JP2019136994A - Resin laminate and resin molded body using the same - Google Patents

Abstract

To provide a resin laminate hardly generating appearance abnormality such as whitening or crack during molding.SOLUTION: There is provided a resin laminate having a resin layer (A) containing a resin (a) and a resin layer (B) laminated on at least one surface of the resin layer (A) and containing a resin (b) different from the resin (a), in which the resin layer (B) has pencil hardness of F or higher, the resin (a) is a polycarbonate copolymer resin. Preferably glass transition temperature (TgA) of the resin (a) is 100 to 135°C, glass transition temperature (TgB) of the resin (b) is 90 to 125°C, and the TgA and the TgB satisfy a relationship of 0≤TgA-TgB≤30.SELECTED DRAWING: None

Description

  The present invention relates to a resin laminate and a resin molded body obtained by molding it.

Glass plates, transparent resin plates, etc. are used for display surface components such as automotive interior parts such as instrument covers, home appliances, OA equipment, personal computers, and small portable devices, and frame parts that hold them are made of resin. The molded body is used.
On the other hand, as a component of a touch panel type display surface used for a mobile phone terminal or the like, a transparent sheet, in particular, a glass plate bonded with a double-sided adhesive tape or the like to a frame part made of injection molded resin is used. As the touch panel type display surface, a thinner one is preferable from the viewpoint of response speed, and a thickness of a certain level or more is necessary from the viewpoint of strength. Therefore, a material having a high elastic modulus is selected. In addition, scratch resistance and fingerprint wiping properties are also required.

  Although the resin molding used for the above uses can be manufactured by shape | molding a resin sheet, various devices are made | formed in order to provide the characteristic according to a use. For example, a resin sheet is modified with a hard coat layer, a decorative sheet, or the like, a resin layer having a different composition is laminated to form a resin sheet, or a resin composition to be used is devised. .

  For example, polycarbonate resin is not only excellent in transparency, but also excellent in processability and impact resistance as compared with glass, and has no fear of toxic gas as compared with other plastic materials. Therefore, the polycarbonate resin is widely used as a material for the resin sheet as described above.

  However, since the polycarbonate resin generally has a low surface hardness, it has a problem that the surface of a molded article made of the polycarbonate resin is easily damaged. Therefore, conventionally, a proposal has been made to form a protective layer containing a hard resin on the surface of the polycarbonate resin layer so that the product surface is not damaged.

  For example, Patent Document 1 discloses a laminate in which an acrylic resin layer having a thickness of 50 to 120 μm is laminated on one surface of a polycarbonate resin layer by coextrusion to have a total thickness of 0.5 to 1.2 mm. It is disclosed.

  Patent Document 2 discloses a multilayer film in which a layer made of methacrylic resin and acrylic rubber particles is laminated on the surface of a polycarbonate resin layer. In addition, a decorative sheet in which one surface of the multilayer film is decorated and a thermoplastic resin sheet is laminated on the decorated surface is also disclosed.

  Patent Document 3 discloses a laminated sheet including a coating layer mainly composed of an acrylic resin on one surface of a base material layer mainly composed of a polycarbonate resin composition.

  As described above, various resin sheets or films for molding have been proposed. However, there is no end to pursuing a resin sheet or film that can produce a resin molded body having characteristics more suitable for use. It is a problem. In addition, these resin sheets or films are also required to have less appearance defects during molding.

JP 2006-103169 A JP 2009-234184 A Patent No. 4971218

  It is an object of the present invention to provide a resin laminate that is less prone to appearance abnormalities such as whitening and cracking during molding.

As a result of diligent research, the present inventors have found that, in a resin laminate in which another resin layer is laminated on a base material layer containing a polycarbonate resin, by using a specific polycarbonate resin as a base material, It has been found that appearance abnormalities such as these are less likely to occur. That is, the present invention is as follows, for example.
[1] A resin layer (B) containing a resin (a) containing a resin (a) and a resin (b) different from the resin (a) laminated on at least one surface of the resin layer (A) )
The resin layer (B) has a pencil hardness of F or more,
The resin (a) is a polycarbonate resin containing a structural unit (a-1) represented by the following formula (1) and a structural unit (a-2) represented by the following formula (2).
Resin laminate:


(In Formula (2), R ₁ is a hydrogen atom or a methyl group; R ₂ is an alkyl group having 4 to 15 carbon atoms; R ₃ and R ₄ are methyl groups; And an integer of 0 to 4).
[2] The glass transition temperature (TgA) of the resin (a) is 100 to 135 ° C., the glass transition temperature (TgB) of the resin (b) is 90 to 125 ° C., and the TgA and the TgB are as follows: The resin laminate according to [1], which satisfies the relationship of formula (1):
0 ≦ TgA−TgB ≦ 30 (1)
[3] The resin laminate according to [1] or [2], wherein the structural unit (a-2) is represented by the following formula (3).

[4] The resin laminate according to any one of [1] to [3], wherein the resin (b) is an acrylic resin or a polycarbonate resin.
[5] The resin (b) is selected from the group consisting of polymethyl (meth) acrylate, methyl methacrylate-vinylcyclohexane copolymer resin, and methyl methacrylate-styrene-maleic anhydride copolymer resin. [4] The resin laminate according to any one of [4].
[6] The thickness of the resin laminate is 0.1 to 3.0 mm, and the thickness ratio of the resin layer (A) to the resin layer (B) is 1: 1 to 50: 1. [1] -Resin laminated body in any one of [5].
[7] The resin laminate according to any one of [1] to [6], further comprising a hard coat layer.
[8] The resin laminate according to [7], wherein the hard coat layer has a thickness of 1 to 30 μm.
[9] The resin laminate according to any one of [1] to [8], which is used in the manufacture of a display cover panel or a touch panel front plate.
[10] The resin laminate according to any one of [1] to [8], which is used in the manufacture of exterior members for mobile phones, smartphones, tablet PCs, or personal computers.
[11] The resin laminate according to any one of [1] to [8], which is used in the manufacture of automobile exterior or interior members.
[12] A resin molded product molded using the resin laminate according to any one of [1] to [11].

  ADVANTAGE OF THE INVENTION According to this invention, the resin laminated body which does not produce appearance abnormalities, such as whitening and a crack, at the time of shaping | molding can be provided.

Hereinafter, embodiments of the present invention will be described in detail.
The resin laminate of the present invention comprises a resin layer (A) containing a resin (a) (hereinafter also referred to as “base material layer”) and the resin laminated on at least one surface of the resin layer (A). A resin layer (B) containing a resin (b) different from (a) (hereinafter also referred to as “protective layer”). And the pencil hardness of the resin layer (B) is F or more, and the resin (a) is a structural unit (a-1) represented by the following formula (1) and a structural unit represented by the following formula (2). It is a polycarbonate resin containing (a-2).


(In Formula (2), R ₁ is a hydrogen atom or a methyl group; R ₂ is an alkyl group having 4 to 15 carbon atoms; R ₃ and R ₄ are methyl groups; And an integer of 0 to 4).

  Conventionally, when thermoforming a multi-layered resin sheet composed of multiple types of resin layers, the glass transition point (Tg) and melt viscosity of the resin contained in each layer are different, so thermoforming so as not to cause defects such as cracks. There was a problem that it was difficult to do. When thermoforming a resin sheet having a multilayer structure into a desired shape, the resin sheet is usually formed in accordance with the molding temperature of the resin most contained in the layer. For example, in the case of a resin sheet using a polycarbonate resin as a base material layer, the polycarbonate resin having a good impact resistance is usually contained in the largest amount, and therefore, thermoforming is performed at a molding temperature according to the polycarbonate resin. . As a result, excessive heat is applied to the resin other than the polycarbonate resin, and peeling occurs at the interface of each layer, and the surface of the molded body may be whitened or cracks may occur. In addition, the resin sheet as described above sometimes foams when the drying before heat formation is insufficient.

  In contrast, the present invention uses a resin having a specific structure as the polycarbonate resin in the base material layer in the laminate in which the protective layer is disposed on the base material layer containing the polycarbonate resin. The present inventors have found that such resin laminates are less susceptible to appearance problems such as whitening, cracking and foaming even when thermoformed at a molding temperature suitable for polycarbonate resin. That is, it can be said that the resin laminate of the present invention is more suitable for thermoforming than the conventional one.

  Therefore, the resin laminate of the present invention can be suitably used for manufacturing a molded product having a bent shape. For example, a component having a bent portion that is continuous with the flat portion can be successfully manufactured, so that a product having a novel design and function can be provided.

  With conventional resin sheets, when trying to manufacture a molded product having the above-mentioned shape, there are problems such as appearance abnormalities such as cracks during thermoforming such as hot press molding, vacuum forming, pressure forming, and TOM forming. Many occurred. Therefore, in order to suppress the occurrence of abnormal appearance during thermoforming, it has been necessary to devise measures such as reducing the hardness of the protective layer laminated on the base material layer. However, when the hardness of the protective layer is reduced, the thermoformability is improved, but there are new problems that it is soft and easily damaged and the chemical resistance is lowered.

  On the other hand, according to the present invention, since the occurrence of abnormal appearance is suppressed as described above, it is possible to provide a resin laminate that can be thermally formed without reducing the hardness of the protective layer. Since the resin laminate of the present invention can be provided with a protective layer having high hardness on the base material layer, it is difficult to be damaged and has high chemical resistance. Utilizing such characteristics, the resin laminate of the present invention is used for display surface components such as a personal computer, a smartphone, a mobile phone, and a tablet PC (for example, a display cover panel, a touch panel front plate, etc.) or for exteriors thereof. It can be used for a member (particularly a casing), an automobile exterior member, and an interior member (particularly a casing).

  Furthermore, the resin laminate of the present invention can suppress whitening, cracks, and foaming even when molded into a right-angle shape. And since the radius R of a right-angle-shaped part can be made into at least 3.0 mm or less, and also in a preferable aspect within 1.0 mm, it can shape | mold with high precision.

  In addition, since the resin laminate of the present invention has the above-described features, for example, a printed layer is formed on the base layer side of the resin laminate, and a molten resin is injection-molded on the printed layer to form a backing layer. By forming, an in-mold molded product having excellent design properties can be produced.

Hereinafter, each structural member of the resin laminated body by this invention is demonstrated.
1. Resin layer (A) (base material layer)
The resin layer (A) is a resin layer mainly containing a polycarbonate resin (a). The polycarbonate resin (a) includes a structural unit (a-1) represented by the following formula (1) and a structural unit (a-2) represented by the following formula (2). The resin layer (A) may contain one type or two or more types of polycarbonate resins (a).


(In Formula (2), R ₁ is a hydrogen atom or a methyl group; R ₂ is an alkyl group having 4 to 15 carbon atoms; R ₃ and R ₄ are methyl groups; And an integer of 0 to 4).

In Formula (2), R ₁ is preferably a hydrogen atom. R ₂ is preferably an alkyl group having 6 to 11 carbon atoms, and more preferably an alkyl group having 8 to 10 carbon atoms. By using an alkyl group having 4 or more carbon atoms, a resin having appropriate fluidity and easy to mold can be obtained. Moreover, the resin layer of suitable hardness can be obtained by setting it as a C15 or less alkyl group. The alkyl group for R ₂ may be linear, branched or cyclic, but is preferably linear or branched, and more preferably linear. Either one of m and n is preferably 0, and the other is preferably 1, and more preferably both are 0.

The structural unit (a-2) is particularly preferably a structural unit represented by the following formula (3).

  The polycarbonate resin (a) may contain one type or two or more types of structural units (a-2) represented by the formula (2). When two or more types are included, one of them is preferably a structural unit represented by the above formula (3).

  The content of the structural unit (a-1) represented by the formula (1) is preferably 65 to 92% by mass, more preferably 80 to 92% by mass, particularly with respect to all the structural units of the polycarbonate resin (a). Preferably it is 89-91 mass%. Further, the content of the structural unit (a-2) represented by the formula (2) is preferably 8 to 35% by mass, more preferably 8 to 20% by mass with respect to all the structural units of the polycarbonate resin (a). Especially preferably, it is 9-11 mass%. The total content of the structural unit (a-1) and the structural unit (a-2) in the polycarbonate resin (a) is preferably 70 to 90% by mass, more preferably based on all the structural units of the polycarbonate resin (a). Is 85 to 95% by mass, particularly preferably 99 to 100% by mass. The polycarbonate resin (a) may contain a structural unit other than the structural unit (a-1) and the structural unit (a-2), but the amount thereof is based on the total structural unit of the polycarbonate resin (a). The content is preferably 0 to 30% by mass, more preferably 0 to 15% by mass, and particularly preferably 0 to 1% by mass. The polycarbonate resin (a) is particularly preferably a resin composed of the structural unit (a-1) and the structural unit (a-2).

  Other structural units that may be contained in the polycarbonate resin (a) are not limited, and examples thereof include 1,1-bis (4-hydroxyphenyl) cyclohexane [= bisphenol Z], 2,2- Examples include structural units derived from bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, and the like.

  The resin layer (A) preferably contains the polycarbonate resin (a) in an amount of 50 to 100% by mass, more preferably 80 to 100% by mass, and 100% by mass with respect to the total mass of the base material layer. Particularly preferred. The resin layer (A) is particularly preferably made of a polycarbonate resin (a). The impact resistance is improved by increasing the content of the polycarbonate resin (a) in the resin layer (A).

  In the present invention, the weight average molecular weight of the polycarbonate resin (a) can affect the impact resistance and molding conditions of the resin laminate. That is, when the weight average molecular weight is too small, the impact resistance of the resin laminate may be lowered. When the weight average molecular weight is too high, an excessive heat source may be required when forming the base material layer containing the polycarbonate resin (a). Further, since a high temperature is required depending on the molding method selected, 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 30,000 to 90,000, and more preferably 40,000 to 80,000. More preferably, it is 50,000-70,000. In addition, the weight average molecular weight in this specification is a weight average molecular weight of standard polystyrene conversion measured by gel permeation chromatography (GPC).

  The polycarbonate resin (a) can be produced by a known method, and the production method is not particularly limited. For example, various synthetic methods including an interfacial polymerization method, a pyridine method, and a transesterification method can be raised.

  The resin layer (A) may contain other resins in addition to the polycarbonate resin (a). Examples of such a resin include PTE-G, PCTG, and PLC. The resin in the resin layer (A) is preferably only the polycarbonate resin (a), but when other resins are included, it is preferably 0 to 30% by mass with respect to the resin layer (A). More preferably, it is 0-10 mass%, and it is especially preferable that it is 0-3 mass%.

  The resin layer (A) may further contain an additive and the like. As additives, those commonly used in resin sheets can be used. Examples of such additives include antioxidants, anti-coloring agents, antistatic agents, mold release agents, lubricants, dyes, Examples thereof include pigments, plasticizers, flame retardants, resin modifiers, compatibilizers, and reinforcing materials such as organic fillers and inorganic fillers. The method of mixing the additive and the resin is not particularly limited, and a method of compounding the whole amount, a method of dry blending the master batch, a method of dry blending the whole amount, and the like can be used. The amount of the additive is preferably 0 to 30% by mass, more preferably 1 to 20% by mass, and particularly preferably 1 to 5% by mass with respect to the total mass of the resin layer (A). preferable.

  The thickness of the resin layer (A) is preferably 0.04 to 2.9 mm, more preferably 0.07 to 2.8 mm, and particularly preferably 0.09 to 2.4 mm.

2. Resin layer (B) (protective layer)
The resin layer (B) is a resin layer which is laminated on the base material layer and mainly contains a resin (b) having a pencil hardness of F or more (hereinafter also referred to as “high hardness resin”). Resin (b) should just be high hardness resin, and the kind is not limited. The resin (b) contained in the resin layer (B) may be one type or two or more types. The resin (b) is preferably an acrylic resin or a polycarbonate resin. When the resin (b) is an acrylic resin, specifically, methyl methacrylic resin (PMMA: also called polymethyl (meth) acrylate) polymerized from methyl methacrylic acid, methyl methacrylate-vinylcyclohexane copolymer resin, methacrylic acid A methyl-styrene-maleic anhydride copolymer resin may be mentioned. When the resin (b) is a polycarbonate resin, specifically, a high-hardness polycarbonate resin containing bisphenol C as a main component can be mentioned.
The polycarbonate resin as the resin (b) has a different structure from the polycarbonate resin as the resin (a).

  The pencil hardness of the resin layer (B) is preferably H or higher, more preferably 2H or higher.

  The resin layer (B) preferably contains the resin (b) in an amount of 40 to 100% by mass with respect to the total mass of the resin layer (B), more preferably 70 to 100% by mass, and 90 to 100%. Mass% is particularly preferred. The resin layer (B) is particularly preferably made of the resin (b). Hardness improves by increasing content of resin (b) in a resin layer (B).

  The resin layer (B) may contain other resins in addition to the resin (b). Examples of such resins include methyl methacrylate-styrene copolymer resin (MS resin), methyl methacrylate-styrene-maleic anhydride copolymer resin, and the like. The resin contained in the resin layer (B) is preferably only the resin (b), but when other resins are contained, it is preferably 0 to 70% by mass with respect to the resin layer (B). 0 to 50% by mass is more preferable, and 0 to 30% by mass is particularly preferable.

  The resin layer (B) may further contain an additive and the like. As an additive, the same additive as described in the above “1. Resin layer (A)” can be used, and the amount thereof is also the same.

  The thickness of the resin layer (B) affects the surface hardness and impact resistance of the resin laminate. That is, when the resin layer (B) is too thin, the surface hardness is lowered, and when it is too thick, the impact resistance is lowered. The thickness of the resin layer (B) is preferably 10 to 150 μm, more preferably 30 to 100 μm, and particularly preferably 40 to 60 μm.

3. Glass transition temperature It is preferable that resin (a) and resin (b) have a glass transition temperature of a predetermined range. That is, the glass transition temperature (TgA) of the resin (a) is preferably 100 to 135 ° C, more preferably 110 to 130 ° C, and particularly preferably 115 to 130 ° C.

By setting the glass transition temperature (TgA) to 100 ° C. or higher, the polycarbonate resin powder is not aggregated and the productivity is not lowered in the granulation and drying steps in the production of the polycarbonate resin. Therefore, within the above range, a higher glass transition point has a wider process margin for producing a polycarbonate resin, and a high-quality polycarbonate resin having a low residual solvent content can be produced efficiently and stably.
On the other hand, by setting TgA to 135 ° C. or lower, it is possible to prevent the hue of the resin from being lowered.

The glass transition temperature (TgB) of the resin (b) is preferably 90 to 125 ° C, more preferably 90 to 120 ° C, and particularly preferably 90 to 110 ° C. Furthermore, it is also preferable that it is 105-125 degreeC. And it is preferable that TgA and TgB satisfy | fill the relationship of the following formula | equation (1).
0 ≦ TgA−TgB ≦ 30 (1)

  In the above formula (1), 0 ≦ TgA−TgB ≦ 20 is more preferable, and 0 ≦ TgA−TgB ≦ 10 is particularly preferable. When TgB is extremely lower than TgA, the high-hardness resin is in a rubber state or a molten state at the time of thermoforming, and becomes easy to move. In such a case, in the structure in which the hard coat layer is provided on the protective layer, the hard coat layer that has a highly cross-linked structure and remains hard even when heated is easily moved. Although it is difficult to follow the movement of (b) and cracks are likely to occur, such a problem can be prevented by setting the above range. Moreover, since it can prevent that resin (b) is heated excessively at the time of shaping | molding, external appearance abnormalities, such as foaming, can be suppressed. On the other hand, if TgB is extremely higher than TgA, there may be a problem that the amount of film drawdown during thermoforming increases.

  A person skilled in the art appropriately selects a resin (a) and a resin (b) having a glass transition point satisfying the above relationship from the resin (a) and the resin (b) as described above. Can be used. In the present specification, the glass transition temperature is a temperature calculated by a midpoint method using a differential scanning calorimeter with a sample of 10 mg and a heating rate of 10 ° C./min.

4). Lamination of Resin Layer (A) and Resin Layer (B) As described above, the resin layer (B) is laminated on at least one surface of the resin layer (A), but the lamination method is not particularly limited. For example, a method in which the individually formed resin layer (A) and the resin layer (B) are overlaid and heat-bonded to each other; the individually formed resin layer (A) and the resin layer (B) are overlaid , A method of adhering both with an adhesive; a method of co-extrusion molding of the resin layer (A) and the resin layer (B); an in-mold of the resin layer (A) into the previously formed resin layer (B) There are various methods such as molding and integration. Among these, the method of coextrusion molding is preferable from the viewpoint of manufacturing cost and productivity.

  Moreover, as for the heat-melting temperature in an extruder, the temperature 80-150 degreeC higher than the glass transition temperature (Tg) of each resin is preferable. In general, the temperature condition of the main extruder for extruding the polycarbonate resin (a) is usually 230 to 290 ° C., preferably 240 to 280 ° C., and the temperature condition of the sub-extruder for extruding the resin (b) is usually 220. It is -270 degreeC, Preferably it is 230-260 degreeC.

  In the case of coextrusion molding, the method is not particularly limited. For example, in the feed block method, the resin layer (B) is arranged on one side of the resin layer (A) with the feed block, extruded into a sheet shape with a T-die, and then cooled while passing through a molding roll to obtain a desired lamination. Form the body. In the multi-manifold system, the resin layer (B) is disposed on one side of the resin layer (A) in the multi-manifold die, extruded into a sheet, and then cooled while passing through a forming roll to obtain a desired laminate. Form.

  In any case, the temperature of the die is preferably set to 230 to 290 ° C., particularly preferably 250 to 280 ° C., and the temperature of the forming roll is usually set to 100 to 190 ° C., particularly 110 to 190 ° C. preferable.

  In the resin laminate, the thickness ratio of the resin layer (A) to the resin layer (B) is preferably 1: 1 to 50: 1, more preferably 2: 1 to 35: 1, and 3: A ratio of 1 to 20: 1 is particularly preferred. By setting it as such a thickness ratio, it is possible to suppress the interface defect between layers, utilizing the characteristic of each layer.

5). Hard coat layer The resin laminate of the present invention may further comprise a hard coat layer. The position where the hard coat layer is provided is not particularly limited, but it is more preferably provided on the resin layer (B). The hard coat layer may be provided on both the resin layer (A) and the resin layer (B), and between the resin layer (A) and the hard coat layer and / or the resin layer (B) and the hard coat layer. There may be additional layers between the two.

As a material of the hard coat layer, a compound that forms a known cross-linked film such as acrylic, silicon, melamine, urethane, and epoxy can be used. As the curing method, a known method such as ultraviolet curing, thermal curing, electron beam curing, or the like can be used. When the hard coat layer is located on the surface layer of the resin laminate, the pencil hardness is preferably H or more. Considering the balance between hardness and heat formability, acrylic and urethane acrylates are preferred as examples.
The hard coat layer can be formed by a method known in the art, and examples thereof include, but are not limited to, a coating method such as a roll coating method, a dipping method, and a transfer method.

  As the acrylic compound that forms the hard coat layer, a crosslinkable polymerizable compound having at least two (meth) acryloyloxy groups (meaning acryloyloxy group and / or methacryloyloxy group) in the molecule can be used. In this case, the residue that binds each (meth) acryloyloxy group is preferably a hydrocarbon or a derivative thereof, and includes an ether bond, a thioether bond, an ester bond, an amide bond, a urethane bond, etc. in the molecule. Is preferred. Moreover, a long chain component having a molecular weight of 1,000 to several thousand can be appropriately added as a component imparting heat formability.

  The hard coat layer preferably has a haze after abrasion of 10% or less. This haze is measured as follows. That is, # 0000 steel wool (manufactured by Nippon Steel Wool Co., Ltd.) having a diameter of about 0.012 mm is mounted on a 33 mm × 33 mm square pad. This pad is placed on the sample surface of the hard coat layer held on the table, and is scratched by reciprocating 15 times under a load of 1000 g. After the sample is washed with ethanol, the haze is measured.

  For example, nano-sized metal particles can be added to the hard coat layer as a scratch-resistant auxiliary agent. Examples of the nano-sized metal particles include, but are not limited to, silicon dioxide and alumina.

  Preferred characteristics of the hard coat layer include elongation in thermoforming and excellent chemical resistance. In particular, among the chemical resistance, it is preferable that the Neutrogena resistance is excellent.

  The thickness of the hard coat layer is preferably 1 to 30 μm, more preferably 3 to 20 μm, and particularly preferably 5 to 10 μm. By setting it as the above thicknesses, the crack of a hard-coat layer can be prevented when heat-shaping a laminated body.

  The hard coat layer may be further modified. For example, any one or more of an antireflection treatment, an antifouling treatment, an antistatic treatment, a weather resistance treatment, and an antiglare treatment can be performed. These processing methods are not particularly limited, and known methods can be used. For example, a method of applying a reflection reducing coating, a method of depositing a dielectric thin film, a method of applying an antistatic coating, and the like can be mentioned.

  According to one embodiment of the present invention, a resin molded product formed using the above-described resin laminate is provided. The molding method is not particularly limited, but thermoforming is suitable from the characteristics of the resin laminate of the present invention. Thermoforming can be performed by a method usually used in this field, and examples thereof include hot press molding, vacuum forming, pressure forming, TOM forming, IML (in-mold lamination) and the like.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, the content of this invention is not limited by this.
(Production Example 1: Production of polycarbonate resin)
To 48.4 kg of a 9 w / w% aqueous sodium hydroxide solution, 7.47 kg (32.76 mol) of bisphenol A (BPA) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1,1-bis (4- Hydroxyphenyl) decane (DED) 0.83 kg (2.55 mol) and 30 g of hydrosulfite were added and dissolved. To this, 35 kg of dichloromethane was added, and while stirring, 4.38 kg of phosgene was blown in over 30 minutes while maintaining the solution temperature in the range of 15 ° C to 25 ° C.

  After completion of the phosgene blowing, 3 kg of a 9 w / w% aqueous sodium hydroxide solution, 19 kg of dichloromethane, and 207.7 g (1.38 mol) of DIC pt-butylphenol (PTBP) were dissolved in 0.5 kg of dichloromethane. The solution was added and vigorously stirred to emulsify. Thereafter, 20 mL of triethylamine was added as a polymerization catalyst, and polymerization was performed for about 40 minutes.

  The polymerization solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing with pure water was repeated until the pH of the washing solution became neutral. By evaporating the organic solvent from the purified polycarbonate resin solution, a polycarbonate resin powder comprising 90 wt% of the structural unit (a-1) and 10 wt% of the structural unit (a-2) was obtained.

Example 1
Resin (a) and resin (b) are each heated and melted in separate extruders, and two types of resins are simultaneously melt-extruded from the slit-shaped discharge port of the T die, and a resin layer (A) (base material layer) and A two-layer laminate comprising the resin layer (B) (protective layer) was produced.
The main extruder for extruding the resin (a) was set to a barrel diameter of 75 mm, a screw L / D = 32, and a cylinder temperature of 270 ° C. The sub-extruder for extruding the resin (b) was set to a barrel diameter of 40 mm, a screw L / D = 32, and a cylinder temperature of 250 ° C.

  As the resin (a), the polycarbonate resin produced in Production Example 1 was used. As the resin (b), an acrylic resin (manufactured by Arkema Co., Ltd., trade name: Altugas V020, composition: polymethyl methacrylate) was used.

A feed block was used to obtain a two layer laminate. The temperature inside the die head was 250 ° C., and the resin laminated in the die was guided to three cast rolls having a mirror-finished horizontal arrangement. At this time, the first roll temperature was 110 ° C, the second roll temperature was 100 ° C, and the third roll temperature was 110 ° C.
The number of revolutions of the main extruder and the sub-extruder is set so that the discharge amount ratio is main / sub = 240/60, and the two layers are co-extruded so that the total thickness becomes 0.3 mm, and the resin lamination A body (thickness of resin layer (A): 240 μm, thickness of resin layer (B): 60 μm) was obtained.

(Example 2)
On the resin layer (B) of the resin laminate produced in Example 1, a hard coat layer (thickness: 5 μm) was formed using a roll coating method. As a material for the hard coat layer, urethane acrylate resin (product name: 363C-224HG, hard coat elongation: 100%) manufactured by China Paint Co., Ltd. was used. The formed hard coat layer was subjected to an abrasion resistance test (# 0000 steel wool manufactured by Nippon Steel Wool Co., Ltd. was attached to a 33 mm × 33 mm square pad, and the surface of the hard coat layer was reciprocated 15 times under a load of 1000 g). It was a practical hard coat layer having a haze after abrasion of 10% or less.

(Example 3)
A resin laminate was produced in the same manner as in Example 1 except that the type of the resin (b) was changed. As the resin (b), an acrylic resin having a structural unit derived from methyl methacrylate and vinylcyclohexane (trade name Optimas 7500, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was used.

Example 4
A hard coat layer was formed in the same manner as in Example 2 on the resin layer (B) of the resin laminate produced in Example 3.

(Example 5)
A resin laminate was produced in the same manner as in Example 1 except that the type of the resin (b) was changed. As the resin (b), an acrylic resin having a structural unit derived from methyl methacrylate, maleic anhydride and styrene (product name: Plexiglas hw55, manufactured by Daicel-Evonik Co., Ltd.) was used.

(Example 6)
A hard coat layer was formed in the same manner as in Example 2 on the resin layer (B) of the resin laminate produced in Example 5.

(Example 7)
A resin laminate was produced in the same manner as in Example 1 except that the type of the resin (b) was changed. As the resin (b), a high-hardness polycarbonate resin (manufactured by Mitsubishi Engineering Corporation, trade name Iupilon KS3410UR) was used.

(Example 8)
On the resin layer (B) of the resin laminate produced in Example 7, a hard coat layer was formed in the same manner as in Example 2.
Example 9
A resin laminate was produced in the same manner as in Example 7 except that the thickness of the resin layer (A) was 120 μm.

(Comparative Example 1)
A resin laminate was produced in the same manner as in Example 1 except that the type of the resin (a) was changed. As the resin (a), an aromatic polycarbonate resin manufactured by using bisphenol A as a raw material (trade name E-2000, manufactured by Mitsubishi Engineering Corporation) was used.

(Comparative Example 2)
A hard coat layer was formed in the same manner as in Example 2 on the resin layer (B) of the resin laminate produced in Comparative Example 1.

<Evaluation>
The following evaluation was performed about the resin laminated body manufactured by the Example and the comparative example. The results are shown in Table 1.
(1) Pencil hardness Based on JIS K5400, the pencil hardness was measured with a load of 759 g. The measurement was performed on the surface of the resin laminate on the resin layer (B) side, and when the hard coat layer was provided, the pencil hardness of the hard coat layer surface was measured.

(2) Molding processability The resin laminates produced in the examples and comparative examples were cut into 210 mm × 297 mm × (thickness) 0.3 mm. The obtained sample sheet was preheated to 165 ° C., and was compressed with a high pressure air of 5 MPa using a right-angle mold having a length of 30 mm, a width of 30 mm, and a height of 8 mm. The appearance (crack, whitening, foaming, unevenness) of the obtained molded body was observed, and when no crack, whitening, foaming, or unevenness was observed, it was evaluated as “no abnormality”. Furthermore, when the radius R of the right-angle-shaped portion is within 3.0 mm and the molded article having no appearance abnormality is comprehensively evaluated as “good”, when at least one of the radius R and the appearance abnormality does not satisfy the above condition, Overall evaluation. In addition, the measurement of the radius R of a right-angle-shaped part was performed by actually measuring the radius R using the contact type contour shape measuring machine CONTOURRECORD2700 / 503 (made by Tokyo Seimitsu Co., Ltd.).

  From Table 1, it can be seen that the resin laminate of the present invention has high hardness, and no appearance abnormality such as cracking, whitening, foaming, and unevenness has occurred after molding. Also, a small value is obtained for the right-angled shape radius of the molded body. Therefore, the resin laminate of the present invention is suitable for thermoforming, and a molded product having high hardness can be produced with high accuracy.

Although several embodiments of the present invention have been described, these embodiments are presented by way of example and are not intended to limit the scope of the invention. These novel embodiments can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the scope of the invention. These embodiments and modifications thereof are included in the scope and gist of the invention, and are included in the invention described in the claims and the equivalents thereof.

Claims (12)

A resin layer (A) containing a resin (a), and a resin layer (B) containing a resin (b) different from the resin (a) laminated on at least one surface of the resin layer (A) Equipped,
The resin layer (B) has a pencil hardness of F or more,
The resin (a) is a polycarbonate resin containing a structural unit (a-1) represented by the following formula (1) and a structural unit (a-2) represented by the following formula (2).
Resin laminate:


(In Formula (2), R ₁ is a hydrogen atom or a methyl group; R ₂ is an alkyl group having 4 to 15 carbon atoms; R ₃ and R ₄ are methyl groups; And an integer of 0 to 4). The glass transition temperature (TgA) of the resin (a) is 100 to 135 ° C, the glass transition temperature (TgB) of the resin (b) is 90 to 125 ° C, and the TgA and the TgB are expressed by the following formula ( The resin laminate according to claim 1, which satisfies the relationship 1).
0 ≦ TgA−TgB ≦ 30 (1) The resin laminate according to claim 1 or 2, wherein the structural unit (a-2) is represented by the following formula (3).
  The resin laminate according to any one of claims 1 to 3, wherein the resin (b) is an acrylic resin or a polycarbonate resin.   The resin (b) is selected from the group consisting of polymethyl (meth) acrylate, methyl methacrylate-vinylcyclohexane copolymer resin, and methyl methacrylate-styrene-maleic anhydride copolymer resin. The resin laminate according to claim 1.   The thickness of the resin laminate is 0.1 to 3.0 mm, and the thickness ratio of the resin layer (A) to the resin layer (B) is 1: 1 to 50: 1. The resin laminate according to any one of the above.   Furthermore, the resin laminated body as described in any one of Claims 1-6 provided with the hard-coat layer.   The resin laminate according to claim 7, wherein the hard coat layer has a thickness of 1 to 30 μm.   The resin laminated body as described in any one of Claims 1-8 used in manufacture of a display cover panel or a touchscreen front plate.   The resin laminate according to any one of claims 1 to 8, which is used in the production of an exterior member for a mobile phone, a smartphone, a tablet PC, or a personal computer.   The resin laminate according to any one of claims 1 to 8, which is used in the production of an automobile exterior or interior member.   The resin molded product shape | molded using the resin laminated body as described in any one of Claims 1-11.