JP7065633B2 - Resin laminate and resin molded product using it - Google Patents

Description

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

Glass plates, transparent resin plates, etc. are used for display surface components such as automobile interior parts such as instrument covers, home appliances, OA equipment, personal computers, and small mobile devices, and the frame parts that hold them are made of resin. 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 frame component made of injection molded resin and a transparent sheet, particularly a glass plate bonded with double-sided adhesive tape or the like, is used. As the touch panel type display surface, a thinner one is preferable from the viewpoint of response speed, and a material having a high elastic modulus is selected because a thickness of a certain degree or more is required from the viewpoint of strength. In addition, scratch resistance and fingerprint wiping resistance are also required.

The resin molded body used for the above-mentioned applications can be manufactured by molding a resin sheet, but various measures have been taken to impart characteristics according to the application. For example, the resin sheet is modified with a hard coat layer, a decorative sheet, or the like, resin layers having different compositions are laminated to form a resin sheet, or the composition of the resin 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 there is no concern about 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 surface hardness of the polycarbonate resin is generally low, there is a problem that the surface of the molded product made of the polycarbonate resin is easily scratched. Therefore, conventionally, it has been proposed to form a protective layer containing a resin having a high hardness on the surface of the polycarbonate resin layer to prevent scratches on the product surface.

For example, Patent Document 1 describes a laminated body 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 has been disclosed.

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

Patent Document 3 discloses a laminated sheet provided with a coating layer containing an acrylic resin as a main component on one side of a base material layer containing a polycarbonate resin composition as a main component.

As described above, various molding resin sheets or films have been proposed, but there is no end to the pursuit of resin sheets or films capable of producing resin molded products having properties more suitable for the intended use. It is an issue. Further, it is also required that these resin sheets or films are less likely to cause defects in appearance during molding.

Japanese Unexamined Patent Publication No. 2006-103169 Japanese Unexamined Patent Publication No. 2009-234184 Patent No. 4971218

An object of the present invention is to provide a resin laminate in which appearance abnormalities such as whitening and cracks are unlikely to occur during molding.

（式（２）中、Ｒ_１は水素原子またはメチル基であり；Ｒ_２は炭素数４～１５のアルキル基であり；Ｒ_３およびＲ_４はメチル基であり；ｍおよびｎは、それぞれ独立して０～４の整数である）。
［２］ 前記樹脂（ａ）のガラス転移温度（ＴｇＡ）が１００～１３５℃であり、前記樹脂（ｂ）のガラス転移温度（ＴｇＢ）が９０～１２５℃であり、前記ＴｇＡおよび前記ＴｇＢが以下の式（１）の関係を満たす、［１］に記載の樹脂積層体。
０≦ＴｇＡ－ＴｇＢ≦３０ （１）
［３］ 前記構成単位（ａ－２）が下記式（３）で表される、［１］または［２］に記載の樹脂積層体。

［４］ 前記樹脂（ｂ）が、アクリル樹脂またはポリカーボネート樹脂である［１］～［３］のいずれかに記載の樹脂積層体。
［５］ 前記樹脂（ｂ）が、ポリメチル（メタ）アクリレート、メタクリル酸メチル－ビニルシクロヘキサン共重合樹脂、およびメタクリル酸メチル－スチレン－無水マレイン酸共重合樹脂からなる群より選択される［１］～［４］のいずれかに記載の樹脂積層体。
［６］ 前記樹脂積層体の厚みが０．１～３．０ｍｍであり、前記樹脂層（Ａ）と前記樹脂層（Ｂ）の厚み比が１：１～５０：１である、［１］～［５］のいずれかに記載の樹脂積層体。
［７］ さらにハードコート層を備えた、［１］～［６］のいずれかに記載の樹脂積層体。
［８］ 前記ハードコート層の厚みが１～３０μｍである、［７］に記載の樹脂積層体。
［９］ ディスプレイカバーパネルまたはタッチパネル前面板の製造において使用される、［１］～［８］のいずれかに記載の樹脂積層体。
［１０］ 携帯電話、スマートフォン、タブレットＰＣまたはパソコンの外装用部材の製造において使用される、［１］～［８］のいずれかに記載の樹脂積層体。
［１１］ 自動車の外装用または内装用部材の製造において使用される、［１］～［８］のいずれかに記載の樹脂積層体。
［１２］ ［１］～［１１］のいずれかに記載の樹脂積層体を用いて成形された樹脂成形品。 As a result of diligent research, the present inventors have made whitening and cracking during molding by using a specific polycarbonate resin as a base material in a resin laminate in which another resin layer is laminated on a base material layer containing a polycarbonate resin. It was found that the appearance abnormality such as is less likely to occur. That is, the present invention is, for example, as follows.
[1] 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). ) And
The resin layer (B) has a pencil hardness of F or more, and 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; m and n are independent of each other. And it is an integer from 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 the 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 hexane copolymer resin, and methyl-styrene-maleic anhydride copolymer resin [1] to [1]. 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] The resin laminate according to 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 of 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 exterior or interior members of automobiles.
[12] A resin molded product molded by using the resin laminate according to any one of [1] to [11].

According to the present invention, it is possible to provide a resin laminate in which appearance abnormalities such as whitening and cracks are unlikely to occur during molding.

（式（２）中、Ｒ_１は水素原子またはメチル基であり；Ｒ_２は炭素数４～１５のアルキル基であり；Ｒ_３およびＲ_４はメチル基であり；ｍおよびｎは、それぞれ独立して０～４の整数である）。 Hereinafter, embodiments of the present invention will be described in detail.
The resin laminate of the present invention is the resin laminated on at least one surface of the resin layer (A) containing the resin (a) (hereinafter, also referred to as “base material layer”) and the resin layer (A). It includes a resin layer (B) (hereinafter, also referred to as a “protective layer”) containing a resin (b) different from (a). 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; m and n are independent of each other. And it is an integer from 0 to 4).

Conventionally, when a resin sheet having a multi-layer structure composed of a plurality of types of resin layers is thermoformed, the glass transition point (Tg) and melt viscosity of the resin contained in each layer are different, so that problems such as cracks do not occur. There was a problem that it was difficult to do. When thermoforming a multi-layered resin sheet into a desired shape, it is usually molded according to 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, since the polycarbonate resin having good impact resistance is usually contained in the largest amount, thermoforming is performed at a molding temperature suitable for the polycarbonate resin. .. As a result, excessive heat was applied to the resin other than the polycarbonate resin, and peeling occurred at the interface of each layer, and the surface of the molded product may be whitened or cracks may occur. In addition, the resin sheet as described above may foam if it is not sufficiently dried before heat formation.

On the other hand, 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 arranged on the base material layer containing the polycarbonate resin. The present inventors have found that such a resin laminate is less likely to cause appearance problems such as whitening, cracking, and foaming even when thermoformed at a molding temperature suitable for a 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 producing a molded product having a bent shape. For example, it is possible to successfully manufacture a component having a flat portion and a continuous bent portion, so that it is possible to provide a product having a new design and a function.

With conventional resin sheets, when trying to manufacture a molded product having the above shape, there are problems such as cracks and other appearance abnormalities during thermoforming such as hot press molding, vacuum forming, compressed air forming, and TOM forming. It occurred a lot. Therefore, in order to suppress the occurrence of appearance abnormalities during thermoforming, it is necessary to take 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, although the thermoformability is improved, there are new problems that the protective layer is soft and easily scratched, and the chemical resistance is lowered.

On the other hand, according to the present invention, since the occurrence of appearance abnormality is suppressed as described above, it is possible to provide a heat-formable resin laminate without lowering the hardness of the protective layer. In the resin laminate of the present invention, since a protective layer having high hardness can be provided on the base material layer, it is not easily scratched and has high chemical resistance. Taking advantage of these characteristics, the resin laminate of the present invention can be used for display surface components (for example, display cover panels, touch panel front plates, etc.) of personal computers, smartphones, mobile phones, tablet PCs, etc., or for their exteriors. It can be used for members (particularly housings), automobile exterior and interior members (particularly housings), and the like.

Further, the resin laminate of the present invention can suppress whitening, cracking, and foaming even when molded into a right-angled shape. Since the radius R of the right-angled portion can be at least 3.0 mm or less, and more preferably 1.0 mm or less, molding can be performed with high accuracy.

Further, since the resin laminate of the present invention has the above-mentioned characteristics, for example, a print layer is formed on the base material layer side of the resin laminate, and a molten resin is injection-molded on the print layer to form a backing layer. It is also possible to manufacture an in-mold molded product having excellent designability by forming the above.

（式（２）中、Ｒ_１は水素原子またはメチル基であり；Ｒ_２は炭素数４～１５のアルキル基であり；Ｒ_３およびＲ_４はメチル基であり；ｍおよびｎは、それぞれ独立して０～４の整数である）。 Hereinafter, each constituent member of the resin laminate according to the present invention will be described.
1. 1. Resin layer (A) (base material layer)
The resin layer (A) is a resin layer mainly containing the 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 the polycarbonate resin (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; m and n are independent of each other. And it is an integer from 0 to 4).

In the formula (2), R ₁ is preferably a hydrogen atom. _R2 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, it is possible to obtain a resin having appropriate fluidity and easy to mold. Further, by using an alkyl group having 15 or less carbon atoms, a resin layer having a suitable hardness can be obtained. The alkyl group of R ₂ may be linear, branched or cyclic, but linear or branched is preferable, and linear is more preferable. One of m and n is preferably 0, the other is preferably 1, and more preferably both are 0.

It is particularly preferable that the structural unit (a-2) is a structural unit represented by the following formula (3).

The polycarbonate resin (a) may contain one type or two or more types of the structural unit (a-2) represented by the formula (2). When two or more types are included, it is preferable that one of them is 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). It is preferably 89 to 91% by mass. 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, based on all the structural units of the polycarbonate resin (a). Particularly preferably, it is 9 to 11% by 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 70 to 90% by mass, 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 relative to all the structural units of the polycarbonate resin (a). It 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).

The structural unit that the polycarbonate resin (a) may contain is not limited, but is not limited to, for example, 1,1-bis (4-hydroxyphenyl) cyclohexane [= bisphenol Z], 2,2-. Examples thereof 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. Especially preferable. It is particularly preferable that the resin layer (A) is made of the polycarbonate resin (a). By increasing the content of the polycarbonate resin (a) in the resin layer (A), the impact resistance is improved.

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, if the weight average molecular weight is too small, the impact resistance of the resin laminate may decrease. If the weight average molecular weight is too high, an excess heat source may be required when forming the substrate layer containing the polycarbonate resin (a). Further, depending on the molding method selected, a high temperature is required, so that 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, more preferably 40,000 to 80,000. More preferably, it is 50,000 to 70,000. The weight average molecular weight in the present specification is a standard polystyrene-equivalent weight average molecular weight 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 such as an interfacial polymerization method, a pyridine method, and a transesterification method can be mentioned.

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

The resin layer (A) may further contain additives and the like. As the additive, those usually used in a resin sheet can be used, and as such an additive, for example, an antioxidant, an anticolorant, an anticharge agent, a mold release agent, a lubricant, a dye, etc. Examples thereof include pigments, plasticizers, flame retardants, resin modifiers, companionants, 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 entire amount, a method of dry-blending the masterbatch, a method of dry-blending the entire 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. 2. Resin layer (B) (protective layer)
The resin layer (B) is a resin layer laminated on a base material layer and mainly containing a resin (b) having a pencil hardness of F or more (hereinafter, also referred to as “high hardness resin”). The resin (b) may be any high-hardness resin, and the type thereof 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, a methylmethacrylic resin (PMMA: also referred to as polymethyl (meth) acrylate) polymerized from methylmethacrylic acid, a methyl methacrylate-vinylcyclohexane copolymer resin, and a methacrylic acid. Examples thereof include a methyl-styrene-maleic anhydride copolymer resin. When the resin (b) is a polycarbonate resin, specific examples thereof include a high-hardness polycarbonate resin containing bisphenol C as a main component.
The polycarbonate resin as the resin (b) has a structure different from that of the polycarbonate resin as the resin (a).

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

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

The resin layer (B) may contain another resin in addition to the resin (b). Examples of such a resin 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 additives and the like. As the additive, the same additive as described in "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, if the resin layer (B) is too thin, the surface hardness is low, and if 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. 3. Glass transition temperature The resin (a) and the resin (b) preferably have a glass transition temperature in 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 does not aggregate and the productivity does not decrease in the granulation and drying steps in the production of the polycarbonate resin. Therefore, within the above range, the higher the glass transition point, the wider the process margin in the production of the polycarbonate resin, and the higher quality polycarbonate resin having a low residual solvent content can be efficiently and stably produced.
On the other hand, by setting TgA to 135 ° C. or lower, it is possible to prevent the hue of the resin from deteriorating.

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. Further, it is also preferable that the temperature is 105 to 125 ° C. Then, it is preferable that TgA and TgB satisfy the relationship of the following formula (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 it becomes easy to move. In such a case, in the structure in which the hard coat layer is provided on the protective layer, the resin has a highly crosslinked structure, and the hard coat layer that has been hard even when heat is applied becomes easy to move. The movement of (b) cannot be followed and cracks are likely to occur, but such a problem can be prevented by setting the range as described above. Further, since it is possible to prevent the resin (b) from being excessively heated during molding, it is possible to suppress appearance abnormalities such as foaming. On the other hand, if TgB is extremely higher than TgA, there may be a problem that the drawdown amount of the film becomes large during thermoforming.

A person skilled in the art will appropriately select a resin (a) and a resin (b) having a glass transition point that satisfy the above relationship from the resins (a) and the resin (b) as described above. Can be used. In the present specification, the glass transition temperature is a temperature calculated by the midpoint method measured at a sample of 10 mg and a heating rate of 10 ° C./min using a differential scanning calorimetry device.

4. Laminating the resin layer (A) and the resin layer (B) As described above, the resin layer (B) is laminated on at least one surface of the resin layer (A), but the laminating method is not particularly limited. For example, a method in which an individually formed resin layer (A) and a resin layer (B) are overlapped and heat-bonded to each other; the individually formed resin layer (A) and the resin layer (B) are overlapped with each other. , A method of adhering the two with an adhesive; a method of coextruding the resin layer (A) and the resin layer (B); There are various methods such as a method of molding and integrating. Of these, the coextrusion molding method is preferable from the viewpoint of manufacturing cost and productivity.

Further, the heating and melting temperature in the extruder is preferably a temperature 80 to 150 ° C. higher than the glass transition temperature (Tg) of each resin. Generally, the temperature condition of the main extruder that extrudes the polycarbonate resin (a) is usually 230 to 290 ° C., preferably 240 to 280 ° C., and the temperature condition of the sub extruder that extrudes the resin (b) is usually 220 ° C. It is about 270 ° C, preferably 230 to 260 ° C.

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) by the feed block, extruded into a sheet shape by a T-die, and then cooled while passing through a molding roll to obtain a desired laminate. Form the body. Further, in the multi-manifold method, the resin layer (B) is arranged on one side of the resin layer (A) in the multi-manifold die, extruded into a sheet shape, and then cooled while passing through a molding roll to obtain a desired laminated body. To form.

In any case, the temperature of the die is usually set to 230 to 290 ° C, particularly 250 to 280 ° C, and the temperature of the molding 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: 1. It is particularly preferably 1 to 20: 1. By setting such a thickness ratio, it is possible to suppress interfacial defects between layers while making the best use of the characteristics of each layer.

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

As the material of the hard coat layer, known compounds that form a crosslinked film, such as acrylic, silicon, melamine, urethane, and epoxy, can be used. Further, as a curing method, known methods such as ultraviolet curing, thermosetting, and electron beam curing can be used. When the hard coat layer is located on the surface layer of the resin laminate, it is preferable that the pencil hardness is H or more. Considering the balance between hardness and heat-forming property, acrylic type and urethane acrylate type are exemplified as preferable ones.
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 dip method, and a transfer method.

As the acrylic compound forming 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 the molecule thereof contains an ether bond, a thioether bond, an ester bond, an amide bond, a urethane bond, or the like. Is preferable. Further, as a component that imparts heat-forming property, a long-chain component having a molecular weight of 1,000 to several thousand can be appropriately added.

The hardcourt layer preferably has a haze of 10% or less after scratching. This haze was measured as follows. That is, # 0000 steel wool (manufactured by Nippon Steel Wool Co., Ltd.) having a diameter of about 0.012 mm is attached to a square pad of 33 mm × 33 mm. 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 washing this sample 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 nano-sized metal particles include, but are not limited to, silicon dioxide, alumina, and the like.

Preferred properties of the hardcourt layer include elongation in thermoforming and excellent chemical resistance. In particular, among the chemical resistance, it is preferable that the resistance to Neutrogena is excellent.

The thickness of the hardcoat layer is preferably 1 to 30 μm, more preferably 3 to 20 μm, and particularly preferably 5 to 10 μm. By setting the thickness as described above, it is possible to prevent cracks in the hard coat layer when the laminate is heat-formed.

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

According to one embodiment of the present invention, a resin molded product molded by using the above-mentioned resin laminate is provided. The molding method is not particularly limited, but thermoforming is suitable because of the characteristics of the resin laminate of the present invention. Thermoforming can be performed by a method usually used in the art, and examples thereof include thermoforming molding, vacuum forming, compressed air forming, TOM forming, IML (in-mold lamination) and the like.

Hereinafter, the present invention will be described in detail with reference to Examples, but the content of the present invention is not limited thereto.
(Manufacturing Example 1: Production of Polycarbonate Resin)
To 48.4 kg of 9 w / w% sodium hydroxide aqueous solution, 7.47 kg (32.76 mol) of bisphenol A (BPA) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., and 1,1-bis (4-) manufactured by Honshu Chemical Industry Co., Ltd. 0.83 kg (2.55 mol) of hydroxyphenyl) decane (DED) and 30 g of hydrosulfite were added and dissolved. To this, 35 kg of dichloromethane was added, and 4.38 kg of phosgene was blown over 30 minutes while keeping the solution temperature in the range of 15 ° C. to 25 ° C. with stirring.

After the injection of phosgene is completed, 3 kg of 9 w / w% sodium hydroxide aqueous solution, 19 kg of dichloromethane, and 207.7 g (1.38 mol) of pt-butylphenol (PTBP) manufactured by DIC Co., Ltd. are dissolved in 0.5 kg of dichloromethane. The solution was added, and the mixture was vigorously stirred to emulsify. Then, 20 mL of triethylamine was added as a polymerization catalyst, and the mixture was polymerized for about 40 minutes.

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

(Example 1)
The resin (a) and the resin (b) are heated and melted by separate extruders, and two types of resins are simultaneously melted and extruded from the slit-shaped discharge port of the T-die, and the resin layer (A) (base material layer) and A two-layer laminate composed of a 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: Altuglas V020, composition: polymethylmethacrylate) was used.

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

(Example 2)
A hard coat layer (thickness: 5 μm) was formed on the resin layer (B) of the resin laminate produced in Example 1 by using a roll coat method. As the material of the hard coat layer, a urethane acrylate resin (product name: 363C-224HG, hard coat elongation rate; 100%) manufactured by Chugoku Paint Co., Ltd. was used. The formed hard coat layer was subjected to a scratch 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 hardcourt layer with a haze of 10% or less after scratching.

(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 (manufactured by Mitsubishi Gas Chemical Company, Inc., trade name: Optimas 7500) having a structural unit derived from methyl methacrylate and vinyl cyclohexane was used.

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

(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 (manufactured by Daicel Evonik Co., Ltd., trade name: PLEXIGLAS hw55) was used.

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

(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-based resin (manufactured by Mitsubishi Engineering Co., Ltd., trade name: Upiron KS3410UR) was used.

(Example 8)
A hard coat layer was formed on the resin layer (B) of the resin laminate produced in Example 7 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 Mitsubishi Engineering Co., Ltd., trade name E-2000) produced from bisphenol A as a raw material was used.

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

<Evaluation>
The resin laminates produced in Examples and Comparative Examples were evaluated as follows. The results are shown in Table 1.
(1) Pencil hardness According to 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 on the surface of the hard coat layer was measured.

(2) Moldability The resin laminates produced in 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 compressed air was formed by using high pressure air of 5 MPa using a right-angled mold having a length of 30 mm, a width of 30 mm, and a height of 8 mm. The appearance (cracks, whitening, foaming, unevenness) of the obtained molded product was observed, and when none of cracks, whitening, foaming or unevenness was observed, it was evaluated as "no abnormality". Further, the molded product having a radius R of the right-angled portion within 3.0 mm and having no appearance abnormality is comprehensively evaluated as "good", and when at least one of the radius R and the appearance abnormality does not satisfy the above conditions, it is "defective". Comprehensive evaluation. The radius R of the right-angled portion was measured by measuring the radius R using a contact type contour shape measuring machine CONTOURECORD 2700/503 (manufactured by Tokyo Seimitsu Co., Ltd.).

From Table 1, it can be seen that the resin laminate of the present invention has a high hardness and does not have appearance abnormalities such as cracks, whitening, foaming, and unevenness after molding. Further, a small value is obtained for the radius of the right-angled shape of the molded product. Therefore, the resin laminate of the present invention is suitable for thermoforming, and a molded product having high hardness can be manufactured with high accuracy.

Although some embodiments of the present invention have been described, these embodiments are presented as examples and are not intended to limit the scope of the invention. These novel embodiments can be implemented in various other embodiments, and various omissions, replacements, and changes can be made without departing from the gist of the invention. These embodiments and modifications thereof are included in the scope and gist of the invention, and are also included in the scope of the invention described in the claims and the equivalent scope 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 with
The resin layer (B) has a pencil hardness of F or more, and 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).
The glass transition temperature (TgA) of the resin (a) is 100 to 135 ° C., and the glass transition temperature (TgB) of the resin (b) is 90 to 125 ° C.
The TgA and the TgB satisfy the relationship of the following formula (1).
0 ≦ TgA-TgB ≦ 30 (1)
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; m and n are independent of each other. And it is an integer from 0 to 4). 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 with
The resin layer (B) has a pencil hardness of F or more, and 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).
The content of the structural unit (a-1) is 65 to 92% by mass with respect to all the structural units of the resin (a), and the content of the structural unit (a-2) is the resin (a). ) Is 8 to 35% by mass with respect to all the constituent units .
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; m and n are independent of each other. And it is an integer from 0 to 4). 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. Any of claims 1 to 4, wherein the resin (b) is selected from the group consisting of polymethyl (meth) acrylate, methyl methacrylate-vinylcyclohexane hexane copolymer resin, and methyl-styrene-maleic anhydride copolymer resin. The resin laminate according to item 1. Claims 1 to 5, wherein 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 item. The resin laminate according to any one of claims 1 to 6, further comprising a 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 laminate according to any one of claims 1 to 8, which is used in the manufacture of a display cover panel or a touch panel front plate. The resin laminate according to any one of claims 1 to 8, which is used in the manufacture of exterior members for mobile phones, smartphones, tablet PCs, and personal computers. The resin laminate according to any one of claims 1 to 8, which is used in the manufacture of exterior or interior members of an automobile. A resin molded product molded by using the resin laminate according to any one of claims 1 to 11.