WO2020261783A1

WO2020261783A1 - Resin layered body, and transparent substrate material and transparent protective material material containing the same

Info

Publication number: WO2020261783A1
Application number: PCT/JP2020/018929
Authority: WO
Inventors: 謙田桑; 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: 2019-06-26
Filing date: 2020-05-12
Publication date: 2020-12-30
Also published as: JPWO2020261783A1; TW202108382A

Abstract

The present invention provides a resin layered body having a layer containing a polycarbonate-based resin (A) comprising a polycarbonate resin as a primary component, and a layer containing a thermoplastic resin (B) disposed on at least one surface of the polycarbonate-based resin. The thermoplastic resin (B) includes a vinyl copolymer (C) and a styrene copolymer (D). The vinyl copolymer (C) contains 60-80 mol% of (meth)acrylic acid ester monomeric units (c1) and 40-20 mol% of aliphatic vinyl monomeric units (c2). The styrene copolymer (D) contains 60-90 mol% of vinyl aromatic monomeric units (d1), 10-20 mol% of cyclic acid anhydride monomeric units (d2) and 0-20 mol% of methacrylic acid ester monomeric units (d3). The haze value is ≤ 1.0%.

Description

Resin laminate and transparent substrate material and transparent protective material containing it

The present invention relates to a resin laminate that is preferably used as a transparent base material or a protective material and has a polycarbonate-based resin layer and a thermoplastic resin layer containing a specific vinyl copolymer and a specific styrene copolymer. ..

Acrylic resin has excellent surface hardness, transparency, scratch resistance and weather resistance. On the other hand, the polycarbonate resin has excellent impact resistance and the like. From this, the laminate having the acrylic resin layer and the polycarbonate resin layer is excellent in surface hardness, transparency, scratch resistance, weather resistance, impact resistance, etc., and is used for automobile parts, home appliances, electronic devices and portable information terminals. It is used for displays. However, the laminate having the acrylic resin layer and the polycarbonate resin layer has a problem that warpage occurs when used outdoors or in a car under high temperature and high humidity.

Patent Document 1 (International Publication No. 2011/145630) reports a laminate having a vinyl copolymer resin layer and a polycarbonate resin layer. It has been reported that such a laminate suppresses warpage at a high temperature and high humidity of 85 ° C. and 85%.

However, since the difference in glass transition temperature between the vinyl copolymer resin layer and the polycarbonate resin layer of the laminate is large, when the glass transition temperature of the polycarbonate resin is approached during hot press molding or thermal bending, the vinyl copolymer resin layer looks like a vinyl copolymer resin layer. Defects occur.
Further, since the difference in refractive index between the vinyl copolymer resin layer and the polycarbonate resin layer of the laminate is large, the reflected light intensity at the interface between the vinyl copolymer resin layer / the polycarbonate resin layer is large, and problems such as interference fringes occur.

Patent Document 2 (Japanese Unexamined Patent Publication No. 2016-196522) reports that a resin having a high glass transition temperature / refractive index is blended with a vinyl copolymer resin, and the glass transition temperature / refractive index is high. As a transparent sheet, Haze is high, and there is no description of warpage under high temperature and high humidity.

International Publication No. 2011/145630 Japanese Unexamined Patent Publication No. 2016-196522

An object of the present invention is to solve at least one of the above-mentioned conventional problems. Preferably, the present invention is used as a transparent base material or protective material, has a polycarbonate resin layer, a thermoplastic resin layer containing a specific vinyl copolymer and a specific styrene copolymer, and has a high temperature. An object of the present invention is to provide a resin laminate having excellent warp deformation resistance and heat resistance even when exposed to high humidity, having a high refractive index, and having a good appearance.

As a result of diligent studies to solve the above problems, the present inventors have found a solution means having the following configuration, and have completed the present invention.
[1] A resin laminate having a layer containing a thermoplastic resin (B) on at least one surface of a layer containing a polycarbonate resin (A) containing a polycarbonate resin as a main component.
The thermoplastic resin (B) contains a vinyl copolymer (C) and a styrene copolymer (D), and the vinyl copolymer (C) is a (meth) acrylic acid ester represented by the following general formula (1). It is a copolymer containing 60 to 80 mol% of the monomer unit (c1) and 40 to 20 mol% of the aliphatic vinyl monomer unit (c2) represented by the following general formula (2).
The styrene copolymer (D) contains 60 to 90 mol% of the vinyl aromatic monomer unit (d1), 10 to 20 mol% of the cyclic acid anhydride monomer unit (d2), and a methacrylic acid ester simple substance. It is a copolymer containing 0 to 20 mol% of a metric unit (d3).
The resin laminate having Haze ≦ 1.0%.

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

(In the formula, R3 represents a hydrogen atom or a methyl group, and R4 represents a cyclohexyl group which may have a hydrocarbon substituent having 1 to 4 carbon atoms.)
[2] The resin laminate according to the above [1], wherein the amount of change in warpage after being held in an environment of a temperature of 85 ° C. and a relative humidity of 85% for 120 hours is 200 μm or less in absolute value.
[3] The resin according to the above [1] or [2], wherein the difference between the glass transition temperature of the polycarbonate resin (A) and the glass transition temperature of the thermoplastic resin (B) is in the range of 0 to 25 ° C. It is a laminated body.
[4] The resin laminate according to any one of the above [1] to [3], wherein the thermoplastic resin (B) is a polymer alloy of a vinyl copolymer (C) and a styrene copolymer (D). Is.
[5] The content of the vinyl copolymer (C) is 5 based on the total content of 100 parts by mass of the vinyl copolymer (C) and the styrene copolymer (D) in the thermoplastic resin (B). The resin laminate according to any one of the above [1] to [4], wherein the styrene copolymer (D) has a content of up to 95 parts by mass and the content of the styrene copolymer (D) is 95 to 5 parts by mass.
[6] The vinyl copolymer (C) is derived from the aromatic vinyl monomer after polymerizing at least one (meth) acrylic acid ester monomer and at least one aromatic vinyl monomer. The resin laminate according to any one of the above [1] to [5], which is obtained by hydrogenating 70% or more of the aromatic double bonds.
[7] The resin laminate according to any one of the above [1] to [6], wherein R1 and R2 in the general formula (1) represent a methyl group.
[8] The resin laminate according to any one of [1] to [7] above, wherein R3 in the general formula (2) represents a hydrogen atom and R4 represents a cyclohexyl group.
[9] The resin laminate according to any one of the above [1] to [8], wherein the vinyl aromatic monomer unit (d1) contained in the styrene copolymer (D) is styrene.
[10] The resin laminate according to any one of the above [1] to [9], wherein the cyclic acid anhydride monomer unit (d2) contained in the styrene copolymer (D) is maleic anhydride. is there.
[11] The resin laminate according to any one of the above [1] to [10], wherein the methacrylic acid ester monomer unit (d3) contained in the styrene copolymer (D) is a methacrylic acid ester. ..
[12] The above [1] to [11], wherein the thickness of the layer containing the thermoplastic resin (B) is 10 to 250 μm, and the total thickness of the resin laminate is in the range of 0.04 to 4.0 mm. The resin laminate according to any one.
[13] The resin laminate according to any one of the above [1] to [12], wherein at least one of the layer containing the polycarbonate resin (A) and the layer containing the thermoplastic resin (B) contains an ultraviolet absorber. Is.
[14] The resin laminate according to any one of [1] to [13] above, further comprising a hard coat layer on the surface of the layer containing the thermoplastic resin (B).
[15] One or both sides of the resin laminate is subjected to any one or more of anti-fingerprint treatment, anti-reflection treatment, anti-glare treatment, weather resistance treatment, anti-static treatment and anti-fouling treatment. ] To [14]. The resin laminate according to any one of.
[16] A transparent substrate material containing the resin laminate according to any one of the above [1] to [15].
[17] A transparent protective material containing the resin laminate according to any one of the above [1] to [15].
[18] A touch panel front protective plate containing the resin laminate according to any one of the above [1] to [15].
[19] A front plate for an OA device or a portable electronic device, which comprises the resin laminate according to any one of the above [1] to [15].

According to the present invention, at least one of the above-mentioned conventional problems can be solved. Further, according to a preferred embodiment of the present invention, a resin laminate having excellent warp deformation resistance and heat resistance, a high refractive index, and a good appearance even when exposed to high temperature and high humidity is provided, and the resin laminate is provided. The body can be used as a transparent substrate material or a transparent protective material. Specifically, in portable display devices such as mobile phone terminals, portable electronic play equipment, personal digital assistants, and mobile PCs, and stationary display devices such as notebook PCs, desktop PC liquid crystal monitors, and liquid crystal televisions, for example, these It can be suitably used as a front plate for protecting the equipment of. Whether or not the appearance is good can be determined by, for example, the presence or absence of interference fringes described in Examples described later.

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

<Polycarbonate resin (A)>
The polycarbonate-based resin (A) used in the present invention is a polycarbonate-based resin (A) containing a polycarbonate resin as a main component. Here, "mainly composed of a polycarbonate resin" means that the content of the polycarbonate resin exceeds 50% by mass. The polycarbonate resin (A) preferably contains 75% by mass or more of the polycarbonate resin, more preferably 90% by mass or more of the polycarbonate resin, and further preferably substantially composed of the polycarbonate resin. .. The polycarbonate resin (A) contains a carbonic acid ester bond in the molecular main chain. That is,-[OR-OCO] -units (in the formula, R contains an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group, and further has a linear structure or a branched structure. Is not particularly limited as long as it contains), but it is particularly preferable to use a polycarbonate containing the structural unit of the following formula (3). By using such polycarbonate, a resin laminate having excellent impact resistance can be obtained.

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

(In the formula, R ₁ represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms.
R 2 _- R ₅ each represents hydrogen, halogen, or a substituent and 1 carbon atoms which may have a 20 alkyl group or an aryl group having 6 to 12 carbon atoms, the substituents are halogen, C 1 - It is an alkyl group of 20 or an aryl group having 6 to 12 carbon atoms. )

The monovalent phenol of the general formula (4) is more preferably a monohydric phenol represented by the following general formula (5).

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

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

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

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

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

As another resin contained in the polycarbonate resin (A), there is a polyester resin. The polyester resin may contain terephthalic acid as a main component as the dicarboxylic acid component, and may contain a dicarboxylic acid component other than terephthalic acid. For example, a glycol component containing 20 to 40 (molar ratio, 100 in total) of 1,4-cyclohexanedimethanol with respect to ethylene glycol 80 to 60 (molar ratio) as the main component and a dicarboxylic acid component are polycondensed. A polyester resin, so-called "PETG", is preferable. Further, the polycarbonate 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, if the weight average molecular weight is too small, the impact resistance of the resin laminate is lowered, which is not preferable. If the weight average molecular weight is too high, an excessive heat source may be required when laminating the layer containing the polycarbonate resin (A), which is not preferable. In addition, since a high temperature is required depending on the molding method, the polycarbonate resin (A) is exposed to a high temperature, which may adversely affect its thermal stability. The weight average molecular weight of the polycarbonate resin (A) is preferably 15,000 to 75,000, more preferably 20,000 to 70,000. More preferably, it is 25,000 to 65,000.

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

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

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

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

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

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

In the (meth) acrylic acid ester monomer unit (c1) represented by the general formula (1), R2 is an alkyl group having 1 to 18 carbon atoms, preferably an alkyl group having 1 to 2 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a butyl group, a lauryl group, a stearyl group, a cyclohexyl group, and an isobornyl group. Among the (meth) acrylic acid ester monomer units (c1), the (meth) acrylic acid ester monomer unit in which R2 is a methyl group and / or an ethyl group is preferable, and R1 is more preferable. It is a methyl methacrylate monomer unit in which R2 is a methyl group.

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

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

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

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

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

The chain transfer agent is used as needed, and examples thereof include α-methylstyrene dimer.

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

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

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

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

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

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

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

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

<Styrene copolymer (D)>
The styrene copolymer (D) contained in the thermoplastic resin (B) according to the present invention contains a vinyl aromatic monomer unit (d1), a cyclic acid anhydride monomer unit (d2), and a methacrylic acid ester simple substance. The total ratio of the vinyl aromatic monomer unit (d1), the cyclic acid anhydride monomer unit (d2), and the methacrylic acid ester monomer unit (d3) is the styrene, including the metric unit (d3). It is 90 to 100 mol% with respect to the total of all the monomer units in the copolymer (D), and the ratio of the vinyl aromatic monomer unit (d1) is in the styrene copolymer (D). It is 60 to 90 mol% with respect to the total of all monomer units, and the ratio of the cyclic acid anhydride monomer unit (d2) is the total of all monomer units in the styrene copolymer (D). 10 to 20 mol% with respect to the total of all the monomer units in the styrene copolymer (D), and the ratio of the methacrylic acid ester monomer unit (d3) is 0 to 20 mol%. It is characterized by being.

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

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

Examples of the methacrylic acid ester monomer unit (d3) of the styrene copolymer (D) include acrylonitrile, metaacrylonitrile, acrylic acid, methacrylic acid, and (meth) acrylic acid ester. Examples of the (meth) acrylic acid ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and 2-ethylhexyl methacrylate. Be done. Among them, methyl methacrylate (MMA) is preferable from the viewpoint of compatibility with acrylic resin. Two or more kinds of these acrylic compound monomers may be mixed.

In the styrene copolymer (D) used in the present invention, the vinyl aromatic monomer unit (d1), the cyclic acid anhydride monomer unit (d2), and the methacrylic acid ester monomer unit (d3). The total ratio with and from is 90 to 100 mol%, preferably 95 to 100 mol%, and more preferably 98 to 100 mol% with respect to the total of all the monomer units in the styrene copolymer (D). Mol%.
That is, the styrene copolymer (D) contains the vinyl aromatic monomer unit (d1) and the cyclic acid anhydride monomer in a range of 10 mol% or less with respect to the total of all the monomer units. It may contain a monomer unit other than the unit (d2) and the methacrylic acid ester monomer unit (d3). Examples of the monomer unit other than the vinyl aromatic monomer unit (d1), the cyclic acid anhydride monomer unit (d2), and the methacrylate ester monomer unit (d3) include N-substituted. Examples include type maleimide monomers. Examples of the N-substituted maleimide monomer include N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-naphthylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, and N-carboxyphenylmaleimide. Examples thereof include N-arylmaleimide such as N-nitrophenylmaleimide and N-tribromophenylmaleimide, and N-phenylmaleimide is preferable from the viewpoint of compatibility with acrylic resin. Two or more kinds of these N-substituted maleimide monomers may be mixed.

The ratio of the vinyl aromatic monomer unit (d1) is 60 to 90 mol%, preferably 65 to 90 mol%, based on the total of all the monomer units in the styrene copolymer (D). It is more preferably 70 to 90 mol%, further preferably 72 to 88 mol%, and particularly preferably 74 to 86 mol%. The ratio of the cyclic acid anhydride monomer unit (d2) is 10 to 20 mol%, preferably 12 to 18 mol%, based on the total of all the monomer units in the styrene copolymer (D). %, More preferably 14 to 16 mol%. The ratio of the methacrylic acid ester monomer unit (d3) is 0 to 20 mol%, preferably 0 to 15 mol%, based on the total of all the monomer units in the styrene copolymer (D). It is more preferably 0 to 10 mol%.
When the ratio of the vinyl aromatic monomer unit (d1) to the total of all the monomer units in the styrene copolymer (D) is less than 60 mol%, the phase with the vinyl copolymer (C) Poor solubility. Further, if it exceeds 90 mol%, sufficient heat resistance cannot be imparted. If the ratio of the cyclic acid anhydride monomer unit (d2) to the total of all the monomer units in the styrene copolymer (D) is less than 10 mol%, the heat resistance is insufficient. If it exceeds 20 mol%, the compatibility with the vinyl copolymer (C) deteriorates.

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

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

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

The styrene copolymer (D) is a binary copolymer containing a vinyl aromatic monomer unit (d1) and a cyclic acid anhydride monomer unit (d2), or a vinyl aromatic monomer unit. It is a ternary copolymer containing (d1), a cyclic acid anhydride monomer unit (d2), and a methacrylic acid ester monomer unit (d3), but a vinyl copolymer (C) may be used in combination. Therefore, the resin laminate has higher hardness than the case where only the styrene copolymer (D) is used, and has shape stability under high temperature and high humidity as compared with the case where only the vinyl copolymer (C) is used. can get.

In the present invention, the mass ratio of the vinyl copolymer (C) to the styrene copolymer (D) is 100 parts by mass in total of the contents of the vinyl copolymer (C) and the styrene copolymer (D). It is preferable that the vinyl copolymer (C) is 5 to 95 parts by mass and the styrene copolymer (D) is 95 to 5 parts by mass based on the above. More preferably, the vinyl copolymer (C) is 15 to 85 parts by mass, and the styrene copolymer (D) is 85 to 15 parts by mass, and more preferably, the vinyl copolymer (C). The styrene copolymer (D) is 75 to 25 parts by mass with respect to 25 to 75 parts by mass, and particularly preferably, the vinyl copolymer (C) is 40 to 60 parts by mass with the styrene. The copolymer (D) is 60 to 40 parts by mass. By keeping the mass ratio within this range, an excellent thermoplastic resin having excellent warp deformation resistance and heat resistance, a high refractive index, and a good appearance even when exposed to high temperature and high humidity while maintaining transparency ( B).

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

In the present invention, the method for producing the thermoplastic resin (B) is not particularly limited, and necessary components are mixed in advance using a mixer such as a tumbler, a Henschel mixer, or a super mixer, and then a Banbury mixer, Known methods such as melt-kneading with a machine such as a roll, a brabender, a single-screw extruder, a twin-screw extruder, or a pressure kneader can be applied.
One of the characteristics of the thermoplastic resin (B) used in the present invention is that the glass transition temperature is relatively high, preferably in the range of 122 to 185 ° C, and preferably in the range of 123 to 160 ° C. It is more preferable, and the range of 125 to 140 ° C. is particularly preferable. Since the glass transition temperature of the thermoplastic resin (B) used in the present invention is relatively high and the difference from the glass transition temperature of the polycarbonate resin (A) is small, the polycarbonate resin is used during hot press molding or heat bending. Even if the temperature approaches the glass transition temperature of (A), there is an advantage that there is little problem that the layer containing the thermoplastic resin (B) has a poor appearance. The difference between the glass transition temperature of the polycarbonate resin (A) and the glass transition temperature of the thermoplastic resin (B) is preferably in the range of 0 to 25 ° C, more preferably in the range of 0 to 20 ° C. It is particularly preferably in the range of 10 to 20 ° C.

<Resin laminate>
The resin laminate of the present invention has Haze ≦ 1.0%, preferably Haze ≦ 0.8%, and more preferably Haze ≦ 0.7%. If Haze exceeds 1.0%, the resin laminate may appear whitish visually.
Further, in the resin laminate of the present invention, the amount of change in warpage measured according to the <warp test in a high temperature and high humidity environment> in Examples described later is preferably 200 μm or less in absolute value, and is 150 μm or less. It is more preferably 100 μm or less, and particularly preferably 100 μm or less. When the absolute value of the amount of change in warpage exceeds 200 μm, deformation of the resin laminate may be visually confirmed.
In the present invention, the thickness of the layer containing the thermoplastic resin (B) affects the surface hardness and impact resistance of the resin laminate. That is, if the thickness of the layer containing the thermoplastic resin (B) is too thin, the surface hardness becomes low, which is not preferable. If the thickness of the layer containing the thermoplastic resin (B) is too large, the impact resistance deteriorates, which is not preferable. The thickness of the layer containing the thermoplastic resin (B) is preferably 10 to 250 μm, more preferably 20 to 200 μm. More preferably, it is 30 to 150 μm.

In the present invention, if the total thickness of the layer containing the polycarbonate resin (A) and the layer containing the thermoplastic resin (B) is too thin or too thick, molding is difficult. The total thickness of the layer containing the polycarbonate resin (A) and the layer containing the thermoplastic resin (B) is preferably 0.04 to 4.0 mm, more preferably 0.05 to 3.5 mm, still more preferably 0. It is 5 to 3.0 mm.

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

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

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

<Arbitrary processing>
In the present invention, the surface of the layer containing the thermoplastic resin (B) or the surface of the layer containing the polycarbonate resin (A) may be subjected to a hard coat treatment. For example, a hard coat layer is formed by a hard coat treatment using a hard coat paint that cures using heat energy and / or light energy. Examples of the hard coat paint to be cured by using heat energy include thermosetting resin compositions such as polyorganosiloxane-based and crosslinked acrylic-based. Further, as a hard coat coating material to be cured using light energy, for example, a photocurable resin obtained by adding a photopolymerization initiator to a resin composition composed of a monofunctional and / or polyfunctional acrylate monomer and / or oligomer. Examples include compositions.

The method of applying the hard coat paint in the present invention is not particularly limited, and a known method can be used. For example, spin coating method, dip method, spray method, slide coating method, bar coating method, roll coating method, gravure coating method, meniscus coating method, flexographic printing method, screen printing method, beat coating method, and handling method can be mentioned. ..

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

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

There are no particular restrictions on the filter used, known ones can be used, and they are appropriately selected according to the operating temperature, viscosity, and filtration accuracy of each material. The filter medium of the filter is not particularly limited, but is a polypropylene, cotton, polyester, viscose rayon or glass fiber non-woven fabric or roving yarn roll, phenol resin impregnated cellulose, metal fiber non-woven fabric sintered body, metal powder sintered body, breaker plate, etc. Alternatively, any combination of these can be used. In particular, considering heat resistance, durability, and pressure resistance, a type obtained by sintering a metal fiber non-woven fabric is preferable.

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

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

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

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

The appearance evaluation of the copolymer obtained in the production example and the appearance evaluation of the resin laminate obtained in the examples and the comparative examples were performed as follows.

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

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

<Mole ratio of monomer unit in copolymer>
It was calculated from the measured values of ¹ H-NMR and ¹³ C-NMR (400 MHz: solvent is CDCl3) using JNM-AL400 manufactured by JEOL Ltd.

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

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

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

<Warp test in high temperature and high humidity environment>
A test piece having a length of 100 mm and a width of 60 mm was cut out from the vicinity of the center of the resin laminate. The test piece was set in a two-point support type holder and placed in an environmental tester set at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours or more to adjust the state, and then the warp was measured. The value at this time was taken as the value of the amount of warpage before processing. Next, the test piece was set in a holder and placed in an environmental tester set at a temperature of 85 ° C. and a relative humidity of 85%, and held in that state for 120 hours. Further, the holder was moved into an environmental tester set at a temperature of 23 ° C. and a relative humidity of 50%, and the warp was measured again after holding for 4 hours in that state. The value at this time was taken as the value of the amount of warpage after processing. To measure the warp, a three-dimensional shape measuring machine equipped with an electric stage is used, and the taken-out test piece is placed horizontally in a convex state and scanned at 1 mm intervals, and the swelling in the center is measured as the warp. did. The difference in the amount of warpage before and after the treatment, that is, (the amount of warpage after treatment)-(the amount of warpage before treatment) was evaluated as the amount of change in warpage. At that time, when the layer side containing the thermoplastic resin (B) was convex, it was evaluated with a “−” code, and when the layer side containing the polycarbonate resin (A) was convex, it was evaluated with a “+” code.

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

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

For examples, polycarbonate resins (A-1), thermoplastic resins (B-1) to (B-4), vinyl copolymers (C-1), and styrene copolymers (D-1). As (D-2), the following materials were used, but the present invention is not limited thereto. On the other hand, for comparative examples, thermoplastic resins (F-1) to (F-5) using the styrene copolymers (E-1) to (E-5) shown below were used.

<Polycarbonate resin (A-1), styrene copolymers (D-1) to (D-2) and styrene copolymers (E-1) to (E-5)>
Polycarbonate resin (A-1): Iupiron S-1000 manufactured by Mitsubishi Engineering Plastics Co., Ltd. (weight average molecular weight: 33,000, glass transition temperature: 147 ° C., refractive index 1.586)
Styrene copolymer (D-1): XIBOND140 manufactured by Polyscape (weight average molecular weight: 114,000, glass transition temperature: 134 ° C., (d1) / (d2) = styrene / maleic anhydride = 85 mol% / 15 mol %)
Styrene copolymer (D-2): KX-454 manufactured by Denka Co., Ltd. (weight average molecular weight: 184,000, glass transition temperature: 130 ° C., (d1) / (d2) / (d3) = styrene / maleic anhydride / Methyl methacrylate = 77 mol% / 15 mol% / 8 mol%)
Styrene copolymer (E-1): XiranSZ08250 manufactured by Polyscape (weight average molecular weight: 250,000, glass transition temperature: 115 ° C., (d1) / (d2) = styrene / maleic anhydride = 92 mol% / 8 mol %)
Styrene copolymer (E-2): R-100 manufactured by Denka Co., Ltd. (weight average molecular weight: 155,000, glass transition temperature: 128 ° C., (d1) / (d2) / (d3) = styrene / maleic anhydride / Methyl methacrylate = 63 mol% / 15 mol% / 22 mol%)
Styrene copolymer (E-3): R-200 manufactured by Denka Co., Ltd. (weight average molecular weight: 190,000, glass transition temperature: 132 ° C., (d1) / (d2) / (d3) = styrene / maleic anhydride / Methyl methacrylate = 54 mol% / 20 mol% / 26 mol%)
Styrene copolymer (E-4): KX-406 manufactured by Denka Co., Ltd. (weight average molecular weight: 120,000, glass transition temperature: 142 ° C., (d1) / (d2) / (d3) = styrene / maleic anhydride / Methyl methacrylate = 69 mol% / 24 mol% / 7 mol%)
Styrene copolymer (E-5): KX-420 manufactured by Denka Co., Ltd. (weight average molecular weight: 63,000, glass transition temperature: 141 ° C., (d1) / (d2) / (d3) = styrene / maleic anhydride / Methyl methacrylate = 54 mol% / 24 mol% / 22 mol%)

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

Production Example 1A [Production of a single-layer film of a thermoplastic resin (B-1)]
After mixing 25 parts by mass of vinyl copolymer (C-1) and 75 parts by mass of styrene copolymer (D-1) with a blender for 20 minutes, a shaft diameter of 32 mmφ with a 280 mm wide single layer die attached. It was put into a single-screw extruder and kneaded under the conditions of a cylinder temperature of 220 ° C. to 290 ° C., an adapter temperature of 290 ° C., a die temperature of 290 ° C., and a discharge rate of 9.0 kg / h. 2 Chill roll temperature: Cooled at 90 ° C. to prepare a single-layer film of a thermoplastic resin (B-1) having a thickness of 70 μm.
The single-layer film of the thermoplastic resin (B-1) had Haze: 0.4%, a glass transition temperature: 131 ° C., and a refractive index: 1.568.

Production Example 2A [Production of a single-layer film of thermoplastic resin (B-2)]
After mixing 40 parts by mass of the vinyl copolymer (C-1) and 60 parts by mass of the styrene copolymer (D-1) with a blender for 20 minutes, a thermoplastic resin having a thickness of 70 μm (similar to Production Example 1A). A single-layer film of B-2) was prepared.
The single-layer film of the thermoplastic resin (B-2) had Haze: 0.4%, a glass transition temperature of 129 ° C., and a refractive index of 1.551.

Production Example 3A [Production of a single-layer film of thermoplastic resin (B-3)]
After mixing 50 parts by mass of the vinyl copolymer (C-1) and 50 parts by mass of the styrene copolymer (D-1) with a blender for 20 minutes, a thermoplastic resin having a thickness of 70 μm (similar to Production Example 1A). A single-layer film of B-3) was prepared.
The monolayer film of the thermoplastic resin (B-3) had Haze: 0.5%, a glass transition temperature: 128 ° C., and a refractive index: 1.543.

Production Example 4A [Production of a single-layer film of thermoplastic resin (B-4)]
After mixing 60 parts by mass of the vinyl copolymer (C-1) and 40 parts by mass of the styrene copolymer (D-1) with a blender for 20 minutes, a thermoplastic resin having a thickness of 70 μm (similar to Production Example 1A). A single-layer film of B-4) was prepared.
The single-layer film of the thermoplastic resin (B-4) had Haze: 0.4%, a glass transition temperature of 127 ° C., and a refractive index of 1.524.

Production Example 5A [Production of a single-layer film of a thermoplastic resin (B-5)]
After mixing 75 parts by mass of the vinyl copolymer (C-1) and 25 parts by mass of the styrene copolymer (D-1) with a blender for 20 minutes, a thermoplastic resin having a thickness of 70 μm (similar to Production Example 1A). A single-layer film of B-5) was prepared.
The single-layer film of the thermoplastic resin (B-5) had Haze: 0.3%, a glass transition temperature: 125 ° C., and a refractive index: 1.519.

Production Example 6A [Production of a single-layer film of thermoplastic resin (B-6)]
After mixing 50 parts by mass of the vinyl copolymer (C-1) and 50 parts by mass of the styrene copolymer (D-2) with a blender for 20 minutes, a thermoplastic resin having a thickness of 70 μm (similar to Production Example 1A). A single-layer film of B-6) was prepared.
The single-layer film of the thermoplastic resin (B-6) had Haze: 0.9%, a glass transition temperature: 128 ° C., and a refractive index: 1.536.

Production Comparative Example 1A [Production of a single-layer film of a thermoplastic resin (F-1)]
After mixing 50 parts by mass of the vinyl copolymer (C-1) and 50 parts by mass of the styrene copolymer (E-1) with a blender for 20 minutes, a thermoplastic resin having a thickness of 70 μm (similar to Production Example 1A). A single-layer film of F-1) was produced.
The single-layer film of the thermoplastic resin (F-1) had Haze: 0.1%, a glass transition temperature of 118 ° C., and a refractive index of 1.537.

Production Comparative Example 2A [Manufacture of a single-layer film of thermoplastic resin (F-2)]
After mixing 50 parts by mass of the vinyl copolymer (C-1) and 50 parts by mass of the styrene copolymer (E-2) with a blender for 20 minutes, a thermoplastic resin having a thickness of 70 μm (similar to Production Example 1A). A single layer film of F-2) was prepared.
The monolayer film of the thermoplastic resin (F-2) had Haze: 1.9%, a glass transition temperature of 124 ° C., and a refractive index of 1.532.

Production Comparative Example 3A [Manufacture of Single Layer Film of Thermoplastic Resin (F-3)]
After mixing 50 parts by mass of the vinyl copolymer (C-1) and 50 parts by mass of the styrene copolymer (E-3) with a blender for 20 minutes, a thermoplastic resin having a thickness of 70 μm (similar to Production Example 1A). A single-layer film of F-3) was prepared.
The single-layer film of the thermoplastic resin (F-3) had Haze: 34.8%, glass transition temperature: two peaks due to incompatibility, and refractive index: incompatible, so that measurement was impossible.

Production Comparative Example 4A [Manufacture of Single Layer Film of Thermoplastic Resin (F-4)]
After mixing 50 parts by mass of the vinyl copolymer (C-1) and 50 parts by mass of the styrene copolymer (E-4) with a blender for 20 minutes, a thermoplastic resin having a thickness of 70 μm (similar to Production Example 1A). A single-layer film of F-4) was prepared.
The monolayer film of the thermoplastic resin (F-4) had Haze: 25.5%, glass transition temperature: two peaks were generated due to incompatibility, and refractive index: could not be measured because of incompatibility.

Production Comparative Example 5A [Production of a single-layer film of a thermoplastic resin (F-5)]
After mixing 50 parts by mass of the vinyl copolymer (C-1) and 50 parts by mass of the styrene copolymer (E-5) with a blender for 20 minutes, a thermoplastic resin having a thickness of 70 μm (similar to Production Example 1A). A single layer film of F-5) was prepared.
The single-layer film of the thermoplastic resin (F-5) had Haze: 54.6%, the glass transition temperature: two peaks were generated due to incompatibility, and the refractive index was incompatible, so measurement was impossible.

Production Comparative Example 6A [Production of a single-layer film of a thermoplastic resin (F-6)]
Using 100 parts by mass of the vinyl copolymer (C-1) (without the styrene copolymer), a single-layer film of a thermoplastic resin (F-6) having a thickness of 70 μm was prepared in the same manner as in Production Example 1A.
The single-layer film of the thermoplastic resin (F-6) had Haze: 0.1%, a glass transition temperature of 121 ° C., and a refractive index of 1.494.

Production Comparative Example 7A [Manufacturing of Single Layer Film of Thermoplastic Resin (F-7)]
Using 100 parts by mass of the styrene copolymer (D-1) (without the vinyl copolymer), a single-layer film of a thermoplastic resin (F-7) having a thickness of 70 μm was prepared in the same manner as in Production Example 1A.
The single-layer film of the thermoplastic resin (F-7) had Haze: 0.3%, a glass transition temperature of 134 ° C., and a refractive index of 1.590.

Production Example 1B [Production of pellets (B-1-1)]
The dry blend ratio of Production Example 1A is 25 parts by mass of vinyl copolymer (C-1) and 75 parts by mass of styrene copolymer (D-1), for a total of 100 parts by mass of phosphorus. Add 500 ppm of the system additive PEP-36 (manufactured by ADEKA Co., Ltd.) and 0.2% by mass of stearate monoglyceride (product name: H-100, manufactured by Riken Vitamin Co., Ltd.), mix for 20 minutes with a blender, and then open 10 μm. Using a twin-screw extruder with a screw diameter of 26 mm (manufactured by Toshiba Machine Co., Ltd., TEM-26SS, L / D≈40) equipped with the above polymer filter, melt-kneaded at a cylinder temperature of 240 ° C. and extruded into strands. It was pelletized with a pelletizer. The pellets could be produced stably.

Production Example 2B [Production of pellets (B-2-1)]
The dry blend ratio is the same as in Production Example 2A, with respect to 40 parts by mass of the vinyl copolymer (C-1) and 60 parts by mass of the styrene copolymer (D-1), for a total of 100 parts by mass. The system additive PEP-36 500 ppm and 0.2% by mass of stearate monoglyceride were added, and the mixture and pelletization were carried out in the same manner as in Production Example 1B. The pellets could be produced stably.

Production Example 3B [Production of pellets (B-3-1)]
Lynn with respect to 50 parts by mass of vinyl copolymer (C-1) and 50 parts by mass of styrene copolymer (D-1), which is the same dry blend ratio as in Production Example 3A, for a total of 100 parts by mass. The system additive PEP-36 500 ppm and 0.2% by mass of stearate monoglyceride were added, and the mixture and pelletization were carried out in the same manner as in Production Example 1B. The pellets could be produced stably.

Production Example 4B [Production of pellets (B-4-1)]
The dry blend ratio is the same as in Production Example 4A, with respect to 60 parts by mass of the vinyl copolymer (C-1) and 40 parts by mass of the styrene copolymer (D-1), for a total of 100 parts by mass. The system additive PEP-36 500 ppm and 0.2% by mass of stearate monoglyceride were added, and the mixture and pelletization were carried out in the same manner as in Production Example 1B. The pellets could be produced stably.

Production Example 5B [Production of pellets (B-5-1)]
The dry blend ratio is the same as in Production Example 5A, with respect to 75 parts by mass of the vinyl copolymer (C-1) and 25 parts by mass of the styrene copolymer (D-1), for a total of 100 parts by mass. The system additive PEP-36 500 ppm and 0.2% by mass of stearate monoglyceride were added, and the mixture and pelletization were carried out in the same manner as in Production Example 1B. The pellets could be produced stably.

Production Example 6B [Production of pellets (B-6-1)]
Lynn with respect to 50 parts by mass of the vinyl copolymer (C-1) and 50 parts by mass of the styrene copolymer (D-2), which is the same dry blend ratio as in Production Example 6A, for a total of 100 parts by mass. The system additive PEP-36 500 ppm and 0.2% by mass of stearate monoglyceride were added, and the mixture and pelletization were carried out in the same manner as in Production Example 1B. The pellets could be produced stably.

Production Comparative Example 6B [Production of pellets (F-6-1)]
To 100 parts by mass of the vinyl copolymer (C-1) which is the same as in Production Comparative Example 6A, 500 ppm of phosphorus-based additive PEP-36 and 0.2% by mass of stearic acid monoglyceride are added, and the same as in Production Example 1B. Was pelletized. The pellets could be produced stably.

Production Comparative Example 7B [Production of pellets (F-7-1)]
To 100 parts by mass of the styrene copolymer (D-1) which is the same as in Production Comparative Example 7A, 500 ppm of phosphorus-based additive PEP-36 and 0.2% by mass of stearic acid monoglyceride are added, and the same as in Production Example 1B. Was pelletized. The pellets could be produced stably.

Example 1 [Manufacturing of resin laminate (G-1)]
Each is a multi-layer extruder having a single-screw extruder with a shaft diameter of 32 mm, a single-screw extruder with a shaft diameter of 65 mm, a feed block connected to all extruders, and a 650 mm wide T-die connected to the feed block. The resin laminate was molded using a multi-layer extruder having a multi-manifold die connected to the extruder. The pellets (B-1-1) obtained in Production Example 1B were continuously introduced into a single-screw extruder having a shaft diameter of 32 mm, and extruded under the conditions of a cylinder temperature of 240 ° C. and a discharge rate of 2.4 kg / h. In addition, a polycarbonate resin (A-1) (manufactured by Mitsubishi Engineering Plastics Co., Ltd., product name: Iupiron S-1000) is continuously introduced into a single-screw extruder with a shaft diameter of 65 mm, and the cylinder temperature is 280 ° C. and the discharge amount is Was extruded at 31.8 kg / h. The feed block connected to the full extruder was equipped with two types and two layers of distribution pins, and the pellet (B-1-1) and the polycarbonate resin (A-1) were introduced and laminated at a temperature of 270 ° C. It is extruded into a sheet with a T-die with a temperature of 270 ° C connected to the tip, and cooled while transferring the mirror surface with three mirror-finishing rolls with temperatures of 130 ° C, 140 ° C, and 180 ° C from the upstream side, and pellets (B). A resin laminate (G-1) of 1-1) and a polycarbonate resin (A-1) was obtained. The total thickness of the central portion of the obtained resin laminate (G-1) was 1000 μm, and the thickness of the surface layer (layer containing the thermoplastic resin (B)) was 70 μm. This resin laminate (G-1) has total light transmittance: 91.0%, haze: 0.4%, pencil hardness: H, warp change amount under high temperature and high humidity environment: -187 μm, interference fringes: 〇. there were.

Example 2 [Manufacturing of resin laminate (G-2)]
The resin laminate (G) of Example 1 except that the discharge amount of the single-screw extruder having a shaft diameter of 32 mm was changed to 1.4 kg / h and the discharge amount of the single-screw extruder having a shaft diameter of 65 mm was changed to 32.8 kg / h. A resin laminate (G-2) of pellets (B-1-1) and a polycarbonate-based resin (A-1) was obtained in the same manner as in -1). The total thickness of the central portion of the obtained resin laminate (G-2) was 1000 μm, and the surface layer thickness was 40 μm. This resin laminate (G-2) has total light transmittance: 90.9%, haze: 0.7%, pencil hardness: H, amount of change in warpage under high temperature and high humidity environment: -76 μm, interference fringes: 〇. there were.

Example 3 [Manufacturing of resin laminate (G-3)]
With the pellet (B-2-1) in the same manner as the resin laminate (G-1) of Example 1 except that the pellet (B-2-1) was used instead of the pellet (B-1-1). A resin laminate (G-3) of a polycarbonate resin (A-1) was obtained. The total thickness of the central portion of the obtained resin laminate (G-3) was 1000 μm, and the surface layer thickness was 70 μm. This resin laminate (G-3) has total light transmittance: 91.0%, haze: 0.3%, pencil hardness: H, amount of change in warpage under high temperature and high humidity environment: -161 μm, interference fringes: 〇. there were.

Example 4 [Manufacturing of resin laminate (G-4)]
With the pellet (B-2-1) in the same manner as the resin laminate (G-2) of Example 2 except that the pellet (B-2-1) was used instead of the pellet (B-1-1). A resin laminate (G-4) of a polycarbonate resin (A-1) was obtained. The total thickness of the central portion of the obtained resin laminate (G-4) was 1000 μm, and the surface layer thickness was 40 μm. This resin laminate (G-4) has total light transmittance: 91.0%, haze: 0.3%, pencil hardness: H, amount of change in warpage under high temperature and high humidity environment: -38 μm, interference fringes: 〇. there were.

Example 5 [Manufacturing of resin laminate (G-5)]
With the pellet (B-3-1) in the same manner as the resin laminate (G-1) of Example 1 except that the pellet (B-3-1) was used instead of the pellet (B-1-1). A resin laminate (G-5) of a polycarbonate resin (A-1) was obtained. The total thickness of the central portion of the obtained resin laminate (G-5) was 1000 μm, and the surface layer thickness was 70 μm. This resin laminate (G-5) has total light transmittance: 91.2%, haze: 0.3%, pencil hardness: H, amount of change in warpage under high temperature and high humidity environment: -141 μm, interference fringes: 〇. there were.

Example 6 [Manufacturing of resin laminate (G-6)]
With the pellet (B-3-1) in the same manner as the resin laminate (G-2) of Example 2 except that the pellet (B-3-1) was used instead of the pellet (B-1-1). A resin laminate (G-6) of a polycarbonate resin (A-1) was obtained. The total thickness of the central portion of the obtained resin laminate (G-6) was 1000 μm, and the surface layer thickness was 40 μm. This resin laminate (G-6) has total light transmittance: 91.2%, haze: 0.2%, pencil hardness: H, amount of change in warpage under high temperature and high humidity environment: -1 μm, interference fringes: 〇. there were.

Example 7 [Manufacturing of resin laminate (G-7)]
With the pellet (B-4-1) in the same manner as the resin laminate (G-1) of Example 1 except that the pellet (B-4-1) was used instead of the pellet (B-1-1). A resin laminate (G-7) of a polycarbonate resin (A-1) was obtained. The total thickness of the central portion of the obtained resin laminate (G-7) was 1000 μm, and the surface layer thickness was 70 μm. This resin laminate (G-7) has total light transmittance: 91.4%, haze: 0.3%, pencil hardness: H, amount of change in warpage under high temperature and high humidity environment: -67 μm, interference fringes: 〇. there were.

Example 8 [Manufacturing of resin laminate (G-8)]
With the pellet (B-4-1) in the same manner as the resin laminate (G-2) of Example 2 except that the pellet (B-4-1) was used instead of the pellet (B-1-1). A resin laminate (G-8) of a polycarbonate resin (A-1) was obtained. The total thickness of the central portion of the obtained resin laminate (G-8) was 1000 μm, and the surface layer thickness was 40 μm. This resin laminate (G-8) has total light transmittance: 91.3%, haze: 0.3%, pencil hardness: H, warpage change amount under high temperature and high humidity environment: + 77 μm, interference fringes: 〇. It was.

Example 9 [Manufacturing of resin laminate (G-9)]
With the pellet (B-5-1) in the same manner as the resin laminate (G-1) of Example 1 except that the pellet (B-5-1) was used instead of the pellet (B-1-1). A resin laminate (G-9) of a polycarbonate resin (A-1) was obtained. The total thickness of the central portion of the obtained resin laminate (G-9) was 1000 μm, and the surface layer thickness was 70 μm. This resin laminate (G-9) has total light transmittance: 91.2%, haze: 0.3%, pencil hardness: 2H, warp change amount under high temperature and high humidity environment: +56 μm, interference fringes: 〇. It was.

Example 10 [Manufacturing of resin laminate (G-10)]
With the pellet (B-5-1) in the same manner as the resin laminate (G-2) of Example 2 except that the pellet (B-5-1) was used instead of the pellet (B-1-1). A resin laminate (G-10) of a polycarbonate resin (A-1) was obtained. The total thickness of the central portion of the obtained resin laminate (G-10) was 1000 μm, and the surface layer thickness was 40 μm. This resin laminate (G-10) has total light transmittance: 91.3%, haze: 0.3%, pencil hardness: 2H, warp change amount under high temperature and high humidity environment: +16 μm, interference fringes: 〇. It was.

Example 11 [Manufacturing of Resin Laminated Body (G-11)]
With the pellet (B-6-1) in the same manner as the resin laminate (G-1) of Example 1 except that the pellet (B-6-1) was used instead of the pellet (B-1-1). A resin laminate (G-11) of a polycarbonate resin (A-1) was obtained. The total thickness of the central portion of the obtained resin laminate (G-11) was 1000 μm, and the surface layer thickness was 70 μm. This resin laminate (G-11) has total light transmittance: 90.9%, haze: 1.0%, pencil hardness: H, warp change amount under high temperature and high humidity environment: +132 μm, interference fringes: 〇. It was.

Example 12 [Manufacturing of resin laminate (G-12)]
With the pellet (B-6-1) in the same manner as the resin laminate (G-2) of Example 2 except that the pellet (B-6-1) was used instead of the pellet (B-1-1). A resin laminate (G-12) of a polycarbonate resin (A-1) was obtained. The total thickness of the central portion of the obtained resin laminate (G-12) was 1000 μm, and the surface layer thickness was 40 μm. This resin laminate (G-12) has total light transmittance: 91.0%, haze: 0.8%, pencil hardness: H, warpage change amount under high temperature and high humidity environment: +56 μm, interference fringes: 〇. It was.

Comparative Example 1 [Manufacturing of Resin Laminated Body (H-1)]
With the pellet (F-6-1) in the same manner as the resin laminate (G-1) of Example 1 except that the pellet (F-6-1) was used instead of the pellet (B-1-1). A resin laminate (H-1) of a polycarbonate resin (A-1) was obtained. The total thickness of the central portion of the obtained resin laminate (H-1) was 1000 μm, and the surface layer thickness was 70 μm. This resin laminate (H-1) has total light transmittance: 91.5%, haze: 0.3%, pencil hardness: 2H, amount of change in warpage under high temperature and high humidity environment: + 220 μm, interference fringes: ×. It was.

Comparative Example 2 [Manufacturing of Resin Laminated Body (H-2)]
With the pellet (F-6-1) in the same manner as the resin laminate (G-2) of Example 2 except that the pellet (F-6-1) was used instead of the pellet (B-1-1). A resin laminate (H-2) of a polycarbonate resin (A-1) was obtained. The total thickness of the central portion of the obtained resin laminate (H-2) was 1000 μm, and the surface layer thickness was 40 μm. This resin laminate (H-2) has total light transmittance: 91.5%, haze: 0.3%, pencil hardness: 2H, amount of change in warpage under high temperature and high humidity environment: +303 μm, interference fringes: ×. It was.

Comparative Example 3 [Manufacturing of Resin Laminated Body (H-3)]
With the pellet (F-7-1) in the same manner as the resin laminate (G-1) of Example 1 except that the pellet (F-7-1) was used instead of the pellet (B-1-1). A resin laminate (H-3) of a polycarbonate resin (A-1) was obtained. The total thickness of the central portion of the obtained resin laminate (H-3) was 1000 μm, and the surface layer thickness was 70 μm. This resin laminate (H-3) has total light transmittance: 90.8%, haze: 0.3%, pencil hardness: F, amount of change in warpage under high temperature and high humidity environment: -205 μm, interference fringes: 〇. there were.

Comparative Example 4 [Manufacturing of Resin Laminated Body (H-4)]
With the pellet (F-7-1) in the same manner as the resin laminate (G-2) of Example 2 except that the pellet (F-7-1) was used instead of the pellet (B-1-1). A resin laminate (H-4) of a polycarbonate resin (A-1) was obtained. The total thickness of the central portion of the obtained resin laminate (H-4) was 1000 μm, and the surface layer thickness was 40 μm. This resin laminate (H-4) has total light transmittance: 90.7%, Haze: 0.4%, pencil hardness: F, amount of change in warpage under high temperature and high humidity environment: -135 μm, interference fringes: 〇. there were.

As described above, by satisfying the conditions of the present invention, it is possible to obtain a resin laminate having excellent warp deformation resistance and heat resistance, a high refractive index, and a good appearance even when exposed to high temperature and high humidity. It has the advantageous effect of being able to do it.

That is, as shown in Table 2, with respect to the thermoplastic resin (B), Production Examples 1A to 6A in which a specific vinyl copolymer (C) and a specific styrene copolymer (D) are blended, and specific vinyl. Comparing with Comparative Example 6A for the production of the copolymer (C) alone, Production Examples 1A to 6A had a higher glass transition temperature, excellent heat resistance, and a higher refractive index.
Further, when Production Examples 1A to 6A are compared with Production Comparative Example 1A in which a specific vinyl copolymer (C) and a styrene copolymer (E) other than the specific styrene copolymer (D) are blended, Production Examples 1A to 6A were superior in heat resistance.
Further, Production Examples 1A to 6A are compared with Production Comparative Examples 2A to 5A in which a specific vinyl copolymer (C) and a styrene copolymer (E) other than the specific styrene copolymer (D) are blended. Then, Production Examples 1A to 6A had a lower haze and a better appearance.

As shown in Table 3, the resin laminate has a specific vinyl copolymer (C) and a specific styrene copolymer (D) characterized by a high glass transition temperature and a high refractive index. Examples 1 to 12 in which a blended and pelletized thermoplastic resin (B) and a polycarbonate resin (A) are laminated, and a thermoplastic resin in which a specific vinyl copolymer (C) is pelletized and a polycarbonate resin are used. Comparing with Comparative Examples 1 and 2 in which the resin (A) was laminated, the resin laminates of Examples 1 to 12 had a smaller amount of change in warpage under a high temperature and high humidity environment, and had better interference fringes.
Further, when Examples 1 to 12 are compared with Comparative Examples 3 to 4 in which a thermoplastic resin obtained by pelletizing a specific styrene copolymer (D) alone and a polycarbonate resin (A) are laminated, Example 1 The resin laminates of ~ 12 had better pencil hardness.

Claims

A resin laminate having a layer containing a thermoplastic resin (B) on at least one surface of a layer containing a polycarbonate resin (A) containing a polycarbonate resin as a main component.
The thermoplastic resin (B) contains a vinyl copolymer (C) and a styrene copolymer (D).
The vinyl copolymer (C) has a (meth) acrylic acid ester monomer unit (c1) represented by the following general formula (1) in an amount of 60 to 80 mol% and is represented by the following general formula (2). A copolymer containing 40 to 20 mol% of an aliphatic vinyl monomer unit (c2).
The styrene copolymer (D) contains 60 to 90 mol% of the vinyl aromatic monomer unit (d1), 10 to 20 mol% of the cyclic acid anhydride monomer unit (d2), and a methacrylic acid ester simple substance. It is a copolymer containing 0 to 20 mol% of the monomer unit (d3).
The resin laminate in which Haze ≦ 1.0%.

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

(In the formula, R3 represents a hydrogen atom or a methyl group, and R4 represents a cyclohexyl group which may have a hydrocarbon substituent having 1 to 4 carbon atoms.)
The resin laminate according to claim 1, wherein the amount of change in warpage after being held in an environment of a temperature of 85 ° C. and a relative humidity of 85% for 120 hours is 200 μm or less in absolute value.
The resin laminate according to claim 1 or 2, wherein the difference between the glass transition temperature of the polycarbonate resin (A) and the glass transition temperature of the thermoplastic resin (B) is in the range of 0 to 25 ° C.
The resin laminate according to claim 1 or 2, wherein the thermoplastic resin (B) is a polymer alloy of a vinyl copolymer (C) and a styrene copolymer (D).
The content of the vinyl copolymer (C) is 5 to 95 mass based on the total content of 100 parts by mass of the vinyl copolymer (C) and the styrene copolymer (D) in the thermoplastic resin (B). The resin laminate according to any one of claims 1 to 4, wherein the content of the styrene copolymer (D) is 95 to 5 parts by mass.
After the vinyl copolymer (C) polymerizes at least one (meth) acrylic acid ester monomer and at least one aromatic vinyl monomer, the aromatic vinyl double is derived from the aromatic vinyl monomer. The resin laminate according to any one of claims 1 to 5, which is obtained by hydrogenating 70% or more of the double bonds.
The resin laminate according to any one of claims 1 to 6, wherein R1 and R2 in the general formula (1) represent a methyl group.
The resin laminate according to any one of claims 1 to 7, wherein R3 in the general formula (2) represents a hydrogen atom and R4 represents a cyclohexyl group.
The resin laminate according to any one of claims 1 to 8, wherein the vinyl aromatic monomer unit (d1) contained in the styrene copolymer (D) is styrene.
The resin laminate according to any one of claims 1 to 9, wherein the cyclic acid anhydride monomer unit (d2) contained in the styrene copolymer (D) is maleic anhydride.
The resin laminate according to any one of claims 1 to 10, wherein the methacrylic acid ester monomer unit (d3) contained in the styrene copolymer (D) is a methacrylic acid ester.
The resin according to any one of claims 1 to 11, wherein the thickness of the layer containing the thermoplastic resin (B) is 10 to 250 μm, and the total thickness of the resin laminate is in the range of 0.04 to 4.0 mm. Laminated body.
The resin laminate according to any one of claims 1 to 12, wherein at least one of the layer containing the polycarbonate resin (A) and the layer containing the thermoplastic resin (B) contains an ultraviolet absorber.
The resin laminate according to any one of claims 1 to 13, further comprising a hard coat layer on the surface of the layer containing the thermoplastic resin (B).
Claims 1 to 14, wherein one or both sides of the resin laminate is subjected to any one or more of anti-fingerprint treatment, anti-reflection treatment, anti-glare treatment, weather resistance treatment, anti-static treatment and anti-fouling treatment. The resin laminate according to any one.
A transparent substrate material containing the resin laminate according to any one of claims 1 to 15.
A transparent protective material containing the resin laminate according to any one of claims 1 to 15.
A touch panel front protective plate containing the resin laminate according to any one of claims 1 to 15.
A front plate for an OA device or a portable electronic device, which comprises the resin laminate according to any one of claims 1 to 15.