17 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B17) layer {thermoplastic resin} = 283 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.064 was passed, and the pencil scratch hardness test The result is 2H, the warp change amount in the high temperature and high humidity environment is 493μm, the total light transmittance is 91.0%, the haze is 0.1%, and the pass is 0.1%. It was a pass in the judgment.

Example 8
A laminate (E18) of (B18) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B18) was used instead of the resin (B11). The total thickness of the obtained laminate (E18) was 1000 μm, and the thickness of the layer made of B18 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B18) layer {thermoplastic resin} = 285 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.071 is passed, and the pencil scratch hardness test The result is 2H, the warp change amount in a high temperature and high humidity environment is 630 μm, the total light transmittance is 91.0%, the haze is 0.1%, and the pass is 0.1%. It was a pass in the judgment.

Example 9
A laminate (E19) of (B19) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B19) was used instead of the resin (B11). The total thickness of the obtained laminate (E19) was 1000 μm, and the thickness of the layer made of B19 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B19) layer {thermoplastic resin} = 278 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.041 is passed, and the pencil scratch hardness test The result is 2H, the warp change amount in a high temperature and high humidity environment is 183μm, the total light transmittance is 91.0%, the haze is 0.1%, and the pass is 0.1%. It was a pass in the judgment.

Example 10
A laminate (E20) of (B20) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B20) was used instead of the resin (B11). The total thickness of the obtained laminate (E20) was 1000 μm, and the thickness of the layer made of B20 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B20) layer {thermoplastic resin} = 280 N / mm ² , the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.049, and passed, and the pencil scratch hardness test The result is 2H, the warp change amount under high temperature and high humidity environment is 397μm, the total light transmittance is 91.0%, the haze is 0.1%, and the pass is 0.1%. It was a pass in the judgment.

Example 11
A laminate (E21) of (B21) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B21) was used instead of the resin (B11). The total thickness of the obtained laminate (E21) was 1000 μm, and the thickness of the layer made of B21 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B21) layer {thermoplastic resin} = 282 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.068 was passed, and the pencil scratch hardness test The result is 2H, the warp change amount in a high temperature and high humidity environment is 501 μm, the total light transmittance is 91.0%, the haze is 0.1%, and the pass is 0.1%. It was a pass in the judgment.

Example 12
A laminate (E22) of (B22) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B22) was used instead of the resin (B11). The total thickness of the obtained laminate (E22) was 1000 μm, and the thickness of the layer made of B22 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B22) layer {thermoplastic resin} = 282 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.056 is passed, and the pencil scratch hardness test The result is 2H, the warp change in a high temperature and high humidity environment is 635μm, the total light transmittance is 90.9%, the haze is 0.1%, and the pass is 0.1%. It was a pass in the judgment.

Example 13
A laminate (E23) of (B23) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B23) was used instead of the resin (B11). The total thickness of the obtained laminate (E23) was 1000 μm, and the thickness of the layer made of B23 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B23) layer {thermoplastic resin} = 275 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.022, which was passed, and the pencil scratch hardness test The result is 2H, the warp change amount in the high temperature and high humidity environment is 649μm, the total light transmittance is 91.4%, the haze is 0.1%, and the pass is 0.1%. It was a pass in the judgment.

Example 14
A laminate (E24) of (B24) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B24) was used instead of the resin (B11). The total thickness of the obtained laminate (E24) was 1000 μm, and the thickness of the layer made of B16 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B24) layer {thermoplastic resin} = 282 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.048 is passed, and the pencil scratch hardness test The result is 2H, the warp change amount in a high temperature and high humidity environment is 69μm, the total light transmittance is 91.2%, the haze is 0.1%, and the pass is 0.1%. It was a pass in the judgment.

Example 15
A laminate (E25) of (B25) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B25) was used instead of the resin (B11). The total thickness of the obtained laminate (E25) was 1000 μm, and the thickness of the layer made of B25 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B25) layer {thermoplastic resin} = 291 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.082 is passed, and the pencil scratch hardness test The result is 3H, the warp change amount under high temperature and high humidity environment is 643μm, the total light transmittance is 90.9%, the haze is 0.2%, and the pass is 0.2%. It was a pass in the judgment.

Example 16
A laminate (E26) of (B26) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B26) was used instead of the resin (B11). The overall thickness of the obtained laminate (E26) was 1000 μm, and the thickness of the layer made of B26 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B26) layer {thermoplastic resin} = 286 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.063 was passed, and the pencil scratch hardness test The result is acceptable at 3H, the amount of warpage change under high temperature and high humidity environment is acceptable at 686 μm, the total light transmittance is acceptable at 90.7%, and the haze is acceptable at 0.2%. It was a pass in the judgment.

Example 17
A laminate (E27) of (B27) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B27) was used instead of the resin (B11). The total thickness of the obtained laminate (E27) was 1000 μm, and the thickness of the layer made of B27 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B27) layer {thermoplastic resin} = 275 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.022, which was passed, and the pencil scratch hardness test The result is 2H, the warp change amount in a high temperature and high humidity environment is 524μm, the total light transmittance is 91.3%, the haze is 0.1%, and the pass is It was a pass in the judgment.

Example 18
A laminate (E28) of (B28) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B28) was used instead of the resin (B11). The total thickness of the obtained laminate (E28) was 1000 μm, and the thickness of the layer made of B28 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B20) layer {thermoplastic resin} = 281 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.045 is passed, and the pencil scratch hardness test The result is 2H, the warp change amount under high temperature and high humidity environment is 117μm, the total light transmittance is 91.2%, the haze is 0.1%, and the pass is 0.1%. It was a pass in the judgment.

Example 19
A laminate (E29) of (B29) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B29) was used instead of the resin (B11). The total thickness of the obtained laminate (E29) was 1000 μm, and the thickness of the layer composed of B29 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B21) layer {thermoplastic resin} = 287 N / mm ² , the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.067, and passed, and the pencil scratch hardness test The result is 3H, the warp change amount in a high temperature and high humidity environment is 104μm, the total light transmittance is 91.1%, the haze is 0.2%, and the pass is 0.2%. It was a pass in the judgment.

Example 20
A laminate (E30) of (B30) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B30) was used instead of the resin (B11). The total thickness of the obtained laminate (E30) was 1000 μm, and the thickness of the layer made of B30 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B30) layer {thermoplastic resin} = 289 N / mm ² , the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.004, and it passed, and the pencil scratch hardness test The result is 3H, the warp change amount in the high temperature and high humidity environment is 29μm, the total light transmittance is 91.0%, the haze is 0.2%, and the pass is 0.2%. It was a pass in the judgment.

Example 21
A laminate (E31) of (B31) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B31) was used instead of the resin (B11). The total thickness of the obtained laminate (E31) was 1000 μm, and the thickness of the layer made of B31 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B31) layer {thermoplastic resin} = 289 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.004 was passed, and the pencil scratch hardness test The result is acceptable at 3H, the amount of warpage change under a high temperature and high humidity environment is 264 μm, the total light transmittance is acceptable at 91.0%, and the haze is acceptable at 0.2%. It was a pass in the judgment.

Example 22
A laminate (E32) of (B32) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B32) was used instead of the resin (B11). The total thickness of the obtained laminate (E32) was 1000 μm, and the thickness of the layer made of B32 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B32) layer {thermoplastic resin} = 289 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.004 was passed, and the pencil scratch hardness test The result is acceptable at 3H, the amount of warpage change under high temperature and high humidity environment is acceptable at 360μm, the total light transmittance is acceptable at 91.0%, and the haze is acceptable at 0.2%. It was a pass in the judgment.

Example 23
A laminate (E33) of (B33) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B33) was used instead of the resin (B11). The total thickness of the obtained laminate (E33) was 1000 μm, and the thickness of the layer made of B33 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B33) layer {thermoplastic resin} = 295 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.097 is passed, and the pencil scratch hardness test The result is acceptable at 3H, the amount of warpage change under high-temperature and high-humidity environment is acceptable at 695 μm, the total light transmittance is acceptable at 90.8%, and the haze is acceptable at 0.1%. It was a pass in the judgment.

Example 24
A laminate (E34) of (B34) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B34) was used instead of the resin (B11). The total thickness of the obtained laminate (E34) was 1000 μm, and the thickness of the layer made of B34 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B34) layer {thermoplastic resin} = 290 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.058 is passed, and the pencil scratch hardness test The result is acceptable at 3H, the amount of warpage change under a high temperature and high humidity environment is acceptable at 151 μm, the total light transmittance is acceptable at 91.1%, and the haze is acceptable at 0.2%. It was a pass in the judgment.

Example 25
A laminate (E35) of (B35) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B35) was used instead of the resin (B11). The total thickness of the obtained laminate (E35) was 1000 μm, and the thickness of the layer made of B35 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B27) layer {thermoplastic resin} = 292 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.066 was passed, and the pencil scratch hardness test The result is acceptable at 3H, the amount of warp change under high temperature and high humidity environment is acceptable at 68μm, the total light transmittance is acceptable at 91.0%, and the haze is acceptable at 0.2%. It was a pass in the judgment.

Example 26
A laminate (E36) of (B36) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B36) was used instead of the resin (B11). The total thickness of the obtained laminate (E36) was 1000 μm, and the thickness of the layer made of B36 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B36) layer {thermoplastic resin} = 291 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.062, which was passed, and the pencil scratch hardness test The result is acceptable at 3H, the amount of warpage change under a high temperature and high humidity environment is acceptable at 7 μm, the total light transmittance is acceptable at 91.0%, and the haze is acceptable at 0.2%. It was a pass in the judgment.

Example 27
A laminate (E37) of (B37) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B37) was used instead of the resin (B11). The total thickness of the obtained laminate (E37) was 1000 μm, and the thickness of the layer made of B37 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B37) layer {thermoplastic resin} = 284 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.068. The result is 2H, the warp change amount in a high temperature and high humidity environment is 529μm, the total light transmittance is 91.2%, the haze is 0.2%, and the pass is 0.2%. It was a pass in the judgment.

Example 28
A laminate (E38) of (B38) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B38) was used instead of the resin (B11). The total thickness of the obtained laminate (E38) was 1000 μm, and the thickness of the layer made of B38 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B38) layer {thermoplastic resin} = 284 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.068 passed, and the pencil scratch hardness test The result is 2H, the warp change amount in a high temperature and high humidity environment is 605 μm, the total light transmittance is 91.2%, the haze is 0.2%, and the pass is It was a pass in the judgment.

Example 29
A laminate (E39) of (B39) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B39) was used instead of the resin (B11). The total thickness of the obtained laminate (E39) was 1000 μm, and the thickness of the layer made of B39 was 60 μm near the center. The HIT hardness {thermoplastic resin} of the thermoplastic resin (B39) layer is 281 N / mm ² and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.052 is passed, and the pencil scratch hardness test The result is acceptable at 2H, the amount of warpage change under high temperature and high humidity environment is acceptable at 679 μm, the total light transmittance is acceptable at 90.9%, and the haze is acceptable at 0.2%. It was a pass in the judgment.

Example 30
A laminate (E40) of (B40) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B40) was used instead of the resin (B11). The total thickness of the obtained laminate (E40) was 1000 μm, and the thickness of the layer made of B40 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B40) layer {thermoplastic resin} = 272 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.024 was passed, and the pencil scratch hardness test The result is 2H, the warp change amount in the high temperature and high humidity environment is 13μm, the total light transmittance is 91.3%, the haze is 0.2%, and the pass is 0.2%. It was a pass in the judgment.

Example 31
A laminate (E41) of (B41) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B41) was used instead of the resin (B11). The overall thickness of the obtained laminate (E41) was 1000 μm, and the thickness of the layer made of B41 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B41) layer {thermoplastic resin} = 274 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.030 was passed, and the pencil scratch hardness test The result is 2H, the warp change amount in the high temperature and high humidity environment is 126μm, the total light transmittance is 91.2%, the haze is 0.2%, and the pass is 0.2%. It was a pass in the judgment.

Example 32
A laminate (E42) of (B42) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B42) was used instead of the resin (B11). The overall thickness of the obtained laminate (E42) was 1000 μm, and the thickness of the layer made of B42 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B42) layer {thermoplastic resin} = 274 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.030 is passed, and the pencil scratch hardness test The result is 2H, the warp change amount in a high temperature and high humidity environment is 171μm, the total light transmittance is 91.2%, the haze is 0.2%, and the pass is 0.2%. It was a pass in the judgment.

Example 33
A laminate (E43) of (B43) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B43) was used instead of the resin (B11). The total thickness of the obtained laminate (E43) was 1000 μm, and the thickness of the layer made of B43 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B43) layer {thermoplastic resin} = 275 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.034 was passed, and the pencil scratch hardness test The result is 2H, the warp change amount in the high temperature and high humidity environment is 296μm, the total light transmittance is 91.1%, the haze is 0.2%, and the pass is 0.2%. It was a pass in the judgment.

Example 34
A laminate (E44) of (B44) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B44) was used instead of the resin (B11). The total thickness of the obtained laminate (E44) was 1000 μm, and the thickness of the layer made of B44 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B44) layer {thermoplastic resin} = 277 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.041 is passed, and the pencil scratch hardness test The result is 2H, the warp change amount in a high temperature and high humidity environment is 458μm, the total light transmittance is 91.1%, the haze is 0.2%, and the pass is 0.2%. It was a pass in the judgment.

Example 35
A laminate (E45) of (B45) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B45) was used instead of the resin (B11). The total thickness of the obtained laminate (E45) was 1000 μm, and the thickness of the layer made of B45 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B45) layer {thermoplastic resin} = 277 N / mm ² , the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.041, and the pencil scratch hardness test The result is 2H, the warp change amount in a high temperature and high humidity environment is 508 μm, the total light transmittance is 91.0%, the haze is 0.2%, and the pass is 0.2%. It was a pass in the judgment.

Example 36
A laminate (E46) of (B46) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B46) was used instead of the resin (B11). The total thickness of the obtained laminate (E46) was 1000 μm, and the thickness of the layer made of B46 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B46) layer {thermoplastic resin} = 271 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.015 was passed, and the pencil scratch hardness test The result is 2H, the warp change amount in a high temperature and high humidity environment is 25μm, the total light transmittance is 91.2%, the haze is 0.2%, and the pass is It was a pass in the judgment.

Example 37
A laminate (E47) of (B47) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B47) was used instead of the resin (B11). The total thickness of the obtained laminate (E47) was 1000 μm, and the thickness of the layer composed of B47 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B47) layer {thermoplastic resin} = 272 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.919. The result is 2H, the warp change amount in a high temperature and high humidity environment is 106μm, the total light transmittance is 91.2%, the haze is 0.2%, and the pass is It was a pass in the judgment.

Example 38
A laminate (E48) of (B48) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B48) was used instead of the resin (B11). The total thickness of the obtained laminate (E48) was 1000 μm, and the thickness of the layer composed of B48 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B48) layer {thermoplastic resin} = 273 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.022, which was passed, and the pencil scratch hardness test The result is 2H, the warp change under high temperature and high humidity environment is 175μm, the total light transmittance is 91.2%, the haze is 0.2%, and the pass is It was a pass in the judgment.

Example 39
A laminate (E49) of (B49) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B49) was used instead of the resin (B11). The total thickness of the obtained laminate (E49) was 1000 μm, and the thickness of the layer made of B49 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B49) layer {thermoplastic resin} = 274 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.026 was passed, and the pencil scratch hardness test The result is 2H, the warp change amount in the high temperature and high humidity environment is 313μm, the total light transmittance is 91.1%, the haze is 0.2%, and the pass is 0.2%. It was a pass in the judgment.

Example 40
A laminate (E50) of (B50) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B50) was used instead of the resin (B11). The total thickness of the obtained laminate (E50) was 1000 μm, and the thickness of the layer composed of B50 was 60 μm near the center. The HIT hardness {thermoplastic resin} of the thermoplastic resin (B48) layer is 275 N / mm ² and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.030 is passed, and the pencil scratch hardness test The result is 2H, the warp change amount in the high temperature and high humidity environment is 464μm, the total light transmittance is 91.1%, the haze is 0.2%, and the pass is It was a pass in the judgment.

Example 41
A laminate (E51) of (B51) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B51) was used instead of the resin (B11). The overall thickness of the obtained laminate (E51) was 1000 μm, and the thickness of the layer made of B51 was 60 μm near the center. The HIT hardness of the thermoplastic resin (B51) layer {thermoplastic resin} = 275 N / mm ² and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.030. The result is 2H, the warp change amount in a high temperature and high humidity environment is 534 μm, the total light transmittance is 91.1%, the haze is 0.2%, and the pass is 0.2%. It was a pass in the judgment.

Comparative Example 1
A laminate (F11) of (D11) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D11) was used instead of the resin (B11). The total thickness of the obtained laminate (F11) was 1000 μm, and the thickness of the layer made of D11 was 60 μm near the center. HIT hardness of the thermoplastic resin (D11) layer {thermoplastic resin} = 255 N / mm ² , HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 0.948, rejected, pencil scratch hardness test The result of the test is F, the warp change amount in a high temperature and high humidity environment is 359 μm, the total light transmittance is 91.2%, and the haze is 0.2%. It was rejected by the comprehensive judgment.

Comparative Example 2
A laminate (F12) of (D12) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D12) was used instead of the resin (B11). The total thickness of the obtained laminate (F12) was 1000 μm, and the thickness of the layer composed of D12 was 60 μm near the center. HIT hardness of the thermoplastic resin (D12) layer {thermoplastic resin} = 253 N / mm ² , HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 0.941, rejected, pencil scratch hardness test The result of F is rejected with F, the amount of warpage change under a high temperature and high humidity environment is 121 μm, the total light transmittance is 91.1%, and the haze is 0.2%. It was rejected by the comprehensive judgment.

Comparative Example 3
A laminate (F13) of (D13) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D13) was used instead of the resin (B11). The total thickness of the obtained laminate (F13) was 1000 μm, and the thickness of the layer made of D13 was 60 μm near the center. The HIT hardness of the thermoplastic resin (D13) layer {thermoplastic resin} = 264 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 0.964 was rejected, and the pencil scratch hardness test The result of is rejected with H, the amount of warpage change under high temperature and high humidity environment is 43 μm, the total light transmittance is passed with 91.1%, and the haze is passed with 0.2%. It was rejected by the comprehensive judgment.

Comparative Example 4
A laminate (F14) of (D14) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D14) was used instead of the resin (B11). The total thickness of the obtained laminate (F14) was 1000 μm, and the thickness of the layer composed of D14 was 60 μm near the center. The HIT hardness of the thermoplastic resin (D14) layer {thermoplastic resin} = 264 N / mm ² , HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 0.964, rejected, pencil scratch hardness test The result of is rejected with H, the amount of warpage change under high temperature and high humidity environment is 65 μm, it is passed, the total light transmittance is passed with 91.0%, and the haze is passed with 0.1%. It was rejected by the comprehensive judgment.

Comparative Example 5
A laminate (F15) of (D15) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D15) was used instead of the resin (B11). The total thickness of the obtained laminate (F15) was 1000 μm, and the thickness of the layer made of D15 was 60 μm near the center. The HIT hardness of the thermoplastic resin (D15) layer {thermoplastic resin} = 263 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 0.989 was rejected, and the pencil scratch hardness test The result of is rejected with H, the amount of warpage change under high temperature and high humidity environment is 238 μm, the total light transmittance is passed with 89.9%, and the haze is passed with 2.1%. It was rejected by the comprehensive judgment.

Comparative Example 6
A laminate (F16) of (D16) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D16) was used instead of the resin (B11). The total thickness of the obtained laminate (F16) was 1000 μm, and the thickness of the layer made of D16 was 60 μm near the center. The HIT hardness of the thermoplastic resin (D16) layer {thermoplastic resin} = 261 N / mm ² , the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 0.981 was rejected, and the pencil scratch hardness test The result of is rejected with H, the amount of warpage change under high temperature and high humidity environment is 286 μm, the total light transmittance is passed with 89.4%, and the haze is passed with 0.9%. It was rejected by the comprehensive judgment.

Comparative Example 7
A laminate (F17) of (D17) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D17) was used instead of the resin (B11). The total thickness of the obtained laminate (F17) was 1000 μm, and the thickness of the layer composed of D17 was 60 μm near the center. The HIT hardness of the thermoplastic resin (D17) layer {thermoplastic resin} = 262 N / mm ² and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 0.981 was rejected, and the pencil scratch hardness test The result of is rejected with H, the amount of warpage change under a high temperature and high humidity environment is 164 μm, the total light transmittance is passed with 89.0%, and the haze is passed with 2.3%. It was rejected by the comprehensive judgment.

Comparative Example 8
A laminate (F18) of (D18) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D18) was used instead of the resin (B11). The total thickness of the obtained laminate (F18) was 1000 μm, and the thickness of the layer composed of D18 was 60 μm near the center. The HIT hardness of the thermoplastic resin (D18) layer {thermoplastic resin} = 261 N / mm ² and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 0.978 was rejected, and the pencil scratch hardness test The result of is rejected with H, the amount of warpage change under high temperature and high humidity environment is 207 μm, the total light transmittance is passed with 88.6%, and the haze is passed with 1.9%. It was rejected by the comprehensive judgment.

Comparative Example 9
A laminate (F19) of (D19) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D19) was used instead of the resin (B11). The total thickness of the obtained laminate (F19) was 1000 μm, and the thickness of the layer composed of D19 was 60 μm near the center. The HIT hardness of the thermoplastic resin (D19) layer {thermoplastic resin} = 265 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 0.985 was rejected, and the pencil scratch hardness test The result of is rejected with H, the amount of warp change in a high temperature and high humidity environment is 159 μm, the total light transmittance is 91.4%, and the haze is 0.2%. It was rejected by the comprehensive judgment.

Comparative Example 10
A laminate (F20) of (D20) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D20) was used instead of the resin (B11). The total thickness of the obtained laminate (F20) was 1000 μm, and the thickness of the layer composed of D20 was 60 μm near the center. The HIT hardness of the thermoplastic resin (D20) layer {thermoplastic resin} = 264 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 0.981 was rejected, and the pencil scratch hardness test The result of is rejected with H, the amount of warpage change under a high temperature and high humidity environment is 275 μm, it is passed, the total light transmittance is passed with 91.2%, and the haze is passed with 0.2%. It was rejected by the comprehensive judgment.

Comparative Example 11
A laminate (F21) of (D21) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D21) was used instead of the resin (B11). The total thickness of the obtained laminate (F21) was 1000 μm, and the thickness of the layer composed of D21 was 60 μm near the center. The HIT hardness of the thermoplastic resin (D21) layer {thermoplastic resin} = 265 N / mm ² and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 0.996 was rejected, and the pencil scratch hardness test The result of is rejected with H, the amount of warpage change under high temperature and high humidity environment is 1 μm, the total light transmittance is passed with 91.2%, and the haze is passed with 0.2%. It was rejected by the comprehensive judgment.

Comparative Example 12
A laminate (F22) of (D22) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D22) was used instead of the resin (B11). The total thickness of the obtained laminate (F22) was 1000 μm, and the thickness of the layer made of D22 was 60 μm near the center. The HIT hardness of the thermoplastic resin (D22) layer {thermoplastic resin} = 264 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 0.992 is rejected, and the pencil scratch hardness test The result of is rejected with H, the amount of warp change under a high temperature and high humidity environment is 167 μm, the total light transmittance is 91.1%, and the haze is 0.2%. It was rejected by the comprehensive judgment.

Comparative Example 13
A laminate (F23) of (D23) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D23) was used instead of the resin (B11). The total thickness of the obtained laminate (F23) was 1000 μm, and the thickness of the layer composed of D23 was 60 μm near the center. The HIT hardness of the thermoplastic resin (D23) layer {thermoplastic resin} = 264 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 0.992 is rejected, and the pencil scratch hardness test The result of is rejected with H, the amount of warpage change under a high temperature and high humidity environment is 309 μm, the total light transmittance is passed with 91.1%, and the haze is passed with 0.2%. It was rejected by the comprehensive judgment.

Comparative Example 14
A laminate (F24) of (D24) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D24) was used instead of the resin (B11). The total thickness of the obtained laminate (F24) was 1000 μm, and the thickness of the layer composed of D24 was 60 μm near the center. The HIT hardness of the thermoplastic resin (D24) layer {thermoplastic resin} = 265 N / mm ² and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 0.993 was rejected, and the pencil scratch hardness test The result of is rejected with H, the amount of warp change under a high temperature and high humidity environment is 35 μm, the total light transmittance is 91.2%, and Haze is 0.2%. It was rejected by the comprehensive judgment.

Comparative Example 15
A laminate (F25) of (D25) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D25) was used instead of the resin (B11). The total thickness of the obtained laminate (F25) was 1000 μm, and the thickness of the layer composed of D25 was 60 μm near the center. HIT hardness of the thermoplastic resin (D25) layer {thermoplastic resin} = 264 N / mm ² , HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 0.989, rejected, pencil scratch hardness test The result of is rejected with H, the amount of warpage change under high temperature and high humidity environment is 24 μm, the total light transmittance is passed with 91.2%, and the haze is passed with 0.2%. It was rejected by the comprehensive judgment.

Comparative Example 16
A laminate (F26) of (D26) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D26) was used instead of the resin (B11). The total thickness of the obtained laminate (F26) was 1000 μm, and the thickness of the layer composed of D26 was 60 μm near the center. The HIT hardness of the thermoplastic resin (D26) layer {thermoplastic resin} = 263 N / mm ² , HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 0.985, rejected, pencil scratch hardness test The result of is rejected with H, the amount of warp change under high temperature and high humidity environment is 422 μm, passed, the total light transmittance is passed with 91.2%, and the haze is passed with 0.2%. It was rejected by the comprehensive judgment.

Comparative Example 17
A laminate (F27) of (D27) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D27) was used instead of the resin (B11). The total thickness of the obtained laminate (F27) was 1000 μm, and the thickness of the layer composed of D27 was 60 μm near the center. The HIT hardness of the thermoplastic resin (D27) layer {thermoplastic resin} = 269 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.000 was rejected, and the pencil scratch hardness test The result of is acceptable at 2H, the amount of warpage change under high-temperature and high-humidity environment is 952μm, is rejected, the total light transmittance is 91.6%, and the haze is 0.1%. It was rejected by the comprehensive judgment.

Comparative Example 18
A laminate (F28) of (D28) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D28) was used instead of the resin (B11). The total thickness of the obtained laminate (F28) was 1000 μm, and the thickness of the layer composed of D28 was 60 μm near the center. The HIT hardness of the thermoplastic resin (D28) layer {thermoplastic resin} = 274 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.000 was rejected, and the pencil scratch hardness test The result of 2 is acceptable at 2H, the amount of warpage change under high temperature and high humidity environment is 552 μm, the total light transmittance is acceptable at 91.3%, and the haze is acceptable at 0.2%, It was rejected by the comprehensive judgment.

Comparative Example 19
A laminate (F29) of (D29) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D29) was used instead of the resin (B11). The total thickness of the obtained laminate (F29) was 1000 μm, and the thickness of the layer composed of D29 was 60 μm near the center. The HIT hardness of the thermoplastic resin (D29) layer {thermoplastic resin} = 266 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.000 was rejected, and the pencil scratch hardness test The result of the test is 2H, the warp change amount in a high temperature and high humidity environment is 378 μm, the total light transmittance is 91.4%, and the haze is 0.2%. It was rejected by the comprehensive judgment.

Comparative Example 20
A laminate (F30) of (D30) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D30) was used instead of the resin (B11). The total thickness of the obtained laminate (F30) was 1000 μm, and the thickness of the layer made of D30 was 60 μm near the center. The HIT hardness of the thermoplastic resin (D30) layer {thermoplastic resin} = 267 N / mm ² , and the HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin} = 1.000 was rejected, and the pencil scratch hardness test The result of 2 is acceptable at 2H, the warpage change amount in a high temperature and high humidity environment is 356 μm, the total light transmittance is 91.2%, and the haze is 0.3%. It was rejected by the comprehensive judgment.

As described above, in the resin laminate according to the present invention, a thermoplastic resin is laminated on a polycarbonate resin layer, and an aromatic vinyl monomer unit, an unsaturated dicarboxylic anhydride monomer unit, and a thermoplastic resin are laminated on the thermoplastic resin. A copolymer containing acrylic compound monomer units in a predetermined ratio, and containing a copolymer in which the mass% of unsaturated dicarboxylic anhydride monomer units is larger than the mass% of acrylic compound monomer units, or By using a thermoplastic resin containing a copolymer and an acrylic resin containing an acrylic compound monomer unit as a main component, it has a surface hardness superior to that of an acrylic resin alone and is resistant to exposure to high temperatures and high humidity. It has the characteristics which are excellent in curvature deformability.
For example, HIT hardness {thermoplastic resin} of a laminate (Comparative Examples 1 to 16) containing a copolymer in which the mass% of unsaturated dicarboxylic acid anhydride monomer units is smaller than the mass% of acrylic compound monomer units Is lower than the HIT hardness {acrylic resin} of the laminates (Comparative Examples 17 to 20) using a single acrylic resin as the thermoplastic resin, and the pencil hardness is not sufficient. Moreover, the laminated body (comparative example 17) which used the acrylic resin single-piece | unit for a thermoplastic resin has not been able to suppress the curvature variation in a high temperature, high humidity environment.
In comparison with this, the laminates (Examples 1 to 41) containing a copolymer in which the mass% of the unsaturated dicarboxylic acid anhydride monomer unit is larger than the mass% of the acrylic compound monomer unit are acrylic resin alone. The HIT hardness {thermoplastic resin} is higher than that of the laminates (Comparative Examples 17 to 20) using No. 1 as the thermoplastic resin, and the amount of change in warpage in a high temperature and high humidity environment is also suppressed.
As described above, the laminate according to the present invention can improve the surface hardness while suppressing the amount of warpage change in the high temperature and high humidity environment of the conventional laminate of acrylic resin and polycarbonate.

As described above, the resin laminate according to the present invention that improves the surface hardness and suppresses the amount of warpage change under a high-temperature and high-humidity environment is suitable as a transparent base material or a transparent protective material as a substitute for glass. In particular, it can be suitably used as a touch panel front protective plate, a front plate for OA devices or portable electronic devices.

Claims

A resin laminate in which a thermoplastic resin (B) is laminated on at least one surface of a polycarbonate resin (A) sheet mainly composed of a polycarbonate resin,
The thermoplastic resin (B) is
50 to 80% by mass of an aromatic vinyl monomer unit, 10 to 25% by mass of an unsaturated dicarboxylic acid anhydride monomer unit, 5 to 24% by mass of an acrylic compound monomer unit, and A copolymer (b1) in which the mass% of the unsaturated dicarboxylic acid anhydride monomer unit is larger than the mass% of the acrylic compound monomer unit, or the copolymer (b1) and the acrylic compound unit A resin laminate comprising an acrylic resin (b2) containing a monomer unit as a main component.
Based on a total of 100 parts by mass of the copolymer (b1) and the acrylic resin (b2) in the thermoplastic resin (B), the copolymer (b1) is 55 to 90 parts by mass, The acrylic resin (b2) is 45 to 10 parts by mass, and the acrylic resin (b2) containing an acrylic compound monomer unit as a main component contains 80% by mass or more of an acrylic compound monomer unit. 1. The resin laminate according to 1.
Based on 100 parts by mass of the total content of the copolymer (b1) and the acrylic resin (b2) in the thermoplastic resin (B), the copolymer (b1) is 10 to 40 parts by mass, The acrylic resin (b2) is 90 to 60 parts by mass, and the acrylic resin (b2) containing an acrylic compound monomer unit as a main component contains an acrylic compound monomer unit of less than 80% by mass. 1. The resin laminate according to 1.
The resin laminate according to any one of claims 1 to 3, wherein the thermoplastic resin (B) is a polymer alloy of the copolymer (b1) and the acrylic resin (b2).
When the indentation hardness of the thermoplastic resin (B) is HIT hardness {thermoplastic resin} and the indentation hardness of the acrylic resin (b2) is HIT hardness {acrylic resin}, the HIT hardness {thermoplastic resin} The resin laminate according to any one of claims 1 to 4, wherein a value obtained by dividing the value by HIT hardness {acrylic resin} (HIT hardness {thermoplastic resin} / HIT hardness {acrylic resin}) is 1.01 or more.
The resin laminate according to any one of claims 1 to 5, wherein a pencil hardness of the surface of the thermoplastic resin (B) is equal to or greater than a pencil hardness of the surface of the acrylic resin (b2) alone.
The resin laminate according to any one of claims 1 to 6, wherein the aromatic vinyl monomer unit contained in the copolymer (b1) is styrene.
The resin laminate according to any one of claims 1 to 7, wherein the unsaturated dicarboxylic anhydride monomer unit contained in the copolymer (b1) is maleic anhydride.
The resin laminate according to any one of claims 1 to 8, wherein the acrylic compound monomer unit contained in the copolymer (b1) is a methacrylic ester.
The resin laminate according to any one of Claims 1 to 9, wherein the copolymer (b1) has a weight average molecular weight (Mw) of 50,000 to 300,000.
The thickness of the thermoplastic resin (B) layer is 10 to 250 µm, and the total thickness of the resin laminate is in the range of 0.05 to 3.0 mm. Resin laminate.
The resin laminate according to any one of claims 1 to 11, wherein the polycarbonate-based resin (A) has a weight average molecular weight of 25,000 to 75,000.
The resin laminate according to any one of claims 1 to 12, wherein the resin laminate has a total light transmittance of 75% or more and a Haze of 30% or less.
The resin laminate according to any one of claims 1 to 13, wherein at least one of the thermoplastic resin (B) layer and the polycarbonate-based resin (A) layer contains an ultraviolet absorber.
The resin laminate according to any one of claims 1 to 14, further comprising a hard coat layer on a surface of the thermoplastic resin (B) layer.
One or more of fingerprint resistance treatment, antireflection treatment, antiglare treatment, weather resistance treatment, antistatic treatment and antifouling treatment are performed on one or both surfaces of the resin laminate. The resin laminate according to any one of the above.
A transparent substrate material comprising the resin laminate according to any one of claims 1 to 16.
A transparent protective material comprising the resin laminate according to any one of claims 1 to 16.
A touch panel front protective plate comprising the resin laminate according to any one of claims 1 to 16.
A front plate for an OA device or a portable electronic device, comprising the resin laminate according to any one of claims 1 to 16.