JP7076664B1 - Multilayers and molded products - Google Patents

Abstract

Provided are multilayer bodies and molded products that can suppress the generation of cracks and the generation of springback even when heat-molded. It has a layer (X) formed from the resin composition (x) and a layer (Y) formed from the resin composition (y) containing a polycarbonate resin, and the resin composition (x) has a differential scanning calorimetry. The initial glass transition temperature (Tig) measured by measurement is 120 ° C. or higher, and the differential impact strength without notch when the resin composition (x) is molded into an ISO test piece having a thickness of 3 mm is 12.0 kJ / m2 or higher. The impact strength without notch is the value measured by changing the thickness of the ISO test piece from 4 mm to 3 mm in JIS K 711-1, and performing the same procedure for the others, and the resin composition (y). Is a multilayer body having an initial glass transition temperature (Tig) of 125 ° C. or lower as measured by differential scanning calorimetry.

Description

The present invention relates to multilayer bodies and molded products.

Polycarbonate resin is widely used in various fields because it has excellent transparency, processability and impact resistance compared to glass, and there is no concern about toxic gas compared to other plastic materials. It is also used as a material for thermoforming such as vacuum forming and pressure forming.

On the other hand, since the surface hardness of the polycarbonate resin is generally low, the surface of the molded product made of the polycarbonate resin tends to be easily scratched. Therefore, when the polycarbonate resin is made into a film, it is being studied to form a layer containing an acrylic resin or a hard coat layer (protective layer) on the surface to prevent scratches on the product surface.
For example, Patent Document 1 describes an acrylic resin on one side of a base material layer containing a polycarbonate resin composition (A) composed of a polymer alloy of aromatic polycarbonate (A1) and another resin (A2) as a main component. A laminated sheet provided with a coating layer containing (B) as a main component, wherein the absolute value of the difference in glass transition temperature between the polycarbonate resin composition (A) and the acrylic resin (B) is within 30 ° C. A molding resin sheet characterized by the above is disclosed.

Japanese Unexamined Patent Publication No. 2009-196153

Here, when a layer formed of a resin composition containing a polycarbonate resin and a layer formed of another resin composition are formed into a multilayer body and heat-molded into a desired shape, cracks occur or heat bending occurs. It was found that the phenomenon (springback) in which the multilayer body returns to its original shape may occur later.
An object of the present invention is to solve such a problem, and to provide a multilayer body and a molded product which can suppress the generation of cracks and the generation of springback even when heat-molded. The purpose.

As a result of the study by the present inventor based on the above problems, the glass transition temperature of the layer formed from the resin composition containing the polycarbonate resin is lowered, and the impact resistance of the layer formed from the other resin composition is reduced. It has been found that the above-mentioned problems can be solved by increasing the temperature and increasing the glass transition temperature.
Specifically, the above problem was solved by the following means.
<1> The resin composition (x) has a layer (X) formed from the resin composition (x) and a layer (Y) formed from the resin composition (y) containing a polycarbonate resin. The initial glass transition temperature (Tig) measured by differential scanning calorimetry is 120 ° C. or higher, and the notchless Charpy impact strength when the resin composition (x) is molded into an ISO test piece having a thickness of 3 mm is 12. The impact strength without notch is 0.0 kJ / m ² or more, and the thickness of the ISO test piece is changed from 4 mm to 3 mm in JIS K 711-1, and the other values are measured in the same manner. The resin composition (y) is a multilayer body having an initial glass transition temperature (Tig) of 125 ° C. or lower as measured by differential scanning calorimetry.
<2> The multilayer body according to <1>, wherein the pencil hardness of the layer (X) is H or more.
<3> The resin composition (x) contains an acrylic resin (a) and a styrene resin (b), and acrylic is based on a total of 100 parts by mass of the contents of the acrylic resin (a) and the styrene resin (b). The multilayer body according to <1> or <2>, wherein the content of the resin (a) is 25 to 65 parts by mass, and the content of the styrene resin (b) is 35 to 75 parts by mass.
<4> The styrene resin (b) contains 68 to 84% by mass of an aromatic vinyl compound unit and 16 to 32% by mass of a cyclic acid anhydride unit (however, the aromatic vinyl compound unit and the cyclic acid anhydride unit. The multilayer body according to any one of <1> to <3> (the total does not exceed 100% by mass).
<5> The multilayer body according to <4>, wherein the aromatic vinyl compound unit in the styrene resin (b) contains styrene.
<6> The multilayer body according to <4> or <5>, wherein the cyclic acid anhydride unit in the styrene resin (b) contains maleic anhydride.
<7> The multilayer body according to any one of <1> to <6>, wherein the resin composition (x) further contains an antioxidant and / or a mold release agent.
<8> Further, any one of <1> to <7>, which includes a hard coat layer, and the hard coat layer is laminated in the order of the layer (Y), the layer (X), and the hard coat layer. The multilayer body described in one.
<9> The multilayer body according to any one of <1> to <8>, which satisfies {thickness of layer (X) / [total thickness of layer (X) and layer (Y)]} <1/5. ..
<10> Further, one or more of one or more of anti-fingerprint treatment, anti-reflection treatment, anti-glare treatment, weather resistance treatment, anti-static treatment, anti-fouling treatment and anti-blocking treatment is applied to one or both sides of the multilayer body. The multilayer body according to any one of <1> to <9>.
<11> The multilayer body according to any one of <1> to <10>, wherein the total thickness of the multilayer body is 10 to 10,000 μm.
<12> A molded product formed from the multilayer body according to any one of <1> to <11>, which has a portion having a radius of curvature of 50 mmR or less.

INDUSTRIAL APPLICABILITY According to the present invention, it has become possible to provide a multilayer body and a molded product which can suppress the generation of cracks and the generation of springback even when heat-molded.

FIG. 1 is a schematic diagram showing the configuration of an example of an antireflection film.

Hereinafter, embodiments for carrying out the present invention (hereinafter, simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and the present invention is not limited to the present embodiment.
In addition, in this specification, "-" is used in the meaning which includes the numerical values described before and after it as the lower limit value and the upper limit value.
In the present specification, various physical property values and characteristic values shall be at 23 ° C. unless otherwise specified.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In the present specification, the notation that does not describe substitution and non-substitution is preferably non-substitution.
In the present specification, the "(meth) acrylic compound" represents both an acrylic compound and / or a methacrylic compound, and a methacrylic compound is preferable. The acrylic resin also contains a methacrylate (co) polymer in addition to the acrylate (co) polymer.
In the present specification, the layer (X), the layer (Y), and the multilayer body are intended to include those in the shape of a film or a sheet, respectively. The "film" and the "sheet" are molded articles that are thin and generally flat with respect to length and width, respectively.
In the present specification, "part by mass" indicates a relative amount of a component, and "mass%" indicates an absolute amount of a component.
If the standards shown in this specification differ from year to year in terms of measurement method, etc., they shall be based on the standards at the time of filing unless otherwise specified.

The multilayer body of the present embodiment has a layer (X) formed from the resin composition (x) and a layer (Y) formed from the resin composition (y) containing a polycarbonate resin, and the resin composition. The object (x) has an initial glass transition temperature (Tig) of 120 ° C. or higher measured by differential scanning calorimetry, and the resin composition (x) is formed into an ISO test piece having a thickness of 3 mm. The impact strength is 12.0 kJ / m ² or more, and the impact strength without notch is changed in JIS K 711-1 by changing the thickness of the ISO test piece from 4 mm to 3 mm, and the other steps are performed in the same manner. It is a measured value, and the resin composition (y) is characterized in that the initial glass transition temperature (Tig) measured by differential scanning calorimetry is 125 ° C. or lower. With such a configuration, a multilayer body capable of suppressing the occurrence of cracks and suppressing the occurrence of springback can be obtained.
When a multilayer body having a layer (X) formed from the resin composition (x) and a layer (Y) formed from the resin composition (y) containing a polycarbonate resin is thermoformed, the layer (X) or Cracks may occur in layers other than the layer (X) and the adjacent layer (Y). In the present embodiment, it is presumed that the generation of cracks could be suppressed by suppressing the thermal deformation of the layer (X) during thermal bending molding by setting the initial glass transition temperature (Tig) of the layer (X) to 120 ° C. or higher. .. However, if the initial glass transition temperature (Tig) of the layer (X) is high, appropriate thermal bending molding cannot be performed, and the layer (X) or other layers other than the layer (Y) adjacent to the layer (X) can be formed. It turned out that cracks may occur. It is presumed that this is one of the causes that the layer (X) becomes brittle when the layer (X) is, for example, a styrene resin layer. In this embodiment, it is presumed that the generation of cracks could be suppressed by using a layer (X) having high impact resistance. Further, as a result of the study by the present inventor, it has been found that springback can be surprisingly suppressed by setting the initial glass transition temperature (Tig) of the layer (Y) containing the polycarbonate resin to 125 ° C. or lower. Based on the above, it is presumed that a multilayer body capable of suppressing crack generation and springback has been provided.

<Layer (X)>
The layer (X) is a layer formed from the resin composition (x), and the resin composition (x) has an initial glass transition temperature (Tig) of 120 ° C. or higher measured by differential scanning calorimetry, and is a resin. When the composition (x) is formed into an ISO test piece having a thickness of 3 mm, the notchless Charpy impact strength is 12.0 kJ / m ² or more. By setting the initial glass transition temperature (Tig) to 120 ° C. or higher, the thermoforming temperature during thermoforming can be set to, for example, about 120 ° C., and further, thermal deformation of the layer (X) is suppressed during thermoforming. By doing so, the occurrence of cracks can be suppressed. Further, by setting the Charpy impact strength to 12.0 kJ / m ² or more, the brittleness of the layer (X) is improved and appropriate bending molding is possible.

The resin composition (x) preferably has an initial glass transition temperature (Tig) of 120 ° C. or higher, preferably 121 ° C. or higher, as measured by differential scanning calorimetry. By setting the value to the lower limit or higher, the occurrence of cracks can be effectively suppressed. Further, the durability of environmental resistance tests such as wet heat test and high temperature test tends to be further improved. The upper limit of the initial glass transition temperature (Tig) is not particularly determined, but is preferably less than 135 ° C, and may be 130 ° C or lower, further may be 126 ° C or lower. By setting the value to the upper limit or less, the effect of suppressing springback during thermal bending tends to be further improved.
In the resin composition (x), the intermediate glass transition temperature (Tmg) measured by differential scanning calorimetry is preferably 123 ° C. or higher, more preferably 124 ° C. or higher, still more preferably 125 ° C. or higher. It is more preferably 126 ° C. or higher. By setting the value to the lower limit or higher, the occurrence of cracks can be effectively suppressed. Further, the durability of environmental resistance tests such as wet heat test and high temperature test tends to be further improved. The upper limit of the intermediate glass transition temperature (Tmg) is not particularly determined, but is practically 139 ° C or lower, and may be 134 ° C or lower, further 130 ° C or lower. By setting the value to the upper limit or less, the effect of suppressing springback during thermal bending tends to be further improved.
In the present embodiment, the difference between Tmg and Tig (Tmg-Tig) in the layer (x) is preferably 1 to 6 ° C, more preferably 3 to 6 ° C, and 4 to 5 ° C. Is even more preferable. By setting it in such a range, the reproducibility of thermal bending molding tends to be further improved.
The glass transition temperature (Tig, Tmg) is measured according to the method described in Examples described later.

In the present embodiment, the notchless Charpy impact strength when the resin composition (x) is molded into an ISO test piece having a thickness of 3 mm is 12.0 kJ / m ² or more. Here, the notchless Charpy impact strength is a value measured by changing the thickness of the ISO test piece from 4 mm to 3 mm in JIS K 711-1, and performing the same procedure for the others, and the details will be described later. Follow the description of the example.
The impact strength of the resin composition (x) without a notch is preferably 12.5 kJ / m ² or more, and more preferably 13.0 kJ / m ² or more. By setting the value to the lower limit or more, the effect of suppressing the occurrence of cracks during thermoforming tends to be further improved. The impact strength of the resin composition (x) without a notch is preferably 30.0 kJ / m ² or less, and more preferably 20.0 kJ / m ² or less.

The resin composition (x) is preferably excellent in transparency. Specifically, the total light transmittance when the resin composition (x) is molded to a thickness of 1 mm is preferably 85.0% or more, more preferably 88.0% or more, 89. It is more preferably 0.0% or more. The ideal upper limit is 100%, but 99.9% or less is practical.
The resin composition (x) also preferably has a haze of 5.0% or less, more preferably 2.0% or less, when the resin composition (x) is molded to a thickness of 1 mm. , 1.0% or less, more preferably 0.4% or less, and even more preferably 0.2% or less. The lower limit is ideally 0%, but 0.01% or more is practical.
Total light transmittance and haze are measured according to the description of Examples described later.

It is preferable that the resin composition (x), that is, the layer (X) has a high pencil hardness (hardness). Specifically, the resin composition (x) is molded to a thickness of 1 mm, and the pencil hardness measured with a pencil hardness tester using a pencil hardness tester in accordance with JIS K5600-5-4: 1999 is the pencil hardness. It is preferably F or more, and more preferably H or more. By setting the pencil hardness of the layer (X) to F or more, the hardness of the entire multilayer body can be increased, and the scratch resistance can be improved. The upper limit is not particularly set, but 3H or less is practical.
Pencil hardness is measured according to the description of Examples described later.

Further, the layer (X) may be a single layer or may be a multi-layer.
The thickness of the layer (X) is not particularly limited, but the lower limit is, for example, 1 μm or more, preferably 10 μm or more, more preferably 20 μm or more, still more preferably 50 μm or more. , 80 μm or more, more preferably 100 μm or more. By setting the value to the lower limit or more, molding tends to be easier and the hardness tends to be improved. The upper limit of the thickness of the layer (X) is not particularly limited, but is preferably 5,000 μm or less, more preferably 2,000 μm or less, still more preferably 1,000 μm or less. It is more preferably 500 μm or less, and even more preferably 300 μm or less. In particular, as will be described in detail later, it is preferable that the layer (X) is thinner than the total thickness of the layer (X) and the layer (Y). With such a configuration, even if the multilayer body is heat-molded, the generation of cracks is effectively suppressed and the generation of springback is effectively suppressed.

Next, the composition of the resin composition (x) will be described.
The resin composition (x) is not particularly defined as long as it satisfies the desired initial glass transition temperature (Tig) and notchless Charpy impact strength. In order to increase the initial glass transition temperature (Tig), it is exemplified to adjust the raw material monomer of the resin. Another example is to increase the molecular weight of the resin. The glass transition temperature of the resin is generally determined by the raw material monomer and the molecular weight, and can be appropriately selected by those skilled in the art. Examples of methods for increasing the Charpy impact strength include blending a known high impact resistant resin such as polymethylmethacrylate, adopting a resin having a high molecular weight, and blending a shock resistant modifier such as rubber. Will be done.

The type of resin contained in the resin composition (x) is not particularly specified, but a thermoplastic resin is preferable, a fluororesin such as acrylic resin, styrene resin, polyvinylidene fluoride, and aromatic poly such as polyphenylene ether. It is more preferable to contain at least one thermoplastic resin selected from ether resins, and acrylic resins and / or styrene resins are even more preferred. The resin composition (x) is usually preferably composed of 90% by mass or more (preferably 95% by mass or more) of the thermoplastic resin.

It is more preferable that the resin composition (x) contains an acrylic resin (a) and a styrene resin (b). By using the acrylic resin (a) and the styrene resin (b) in combination, the pencil hardness, heat resistance, and impact resistance tend to be improved more effectively. That is, by blending the acrylic resin (a), the pencil hardness is improved, and by blending the styrene resin (b), the difference in the refractive index from the layer (Y) can be reduced, and the appearance derived from rainbow unevenness or the like can be reduced. Defects can be effectively suppressed.
When the resin composition (x) contains the acrylic resin (a) and the styrene resin (b), the blend ratio thereof is based on 100 parts by mass of the total contents of the acrylic resin (a) and the styrene resin (b). The content of the acrylic resin (a) is 25 to 65 parts by mass, the content of the styrene resin (b) is 35 to 75 parts by mass, and more preferably the content of the acrylic resin (a). Is 30 to 60 parts by mass, and the content of the styrene resin (b) is 40 to 70 parts by mass. Further, by setting the content of the acrylic resin (a) to 25 parts by mass or more based on the total content of 100 parts by mass of the acrylic resin (a) and the styrene resin (b), the pencil hardness and the impact resistance can be improved. It tends to improve more effectively. Further, by setting the content of the acrylic resin (a) to 65 parts by mass or less based on the total content of 100 parts by mass of the acrylic resin (a) and the styrene resin (b), the effect of suppressing the decrease in heat resistance is achieved. Tends to improve.
When the resin composition (x) contains the acrylic resin (a) and the styrene resin (b), the acrylic resin (a) and the styrene resin (b) may contain only one type or two types, respectively. The above may be included. When two or more kinds are contained, it is preferable that the total amount is within the above range.
When the resin composition (x) contains the acrylic resin (a) and the styrene resin (b), the total of the acrylic resin (a) and the styrene resin (b) is 85% by mass of the resin composition (x). It is preferable to occupy the above, more preferably 90% by mass or more, further preferably 95% by mass or more, and may occupy 99% by mass or more.

Next, the acrylic resin (a) will be described.
The acrylic resin (a) preferably contains a (meth) acrylic compound unit, and the proportion thereof is preferably more than 50% by mass, and preferably 76% by mass or more in all the constituent units excluding the terminal group. More preferably, it is more preferably 80% by mass or more, further preferably 90% by mass or more, and even more preferably 95% by mass or more. By setting the value to the lower limit or higher, the pencil hardness and impact resistance tend to be further improved. Here, the (meth) acrylic compound unit means a structural unit composed of the (meth) acrylic compound in the resin (the same applies to the “aromatic vinyl compound unit” and the like described later). The upper limit of the ratio of the (meth) acrylic compound unit in the acrylic resin (a) is 100% by mass in all the constituent units excluding the terminal group.
The acrylic resin (a) may contain only one type of (meth) acrylic compound unit, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.

（式（ａ１）中、Ｒａ^１は、水素原子またはメチル基であり、Ｒａ^２は、脂肪族基である。）
上記式（ａ１）において、Ｒａ^１は、水素原子またはメチル基であり、メチル基が好ましい。Ｒａ^２は、脂肪族基であり、直鎖または分岐の脂肪族基であることが好ましく、直鎖の脂肪族基であることがより好ましい。脂肪族基は、アルキル基（シクロアルキル基を含む）、アルキニル基（シクロアルキニル基を含む）、アルケニル基（シクロアルケニル基を含む）等が例示され、アルキル基が好ましく、直鎖または分岐のアルキル基がより好ましく、直鎖のアルキル基がさらに好ましい。Ｒａ^２である脂肪族基の炭素原子数は、１～１０であることが好ましく、１～５であることがより好ましく、１～３であることがさらに好ましく、１または２であることが一層好ましく、１であることがより一層好ましい。
式（ａ１）で表される（メタ）アクリル化合物は、アルキル（メタ）アクリレート（好ましくはアルキルメタクリレート）であることが好ましく、メチル（メタ）アクリレート（好ましくはメチルメタクリレート）であることがより好ましい。メチルメタクリレートを用いることにより、得られる層（Ｘ）の耐衝撃強さが向上する傾向にある。The (meth) acrylic compound is not particularly specified as long as it contains a (meth) acrylic group, but a compound represented by the formula (a1) is preferable.

(In the formula (a1), Ra ¹ is a hydrogen atom or a methyl group, and Ra ² is an aliphatic group.)
In the above formula (a1), Ra ¹ is a hydrogen atom or a methyl group, and a methyl group is preferable. Ra ² is an aliphatic group, preferably a linear or branched aliphatic group, and more preferably a linear aliphatic group. Examples of the aliphatic group include an alkyl group (including a cycloalkyl group), an alkynyl group (including a cycloalkynyl group), an alkenyl group (including a cycloalkenyl group), and the like, and an alkyl group is preferable, and a linear or branched alkyl is preferable. Groups are more preferred, and straight chain alkyl groups are even more preferred. The number of carbon atoms of the aliphatic group of Ra ² is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and further preferably 1 or 2. It is preferably 1, and even more preferably 1.
The (meth) acrylic compound represented by the formula (a1) is preferably an alkyl (meth) acrylate (preferably alkyl methacrylate), and more preferably a methyl (meth) acrylate (preferably methyl methacrylate). By using methyl methacrylate, the impact resistance of the obtained layer (X) tends to be improved.

The acrylic resin (a) may contain a monomer unit other than the (meth) acrylic compound unit. Examples of other monomers include cyclic acid anhydride units, N-substituted maleimide units, aromatic vinyl compound units, and aliphatic vinyl compound units, and cyclic acid anhydride units and / or N-substituted maleimide units are preferable.
The ratio of the other monomer units is preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 1% by mass or less of all the constituent units excluding the terminal group. Further, a monomer that forms a lactone ring unit is also preferably used.
The acrylic resin (a) may contain only one type of other monomer unit, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.

The initial glass transition temperature (Tig) of the acrylic resin (a) is preferably 99 ° C. or higher, more preferably 102 ° C. or higher, and even more preferably 105 ° C. or higher. By setting the value to the lower limit or more, the effect of suppressing the generation of cracks during thermal bending tends to be further improved. The initial glass transition temperature (Tig) of the acrylic resin (a) is preferably 117 ° C. or lower, more preferably 114 ° C. or lower, and even more preferably 112 ° C. or lower. By setting the value to the upper limit or less, the effect of suppressing springback during thermal bending tends to be further improved.
When the resin composition (x) contains two or more kinds of acrylic resin (a), the initial glass transition temperature (Tig) of the acrylic resin (a) is Tig of the mixture. The method for measuring the glass transition temperature follows the method described in Examples described later (hereinafter, the same applies to the weight average molecular weight and pencil hardness, and the weight average molecular weight and pencil hardness of the styrene resin (b)).

The weight average molecular weight of the acrylic resin (a) is preferably 50,000 or more, more preferably 60,000 or more, further preferably 70,000 or more, and more preferably 80,000 or more. It is more preferably 90,000 or more, and even more preferably 90,000 or more. By setting the value to the lower limit or more, the impact resistance of the obtained layer (X) can be further improved. The weight average molecular weight of the acrylic resin (a) is preferably 300,000 or less, more preferably 250,000 or less, further preferably 200,000 or less, and more preferably 170,000 or less. It is more preferably 150,000 or less, and even more preferably 150,000 or less. By setting the value to the upper limit or less, the melt viscosity of the resin composition can be effectively lowered, and the molding of the multilayer body becomes easy.

The pencil hardness of the acrylic resin (a) is preferably H or higher, more preferably 2H or higher, and even more preferably 3H or higher. By setting the value to the lower limit or more, the scratch resistance tends to be further improved. Further, the pencil hardness of the acrylic resin (a) is preferably 4H or less, and more preferably 3H or less.

Next, the styrene resin (b) will be described.
The styrene resin (b) is a resin containing at least one styrene-based monomer unit such as a styrene unit, an α-methylstyrene unit, an o-methylstyrene unit, and a p-methylstyrene unit as an aromatic vinyl compound unit. , Styrene units are preferably included. The ratio of the aromatic vinyl compound unit (preferably the styrene-based monomer unit) in the styrene resin (b) is preferably more than 50% by mass and 55% by mass or more in all the constituent units excluding the terminal group. Is more preferably 60% by mass or more, further preferably 65% by mass or more, and even more preferably 70% by mass or more. By setting the value to the lower limit or more, the effect of suppressing interference fringes when laminated with the polycarbonate resin layer tends to be further improved by improving the refractive index. The upper limit of the ratio of the aromatic vinyl compound unit in the styrene resin (b) is 100% by mass in all the constituent units excluding the terminal group.
The styrene resin (b) may contain only one type of aromatic vinyl compound unit (further, a styrene-based monomer unit), or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.

The styrene resin (b) may contain a monomer unit other than the aromatic vinyl compound unit and an aromatic vinyl compound unit other than the styrene-based monomer unit. Examples of the other monomer include monomers other than the aromatic vinyl compound and which can be copolymerized with the aromatic vinyl compound.
Specific examples of the other monomer unit include a cyclic acid anhydride unit, an N-substituted maleimide unit, a (meth) acrylic compound unit, and a cyanide alkenyl unit, and a cyclic acid anhydride unit is preferable.

Examples of the cyclic acid anhydride unit include a maleic anhydride unit and a glutaric anhydride unit, and the maleic anhydride unit is preferable. By containing the cyclic acid anhydride unit, particularly the maleic acid unit, the compatibility with the acrylic resin and the heat resistance tend to be further improved.

The styrene resin (b) contains 68 to 84% by mass of the aromatic vinyl compound unit and 16 to 32% by mass of the cyclic acid anhydride unit (however, the total of the aromatic vinyl compound unit and the cyclic acid anhydride unit is 100). It does not exceed% by mass). When the aromatic vinyl compound unit is 68% by mass or more, the compatibility with the acrylic resin is improved, and the transparency of the entire resin tends to be further improved. Further, when the aromatic vinyl compound unit is 84% by mass or less, the turbidity of the layer (X) can be effectively suppressed, and the generation of cracks during thermal bending molding can be suppressed. The styrene resin (b) preferably contains 70 to 83% by mass of an aromatic vinyl compound unit and 17 to 30% by mass of a cyclic acid anhydride unit, and 75 to 83% by mass of an aromatic vinyl compound unit. It is more preferable to contain 17 to 25% by mass of the acid anhydride unit, preferably 78 to 83% by mass of the aromatic vinyl compound unit, and 17 to 22% by mass of the cyclic acid anhydride unit.

In the styrene resin (b), the total of the aromatic vinyl compound unit and the cyclic acid anhydride unit preferably occupies 90% by mass or more of all the constituent units excluding the terminal of the styrene resin (b), preferably 95% by mass or more. It is more preferable to occupy 99% by mass or more, and it is further preferable to occupy 99% by mass or more.
The styrene resin (b) may contain only one type or two or more types of the aromatic vinyl compound unit and the cyclic acid anhydride unit, respectively. When two or more kinds are contained, it is preferable that the total amount is within the above range.

Next, the aromatic vinyl compound will be described.
The aromatic vinyl compound is a compound having a vinyl group and an aromatic ring group, and a compound copolymerizable with (meth) acrylate can be widely adopted. The aromatic vinyl compound is preferably a compound represented by CH ₂ = CH-L ¹ -Ar ¹ . Here, L ¹ is a single bond or a divalent linking group, preferably a single bond or a divalent linking group having a formula of 100 to 500, and a single bond or a divalent link having a formula of 100 to 300. It is more preferably a group, and even more preferably a single bond. When L ¹ is a divalent linking group, it is preferably an aliphatic hydrocarbon group or a group composed of a combination of an aliphatic hydrocarbon group and —O—. Here, the formula amount means the mass (g) per mole of the portion corresponding to L ¹ of the aromatic vinyl compound. Hereinafter, other "formulas" will be considered in the same manner. Ar ¹ is an aromatic ring group, preferably a substituted or unsubstituted benzene ring group or a naphthalene ring (preferably a benzene ring), and more preferably an unsubstituted benzene ring group.

（式（ｂ１）中、Ｒａ^３は、置換基であり、ｎａは、０～６の整数である。）More specifically, the aromatic vinyl compound preferably contains an aromatic vinyl compound represented by the formula (b1).
Equation (b1)

(In the formula (b1), Ra ³ is a substituent and na is an integer of 0 to 6).

In the formula (b1), Ra ³ is a substituent, which is a halogen atom (preferably a chlorine atom, a fluorine atom or a bromine atom), a hydroxyl group, an alkyl group (preferably an alkyl group having 1 to 5 carbon atoms), and an aryl. A group (preferably a phenyl group), an alkenyl group (preferably an alkenyl group having 2 to 5 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms), and an aryloxy group (preferably a phenoxy group). Illustrated. When na is 2 or more, the plurality of Ra ^3s may be the same or different.
na is preferably an integer of 5 or less, more preferably an integer of 4 or less, further preferably an integer of 3 or less, further preferably an integer of 2 or less, and an integer of 1 or less. Is even more preferable, and 0 is even more preferable.

(B1) The aromatic vinyl compound is preferably a compound having a molecular weight of 104 to 600, and more preferably a compound having a molecular weight of 104 to 400.
(B1) The aromatic vinyl compound is specifically styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, vinylnaphthalene, etc. Examples thereof include styrene-based monomers (styrene derivatives) such as methoxystyrene, monobromostyrene, dibromostyrene, fluorostyrene, and tribromostyrene, and styrene is particularly preferable.

Next, the cyclic acid anhydride will be described.
Examples of the cyclic acid anhydride unit include maleic anhydride unit and glutaric anhydride, and maleic anhydride unit is preferable. By containing the cyclic acid anhydride unit, particularly the maleic acid unit, the glass transition temperature of the obtained styrene resin (b) can be increased.

The styrene resin (b) may contain other monomer units other than the above. Specific examples of other monomers include N-substituted maleimide units and (meth) acrylic compound units.

The initial glass transition temperature (Tig) of the styrene resin (b) is preferably 115 ° C. or higher, more preferably 120 ° C. or higher, and even more preferably 125 ° C. or higher. By setting the value to the lower limit or more, the crack suppressing effect at the time of thermal bending tends to be further improved. The initial glass transition temperature (Tig) of the styrene resin (b) is preferably 180 ° C. or lower, more preferably 170 ° C. or lower, and even more preferably 150 ° C. or lower. By setting the value to the upper limit or less, the effect of suppressing springback during thermal bending tends to be further improved.

The weight average molecular weight of the styrene resin (b) is preferably 20,000 or more, more preferably 50,000 or more, further preferably 80,000 or more, and more preferably 90,000 or more. Is even more preferable. By setting the value to the lower limit or more, the impact resistance of the obtained layer (X) can be further improved. The weight average molecular weight of the styrene resin (b) is preferably 200,000 or less, more preferably 150,000 or less, and even more preferably 120,000 or less. By setting the value to the upper limit or less, the melt viscosity of the resin composition can be effectively lowered.

The pencil hardness of the styrene resin (b) is preferably B or higher, and more preferably HB or higher. By setting the value to the lower limit or more, the scratch resistance tends to be further improved. Further, the pencil hardness of the styrene resin (b) is preferably F or less, and more preferably HB or less.

Further, the resin composition (x) preferably contains an antioxidant.
Examples of the antioxidant include a phenol-based antioxidant, an amine-based antioxidant, a phosphorus-based antioxidant, and a thioether-based antioxidant. Above all, in this embodiment, a phosphorus-based antioxidant and a phenol-based antioxidant (more preferably, a hindered phenol-based antioxidant) are preferable. Phosphorus-based antioxidants are particularly preferable because they are excellent in hue of molded products.

（式（１）中、Ｒ^１１およびＲ^１２はそれぞれ独立に、炭素原子数１～３０のアルキル基または炭素原子数６～３０のアリール基を表す。）

（式（２）中、Ｒ^１３～Ｒ^１７は、それぞれ独立に、水素原子、炭素原子数６～２０のアリール基または炭素原子数１～２０のアルキル基を表す。）As the phosphorus-based antioxidant, a phosphite-based antioxidant is preferable, and a phosphite compound represented by the following formula (1) or (2) is preferable.

(In the formula (1), R ¹¹ and R ¹² independently represent an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms.)

(In the formula (2), R ¹³ to R ¹⁷ independently represent a hydrogen atom, an aryl group having 6 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms.)

In the above formula (1), the alkyl groups represented by R ¹¹ and R ¹² are preferably linear or branched alkyl groups having 1 to 10 carbon atoms, respectively. When R ¹¹ and R ¹² are aryl groups, an aryl group represented by any of the following formulas (1-a), (1-b), or (1-c) is preferable. * In the formula represents the bond position.

（式（１－ａ）中、Ｒ^Ａは、それぞれ独立に、炭素原子数１～１０のアルキル基を表す。式（１－ｂ）中、Ｒ^Ｂは、それぞれ独立に、炭素原子数１～１０のアルキル基を表す。）

(In formula (1-a), ^RA independently represents an alkyl group having 1 to 10 carbon atoms. In formula (1- ^b ), RB independently represent 1 to 10 carbon atoms. Represents an alkyl group of 10.)

As the hindered phenolic antioxidant, the description in paragraph 0063 of JP-A-2018-090677 and paragraph 0076 of JP-A-2018-188496 can be referred to, and the contents thereof are incorporated in the present specification.

In addition to the above, the antioxidant can be referred to in paragraphs 0057 to 0061 of JP-A-2017-031313, the contents of which are incorporated herein.

The content of the antioxidant is preferably 0.001 part by mass or more, and more preferably 0.008 part by mass or more, based on 100 parts by mass of the resin composition. The upper limit of the content of the antioxidant is preferably 0.5 parts by mass or less, more preferably 0.3 parts by mass or less, and 0.2 parts by mass or less with respect to 100 parts by mass of the resin composition. It is even more preferably 0.15 parts by mass or less, further preferably 0.10 parts by mass or less, and even more preferably 0.08 parts by mass or less.

By setting the content of the antioxidant to the above lower limit value or more, a molded product having better hue and heat-resistant discoloration can be obtained. Further, by setting the content of the antioxidant to be equal to or less than the above upper limit value, it is possible to obtain a molded product having good moist heat stability without deteriorating the heat discoloration property.
Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, the total amount is preferably in the above range.

Further, the resin composition (x) preferably contains a mold release agent.
The type of the release agent is not particularly specified, but for example, an aliphatic carboxylic acid, an ester of an aliphatic carboxylic acid and an alcohol, an aliphatic hydrocarbon compound having a number average molecular weight of 200 to 15,000, and a number average molecular weight of 100 to 100. Examples thereof include 5,000 polyethers and polysiloxane-based silicone oils.

For details of the release agent, the description in paragraphs 0035 to 0039 of International Publication No. 2015/190162 can be referred to, and these contents are incorporated in the present specification.

The content of the release agent is preferably 0.001 part by mass or more, more preferably 0.005 part by mass or more, and 0.01 part by mass or more with respect to 100 parts by mass of the resin composition. It is more preferable to have. The upper limit value is preferably 0.5 parts by mass or less, more preferably 0.3 parts by mass or less, and further preferably 0.2 parts by mass or less.
Only one type of release agent may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is within the above range.

In addition to the above components, the resin composition (x) contains a thermoplastic resin other than the above, an ultraviolet absorber, a heat stabilizer, a flame retardant, a flame retardant aid, a colorant, an antistatic agent, a fluorescent whitening agent, and an antifogging agent. It may contain an agent, a fluidity improver, a plasticizer, a dispersant, an antibacterial agent, an antiblocking agent, an impact improver, a sliding improver, a hue improver, an acid trapping agent and the like. One of these components may be used, or two or more thereof may be used in combination.
When contained, the content of the above components is preferably 0.1 to 5% by mass in total of the resin composition.

<Layer (Y)>
The layer (Y) is a layer formed from the resin composition (y) containing a polycarbonate resin, and the initial glass transition temperature (Tig) measured by differential scanning calorimetry is 125 ° C. or lower and 124 ° C. or lower. Is preferable. By using the polycarbonate resin, the impact resistance and rigidity of the entire sheet are more effectively guaranteed. Further, by setting the initial glass transition temperature to 125 ° C. or lower, the effect of suppressing springback is exhibited when hot bending is performed at about 120 ° C.
In the resin composition (y), the lower limit of the initial glass transition temperature (Tig) measured by differential scanning calorimetry is preferably 100 ° C. or higher, more preferably 105 ° C. or higher, and 110 ° C. or higher. More preferably, it is more preferably 115 ° C. or higher, and even more preferably 120 ° C. or higher. By setting the value to the lower limit or more, the effect of improving the durability of environmental tests such as high temperature test and wet heat test tends to be further improved.

The polycarbonate resin used in the present embodiment may be an aromatic polycarbonate resin or an aliphatic polycarbonate resin, but an aromatic polycarbonate resin is preferable. By using an aromatic polycarbonate resin, it is strong in environmental tests such as a moist heat test and a high temperature test, and resin deterioration due to a decrease in molecular weight or the like is less likely to occur.
In the present embodiment, the aromatic polycarbonate resin is preferably a bisphenol type polycarbonate resin, more preferably a bisphenol A type and / or a bisphenol C type polycarbonate resin, and further preferably a bisphenol A type polycarbonate resin. ..

The bisphenol A type and bisphenol C type polycarbonate resin may also have other structural units other than the carbonate structural unit derived from bisphenol A or bisphenol C and its derivatives. Examples of the dihydroxy compound constituting such another structural unit include aromatic dihydroxy compounds described in paragraph 0014 of JP-A-2018-154819, and the contents thereof are incorporated in the present specification. ..
In the bisphenol type polycarbonate resin in the present embodiment, bisphenol A or bisphenol C and a carbonate constituent unit derived from the derivative thereof preferably occupy 90% by mass or more, and occupy 95% by mass or more of all the constituent units excluding the terminal structure. It is more preferable, and it is further preferable to occupy 97% by mass or more.

The method for producing the bisphenol A type polycarbonate resin is not particularly limited, and any method can be adopted. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method for a cyclic carbonate compound, and a solid phase transesterification method for a prepolymer.

The weight average molecular weight of the polycarbonate resin is not particularly determined, but is preferably 10,000 or more, more preferably 20,000 or more, still more preferably 30,000 or more, and 40, It is more preferably 000 or more, and even more preferably 50,000 or more. By setting the value to the lower limit or more, the impact resistance of the multilayer body and the suppression of flow marks during molding tend to be further improved. The weight average molecular weight of the polycarbonate resin is preferably 200,000 or less, more preferably 150,000 or less, further preferably 100,000 or less, and more preferably 80,000 or less. It is more preferably 60,000 or less, and even more preferably 60,000 or less. By setting the value to the upper limit or less, the formability of the multilayer body tends to be improved.

The polycarbonate resin used in this embodiment preferably has a low glass transition temperature. By using such a polycarbonate resin, the glass transition temperature of the resin composition (y) can be lowered.
The initial glass transition temperature (Tig) of the polycarbonate resin used in the present embodiment is preferably 145 ° C. or lower, more preferably 140 ° C. or lower, further preferably 135 ° C. or lower, and 130 ° C. or lower. It is more preferable that the temperature is 125 ° C. or lower, and it is even more preferable that the temperature is 125 ° C. or lower. By setting the value to the upper limit or less, the thermal bending formability of the multilayer body tends to be further improved. The initial glass transition temperature (Tig) of the polycarbonate resin used in the present embodiment is preferably 121 ° C. or higher, more preferably 122 ° C. or higher, and even more preferably 123 ° C. or higher. By setting the value to the lower limit or more, the durability of environmental resistance tests such as moist heat test and high temperature test tends to be further improved.

（式（１）中、Ｒ^１は、炭素原子数８～３６のアルキル基、または、炭素原子数８～３０のアルケニル基を表す。Ｒ^２は、それぞれ独立に、ハロゲン原子、炭素原子数１～２０のアルキル基、または、炭素原子数６～１２のアリール基を表す。ｎは０～４の整数を表す。＊は、他の部位との結合部位である。）The resin composition (y) preferably contains an aromatic polycarbonate resin having a terminal structure represented by the formula (1). By using an aromatic polycarbonate resin having a terminal structure represented by the formula (1), the glass transition temperature of the polycarbonate resin can be lowered.

(In the formula (1), R ¹ represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 30 carbon atoms. R ² independently represents a halogen atom and 1 carbon atom. It represents an alkyl group of up to 20 or an aryl group having 6 to 12 carbon atoms. N represents an integer of 0 to 4. * Is a bonding site with another site.)

R ¹ represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 30 carbon atoms, preferably an alkyl group or an alkenyl group having 10 or more carbon atoms, and preferably 12 or more alkyl groups. Alternatively, it is more preferably an alkenyl group, and further preferably 14 or more alkyl groups or alkenyl groups. This tends to lower the glass transition temperature of the resin and improve the thermal bendability of the multilayer body. Further, R ¹ is preferably an alkyl group or an alkenyl group having 22 or less carbon atoms, and more preferably an alkyl group or an alkenyl group having 18 or less carbon atoms. R ¹ is preferably an alkyl group. The alkyl group and alkenyl group are preferably a linear or branched alkyl group or alkenyl group, and more preferably a linear alkyl group or alkenyl group.
In this embodiment, R ¹ is particularly preferably a hexadecyl group.
Further, ^R1 -OC (= O)-may be located at any of the meta position, the para position, and the ortho position, but it is preferably located at the meta position or the para position, and the para position is preferable. It is more preferable to be located in.

R ² independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and represents a fluorine atom, a chlorine atom, a methyl group, an ethyl group, or a phenyl. It is preferably a group, more preferably a fluorine atom, a chlorine atom or a methyl group.
n represents an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.

The aromatic polycarbonate resin having the terminal structure represented by the formula (1) is preferably a bisphenol A type polycarbonate resin.
The terminal structure represented by the formula (1) can be added to the polycarbonate resin by using a terminal encapsulant such as parahydroxybenzoic acid hexadecyl ester. For these details, the description in paragraphs 0022 to 0030 of JP-A-2019-002023 can be referred to, and these contents are incorporated in the present specification.

As a method for lowering the glass transition temperature of the resin composition (y), a polycarbonate resin having a low glass transition temperature such as an aromatic polycarbonate resin having a terminal structure represented by the formula (1) or a bisphenol C type polycarbonate resin is used. In addition to being used, it can also be lowered by adding other thermoplastic resins or additives. For example, blending a polyether having a number average molecular weight of 6000 or less, blending a polycyclohexanedimethylene terephthalate, blending a phosphoric acid ester compound, and the like are exemplified. In the present embodiment, it is preferable to use an aromatic polycarbonate resin having a terminal structure represented by the formula (1) and / or a bisphenol C type polycarbonate resin, and an aromatic polycarbonate having a terminal structure represented by the formula (1). It is more preferable to use a resin. By using the aromatic polycarbonate resin and / or the bisphenol C-type polycarbonate resin having the terminal structure represented by the formula (1), the polycarbonate resin layer is less likely to become brittle and the sheet is less likely to become brittle than when an additive is added. The impact resistance at times tends to be high. Further, it is possible to prevent whitening after the wet heat test.

The proportion of the polycarbonate resin in the layer (Y) is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more.
The layer (Y) may contain only one type of polycarbonate resin, or may contain two or more types of polycarbonate resin. When two or more kinds are contained, it is preferable that the total amount is within the above range.

In addition to the above components, the resin composition (y) contains a thermoplastic resin other than the polycarbonate resin, an antioxidant, a mold release agent, an ultraviolet absorber, a heat stabilizer, a flame retardant, a flame retardant aid, a colorant, and an antistatic agent. Contains agents, fluorescent whitening agents, antifogging agents, fluidity improving agents, plasticizers, dispersants, antibacterial agents, antiblocking agents, impact improving agents, sliding improving agents, hue improving agents, acid trapping agents, etc. May be good. One of these components may be used, or two or more thereof may be used in combination.
When contained, the content of the above components is preferably 0.1 to 5% by mass of the resin composition (y) in total.

Further, the layer (Y) may be a single layer or may be a multi-layer.
The thickness of the layer (Y) is not particularly limited, but is, for example, 1 μm or more, preferably 30 μm or more, more preferably 35 μm or more, further preferably 40 μm or more, and 50 μm or more. It is more preferably 100 μm or more, further preferably 300 μm or more, particularly preferably 500 μm or more, and may be 700 μm or more. The thickness of the layer (Y) is preferably 10,000 μm or less, more preferably 5,000 μm or less, 3,000 μm or less, or 2,500 μm or less. ..

<Layer structure of multilayer body>
The multilayer body of the present embodiment includes the layer (X) and the layer (Y). At this time, the relationship between the thickness of the layer (X) and the thickness of the layer (Y) can satisfy {the thickness of the layer (X) / [the total thickness of the layer (X) and the layer (Y)]} <1/5. preferable. By satisfying this relationship, the layer (X) becomes thin as a whole of the multilayer body, so that even if the multilayer body is heat-molded, the generation of cracks is effectively suppressed and the generation of springback is effective. Is suppressed. More specifically, in order to suppress the springback, it is more effective to relax the residual stress due to the bending remaining in the entire multilayer body when the multilayer body is bent. From this point of view, it is more preferable to relax the residual stress not only in the layer (Y) but also in the layer (X). By making the layer (X) and the layer (Y) satisfy the above relationship, the residual stress derived from the layer (X) can be easily relaxed, and the springback can be suppressed more effectively. In the present embodiment, {thickness of layer (X) / [total thickness of layer (X) and layer (Y)]} <1/6 is more preferable, and {thickness of layer (X) / [layer (X)). And the total thickness of the layer (Y)]} <1/8 is more preferable. Further, it is preferably 1/35 << {thickness of layer (X) / [total thickness of layer (X) and layer (Y)]}, and 1/25 << {thickness of layer (X) / [layer ( The total thickness of X) and the layer (Y)]} is more preferable. In particular, in the present embodiment, it is more preferable that the layer (X) and the layer (Y) satisfy the above-mentioned preferable range of the predetermined thickness, and the multilayer body satisfies the above-mentioned relationship while satisfying the preferable range of the thickness described later. .. With such a configuration, the effect of the present invention is more effectively achieved.
Further, by using an acrylic resin for the layer (X), a multilayer body having excellent surface hardness can be obtained.

In particular, in the present embodiment, it is preferable that the initial glass transition temperature (Tig) of the layer (X), the initial glass transition temperature (Tig) of the layer (Y), and the thermal bending molding temperature (° C.) satisfy the following relationship.
Tig of layer (X) ≥ thermal bending temperature (° C)> [Initial glass transition temperature of layer (Y) (Tig) -15 ° C]
More preferably, Tig of the layer (X)> thermal bending molding temperature (° C.)> [initial glass transition temperature (Tig) of the layer (Y) -15 ° C.]
More preferably
Tig of layer (X)> thermal bending temperature (° C)> [initial glass transition temperature (Tig) -10 ° C of layer (Y)]
By doing so, the suppression of springback and the suppression of crack generation tend to be further improved.

The multilayer body of the present embodiment further preferably includes a hard coat layer. The hard coat layer is preferably laminated in the order of the layer (Y), the layer (X), and the hard coat layer. Further, the hard coat layer may be provided on the layer (Y) side as well. It should be noted that another layer is provided between the layer (Y) and the layer (X) and between the layer (X) and the hardcoat layer to the extent that the gist of the present embodiment is not deviated. May be.

Next, the details of the hard coat layer will be described. The hard coat layer that may be included in the multilayer body of the present embodiment is a layer having a higher surface hardness than the polycarbonate resin layer. By including such a hard coat layer, the surface hardness of the multilayer body or the molded product can be increased.
The thickness of the hard coat layer is preferably 0.5 μm or more, more preferably 1 μm or more, further preferably 2 μm or more, further preferably 4 μm or more, and further preferably 5 μm or more. Is even more preferable. By setting the value to the lower limit or more, the pencil hardness of the entire multilayer body due to the hard coat layer tends to be further improved. The upper limit of the thickness of the hard coat layer is preferably 20 μm or less, more preferably 15 μm or less, further preferably 12 μm or less, further preferably 10 μm or less, and further preferably 8 μm or less. Is even more preferable. By setting the value to the upper limit or less, the workability at the time of thermal bending tends to be further improved.

The hard coat layer is preferably obtained by applying a hard coat material that can be heat-cured or cured by an active energy ray and then curing it.
Examples of the coating material to be cured using the active energy ray include a resin composition composed of one or more monofunctional or polyfunctional (preferably 2 to 10 functional) (meth) acrylate monomers or oligomers, which is preferable. Examples thereof include a resin composition containing a monofunctional or polyfunctional (preferably 2 to 10 functional) urethane (meth) acrylate oligomer. It is preferable to add a photopolymerization initiator as a curing catalyst to these resin compositions.
Examples of the thermosetting resin paint include polyorganosiloxane-based paints and cross-linked acrylic-based paints. Some of such resin compositions are commercially available as acrylic resins, polycarbonate resin films, or hard coat agents for sheets, and may be appropriately selected in consideration of suitability with the coating line.
As the hard coat layer, the description of paragraphs 0045 to 0055 of JP2013-020130, the description of paragraphs 0073 to 0076 of JP-A-2018-103518, and the description of paragraphs 0062-0087 of JP-A-2017-21771. These contents are incorporated herein by reference.

Further, it is also preferable that the multilayer body of the present embodiment has a low refractive index layer on the hard coat layer and on the surface opposite to the layer (Y). That is, the multilayer body can be used as an antireflection film.
FIG. 1 is a schematic view showing an example of an antireflection film, in which 1 is a layer (Y), 2 is a layer (X), 3 is a hard coat layer, and 4 is an antireflection layer. In FIG. 1, the layer (Y) 1, the layer (X) 2, the hard coat layer 3 and the antireflection layer 4 are laminated in the above-mentioned order, but other layers are provided as long as the gist of the present embodiment is not deviated. You may have. When the multilayer body has another layer, one side or both sides of the multilayer body are subjected to fingerprint resistance treatment, antireflection treatment, antiglare treatment, weather resistance treatment, antistatic treatment, antifouling treatment and the like. It is preferable that any one or more of the anti-blocking treatments are applied. An example of the outermost surface of the multilayer body at this time is a hard coat layer. Further, the anti-blocking treatment refers to a treatment that enables the films to be easily peeled off even if they are in close contact with each other, and examples thereof include adding an anti-blocking agent and providing irregularities on the surface of the multilayer body.
Further, the multilayer body of the present embodiment may have other layers in addition to the above. Specifically, an adhesive layer, an adhesive layer, an antifouling layer and the like are exemplified.

The total thickness of the multilayer body of the present embodiment is not particularly limited, but is preferably 10 μm or more, more preferably 20 μm or more, and further preferably 100 μm or more. The thicker the layer, the higher the rigidity of the multilayer body tends to be. Further, the total thickness of the multilayer body is preferably 10,000 μm or less, more preferably 5,000 μm or less, and may be 2,000 μm or less. By setting such a layer thickness, the multilayer sheet is crimped between the rolls at the time of forming the multilayer body, and when the resin is cooled, the resin is cooled to the inside of the multilayer body, so that the moldability of the multilayer body is improved. Can be made to.

<Manufacturing method of multilayer body>
The multilayer body of the present embodiment uses a main extruder for extruding the resin composition (x) and a sub extruder for extruding the resin composition (y), and melts and extrudes the resin under the conditions of the resin to be used. A multilayer body can be formed by guiding the die and laminating inside the die to form a sheet, or by forming the sheet and then laminating.

<Molded products and manufacturing methods for molded products>
Next, a molded product and a method for manufacturing the molded product using the multilayer body of the present embodiment will be described.
The molded product of the present embodiment is a molded product formed from the multilayer body of the present embodiment.
Since the multilayer body of the present embodiment is also excellent in thermal bending resistance, it is also suitable for applications having a bent portion. For example, it is also preferably used for a molded product having a portion having a radius of curvature of 50 mmR or less (preferably a radius of curvature of 40 to 50 mmR).
The molded product of the present embodiment is preferably obtained by thermally bending the multilayer body of the present embodiment at 100 ° C. or higher and lower than 130 ° C. Since the multilayer body of the present embodiment is excellent in thermal bending resistance, it is particularly useful when a molded product having a portion having a radius of curvature of 50 mmR or less is formed. In particular, since the thermoforming temperature can be lowered, relaxation after thermoforming of each layer (layer (X), layer (Y), etc.) of the multilayer body is likely to occur, and thermoforming can be facilitated. In the present embodiment, the thermal bending temperature is preferably 115 ° C. or higher, more preferably 118 ° C. or higher, and more preferably 125 ° C. or lower, from the viewpoint of the occurrence of springback and cracks. It is more preferably 123 ° C. or lower, and even more preferably 121 ° C. or lower.

<Use>
The multilayer body and molded product of the present embodiment can be suitably used for optical parts, design products, antireflection molded products and the like.
The multilayer body and molded product of the present embodiment are suitably used for parts such as display devices, electrical and electronic devices, OA devices, mobile information terminals, mechanical parts, home appliances, vehicle parts, various containers, lighting equipment and the like. Among these, in particular, various displays, electrical and electronic equipment, OA equipment, mobile information terminals and housings of home appliances, lighting equipment and vehicle parts (particularly vehicle interior parts), surface film such as smartphones and touch panels, optical materials, etc. Suitable for optical discs. In particular, the molded product of this embodiment is preferably used as an antireflection molded product for a touch panel sensor film or various displays.

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.
When the measuring device or the like used in the examples is difficult to obtain due to a discontinued number or the like, measurement can be performed using another device having the same performance.

1. 1. Raw Material Acrylic Resin (a) Used in Raw Material / Resin Composition (x)
(A1) manufactured by Arkema, ALTUGLAS (registered trademark) V020, methyl methacrylate: methyl acrylate = 97% by mass: 3% by mass, Tig: 109 ° C., weight average molecular weight: 127,000, pencil hardness: 3H.

(A2) Resin obtained in the following synthetic example << Synthetic example >>
74.3 parts by mass of purified methyl methacrylate (manufactured by Mitsubishi Gas Chemicals) and 25.7 parts by mass of purified styrene (manufactured by Wako Pure Chemical Industries, Ltd.) as monomer components, and t-amylper as a polymerization initiator. Oxy-2-ethylhexanoate (manufactured by Alchema Yoshitomi, trade name: Luperox 575) 0.00045 parts by mass of a monomer composition is continuously supplied to a 10 L complete mixing tank with helical ribbon wings at 1 kg / h. Continuous polymerization was carried out at an average residence time of 2.5 hours and a polymerization temperature of 150 ° C. The liquid level in the polymerization tank was continuously withdrawn from the bottom so as to be constant, and introduced into a solvent removing device to obtain a pellet-shaped copolymer. The proportion of the (meth) acrylic acid ester monomer unit derived from methyl methacrylate in the obtained copolymer was 73 mol%. This copolymer was dissolved in methyl isobutyrate (manufactured by Kanto Chemical Co., Inc.) to prepare a 10% by mass methyl isobutyrate solution. A 1000 mL autoclave device was charged with 500 parts by mass of a 10 mass% methyl isobutyrate solution of this polymer and 1 mass% Pd / C (manufactured by NE Chemcat) as a hydrogenation catalyst at a hydrogen pressure of 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%. Moreover, in the obtained vinyl copolymer (a2), the ratio of the structural unit derived from methyl methacrylate was 73% by mass.
The obtained resin had Tig: 118 ° C., weight average molecular weight: 140,500, and pencil hardness: 3H.

(B) Styrene resin (b1) manufactured by Fine-blend Polymer, SAM-020, styrene: maleic anhydride = 83% by mass: 17% by mass, Tig: 129 ° C., weight average molecular weight: 107,200, pencil hardness: HB
(B2) Made by Polyscope, XIRANSO23110, Styrene: Maleic anhydride = 77% by mass: 23% by mass, Tig: 145 ° C., Weight average molecular weight: 74,300, Pencil hardness: HB
(B3) Made by Polyscope, XIRANSO26080, Styrene: Maleic anhydride = 74% by mass: 26% by mass, Tig: 150 ° C., Weight average molecular weight: 47,600, Pencil hardness: HB
(B4) Made by Polyscope, XIBOND140, Styrene: Maleic anhydride = 85% by mass: 15% by mass, Tig: 129 ° C., Weight average molecular weight: 134,000, Pencil hardness: HB

(C) Antioxidant: Adecasterb PEP-36, the following compound, tBu represents a t-butyl group.

(D) Release agent: Glycerin monostearate, manufactured by Riken Vitamin Co., Ltd., Rikemar S-100A

Polycarbonate resin composition with raw material (y1) Tig of 125 ° C. or lower used in the resin composition (y) T-1380: Bisphenol A type polycarbonate resin using parahydroxybenzoic acid hexadecyl ester as an end sealant, Mitsubishi Gas Made by Chemical Co., Ltd., Weight average molecular weight: 55,000, Tig: 124 ° C.

(Y2) Polycarbonate resin composition having a Tig of 125 ° C. or higher E-2000F: Bisphenol A type polycarbonate resin using paratarshal butylphenol as an end sealant, manufactured by Mitsubishi Engineering Plastics Co., Ltd., weight average molecular weight: 53,000, Tig: 149 ° C

<Measurement of glass transition temperature>
The glass transition temperature of various resins and resin compositions was increased and decreased in two cycles according to the following differential scanning calorimetry (DSC measurement) conditions, and the glass transition temperature at the time of the second cycle of temperature increase was measured. ..
The intersection of the straight line extending the baseline on the low temperature side to the high temperature side and the tangent line of the turning point is the starting glass transition temperature (Tig), and the straight line extending the baseline on the high temperature side to the low temperature side and the tangent line of the turning point. The intersection of the above was defined as the end glass transition temperature, and the intermediate point between the start glass transition temperature and the end glass transition temperature was defined as the intermediate glass transition temperature (Tmg). The measurement start temperature was 30 ° C., the temperature rise rate was 10 ° C./min, the ultimate temperature was 250 ° C., and the temperature decrease rate was 20 ° C./min. The unit is shown in ° C.
As a measuring device, a differential scanning calorimeter (DSC, manufactured by Hitachi High-Tech Science Corporation, "DSC7020") was used.

<Measurement method of weight average molecular weight>
The weight average molecular weight (Mw) of various resins and resin compositions was measured by gel permeation chromatography.
Specifically, an LC-20AD system (manufactured by Shimadzu Corporation) was used as a gel permeation chromatography apparatus, and an LF-804 (manufactured by Shodex) was connected and used as a column. The column temperature was 40 ° C. The detector used was an RI detector of RID-10A (manufactured by Shimadzu Corporation). Chloroform was used as the eluent, and the calibration curve was prepared using standard polystyrene manufactured by Tosoh Corporation.
If the gel permeation chromatography device, column, or detector is difficult to obtain, measurement is performed using another device having equivalent performance.

2. 2. Examples 1 and 2, Comparative Examples 1 to 14
<Manufacturing of resin composition (pellet)>
Each component described above was weighed so as to have an addition amount shown in Tables 1 to 4 (each component in Tables 1 to 4 is expressed in parts by mass). Then, after mixing with a tumbler for 15 minutes, the mixture was melt-kneaded at a cylinder temperature of 260 ° C. by a twin-screw extruder with a vent having a screw diameter of 32 mm (“TEX30α” manufactured by Japan Steel Works, Ltd.), and pellets were obtained by strand cutting.

<Manufacturing of 1 mm thick flat plate molded body (layer (X))>
Pellets (resin composition) of the obtained resin composition (x) are subjected to a biaxial injection molding machine with a vent (“PE-100” manufactured by Sodick Co., Ltd., a meshing type co-rotating type with a biaxial screw diameter of 29 mm, and a plunger diameter. 28 mm) was melt-kneaded at a cylinder temperature of 260 ° C. to form a flat plate-shaped molded product (100 × 100 × 1 mm) (layer (X)) under the condition of a mold temperature of 80 ° C.

<Measurement of total light transmittance and haze>
Using a haze meter, the total light transmittance (unit:%) and haze (unit:%) of the flat plate-shaped molded product obtained above were measured under the condition of a D65 light source 10 ° field of view.
As the haze meter, "HM-150" manufactured by Murakami Color Technology Research Institute was used.

<Pencil hardness>
For the flat plate-shaped molded body (layer (X)) produced above, the pencil hardness measured with a 750 g load was determined using a pencil hardness tester in accordance with JIS K5600-5-4: 1999. The evaluation was conducted by five experts and judged by majority vote.

<Measurement of Charpy impact strength>
The Charpy impact strength was measured in JIS K7111-1 by changing the thickness of the ISO test piece from 4 mm to 3 mm and performing the same procedure for the others.
Specifically, the obtained resin composition (pellet) is subjected to a biaxial injection molding machine with a vent (“PE-100” manufactured by Sodick Co., Ltd., a meshing type co-rotating type with a biaxial screw diameter of 29 mm, and a plunger diameter of 28 mm). A molded product (test piece) having a length of 80 mm, a width of 10 mm, and a thickness of 3 mm was produced by melting and kneading at a cylinder temperature of 260 ° C. and a mold temperature of 70 ° C. After that, a Charpy impact test without a notch was performed in accordance with JIS K7111-1 except for the thickness, and the Charpy impact strength was measured. The unit is kJ / m ² .

<Manufacturing of multilayer body>
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. Multilayers were molded using a multi-layer extruder with a multi-manifold die coupled to the extruder. The resin composition (x) of Examples or Comparative Examples shown in Tables 1 to 4 was introduced into a single-screw extruder having a shaft diameter of 32 mm, and extruded under the conditions of a cylinder temperature of 250 ° C. and a discharge rate of 3.6 kg / h. .. Further, the resin composition (y) was continuously introduced into a single-screw extruder having a shaft diameter of 65 mm, and the resin composition (y) was extruded at a cylinder temperature of 280 ° C. and a discharge rate of 32.4 kg / h. The feed block connected to all extruders was equipped with two types and two layers of distribution pins, extruded at a temperature of 270 ° C., and laminated. A T-die with a temperature of 270 ° C connected to the tip extrudes it into a sheet, and three mirror-finishing rolls with temperatures of 130 ° C, 140 ° C, and 180 ° C are used to cool the mirror while transferring the mirror surface. Got The total thickness of the central portion of the obtained multilayer body was 1000 μm, and the thickness of the acrylic resin layer (layer (X)) was 100 μm.

<Hard coat coating>
6-functional urethane acrylate oligomer (product name: U6HA, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 60 parts by mass, PEG200 # diacrylate (product name: 4EG-A, manufactured by Kyoeisha Chemical Co., Ltd.) 35 parts by mass, and fluorine-containing group. Photopolymerization initiator (product name: I-184) for a total of 100 parts by mass of 5 parts by weight of a hydrophilic group, an oil-based group, and a UV-reactive group-containing oligomer (product name: RS-90, manufactured by DIC Co., Ltd.). A paint containing 1% by mass of [Compound name: 1-hydroxy-cyclohexylphenylketone] manufactured by BASF Co., Ltd.) is applied to the surface of the acrylic resin layer (x) of the multilayer body prepared above with a bar coater, and metal halide is applied. A lamp (20 mW / cm ² ) was applied for 5 seconds to cure the hard coat. The film thickness of the hard coat layer was 6 μm.

<Heat press molding processability (crack)>
For the multilayer body obtained above, convex (male) and concave (female) molds having a radius of curvature of 50 mmR were produced. The multilayer body coated with the hard coat layer is preheated at 90 ° C. for 1 minute before molding, placed in a mold so that the surface on the multilayer body side coated with the hard coat layer is convex, and the mold temperature is 120 ° C. 3 A hot press molded product was produced by pressing for a minute and allowing it to cool naturally.
The cracks in the bent portion of the hot press molded product were visually evaluated. The evaluation was conducted by five experts and judged by majority vote.
A: No crack was confirmed in the bent portion of the hot press molded body.
B: Cracks were confirmed in the bent portion of the hot press molded body.

<Spring back>
The hot press molded product was placed along a 50 mmR cylinder, and a pass / fail judgment of springback was performed according to the following criteria, and A was regarded as acceptable. The evaluation was conducted by five experts and judged by majority vote.
A: Along the cylinder. (No spring back)
B: Does not follow the cylinder. (With spring back)

1 layer (Y) (polycarbonate resin layer)
2 layers (X) (acrylic resin layer)
3 Hardcourt layer 4 Antireflection layer

Claims (12)

It has a layer (X) formed from the resin composition (x) and a layer (Y) formed from the resin composition (y) containing a polycarbonate resin.
The resin composition (x) has an initial glass transition temperature (Tig) of 120 ° C. or higher measured by differential scanning calorimetry.
When the resin composition (x) is formed into an ISO test piece having a thickness of 3 mm, the notchless Charpy impact strength is 12.0 kJ / m ² or more, and the notchless Charpy impact strength is JIS K 7111-. In 1, the thickness of the ISO test piece was changed from 4 mm to 3 mm, and the other values were measured in the same manner.
The resin composition (y) has an initial glass transition temperature (Tig) of 125 ° C. or lower as measured by differential scanning calorimetry.
Multilayer. The multilayer body according to claim 1, wherein the pencil hardness of the layer (X) is H or more. The resin composition (x) contains an acrylic resin (a) and a styrene resin (b), and the acrylic resin (a) is based on a total of 100 parts by mass of the contents of the acrylic resin (a) and the styrene resin (b). The multilayer body according to claim 1 or 2, wherein the content of) is 25 to 65 parts by mass, and the content of the styrene resin (b) is 35 to 75 parts by mass. The styrene resin (b) contains 68 to 84% by mass of an aromatic vinyl compound unit and 16 to 32% by mass of a cyclic acid anhydride unit (however, the total of the aromatic vinyl compound unit and the cyclic acid anhydride unit is 100). The multilayer body according to claim 3 (which does not exceed% by mass). The multilayer body according to claim 4, wherein the aromatic vinyl compound unit in the styrene resin (b) contains styrene. The multilayer body according to claim 4 or 5, wherein the cyclic acid anhydride unit in the styrene resin (b) contains maleic anhydride. The multilayer body according to any one of claims 1 to 6, wherein the resin composition (x) further contains an antioxidant and / or a mold release agent. The method according to any one of claims 1 to 7, further comprising a hard coat layer, wherein the hard coat layer is laminated in the order of the layer (Y), the layer (X), and the hard coat layer. Multilayer. The multilayer body according to any one of claims 1 to 8, which satisfies {thickness of layer (X) / [total thickness of layer (X) and layer (Y)]} <1/5. Further, one or more of the fingerprint resistant treatment, the antireflection treatment, the antiglare treatment, the weather resistance treatment, the antistatic treatment, the antifouling treatment and the antiblocking treatment are applied to one or both sides of the multilayer body. The multilayer body according to any one of claims 1 to 9. The multilayer body according to any one of claims 1 to 10, wherein the total thickness of the multilayer body is 10 to 10,000 μm. A molded product formed from the multilayer body according to any one of claims 1 to 11, wherein the molded product has a portion having a radius of curvature of 50 mmR or less.

Images