阅读说明：本技术 高硬度成型用树脂片和使用其的成型品 (Resin sheet for high-hardness molding and molded article using same ) 是由 鸨田敦大 野中健太 高崎雅登 于 2020-02-25 设计创作，主要内容包括：本发明的一个实施方式提供一种成型用树脂片,该树脂片包含：含有聚碳酸酯树脂(a1)的基材层；含有高硬度树脂的高硬度树脂层；和硬涂防眩层,其中,上述高硬度树脂层位于上述基材层与上述硬涂防眩层之间,上述聚碳酸酯树脂(a1)和上述高硬度树脂的玻璃化转变温度满足以下的关系：－10℃≤(高硬度树脂的玻璃化转变温度)－(聚碳酸酯树脂(a1)的玻璃化转变温度)≤40℃,在上述树脂片的两面分别重叠贴合有2片保护膜。(One embodiment of the present invention provides a resin sheet for molding, including: a substrate layer containing a polycarbonate resin (a 1); a high-hardness resin layer containing a high-hardness resin; and a hard coating antiglare layer, wherein the high hardness resin layer is located between the base material layer and the hard coating antiglare layer, and glass transition temperatures of the polycarbonate resin (a1) and the high hardness resin satisfy the following relationship: the glass transition temperature of the high-hardness resin (the glass transition temperature of the polycarbonate resin (a 1)) is not more than 10 ℃ and not more than 40 ℃, and 2 protective films are respectively laminated on both surfaces of the resin sheet.)

1. A molding resin sheet comprising:

a substrate layer containing a polycarbonate resin (a 1);

a high-hardness resin layer containing a high-hardness resin; and

a hard-coated anti-glare layer is formed,

the high-hardness resin layer is positioned between the substrate layer and the hard-coated antiglare layer,

the polycarbonate resin (a1) and the high-hardness resin have glass transition temperatures satisfying the following relationship:

a glass transition temperature of the high-hardness resin (glass transition temperature of the polycarbonate resin (a 1)) of not more than 10 ℃ below zero and not more than 40 ℃,

two protective films were laminated on each of both surfaces of the resin sheet.

2. The molding resin sheet according to claim 1, wherein:

the polycarbonate resin (a1) is an aromatic polycarbonate resin.

3. The molding resin sheet according to claim 2, wherein:

the aromatic polycarbonate resin contains a structural unit represented by the following general formula (4a),

4. the resin sheet for molding as defined in any one of claims 1 to 3, wherein:

the content of the polycarbonate resin (a1) is 75 to 100 mass% based on the total mass of the base material layer.

5. The resin sheet for molding as defined in any one of claims 1 to 4, wherein:

the high-hardness resin is selected from the following resins (B1) to (B5):

resin (B1): a copolymer containing a (meth) acrylate structural unit (a) represented by the following general formula (1) and an aliphatic vinyl structural unit (B) represented by the following general formula (2), or an alloy of the copolymer and a resin (B2),

in the formula (1), R1 is a hydrogen atom or a methyl group, R2 is an alkyl group having 1 to 18 carbon atoms,

in the formula (2), R3 is a hydrogen atom or a methyl group, and R4 is a cyclohexyl group which may be substituted with a hydrocarbon group having 1 to 4 carbon atoms;

resin (B2): a copolymer (D) containing 6 to 77 mass% of a (meth) acrylate structural unit, 15 to 71 mass% of a styrene structural unit, and 8 to 23 mass% of an unsaturated dicarboxylic acid structural unit, an alloy of the copolymer (D) and the copolymer (D), an alloy of the copolymer (D) and another high-hardness resin, or an alloy of the copolymer (D) and an acrylic resin;

resin (B3): a copolymer containing a structural unit (c) represented by the following general formula (6) and optionally containing a structural unit (d) represented by the following general formula (7),

resin (B4): a copolymer (G) containing 5 to 20 mass% of a styrene structural unit, 60 to 90 mass% of a (meth) acrylate structural unit and 5 to 20 mass% of an N-substituted maleimide structural unit, or an alloy of the copolymer (G) and the resin (B2);

resin (B5): a resin containing a structural unit (e) represented by the following general formula (8),

6. the resin sheet for molding as defined in any one of claims 1 to 5, wherein:

the content of the high-hardness resin is 70-100% by mass relative to the total mass of the high-hardness resin layer.

7. The resin sheet for molding as defined in any one of claims 1 to 6, wherein:

the total thickness of the substrate layer and the high-hardness resin layer is 0.5mm to 3.5 mm.

8. The resin sheet for molding as defined in any one of claims 1 to 7, wherein:

the ratio of the thickness of the base material layer to the total thickness of the base material layer and the high-hardness resin layer is 75% to 99%.

9. The resin sheet for molding as defined in any one of claims 1 to 8, wherein:

the haze of the resin sheet for molding is 2 to 30%.

10. The resin sheet for molding as defined in any one of claims 1 to 9, wherein:

the pencil hardness of the surface of the hard-coated antiglare layer in the molding resin sheet is 2H or more.

11. The resin sheet for molding as defined in any one of claims 1 to 10, wherein: in the case where 2 protective films of the molding resin sheet are laminated, the side in contact with the resin sheet is used as a first protective film and the outer side is used as a second protective film, the first protective film is composed of a polyolefin film having a melting point of 100 to 130 ℃, and the second protective film is composed of a polyolefin film having a melting point of 140 ℃ or higher.

12. The resin sheet for molding as defined in any one of claims 1 to 10, wherein: in the case where 2 protective films of the molding resin sheet are laminated, the side in contact with the resin sheet is used as a first protective film and the outer side is used as a second protective film, the first protective film is composed of a polyolefin-based film having a melting point of 100 to 130 ℃, and the second protective film is composed of a PET-based protective film.

13. A resin molded article molded using the resin sheet for molding according to any one of claims 1 to 10.

Technical Field

The present invention relates to a resin sheet for high-hardness molding and a molded article using the same.

Background

In automobile interior parts such as instrument covers and components of display surfaces of home appliances, OA equipment, personal computers, small portable devices, etc., glass plates, transparent resin plates, etc. are used, and in frame members for holding them, molded bodies made of resin are used. On the other hand, as a component of a touch panel type display surface used in a mobile phone terminal or the like, a component in which a transparent sheet, particularly a glass plate, is bonded to a frame member made of an injection-molded resin by a double-sided tape or the like is used. As the touch panel type display surface, a material having a high elastic modulus is selected because the thinner the thickness is, the better the response speed is, and the thicker the thickness is, the more the thickness is required to some extent from the strength. Further, scratch resistance, fingerprint wiping property, and the like are also required.

Resin molded articles used for the above applications can be produced by molding a resin sheet, but various improvements have been made to provide properties suitable for the applications. For example, a resin sheet is modified with a hard coat layer, a decorative sheet, or the like, and resin layers having different compositions are stacked to constitute the resin sheet, or a composition using the resin is improved.

As the decorative sheet, for example, an acrylic resin may be used, and a sheet having a hard coat layer, a sheet obtained by further laminating a film after providing an appearance design such as printing, or the like may be used.

For example, patent document 1 discloses a decorative sheet in which a transparent acrylic resin sheet layer, a pattern printing ink layer, an ABS resin sheet layer, and an ABS resin backing layer are laminated in this order from the front side. Patent document 2 discloses a multilayer film in which a layer composed of a methacrylic resin and acrylic rubber particles is laminated on the surface of a polycarbonate resin layer, and also discloses a decorative sheet in which a decoration is applied to one surface of the multilayer film and a thermoplastic resin sheet is laminated on the decoration surface. Also disclosed is a decorative molded article produced by injection molding a thermoplastic resin on the decorative surface.

Patent document 3 discloses a resin molded article molded using a sheet having a thermosetting or ultraviolet-curable hard coat layer provided on a resin base material.

Patent document 4 discloses a decorative hard coat film having a layer formed by using a hard coat paint having a specific composition on one surface of a base film, and also discloses that a print layer can be provided on the base film. The decorative film is capable of being thermoformed. The decorative film described in patent document 4 is integrated with a molding resin to form a decorative molded article.

Patent document 5 discloses a laminate sheet having a coating layer containing an acrylic resin as a main component on one surface of a base material layer containing a polycarbonate resin composition as a main component.

In addition, in order to diffuse reflection of external light and make display contents more visible, many components of the display surface are provided with an antiglare layer. The antiglare treatment is performed by imparting a fine structure or shape to the surface.

If the display surface is curved, when a glass plate is used as a member, the glass plate needs to be curved and then subjected to antiglare treatment. This is because the antiglare layer cannot withstand the bending temperature of glass and disappears. However, it is difficult to uniformly perform the antiglare treatment on the curved surface. On the other hand, in the case of using a resin plate, a plate material obtained by performing an anti-glare treatment on a flat plate in advance can be bent. The resin plate has a bending temperature significantly lower than that of glass, and the antiglare layer does not disappear, so that there is an advantage that antiglare treatment is not required for a curved surface.

In bending a resin plate, the heated resin plate is often heated by pressing it with a metal mold, a wood mold, a resin mold, or the like. When a resin plate is bent as in patent document 6, if protective films are attached to both surfaces of the resin plate and the resin plate is bent, there are advantages in that foreign matter can be prevented from being mixed in and transfer of a mold scratch can be prevented. Patent document 6 describes the effect thereof, but the polycarbonate resin is exposed on the outermost surface of the curved resin plate, and the protective film is very easily damaged when the protective film is removed for actual use.

As described above, various molding resin sheets or films have been proposed, but there is no problem to seek a resin sheet or film that can produce a resin molded product having characteristics suitable for the application.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2001-334609

Patent document 2: japanese patent laid-open publication No. 2009-234184

Patent document 3: japanese examined patent publication (Kokoku) No. 4-40183

Patent document 4: japanese laid-open patent publication No. 2010-284910

Patent document 5: japanese laid-open patent publication No. 2009-196153

Patent document 6: japanese patent No. 3856107

Disclosure of Invention

Technical problem to be solved by the invention

The invention aims to provide a molding resin sheet which has high hardness, is not easy to generate appearance abnormity during molding and is pre-treated with anti-dazzle treatment, and a resin molded product using the molding resin sheet.

Technical solution for solving technical problem

The present inventors have conducted intensive studies on a molding resin sheet containing a polycarbonate resin as a base material, the resin sheet having a hard coat layer provided on a surface thereof. As a result, it has been found that a resin sheet for molding having high hardness and being less likely to cause appearance abnormalities such as cracks and flow marks during molding can be provided by providing a high-hardness resin layer between a polycarbonate resin layer and a hard coat layer and selecting a resin having a glass transition temperature satisfying a predetermined relationship as the polycarbonate resin and the high-hardness resin. Further, by laminating two protective films on both surfaces of the resin sheet, transfer of a flaw of the mold, mixing of foreign matter, and orange peel on the surface of the molded article, which are generated during molding, can be suppressed. Further, by setting the melting point of the two protective films to a predetermined melting point, it is possible to provide a molding resin sheet capable of suppressing fusion of the protective films with the metal mold or the resin sheet. That is, the present invention is as follows, for example.

< 1 > a resin sheet for molding, which comprises: a substrate layer containing a polycarbonate resin (a 1); a high-hardness resin layer containing a high-hardness resin; and a hard-coated anti-glare layer, wherein,

the high-hardness resin layer is located between the base material layer and the hard-coated antiglare layer,

the polycarbonate resin (a1) and the high-hardness resin have glass transition temperatures satisfying the following relationship:

a glass transition temperature of the high-hardness resin (glass transition temperature of the polycarbonate resin (a 1)) of not more than 10 ℃ and not more than 40 DEG C

Two surfaces of the resin sheet were laminated with 2 protective films.

< 2 > the resin sheet for molding according to the above < 1 >, wherein the polycarbonate resin (a1) is an aromatic polycarbonate resin.

< 3 > the resin sheet for molding as described in the above < 2 >, wherein the aromatic polycarbonate resin contains a structural unit represented by the following general formula (4 a).

[ 4 ] the resin sheet for molding according to any one of the above [ 1] to [ 3 ], wherein the polycarbonate resin (a1) is contained in an amount of 75 to 100 mass% based on the total mass of the base material layer.

< 5 > the resin sheet for molding according to any one of the above < 1 > -4 >, wherein the resin having high hardness is selected from the following resins (B1) to (B5):

resin (B1): a copolymer containing a (meth) acrylate structural unit (a) represented by the following general formula (1) and an aliphatic vinyl structural unit (B) represented by the following general formula (2), or an alloy of the copolymer and a resin (B2),

(wherein R1 represents a hydrogen atom or a methyl group; R2 represents an alkyl group having 1 to 18 carbon atoms.)

(wherein R3 represents a hydrogen atom or a methyl group; R4 represents a cyclohexyl group which may be substituted with a hydrocarbon group having 1 to 4 carbon atoms);

resin (B2): a copolymer (D) containing 6 to 77 mass% of a (meth) acrylate structural unit, 15 to 71 mass% of a styrene structural unit, and 8 to 23 mass% of an unsaturated dicarboxylic acid structural unit, an alloy of the copolymer (D) and the copolymer (D), an alloy of the copolymer (D) and another high-hardness resin, or an alloy of the copolymer (D) and an acrylic resin;

resin (B3): a copolymer containing a structural unit (c) represented by the following general formula (6) and optionally containing a structural unit (d) represented by the following general formula (7);

resin (B4): a copolymer (G) containing 5 to 20 mass% of a styrene structural unit, 60 to 90 mass% of a (meth) acrylate structural unit and 5 to 20 mass% of an N-substituted maleimide structural unit, or an alloy of the copolymer (G) and the resin (B2);

resin (B5): a resin containing a structural unit (e) represented by the following general formula (8).

[ 6 ] the resin sheet for molding according to any one of the above [ 1] to [ 5 ], wherein the content of the high-hardness resin is 70 to 100% by mass based on the total mass of the high-hardness resin layer.

[ 7 ] the resin sheet for molding according to any one of the above [ 1] to [ 6 ], wherein the total thickness of the base material layer and the high-hardness resin layer is 0.5mm to 3.5 mm.

[ 8 ] the resin sheet for molding according to any one of the above [ 1] to [ 7 ], wherein the ratio of the thickness of the base layer to the total thickness of the base layer and the high-hardness resin layer is 75% to 99%.

The resin sheet for molding of < 9 > according to any one of the above < 1 > to < 8 >, wherein the resin sheet for molding has a haze of 2 to 30%.

[ 10 ] the molding resin sheet according to any one of the above [ 1] to [ 9 ], wherein a pencil hardness of a surface of the hard-coated antiglare layer in the molding resin sheet is 2H or more.

< 11 > the resin sheet for molding according to any one of the above < 1 > to < 10 >, wherein when the side of the 2 protective films laminated on the resin sheet for molding is a first protective film and the outside is a second protective film, the first protective film is composed of a polyolefin film having a melting point of 100 to 130 ℃ and the second protective film is composed of a polyolefin film having a melting point of 140 ℃ or higher.

< 12 > the molding resin sheet according to any one of the above < 1 > to < 10 >, wherein when the side of the 2 protective films laminated on the molding resin sheet is a first protective film and the outside is a second protective film, the first protective film is composed of a polyolefin-based film having a melting point of 100 to 130 ℃, and the second protective film is composed of a PET-based protective film.

< 13 > a resin molded article molded using the resin sheet for molding described in any one of the above < 1 > -to < 10 >.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, it is possible to provide a molding resin sheet having high hardness, which is less likely to cause appearance abnormality during molding, and which is provided with antiglare properties, and a resin molded article using the molding resin sheet. In the present invention, since the high-hardness resin layer is provided on the polycarbonate and the hard-coated antiglare layer is provided on the outer side, a resin plate which is less likely to be damaged, has antiglare properties, has good visibility, and is easily thermally bent can be provided.

Detailed Description

The present invention will be described in detail below by way of examples of manufacturing examples, and the like, but the present invention is not limited to the examples of manufacturing examples, and the like, and can be carried out by changing to any method as long as the method does not largely deviate from the scope of the present invention.

The resin sheet for molding (hereinafter, also simply referred to as "resin sheet") of the present invention has a base material layer containing a polycarbonate resin (a1), a high-hardness resin layer containing a high-hardness resin, and a hard-coated antiglare layer, and the high-hardness resin layer is located between the base material layer and the hard-coated antiglare layer. Other layers may be present between the base layer and the high-hardness resin layer, and between the high-hardness resin layer and the hard-coated antiglare layer, respectively. Examples of the other layers include, but are not limited to, an adhesive layer and an undercoat layer. As 1 embodiment, there is provided a resin sheet having: a substrate layer containing a polycarbonate resin (a 1); a high-hardness resin layer laminated on at least one surface of the base material layer; and a hard coating antiglare layer laminated on the high-hardness resin layer.

The high-hardness resin layer and the hard-coated antiglare layer may be provided on at least one side of the base material layer, and the structure of the other side is not particularly limited. In this case, the hard coat antiglare layer may be provided on one or both of the high-hardness resin layers. In the case where the high-hardness resin layers are provided on both sides of the base material layer, it is preferable to use the same high-hardness resin for 2 high-hardness resin layers from the viewpoint of obtaining a stable resin sheet with little warpage.

In the molding resin sheet of the present invention, as described above, the high-hardness resin layer is provided between the base layer and the hard-coated antiglare layer, and the glass transition temperatures of the polycarbonate resin (a1) in the base layer and the high-hardness resin in the high-hardness resin layer satisfy a predetermined relationship, whereby a molding resin sheet having high hardness and being less likely to cause appearance abnormalities such as cracks and flow marks during molding can be obtained. In particular, the resin sheet is less likely to have an abnormal appearance during thermoforming, and the conditions (temperature, heating time, etc.) during thermoforming can be set widely, and therefore, the resin sheet is suitable for thermoforming.

The resin sheet having a hard-coated antiglare layer with high hardness on the surface as in the present invention, particularly the resin sheet using a polycarbonate resin as a base material, is excellent in impact resistance, high in safety, and light in weight as compared with a conventional glass plate. And, it is easier to bend than conventional glass plates and will not crack due to slight bending. This is presumably because the hard coat antiglare layer in the resin sheet has a certain degree of flexibility.

By providing the high-hardness resin layer between the base layer and the hard-coated antiglare layer, the hardness of the resin sheet can be further improved. When a hard-coated antiglare layer is directly provided on a polycarbonate resin layer, there is a possibility that the hard-coated antiglare layer has a low elastic modulus and is easily buckled, but such a problem is also solved by providing a high-hardness resin layer.

In the present invention, the glass transition temperatures of the polycarbonate resin (a1) in the base layer and the high-hardness resin in the high-hardness resin layer satisfy the following relationship.

A glass transition temperature of the high-hardness resin (glass transition temperature of the polycarbonate resin (a 1)) of not more than 10 ℃ and not more than 40 DEG C

Conventionally, when different types of resin layers are laminated and a hard coat layer is provided thereon, there is a problem that the resins contained in the respective layers have different glass transition temperatures (Tg) and melt viscosities, and it is difficult to perform thermoforming without causing defects such as cracks. However, according to the present invention, such a problem is also solved by using the polycarbonate resin (a1) and the high-hardness resin which satisfy the above-described relationship.

When thermoforming a resin sheet having a multilayer structure into a desired shape, generally, the resin sheet is molded at a molding temperature matching the resin having the largest content in the layer. For example, in the case of a resin sheet using a polycarbonate resin as a base layer, the polycarbonate resin having a high impact resistance is generally used in the largest amount, and therefore, thermoforming is performed at a molding temperature suitable for the polycarbonate resin. Since the resin sheet of the present invention uses the polycarbonate resin (a1) and the high-hardness resin satisfying the above-described relationship, the problem of abnormal appearance is unlikely to occur even when thermoforming is performed at a temperature suitable for the molding temperature of the polycarbonate resin. Therefore, the resin sheet of the present invention can be said to be a resin sheet more suitable for thermoforming than conventional ones.

As to the glass transition temperatures of the polycarbonate resin (a1) and the high-hardness resin, it is preferably not less than-5 ℃ (glass transition temperature of the high-hardness resin) - (glass transition temperature of the polycarbonate resin (a 1)) not more than 30 ℃, more preferably not less than 0 ℃ (glass transition temperature of the high-hardness resin) - (glass transition temperature of the polycarbonate resin (a 1)) not more than 30 ℃. If the Tg of the high-hardness resin is extremely lower than the Tg of the polycarbonate resin (a1), the high-hardness resin becomes in a rubber state or a molten state during thermoforming, and becomes easy to move. In this case, the hard-coated antiglare layer having a highly crosslinked structure and being kept hard even when heat is applied cannot follow the movement of the high-hardness resin which becomes easy to move, and cracks are likely to occur. On the other hand, when the Tg of the high-hardness resin is too high as compared with the Tg of the polycarbonate resin (a1), the difference in viscosity between the high-hardness resin and the polycarbonate resin becomes large, and when these are laminated, the interface becomes rough, and flow marks may occur.

The resin sheet of the present invention can be suitably used for producing a molded article having a desired hardness and a curved shape. For example, a component having a bent portion continuous with the flat surface portion can be smoothly manufactured, and thus a product having a novel design and function can also be provided.

When a molded article having such a shape as described above is produced using a conventional resin sheet, defects such as cracks frequently occur in thermoforming such as hot press molding, vacuum molding, air pressure molding, and TOM molding. Therefore, in order to suppress the occurrence of cracks during hot forming, it is necessary to perform an operation such as a reduction in the hardness of the hard coat layer. However, when the hardness of the hard coat layer is reduced, the thermoformability can be improved, but the hard coat layer is soft, and therefore, there is a new problem that the hard coat layer is easily damaged and the chemical resistance is reduced.

In contrast, according to the present invention, since the occurrence of cracks can be suppressed as described above, a resin sheet that can be thermally formed without lowering the hardness of the hard coat layer can be provided. The resin sheet of the present invention can provide a hard-coated antiglare layer on the surface layer, and therefore, is less likely to be damaged and has high chemical resistance. By utilizing such characteristics, the resin sheet of the present invention can be used for a component of a display surface of a personal computer, a mobile phone, or the like, an exterior or interior part of an automobile, a mobile phone terminal, a personal computer, a tablet PC, a car navigation, or the like, which has a curved surface, a front panel, or the like.

Hereinafter, each component of the resin sheet of the present invention will be described.

1. Substrate layer

The substrate layer is a resin layer mainly containing a polycarbonate resin (a 1). The number of the polycarbonate resins (a1) contained in the base layer may be 1, or 2 or more. The content of the polycarbonate resin (a1) in the base material layer is preferably 75 to 100 mass%, more preferably 90 to 100 mass%, and particularly preferably 100 mass% with respect to the total mass of the base material layer. By increasing the content of the polycarbonate resin, impact resistance can be improved.

The polycarbonate resin (a1) is not particularly limited as long as it contains a carbonate bond, i.e., - [ O-R-OCO ] -unit in the molecular main chain (wherein R may contain an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group, and may have a linear structure or a branched structure), but is preferably an aromatic polycarbonate resin, and particularly preferably a polycarbonate resin containing a structural unit represented by the following formula (4 a). By using such a polycarbonate resin, a resin sheet having more excellent impact resistance can be obtained.

Specifically, as the polycarbonate resin (a1), an aromatic polycarbonate resin (for example, Ipiplon S-2000, Ipiplon S-1000, Ipiplon E-2000; manufactured by Mitsubishi engineering plastics Co., Ltd.) or the like can be used.

In recent years, for the purpose of controlling the glass transition temperature of a polycarbonate resin, a polycarbonate resin obtained by adding 1-membered phenol represented by the following general formula (4) as an end terminator has also been used. In the present invention, a polycarbonate resin to which such a terminal terminator is added can be used.

(in the formula, R₁Represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms; r₂～R₅Each independently represents a hydrogen atom, a halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 12 carbon atoms; wherein the substituent is halogen, alkyl with 1-20 carbon atoms or aryl with 6-12 carbon atoms. )

In the present specification, "alkyl" and "alkenyl" may be linear or branched and may have a substituent.

More preferably, the 1-membered phenol represented by the general formula (4) is a substance represented by the following general formula (5).

(in the formula, R₁Represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms. )

More preferably R in the general formula (4) or the general formula (5)₁Within a specified range of values. Specifically, as R₁The upper limit of the number of carbon atoms of (b) is preferably 36, more preferably 22, and particularly preferably 18. In addition, as R₁The lower limit of the number of carbon atoms of (c) is preferably 8, more preferably 12.

Among the 1-membered phenols represented by the general formula (4) or the general formula (5), it is particularly preferable to use either or both of cetyl paraben and 2-hexyldecyl paraben as the terminal terminator.

For example, use is made of R in the formula (5)₁When a 1-membered phenol having an alkyl group having 16 carbon atoms is used as the end terminator, a polycarbonate resin having excellent glass transition temperature, melt flowability, moldability, sag resistance and the like can be obtained, and the 1-membered phenol is particularly preferable because it has excellent solvent solubility in the production of a polycarbonate resin.

On the other hand, if R in the formula (4) or the formula (5)₁When the number of carbon atoms of (2) is excessively increased, the solubility of the 1-membered phenol (terminal terminator) in an organic solvent tends to be lowered, and the productivity in the production of a polycarbonate resin may be lowered.

As an example, if R₁When the number of carbon atoms of (2) is 36 or less, the productivity in the production of a polycarbonate resin is high and the economical efficiency is also good. If R is₁When the carbon number of (2) is 22 or less, the organic solvent solubility of the 1-membered phenol is particularly excellent, and the productivity can be extremely increased and the economical efficiency can be improved in the production of a polycarbonate resin. Examples of the polycarbonate resin using such a 1-membered phenol include Ipipzeta T-1380 (manufactured by Mitsubishi gas chemical Co., Ltd.).

R in the general formula (4) or the general formula (5)₁When the number of carbon atoms is too small, the glass transition temperature of the polycarbonate resin may not be sufficiently low, and the thermoformability may be deteriorated.

In the present invention, the weight average molecular weight of the polycarbonate resin (a1) affects the impact resistance and molding conditions of the resin sheet. In other words, when the weight average molecular weight is too small, the impact resistance of the resin sheet may be lowered. When the weight average molecular weight is too high, an excessive heat source may be required to form the substrate layer containing the polycarbonate resin (a 1). Further, since a high temperature is required depending on the selected molding method, the polycarbonate resin (a1) may be exposed to a high temperature and may adversely affect its thermal stability. The weight average molecular weight of the polycarbonate resin (a1) is preferably 15,000 to 75,000, more preferably 20,000 to 70,000. More preferably 20,000 to 65,000. The weight average molecular weight in the present specification is a weight average molecular weight in terms of standard polystyrene measured by Gel Permeation Chromatography (GPC).

As long as those skilled in the art can appropriately select and use a polycarbonate resin (a1) having a Tg satisfying the above relationship from among known polycarbonate resins in consideration of the glass transition temperature (Tg) of the high hardness resin used. The polycarbonate resin (a1) preferably has a Tg of 90 to 190 ℃, more preferably 100 to 170 ℃, and particularly preferably 110 to 150 ℃. In the present specification, the glass transition temperature is a temperature calculated by a midpoint method by measuring 10mg of a sample at a temperature increase rate of 10 ℃/min using a differential scanning calorimetry measuring apparatus.

The base material layer may contain other resins in addition to the polycarbonate resin (a 1). Examples of such a resin include polyester resins. The polyester resin preferably contains terephthalic acid as the dicarboxylic acid component, and may contain a dicarboxylic acid component other than terephthalic acid.

For example, a polyester resin (so-called "PETG") obtained by polycondensation of a glycol component containing 20 to 40 mol% (total 100 mol%) of 1, 4-cyclohexanedimethanol with respect to 80 to 60 mol% of ethylene glycol as a main component is preferable. The resin in the base material layer is preferably only the polycarbonate resin (a1), but when other resins are contained, the amount thereof is preferably 0 to 50 mass%, more preferably 0 to 30 mass%, and particularly preferably 0 to 20 mass% with respect to the total mass of the base material layer.

The base material layer may further contain additives and the like. As the additive, an additive generally used in a resin sheet can be used, and examples of such an additive include an antioxidant, a coloring inhibitor, an antistatic agent, a mold release agent, a lubricant, a dye, a pigment, a plasticizer, a flame retardant, a resin modifier, a compatibilizer, a reinforcing agent such as an organic filler or an inorganic filler, and the like. The method of mixing the additive with the resin is not particularly limited, and a method of mixing the total amount, a method of dry blending the master batch, a method of dry blending the total amount, and the like can be employed. The amount of the additive is preferably 0 to 10 mass%, more preferably 0 to 7 mass%, and particularly preferably 0 to 5 mass% with respect to the total mass of the base material layer.

The thickness of the substrate layer is preferably 0.3-10 mm, more preferably 0.3-5 mm, and particularly preferably 0.3-3.5 mm.

2. High-hardness resin layer

The high-hardness resin layer is a resin layer mainly containing a high-hardness resin. In the present specification, the high-hardness resin is a resin having a hardness higher than that of the polycarbonate resin serving as the base material, and means a resin having a pencil hardness of HB or more. The pencil hardness of the high-hardness resin is preferably HB to 3H, more preferably H to 3H, and particularly preferably 2H to 3H. The high-hardness resin contained in the high-hardness resin layer may be 1 kind or 2 or more kinds. As long as the person skilled in the art can appropriately select and use a high-hardness resin having a Tg satisfying the relationship of "-10 ℃ or less (glass transition temperature of high-hardness resin) - (glass transition temperature of polycarbonate resin (a1) ≦ 40 ℃" from known high-hardness resins in consideration of the glass transition temperature (Tg) of the polycarbonate resin used. The high-hardness resin is preferably at least 1 selected from the following resins (B1) to (B5).

< resin (B1) >)

The resin (B1) is a copolymer containing a (meth) acrylate structural unit (a) represented by the following general formula (1) and an aliphatic vinyl structural unit (B) represented by the following general formula (2), or an alloy of the copolymer and the resin (B2) described below.

(wherein R1 represents a hydrogen atom or a methyl group; R2 represents an alkyl group having 1 to 18 carbon atoms.)

(wherein R3 represents a hydrogen atom or a methyl group; R4 represents a cyclohexyl group which may be substituted with a hydrocarbon group having 1 to 4 carbon atoms.)

In the present specification, the "hydrocarbon group" may be linear, branched or cyclic, and may have a substituent.

In the (meth) acrylate structural unit (a) represented by the general formula (1), R2 is an alkyl group having 1 to 18 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Specific examples thereof include methyl, ethyl, butyl, lauryl, stearyl, cyclohexyl and isobornyl.

Among the (meth) acrylate structural units (a), preferred are (meth) acrylate structural units in which R2 is a methyl group or an ethyl group, and more preferred are methyl methacrylate structural units in which R1 is a methyl group and R2 is a methyl group.

In the aliphatic vinyl structural unit (b) represented by the general formula (2), R3 is a hydrogen atom or a methyl group, and more preferably a hydrogen atom. R4 is a cyclohexyl group or a cyclohexyl group substituted with a hydrocarbon group having 1 to 4 carbon atoms, and is preferably a cyclohexyl group having no substituent.

Therefore, among the aliphatic vinyl structural units (b), an aliphatic vinyl structural unit in which R3 is a hydrogen atom and R4 is a cyclohexyl group is more preferable.

The resin (B1) may contain 1 or 2 or more types of (meth) acrylate structural units (a), and may contain 1 or 2 or more types of aliphatic vinyl structural units (B).

The total content of the (meth) acrylate structural unit (a) and the aliphatic vinyl structural unit (B) is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, and particularly preferably 98 to 100 mol%, based on the total structural units of the resin (B1).

That is, the resin (B1) may contain a structural unit other than the (meth) acrylate structural unit (a) and the aliphatic vinyl structural unit (B). The amount thereof is preferably 10 mol% or less, more preferably 5 mol% or less, and particularly preferably 2 mol% or less, based on the whole structural units of the resin (B1).

Examples of the structural units other than the (meth) acrylate structural unit (a) and the aliphatic vinyl structural unit (b) include: and a structural unit derived from an aromatic vinyl monomer having an aromatic double bond that is not hydrogenated, which is generated in the process of producing the resin (B1) by polymerizing a (meth) acrylate monomer and an aromatic vinyl monomer and then hydrogenating an aromatic double bond derived from the aromatic vinyl monomer.

The content of the (meth) acrylate structural unit (a) represented by the general formula (1) is preferably 65 to 80 mol%, more preferably 70 to 80 mol%, based on the total structural units in the resin (B1). When the proportion of the (meth) acrylate structural unit (a) is 65 mol% or more based on the total structural units in the resin (B1), a resin layer having excellent adhesion to the base material layer and excellent surface hardness can be obtained. When the amount is 80 mol% or less, warpage due to water absorption of the resin sheet is less likely to occur.

The content of the aliphatic vinyl structural unit (B) represented by the general formula (2) is preferably 20 to 35 mol%, more preferably 20 to 30 mol%, based on the total structural units in the resin (B1). When the content of the aliphatic vinyl structural unit (b) is 20 mol% or more, warpage under high temperature and high humidity can be prevented, and when the content is 35 mol% or less, peeling at the interface with the substrate can be prevented.

In the present specification, the "copolymer" may have any structure of random, block, and alternating copolymers.

The method for producing the resin (B1) is not particularly limited, and is preferably a resin obtained by polymerizing at least 1 (meth) acrylate monomer and at least 1 aromatic vinyl monomer and then hydrogenating the aromatic double bond derived from the aromatic vinyl monomer. Wherein, (meth) acrylic acid represents methacrylic acid and/or acrylic acid.

Specific examples of the aromatic vinyl monomer used in this case include styrene, α -methylstyrene, p-hydroxystyrene, alkoxystyrene, chlorostyrene, and derivatives thereof. Among these, styrene is preferred.

The polymerization of the (meth) acrylate monomer and the aromatic vinyl monomer can be carried out by a known method, and can be produced by, for example, bulk polymerization, solution polymerization, or the like.

The bulk polymerization method is carried out by a method in which a monomer composition containing the above-mentioned monomer and a polymerization initiator is continuously supplied to a complete mixing tank and continuously polymerized at 100 to 180 ℃. The monomer composition may contain a chain transfer agent as necessary.

The polymerization initiator is not particularly limited, and examples thereof include organic peroxides such as t-amyl peroxide-2-ethylhexanoate, t-butyl peroxide-2-ethylhexanoate, benzoyl peroxide, 1-bis (t-hexylperoxy) -3, 3, 5-trimethylcyclohexane, 1-bis (t-hexylperoxy) cyclohexane, 1-bis (t-butylperoxy) cyclohexane, t-hexylpropoxyiisopropyl monocarbonate, t-amyl peroxide-n-octanoate, t-butylisopropyl monocarbonate, and di-t-butyl peroxide, azo compounds such as 2,2' -azobisisobutyronitrile, 2' -azobis (2-methylbutyronitrile), and 2,2' -azobis (2, 4-dimethylvaleronitrile). These can be used alone or in combination of 2 or more.

The chain transfer agent may be used as needed, and for example, α -methylstyrene dimer is cited.

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

The solvent used in the hydrogenation reaction after the polymerization of the (meth) acrylate monomer and the aromatic vinyl monomer may be the same as or different from the polymerization solvent described above. Examples thereof include hydrocarbon solvents such as cyclohexane and methylcyclohexane, ester solvents such as ethyl acetate and methyl isobutyrate, ketone solvents such as acetone and methyl ethyl ketone, ether solvents such as tetrahydrofuran and dioxane, and alcohol solvents such as methanol and isopropanol.

As described above, the resin (B1) used in the present invention is obtained by polymerizing the (meth) acrylate monomer and the aromatic vinyl monomer and then hydrogenating the aromatic double bond derived from the aromatic vinyl monomer.

The method of hydrogenation is not particularly limited, and a known method can be used. For example, the reaction can be carried out by a batch-wise or continuous flow method under a hydrogen pressure of 3 to 30MPa and a reaction temperature of 60 to 250 ℃. By setting the temperature to 60 ℃ or higher, the reaction time is not excessively long, and by setting the temperature to 250 ℃ or lower, the molecular chain cleavage and the hydrogenation of the ester portion are less likely to occur.

Examples of the catalyst used in the hydrogenation reaction include solid catalysts in which metals such as nickel, palladium, platinum, cobalt, ruthenium, and rhodium, or oxides, salts, or complexes of these metals are supported on a porous support such as carbon, alumina, silica-alumina, and diatomaceous earth.

The resin (B1) is preferably a resin in which 70% or more of the aromatic double bonds derived from the aromatic vinyl monomer are hydrogenated. That is, the unhydrogenated ratio of the aromatic double bond contained in the structural unit derived from the aromatic vinyl monomer is preferably less than 30%. By making the unhydrogenated ratio less than 30%, a resin having excellent transparency can be obtained. The unhydrogenated ratio is more preferably less than 10%, still more preferably less than 5%.

The weight average molecular weight of the resin (B1) is not particularly limited, but is preferably 50,000 to 400,000, more preferably 70,000 to 300,000, from the viewpoint of strength and moldability.

The glass transition temperature of the resin (B1) is preferably in the range of 110 to 140 ℃, more preferably 110 to 135 ℃, and particularly preferably 110 to 130 ℃. When the glass transition temperature is 110 ℃ or higher, the resin sheet provided by the present invention is less likely to deform or crack in a hot environment or a moist-heat environment. On the other hand, when molding is performed at 140 ℃ or lower by continuous thermal molding using a mirror surface roller or a molding roller, or by batch thermal molding using a mirror surface mold or a molding die, the processability is excellent.

Specific examples of the resin (B1) include Optimas 7500 and 6000 (manufactured by mitsubishi gas chemical corporation).

When resin (B1) is used as the high-hardness resin, Ipipzeta T-1380 (manufactured by Mitsubishi gas chemical corporation) is preferably used as the polycarbonate resin (a 1). Particularly, it is preferable to use a copolymer containing 75 mol% of the structural unit represented by the general formula (1) (both of R1 and R2 are methyl groups; methyl methacrylate) and 25 mol% of the structural unit represented by the general formula (2) (R3 is a hydrogen atom and R4 is a cyclohexyl group) as the resin (B1), a polycarbonate resin containing the structural unit represented by the general formula (4a) as the polycarbonate resin (a1), and a 1-membered phenol represented by the general formula (5) (R1 has 8 to 22 carbon atoms) as the end terminator.

< resin (B2) >)

The resin (B2) is a resin which is an alloy of the copolymer (D) and the copolymer (D), and a resin which is an alloy of the copolymer (D) and a high-hardness resin other than the resin (B2), or a resin which is an alloy of the copolymer (D) and an acrylic resin, and which contains 6 to 77 mass% of a (meth) acrylate structural unit, 15 to 71 mass% of a styrene structural unit, and 8 to 23 mass% of an unsaturated dicarboxylic acid structural unit. Examples of the high-hardness resin other than the resin (B2) include a methyl methacrylate-styrene copolymer, an acrylonitrile-butadiene-styrene copolymer, and the like. Examples of the acrylic resin include polymethyl methacrylate, and a copolymer of methyl methacrylate and methyl acrylate or ethyl acrylate. Further, commercially available products can be used, and specific examples thereof include ACRYPET available from mitsubishi chemical corporation, sumiex available from sumitomo chemical corporation, and parafet available from korea corporation. In the case of making an alloy, in order to avoid lowering the Tg of the high-hardness resin, an alloy of resins having higher Tg is preferable.

Examples of the (meth) acrylate monomer constituting the (meth) acrylate structural unit include acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate, and methyl methacrylate is particularly preferable. These (meth) acrylate monomers may be used in combination of 2 or more.

The content of the (meth) acrylate structural unit is 6 to 77% by mass, preferably 20 to 70% by mass, based on the total mass of the resin (B2).

The styrene structural unit is not particularly limited, and any known styrene monomer can be used. From the viewpoint of easy availability, styrene, α -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, and the like are preferable. Among these, styrene is particularly preferable from the viewpoint of compatibility. These styrene monomers may be used in combination of 2 or more.

The content of the styrene structural unit is 15 to 71 mass%, preferably 20 to 66 mass%, based on the total mass of the resin (B2).

Examples of the unsaturated dicarboxylic anhydride monomer constituting the unsaturated dicarboxylic acid structural unit include anhydrides of maleic acid, itaconic acid, citraconic acid, aconitic acid, and the like, and maleic anhydride is preferable from the viewpoint of compatibility with a styrene monomer. These unsaturated dicarboxylic anhydride monomers may be used in combination of 2 or more.

The content of the unsaturated dicarboxylic acid structural unit is 8 to 23% by mass, preferably 10 to 23% by mass, based on the total mass of the resin (B2).

The total content of the (meth) acrylate structural unit, the styrene structural unit, and the unsaturated dicarboxylic acid structural unit is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, and particularly preferably 98 to 100 mol% based on the total structural units of the resin (B2).

That is, the resin (B2) may contain a structural unit other than the above (meth) acrylate structural unit, styrene structural unit, and unsaturated dicarboxylic acid structural unit. The amount thereof is preferably 10 mol% or less, more preferably 5 mol% or less, and particularly preferably 2 mol% or less, based on the whole structural units of the resin (B2).

Examples of the other structural unit include N-phenylmaleimide and the like.

The method for producing the resin (B2) is not particularly limited, and a bulk polymerization method and a solution polymerization method are exemplified.

Specific examples of the resin (B2) include RESISFY R100, R200, R310 (manufactured by DENKA K.K.), DELPET 980N (manufactured by Asahi Kasei Chemicals Co., Ltd.), and hw55 (manufactured by DAICEL EVONIK).

The weight average molecular weight of the resin (B2) is not particularly limited, but is preferably 50,000 to 300,000, more preferably 80,000 to 200,000.

The glass transition temperature of the resin (B2) is preferably 90 to 150 ℃, more preferably 100 to 150 ℃, and particularly preferably 115 to 150 ℃.

When the resin (B2) is used as the high-hardness resin, a polycarbonate resin containing a structural unit of the general formula (4a) is preferably used as the polycarbonate resin (a 1). In particular, a mode of using a 1-membered phenol represented by the general formula (5) (the carbon number of R1 is 8 to 22) as a terminal terminator is preferable. Examples of such a polycarbonate resin include Ifpizeta T-1380 (manufactured by Mitsubishi gas chemical Co., Ltd.), Ifpilon E-2000 (manufactured by Mitsubishi engineering plastics Co., Ltd.), and the like. A preferred embodiment is a method in which a copolymer (R100, R200 or R310; manufactured by DENKA) comprising 6 to 26 mass% of a methyl methacrylate structural unit, 55 to 21 mass% of a styrene structural unit and 15 to 23 mass% of a maleic anhydride structural unit is used as the resin (B2) and Iipizeta T-1380 is used as the polycarbonate resin (a 1). In particular, a copolymer (R310; manufactured by DENKA K.K.) comprising 6% by mass of a methyl methacrylate structural unit, 71% by mass of styrene and 23% by mass of maleic anhydride is preferably used as the resin (B2), and Iipizeta T-1380 is preferably used as the polycarbonate resin (a 1).

< resin (B3) >)

The resin (B3) is a copolymer containing a structural unit (c) represented by the following general formula (6) and optionally containing a structural unit (d) represented by the following general formula (7). The resin (B3) may or may not contain the structural unit (d), but is preferably contained.

The proportion of the structural unit (c) in the total structural units of the resin (B3) is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, and particularly preferably 70 to 100 mol%. The proportion of the structural unit (d) in the total structural units of the resin (B3) is preferably 0 to 50 mol%, more preferably 0 to 40 mol%, and particularly preferably 0 to 30 mol%.

The total content of the structural unit (c) and the structural unit (d) is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, and particularly preferably 98 to 100 mol% with respect to the resin (B3).

The resin (B3) may contain a structural unit other than the structural unit (c) and the structural unit (d). When other structural units are contained, the amount thereof is preferably 10 mol% or less, more preferably 5 mol% or less, and particularly preferably 2 mol% or less, based on the total structural units of the resin (B3).

Examples of the other structural unit include a structural unit represented by the following general formula (4 a).

The method for producing the resin (B3) is not particularly limited, and can be produced by the same method as the method for producing the polycarbonate resin (a1) except that bisphenol C is used as a monomer.

Specific examples of the resin (B3) include Iupilon KH3410UR, KH3520UR, and KS3410UR (manufactured by Mitsubishi engineering plastics Co., Ltd.).

The weight average molecular weight of the resin (B3) is preferably 15,000 to 75,000, more preferably 20,000 to 70,000, and particularly preferably 25,000 to 65,000.

The glass transition temperature of the resin (B3) is preferably 105 to 150 ℃, more preferably 110 to 140 ℃, and particularly preferably 110 to 135 ℃.

When the resin (B3) is used as the high-hardness resin, a polycarbonate resin containing a structural unit of the general formula (4a) is preferably used as the polycarbonate resin (a 1). In particular, a mode of using a 1-membered phenol represented by the general formula (5) (the carbon number of R1 is 8 to 22) as a terminal terminator is preferable. Examples of such a polycarbonate resin include Ipipzeta T-1380 (manufactured by Mitsubishi gas chemical Co., Ltd.). Particularly preferably used are Ilpilon KS3410UR (manufactured by Mitsubishi engineering plastics Co., Ltd.) as the resin (B3) and Ilpizeta T-1380 (manufactured by Mitsubishi gas chemical Co., Ltd.) as the polycarbonate resin (a 1).

When the resin (B3) is used as the high-hardness resin, the other resin contained in the high-hardness resin layer is preferably a resin containing the structural unit (d) without containing the structural unit (c), and more preferably a resin composed of only the structural unit (d). Specifically, an aromatic polycarbonate resin (for example, Ipiplon S-2000, Ipiplon S-1000, Ipiplon E-2000; manufactured by Mitsubishi engineering plastics Co., Ltd.) or the like can be used. When another resin is contained, the resin (B3) is contained in a proportion of preferably 45 mass% or more, more preferably 55 mass% or more, with respect to the total resin contained in the high-hardness resin layer.

< resin (B4) >)

The resin (B4) is a copolymer (G) containing 5 to 20 mass% of styrene structural units, 60 to 90 mass% of (meth) acrylate structural units and 5 to 20 mass% of N-substituted maleimide structural units, or an alloy of the copolymer (G) and the resin (B2). In the case of an alloy, in order to avoid lowering of Tg of the high-hardness resin layer, an alloy of resins having higher Tg is preferable.

The styrene structural unit is not particularly limited, and any known styrene monomer can be used, and from the viewpoint of easy availability, styrene, α -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, and the like are preferable. Among these, styrene is particularly preferable from the viewpoint of compatibility. The copolymer (G) may contain 2 or more of these styrene structural units. The content of the styrene structural unit is 5 to 20% by mass, preferably 5 to 15% by mass, and more preferably 5 to 10% by mass, based on the total mass of the resin (B4).

Examples of the (meth) acrylate structural unit include structural units derived from acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, and the like, and structural units derived from methyl methacrylate are particularly preferred. The copolymer (G) may contain 2 or more of these (meth) acrylate structural units. The content of the (meth) acrylate structural unit is 60 to 90% by mass, preferably 70 to 90% by mass, and more preferably 80 to 90% by mass, based on the total mass of the resin (B4).

Examples of the N-substituted maleimide structural unit in the resin (B4) include structural units derived from N-arylmaleimides such as N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-naphthylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide and N-tribromophenylmaleimide, and the structural units derived from N-phenylmaleimide are preferable from the viewpoint of compatibility with acrylic resins. The copolymer (G) may contain 2 or more of these N-substituted maleimide structural units. The content of the N-substituted maleimide structural unit is 5 to 20 mass%, preferably 5 to 15 mass%, more preferably 5 to 10 mass% with respect to the total mass of the resin (B4).

The total content of the styrene structural unit, the (meth) acrylate structural unit, and the N-substituted maleimide structural unit is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, and particularly preferably 98 to 100 mol% with respect to the resin (B4).

The resin (B4) may contain a structural unit other than the above-described structural units. When other structural units are contained, the amount thereof is preferably 10 mol% or less, more preferably 5 mol% or less, and particularly preferably 2 mol% or less, based on the total structural units of the resin (B4).

Examples of the other structural units include a structural unit derived from the following general formula (1) and a structural unit derived from the general formula (2).

(wherein R1 represents a hydrogen atom or a methyl group; R2 represents an alkyl group having 1 to 18 carbon atoms.)

(wherein R3 represents a hydrogen atom or a methyl group; R4 represents a cyclohexyl group which may be substituted with a hydrocarbon group having 1 to 4 carbon atoms.)

The method for producing the resin (B4) is not particularly limited, and it can be produced by solution polymerization, bulk polymerization, or the like.

Specific examples of the resin (B4) include DELPET PM120N (available from Asahi Kasei Chemicals Co., Ltd.).

The weight average molecular weight of the resin (B4) is preferably 50,000 to 250,000, more preferably 100,000 to 200,000.

The glass transition temperature of the resin (B4) is preferably 110 to 150 ℃, more preferably 115 to 140 ℃, and particularly preferably 115 to 135 ℃.

When the resin (B4) is used as the high-hardness resin, a polycarbonate resin containing a structural unit of the general formula (4a) is preferably used as the polycarbonate resin (a 1). In particular, a mode of using a 1-membered phenol represented by the general formula (5) (the carbon number of R1 is 8 to 22) as a terminal terminator is preferable. Examples of such a polycarbonate resin include Ipipzeta T-1380 (manufactured by Mitsubishi gas chemical Co., Ltd.). Particularly, a preferred embodiment is a method in which DELPET PM-120N comprising 7% of styrene structural units, 86% of (meth) acrylate structural units and 7% of N-substituted maleimide structural units is used as the resin (B4), and Iipizeta T-1380 is used as the polycarbonate resin (a 1).

< resin (B5) >)

The resin (B5) is a resin containing a structural unit (e) represented by the following general formula (8).

The proportion of the structural unit (e) in the total structural units of the resin (B5) is preferably 80 to 100 mol%, more preferably 90 to 100 mol%, and particularly preferably 95 to 100 mol%.

The resin (B5) may contain a structural unit other than the structural unit (e), but is preferably a polycarbonate resin composed of only the structural unit (e). When other structural units are contained, the amount thereof is preferably 20 mol% or less, more preferably 10 mol% or less, and particularly preferably 5 mol% or less, based on the total structural units of the resin (B5).

Examples of the other structural units include a structural unit represented by the following general formula (6) and a structural unit represented by the following general formula (7).

The method for producing the resin (B5) is not particularly limited, and can be produced by the same method as the method for producing the polycarbonate resin (a1) except that bisphenol AP is used as a monomer.

Specific examples of the resin (B5) include Ipipzeta FPC0220 (manufactured by Mitsubishi gas chemical Co., Ltd.).

The weight average molecular weight of the resin (B5) is preferably 10,000 to 1,000,000, more preferably 15,000 to 50,000.

The glass transition temperature of the resin (B5) is preferably 120 to 200 ℃, more preferably 130 to 190 ℃, and particularly preferably 140 to 190 ℃.

When the resin (B5) is used as the high-hardness resin, a polycarbonate resin containing a structural unit of the general formula (4a) is preferably used as the polycarbonate resin (a 1). As such a polycarbonate resin, Ipiplon E-2000 (manufactured by Mitsubishi engineering plastics Co., Ltd.) can be mentioned. Particularly preferably used are Ifpc 0220 (manufactured by Mitsubishi gas chemical corporation) as the resin (B5) and Ifplon E-2000 (manufactured by Mitsubishi engineering plastics Co., Ltd.) as the polycarbonate resin (a 1).

When the resin (B5) is used as the high-hardness resin, the other resin contained in the high-hardness resin layer is preferably a resin containing the structural unit (d) described in the resin (B3) without containing the structural unit (e), and more preferably a resin composed of only the structural unit (d). Specifically, an aromatic polycarbonate resin (for example, Ipiplon S-2000, Ipiplon S-1000, Ipiplon E-2000; manufactured by Mitsubishi engineering plastics Co., Ltd.) or the like can be used. When other resin is contained, the resin (B5) is contained in a proportion of preferably 45 mass% or more, more preferably 55 mass% or more, with respect to the total resin contained in the high-hardness resin layer.

The high-hardness resin contained in the high-hardness resin layer may be 1 kind or 2 or more kinds, and when 2 or more kinds are selected from the resins (B1) to (B5), the high-hardness resin may be selected from the same or different types, and may contain a high-hardness resin other than the resins (B1) to (B5). The content of the high-hardness resin in the high-hardness resin layer is preferably 70 to 100 mass%, more preferably 80 to 100 mass%, and particularly preferably 100 mass%.

The high-hardness resin layer may contain other resins in addition to the high-hardness resin described above. Examples of such resins include methyl methacrylate-styrene copolymers, polymethyl methacrylate, polystyrene, polycarbonate, cycloolefin (co) polymer resins, acrylonitrile-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, and various elastomers. The resin in the high-hardness resin layer is preferably only a high-hardness resin, and when other resins are contained, the content thereof is preferably 35% by mass or less, more preferably 25% by mass or less, and particularly preferably 10% by mass or less with respect to the high-hardness resin layer.

The high-hardness resin layer may further contain additives and the like. As the additive, the same additives as described in the above "1. base material layer" can be used, and the amounts thereof are also the same.

The thickness of the high-hardness resin layer affects the surface hardness and impact resistance of the molding resin sheet. That is, when the high-hardness resin layer is too thin, the surface hardness becomes low, and when it is too thick, the impact resistance is lowered. The thickness of the high-hardness resin layer is preferably 10 to 250 μm, more preferably 30 to 200 μm, and particularly preferably 60 to 150 μm.

3. Lamination of substrate layer and high-hardness resin layer

As described above, another layer may be present between the base material layer and the high-hardness resin layer, but here, a case where the high-hardness resin layer is laminated on the base material layer will be described. The lamination method is not particularly limited, and lamination can be similarly performed even when another layer is present. Examples include: a method of overlapping the substrate layer and the high-hardness resin layer formed separately and heating and pressure-bonding the two; a method of stacking the substrate layer and the high-hardness resin layer formed separately and bonding the two layers with an adhesive; a method of co-extruding the base material layer and the high-hardness resin layer; various methods such as a method of integrating a base material layer on a high-hardness resin layer formed in advance by in-mold molding. Among these, the coextrusion molding method is preferred from the viewpoint of production cost and productivity.

The method of coextrusion is not particularly limited. For example, in the feedblock method, a high-hardness resin layer is disposed on one surface of a base material layer in a feedblock, and the resulting material is extruded into a sheet shape by a T die, and then cooled while passing through a forming roll to form a desired laminate. In the multi-manifold system, a high-hardness resin layer is disposed on one surface of a base material layer in a multi-manifold die, and the extruded layer is cooled while passing through a forming roll to form a desired laminate.

The total thickness of the substrate layer and the high-hardness resin layer is preferably 0.5 to 3.5mm, more preferably 0.5 to 3.0mm, and particularly preferably 1.2 to 3.0 mm. By setting the total thickness to 0.5mm or more, the rigidity of the sheet can be maintained. In addition, by setting the thickness to 3.5mm or less, it is possible to prevent the sensitivity of the touch sensor from deteriorating when the touch panel is provided under the sheet. The ratio of the thickness of the base material layer to the total thickness of the base material layer and the high-hardness resin layer is preferably 75% to 99%, more preferably 80% to 99%, and particularly preferably 85% to 99%. When the amount is within the above range, both hardness and impact resistance can be achieved.

4. Hard coating anti-dazzle layer

The resin sheet of the present invention has a hard-coated antiglare layer. Between the hard coat antiglare layer and the high-hardness resin layer, although another layer may be present, it is preferable to laminate the hard coat antiglare layer on the high-hardness resin layer. The hard coating antiglare layer is preferably made of an acrylic hard coating layer. In the present specification, "acrylic hard coat layer" means: a coating film having a crosslinked structure is formed by polymerizing a monomer, oligomer or prepolymer containing a (meth) acryloyl group as a polymerizable group. The composition of the acrylic hard coat layer preferably contains 2 to 98 mass% of a (meth) acrylic monomer, 2 to 98 mass% of a (meth) acrylic oligomer, and 0 to 15 mass% of a surface modifier, and further preferably contains 0.001 to 7 parts by mass of a photopolymerization initiator with respect to 100 parts by mass of the total of the (meth) acrylic monomer, the (meth) acrylic oligomer, and the surface modifier.

The hard coat antiglare layer more preferably contains 5 to 50 mass% of a (meth) acrylic monomer, 50 to 94 mass% of a (meth) acrylic oligomer, and 1 to 10 mass% of a surface modifier, and particularly preferably contains 20 to 40 mass% of a (meth) acrylic monomer, 60 to 78 mass% of a (meth) acrylic oligomer, and 2 to 5 mass% of a surface modifier.

The amount of the photopolymerization initiator is more preferably 0.01 to 5 parts by mass, and particularly preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the total of the (meth) acrylic monomer, the (meth) acrylic oligomer, and the surface modifier.

(1) (meth) acrylic acid-based monomer

The (meth) acrylic monomer may be any monomer as long as a (meth) acryloyl group is present in the molecule as a functional group, and may be a 1-functional monomer, a 2-functional monomer, or a 3-or more-functional monomer.

Examples of the 1-functional monomer include (meth) acrylic acid and (meth) acrylate, and specific examples of the 2-functional and/or 3-functional or higher (meth) acrylic monomer include diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, bisphenol a diglycidyl ether di (meth) acrylate, tetraethylene glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol diacrylate, neopentyl glycol di (meth) acrylate, 1, 4-butanediol diacrylate, 1, 3-butanediol di (meth) acrylate, dicyclopentyl di (meth) acrylate, polyethylene glycol diacrylate, 1, 4-butanediol oligoacrylate, neopentyl glycol oligoacrylate, and mixtures thereof, 1, 6-hexanediol oligomeric acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane propoxytrimethylene tri (meth) acrylate, pentaerythritol tri (meth) acrylate, glycerol propoxytrimethylene tri (meth) acrylate, trimethylolpropane trimethacrylate, trimethylolpropane ethylene oxide adduct triacrylate, glycerol propylene oxide adduct triacrylate, pentaerythritol tetraacrylate, and the like.

The hard coating antiglare layer may contain 1 or 2 or more (meth) acrylic monomers.

(2) (meth) acrylic oligomer

Examples of the (meth) acrylic oligomer include a 2-or more-functional polyfunctional urethane (meth) acrylate oligomer [ hereinafter, also referred to as a polyfunctional urethane (meth) acrylate oligomer ], a 2-or more-functional polyfunctional polyester (meth) acrylate oligomer [ hereinafter, also referred to as a polyfunctional polyester (meth) acrylate oligomer ], a 2-or more-functional polyfunctional epoxy (meth) acrylate oligomer [ hereinafter, also referred to as a polyfunctional epoxy (meth) acrylate oligomer ], and the like. The hard coating antiglare layer may contain 1 or 2 or more kinds of (meth) acrylic oligomers.

As the polyfunctional urethane (meth) acrylate oligomer, there may be mentioned: a urethanization reaction product of a (meth) acrylate monomer having at least 1 (meth) acryloyloxy group and a hydroxyl group in 1 molecule and a polyisocyanate; and urethane-forming reaction products of isocyanate compounds obtained by reacting polyols and polyisocyanates with (meth) acrylate monomers having at least 1 or more (meth) acryloyloxy groups and hydroxyl groups in 1 molecule.

Examples of the (meth) acrylate monomer having at least 1 (meth) acryloyloxy group and hydroxyl group in 1 molecule used in the urethane-forming reaction include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate.

Examples of the polyisocyanate used in the urethane formation reaction include hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate, xylylene diisocyanate, diisocyanates obtained by hydrogenating aromatic isocyanates among these diisocyanates (e.g., hydrogenated toluene diisocyanate, hydrogenated xylylene diisocyanate and other diisocyanates), diisocyanates or polyisocyanates of triisocyanate such as triphenylmethane triisocyanate and dimethylene triphenyltriisocyanate, and polyisocyanates obtained by polymerizing diisocyanates.

As the polyol used in the urethane-forming reaction, in addition to aromatic, aliphatic and alicyclic polyols which are generally used, polyester polyol, polyether polyol and the like can be used. In general, examples of the aliphatic and alicyclic polyols include 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, ethylene glycol, propylene glycol, trimethylolethane, trimethylolpropane, dimethylolheptane, dimethylolpropionic acid, dimethylolbutyric acid, glycerin, hydrogenated bisphenol A, and the like.

Examples of the polyester polyol include those obtained by a dehydration condensation reaction of the above-mentioned polyhydric alcohol and a polycarboxylic acid. Specific examples of the polycarboxylic acid include succinic acid, adipic acid, maleic acid, trimellitic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, and terephthalic acid. These polycarboxylic acids may be anhydrides. The polyether polyol may be a polyoxyalkylene-modified polyol obtained by reacting the above polyol or phenol with an alkylene oxide, in addition to the polyalkylene glycol.

In addition, the polyfunctional polyester (meth) acrylate oligomer can be obtained by a dehydration condensation reaction using (meth) acrylic acid, a polycarboxylic acid, and a polyol. Examples of the polycarboxylic acid used in the dehydration condensation reaction include succinic acid, adipic acid, maleic acid, itaconic acid, trimellitic acid, pyromellitic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, and terephthalic acid. These polycarboxylic acids may also be anhydrides. Examples of the polyhydric alcohol used in the dehydration condensation reaction include 1, 4-butanediol, 1, 6-hexanediol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, dimethylolheptane, dimethylolpropionic acid, dimethylolbutyric acid, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, and the like.

The polyfunctional epoxy (meth) acrylate oligomer can be obtained by addition reaction of a polyglycidyl ether with (meth) acrylic acid. Examples of the polyglycidyl ether include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, and bisphenol a diglycidyl ether.

(3) Surface modifier

The surface modifier used in the present invention is a substance capable of modifying the surface properties of a hard-coated antiglare layer, such as a leveling agent, an antistatic agent, a surfactant, a water and oil repellent agent, inorganic particles, organic particles, and the like.

Examples of the leveling agent include polyether-modified polyalkylsiloxane, polyether-modified siloxane, polyester-modified hydroxyl-containing polyalkylsiloxane, polyether-modified polydimethylsiloxane having an alkyl group, modified polyether, and silicon-modified acrylic acid.

Examples of the antistatic agent include glycerin fatty acid ester monoglyceride, glycerin fatty acid ester organic acid monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid ester, cationic surfactant, anionic surfactant, and the like.

Examples of the inorganic particles include silica particles, alumina particles, zirconia particles, silica particles, silver particles, and glass particles.

Examples of the organic particles include acrylic particles and silicon particles.

Examples of the surfactant and water and oil repellent agent include fluorine-containing surfactants and oil repellent agents such as oligomers containing a fluorine group and a lipophilic group, and oligomers containing a fluorine group, a hydrophilic group, a lipophilic group, and a UV reactive group.

(4) Photopolymerization initiator

The hard coat antiglare layer may contain a photopolymerization initiator. In the present specification, the photopolymerization initiator refers to a photo radical generator.

Examples of the monofunctional photopolymerization initiator that can be used in the present invention include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone [ DAROCUR-2959: manufactured by merck corporation ]; α -hydroxy- α, α' -dimethylacetophenone [ DAROCUR-1173: manufactured by merck corporation ]; acetophenone initiators such as methoxyacetophenone, 2' -dimethoxy-2-phenylacetophenone [ Irgacure-651 ], and 1-hydroxy-cyclohexyl phenyl ketone; benzoin ether-based initiators such as benzoin ethyl ether and benzoin isopropyl ether; and halogenated ketones, acylphosphine oxides, acylphosphonates, and the like.

(5) Method for forming hard coating anti-dazzle layer

The method for forming the hard coating antiglare layer is not particularly limited, and for example, the hard coating antiglare layer can be formed by applying a hard coating liquid to a layer (for example, a high-hardness resin layer) located below the hard coating antiglare layer and then subjecting the layer to photopolymerization.

The method for applying the hard coating liquid (polymerizable composition) is not particularly limited, and a known method can be used. Examples thereof include spin coating, dipping, spraying, slide coating, bar coating, roll coating, gravure coating, meniscus coating, flexographic printing, screen printing, brush coating, and the like.

As a lamp used for light irradiation in photopolymerization, a lamp having a light emission distribution with a light wavelength of 420nm or less can be used, and examples thereof include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a chemical lamp, a black light lamp, a microwave excitation mercury lamp, a metal halide lamp, and the like. Among them, a high-pressure mercury lamp or a metal halide lamp is preferable because it can efficiently emit light in the active wavelength region of the initiator, but does not emit much light of a short wavelength that degrades the viscoelasticity properties of the resulting polymer by crosslinking or light of a long wavelength that evaporates the reaction composition by heating.

The irradiation intensity of the lamp is a factor that influences the degree of polymerization of the obtained polymer, and is appropriately controlled depending on the properties of each target product. When a conventional cleavage type initiator having a acetophenone group is blended, the illuminance is preferably 0.1 to 300mW/cm²The range of (1). Particularly preferably, a metal halide lamp is used so that the illuminance is 10-40 mW/cm²。

Photopolymerization is hindered by oxygen in the air or oxygen dissolved in the reactive composition. Therefore, it is desirable to perform light irradiation by a method capable of eliminating the inhibition of the reaction by oxygen. As one of such methods, there is a method in which the reactive composition is covered with a film made of polyethylene terephthalate or TEFLON to block contact with oxygen, and then the reactive composition is irradiated with light through the film. In addition, the composition may be irradiated with light through a light-transmitting window in an inert atmosphere in which oxygen is replaced with an inert gas such as nitrogen or carbon dioxide.

When light irradiation is performed in an inert atmosphere, a certain amount of inert gas is continuously introduced in order to keep the atmospheric oxygen concentration at a low level. Due to the introduction of the inert gas, a gas flow is generated on the surface of the reactive composition, causing the monomer to evaporate. In order to suppress the level of evaporation of the monomer, the flow velocity of the inert gas is preferably 1m/sec or less, more preferably 0.1m/sec or less, relative to the relative velocity of the laminate coated with the hard coating liquid moving under the inert gas atmosphere. By setting the gas flow velocity in the above range, the evaporation of the monomer due to the gas flow can be substantially suppressed.

The coated surface may be pretreated for the purpose of improving the adhesion of the hard-coated antiglare layer. Examples of the treatment include known methods such as a sand blast method, a solvent treatment method, a corona discharge treatment method, a chromic acid treatment method, a flame treatment method, a hot air treatment method, an ozone treatment method, an ultraviolet treatment method, and an undercoating treatment method using a resin composition.

The hard coat antiglare layer is preferably 20mW/cm in irradiation output using UV light (254nm)²The metal halide lamp of (3) has a pencil hardness of 2H or more when irradiated with ultraviolet rays.

The film thickness of the hard coat antiglare layer is preferably 1 μm to 40 μm, more preferably 2 μm to 10 μm. When the film thickness is 1 μm or more, more sufficient hardness can be obtained. Further, the film thickness of 40 μm or less can suppress the occurrence of cracks during bending. The film thickness of the hard-coated antiglare layer can be measured by observing a cross section with a microscope or the like, and actually measuring the interface to the surface of the coating film.

The hard-coated antiglare layer can be produced by applying an acrylic hard-coating agent between an antiglare mold and a high-hardness resin, curing the hard-coated antiglare layer by irradiation with UV light, and then releasing the hard-coated antiglare layer from the antiglare mold. The material of the glare-proof mold is only required to be capable of transmitting UV light, and the material may be glass, transparent resin, or the like.

The hard-coated antiglare layer can be further modified. For example, any one or more of antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment, and antiglare treatment can be performed. These treatment methods are not particularly limited, and known methods can be used. Examples thereof include a method of applying an antireflection coating, a method of depositing a dielectric thin film, and a method of applying an antistatic coating.

The pencil hardness of the resin sheet of the present invention is preferably 2H or more, for example, 2H to 4H, and particularly preferably 3H to 4H. The pencil hardness of the resin sheet as used herein means: when the surface of the hard coating antiglare layer was pressed with a pencil at an angle of 45 degrees and a load of 750g and the hardness was increased in this order, the hardest pencil hardness without causing any mark was obtained (refer to the pencil scratch hardness test of JIS K5600-5-4).

5. Protective film

The protective film has a first protective film on the side contacting the resin sheet and a second protective film on the outer side. The first protective film is, for example, a polyolefin-based film, and examples thereof include a polyethylene film and a film obtained from a mixture of polyethylene and polypropylene. The melting point of the first protective film is preferably 100 to 130 ℃. The first protective film contains a polyolefin material having a melting point of 100 to 130 ℃, melts during thermoforming, and functions as a buffer material when a flaw or foreign matter is present on the surface of a hot-press mold, thereby suppressing the adhesion of the flaw or the scratch to the mold of a molded product. In the case of a film of a mixture of polyethylene and polypropylene, a melting point of 140 ℃ or higher derived from polypropylene may be measured, but the melting point may be measured at 100 ℃ to 130 ℃. The thickness of the first protective film is preferably 20 to 100 μm, and more preferably 30 to 80 μm. Examples thereof include MX-217Y, MX-318N manufactured by MATAI of Japan and E MASK 100 manufactured by Nissan electric engineering.

The second protective film is, for example, a polyolefin-based film, preferably a polyolefin film, a polypropylene film or a PET film. The melting point of the second protective film is preferably 140 ℃ or higher if it is a polyolefin-based film. This is because the second protective film needs to maintain heat resistance at the mold temperature of 124 ℃ and 143 ℃ during thermoforming, and to prevent fusion to the mold. The second protective film preferably has a film thickness of 20 to 100 μm, more preferably 30 to 80 μm. Examples of the polyolefin film include HITALEX L-3330 and L-3340 which are formed by Hitachi, TORETEC R200A which is manufactured by Toray film processing Co., Ltd, and examples of the PET film include K3940B which is formed by Hitachi.

The haze of the resin sheet of the present invention is preferably 2 to 30%, more preferably 4 to 25%. The haze is a value measured according to JIS K7136 using HR-100 type manufactured by village color technical research.

According to one embodiment of the present invention, a resin molded article molded using the above-described molding resin sheet can be provided. The molding method is not particularly limited, and the resin sheet of the present invention is suitable for thermoforming according to its properties. Thermoforming can be performed by a method generally used in this field, and examples thereof include hot press molding, air pressure molding, vacuum molding, and TOM molding. The molding temperature is preferably 100 ℃ to 200 ℃.

Examples

The following examples of the present invention are shown, but the present invention is not limited by the examples. < measurement of glass transition temperature (Tg) and melting Point >

The glass transition temperatures of the polycarbonate resins and the high-hardness resins used in examples and comparative examples and the melting point of the protective film were measured at a temperature increase rate of 10 ℃/min under a nitrogen atmosphere using a differential scanning calorimeter DSC7020 manufactured by Hitachi high tech science. The weight of the resin used is 10 to 20 mg.

< determination of Pencil hardness of resin sheet >

The resin sheets produced in examples and comparative examples were evaluated by a pencil scratch hardness test in compliance with JIS K5600-5-4. The surface of the hard-coated antiglare layer was pressed with a pencil at an angle of 45 degrees and a load of 750g, and the hardness of the hardest pencil with no mark was evaluated as the pencil hardness. The hardness of 2H or more was determined as acceptable.

< production of molded article having curved shape and evaluation of hard coat crack after molding >

The resin sheets manufactured in examples and comparative examples were subjected to thermoforming. Examples 1 to 3 and 5 to 13 and comparative examples 1 to 5 and 7 to 10 used a hot-pressing mold having a gap (gap between upper and lower molds that sandwich a molding piece) of 2mm and a molding R of 50mm, and examples 4 and 6 used a hot-pressing mold having a gap of 3.5mm and a molding R of 100 mm. The pressure applied to the hot press mold was 0.6 MPa. The material of the mould is aluminium. The temperature of the mold during thermoforming was 124 ℃ in examples 1 to 5, 7 to 11 and 13 and comparative examples 1 to 3, 8 and 9, and 143 ℃ in examples 6 and 12 and comparative examples 4 to 7 and 10.

The molded article thus obtained was found to have cracks in 50mmR portions or 100mmR portions. When a resin sheet having a total thickness of 0.5mm, 1.2mm or 1.5mm of the base material layer and the high-hardness resin layer is molded using a hot-press mold having a gap of 2mm, a single-layer polycarbonate sheet having a total thickness of 2mm is formed by hot-press molding with 1.5mm, 0.8mm or 0.5mm being placed below the resin sheet.

< flow mark >

The laminates of the high-hardness resin layer and the polycarbonate resin layer before hard coating, which were produced in examples and comparative examples, were visually inspected for appearance under a 3-wavelength fluorescent lamp to confirm the presence or absence of fish-scale streaks and white turbidity. The evaluation was "no flow mark" when neither scaly streaks nor white turbidity was observed, and was "flow mark" when any phenomenon of scaly streaks or white turbidity was observed.

< transfer of mold scar >

The first protective film and the second protective film were peeled from the hot-press molded products of the molding resin sheets produced in examples and comparative examples, and appearance inspection was performed visually under a 3-wavelength fluorescent lamp to confirm whether or not the mold flaw was transferred to the resin sheet.

< fusion of protective film >

After the molding resin sheets produced in examples and comparative examples were hot-pressed and molded, whether or not the protective film was fused to the mold or the resin sheet was visually checked. In the case where the protective film is fused to the mold, it is necessary to remove the protective film before the next hot press molding, which is a disadvantage. In addition, when the first protective film and the second protective film are fused to the resin sheet, a peeling failure occurs in the first protective film and the second protective film, which is a failure.

< measurement of haze of resin sheet >

HR-100 type according to the village color technical research was used, and the evaluation was made in accordance with JIS K7136.

Example 1: r100(Tg124 ℃ C.)/low TgPC (Tg125 ℃ C.)/1.2 mmt

A multilayer extrusion apparatus having a single-screw extruder having an axial diameter of 35mm, a single-screw extruder having an axial diameter of 65mm, and a feed block connected to the respective extruders was used to mold a laminate composed of a base material layer and a high-hardness resin layer. Specifically, a high-hardness resin (B2) (a copolymer comprising 21 mass% of methyl methacrylate structural units, 64 mass% of styrene structural units and 15 mass% of maleic anhydride structural units; RESISFY R100 (manufactured by DENKA Co., Ltd.) was continuously introduced into a single-screw extruder having an axial diameter of 35mm, and extruded at a cylinder temperature of 230 ℃ and an extrusion rate of 2.6 kg/h. Then, a polycarbonate resin (Ipipzeta T-1380; manufactured by Mitsubishi gas chemical) was continuously introduced into a single-screw extruder having an axial diameter of 65mm, and extruded at a cylinder temperature of 240 ℃ and a discharge rate of 50.0 kg/h.

The extruded high hardness resin and polycarbonate resin were introduced into a feedblock having 2 kinds of 2-layer distribution pins, and the high hardness resin and polycarbonate resin were laminated at a temperature of 240 ℃. Then, the sheet was introduced into a T die having a temperature of 240 ℃ and extruded into a sheet form, and the sheet was cooled while transferring the mirror surface by 3 mirror-finishing rolls having a temperature of 120 ℃ to 130 ℃ to 190 ℃ from the upstream side, to obtain a laminate of a high-hardness resin layer and a polycarbonate resin layer (base material layer). The thickness of the laminate was 1.2mm, and the thickness of the high-hardness resin layer was 60 μm in the vicinity of the center.

A hard-coated antiglare layer was formed on the high-hardness resin layer side of the laminate obtained above. The materials of the hard coating antiglare layer are as follows.

U6 HA: 60% by mass of a 6-functional urethane acrylate oligomer (produced by Ningmura chemical industries, Ltd.);

4 EG-A: 35% by mass of PEG200# diacrylate (produced by Kyoeisha chemical Co., Ltd.); and

RS-90: 5% by mass of an oligomer (produced by DIC) containing a fluorine-containing hydrophilic group, a lipophilic group and a UV reactive group,

the composition contains the following components in 100 parts by mass of a mixture of the components:

photopolymerization initiator: 1 part by mass of I-184 (product of BASF corporation [ compound name: 1-hydroxy-cyclohexylphenylketone ]).

The above-mentioned material was applied to a laminate by a bar coater, the uneven surface of a 2mm thick ground glass plate having a haze of 10% was covered with the material, and a 5-second metal halide lamp (20 mW/cm) was irradiated from the glass plate²) After the hard coat layer was cured and the hard coat antiglare layer was adhered, the ground glass plate was peeled off to prepare a resin sheet. The film thickness of the hard coating antiglare layer was 6 μm. The haze of the resin sheet was 9%.

Both sides of the resin sheet were covered with MX-318N (melting point: 121 ℃ C., 161 ℃ C.) made by MATAI in Japan, and pressure-bonded between 2 rubber rollers at room temperature (load: 5 kg/cm)²) And adhering the first protective film. Then, a resin sheet for molding was prepared by placing L-3330 (melting point: 164 ℃ C.) made by Hitachi chemical method on both sides, and pressure-bonding a second protective film between the rubber rollers in the same manner.

Example 2: r100(Tg124 ℃ C.)/low TgPC (Tg125 ℃ C.)/2 mmt

A molding resin sheet was produced in the same manner as in example 1, except that the discharge speed when the polycarbonate resin was extruded by a uniaxial extruder was 83.0kg/h, and the thickness of the laminate of the high-hardness resin layer and the polycarbonate resin layer (base material layer) was 2mm (the thickness of the high-hardness resin layer was 60 μm in the vicinity of the center).

Example 3: r100(Tg124 ℃ C.)/low TgPC (Tg125 ℃ C.)/0.5 mmt

A molding resin sheet was produced in the same manner as in example 1, except that the discharge speeds when the high-hardness resin (B2) and the polycarbonate resin were extruded by a single-shaft extruder were set to 4.8kg/h and 35.0kg/h, respectively, and the thickness of the laminate of the high-hardness resin layer and the polycarbonate resin layer (substrate layer) was set to 0.5mm (the thickness of the high-hardness resin layer was 60 μm in the vicinity of the center).

Example 4: r100(Tg124 ℃ C.)/low TgPC (Tg125 ℃ C.)/3.5 mmt

A molding resin sheet was produced in the same manner as in example 1, except that the discharge speeds when the high-hardness resin (B2) and the polycarbonate resin were extruded by a single-shaft extruder were 1.3kg/h and 72.0kg/h, respectively, and the thickness of the laminate of the high-hardness resin layer and the polycarbonate resin layer (substrate layer) was 3.5mm (the thickness of the high-hardness resin layer was 60 μm in the vicinity of the center).

Example 5: r310(Tg141 ℃ C.)/low TgPC (Tg125 ℃ C.)/2 mmt

A laminate composed of a base material layer and a high-hardness resin layer was formed using the same multilayer extrusion apparatus as in example 1. Specifically, a high-hardness resin (B2) (a copolymer comprising 6 mass% of methyl methacrylate structural units, 71 mass% of styrene structural units and 23 mass% of maleic anhydride structural units; RESISFY R310 (manufactured by DENKA Co., Ltd.) was continuously introduced into a single-screw extruder having an axial diameter of 35mm, and extruded at a cylinder temperature of 240 ℃ and a discharge rate of 2.6 kg/h. Then, a polycarbonate resin (Ipipzeta T-1380; manufactured by Mitsubishi gas chemical) was continuously introduced into a single-screw extruder having an axial diameter of 65mm, and extruded at a cylinder temperature of 240 ℃ and a discharge rate of 83.0 kg/h.

Then, a laminate of a high-hardness resin layer and a polycarbonate resin layer (base material layer) was obtained by T-die extrusion in the same manner as in example 1. The thickness of the laminate was 2mm, and the thickness of the high-hardness resin layer was 60 μm in the vicinity of the center.

The hard coating antiglare layer was formed in the same manner as in example 1.

Both sides of the resin sheet were covered with MX-217Y (melting point: 106 ℃ C., 124 ℃ C.) made by MATAI in Japan, and pressure-bonded between 2 rubber rollers at room temperature (load: 5 kg/cm)²) And attaching the first protective film. Thereafter, a resin sheet for molding was prepared by laminating a second protective film on both sides of a # 40-R200A (melting point: 148 ℃ C.) manufactured by Toray film processing Co., Ltd, by pressure bonding between rubber rolls in the same manner.

Example 6: r310(Tg141 ℃ C.)/S-1000 (Tg147 ℃ C.)/2 mmt

A laminate composed of a base material layer and a high-hardness resin layer was formed using the same multilayer extrusion apparatus as in example 1. Specifically, a high-hardness resin (B2) (a copolymer comprising 6 mass% of methyl methacrylate structural units, 71 mass% of styrene structural units and 23 mass% of maleic anhydride structural units; RESISFY R310 (manufactured by DENKA Co., Ltd.) was continuously introduced into a single-screw extruder having an axial diameter of 35mm, and extruded at a cylinder temperature of 240 ℃ and a discharge rate of 2.6 kg/h. Polycarbonate resin (Ipiplon S-1000; manufactured by Mitsubishi engineering plastics Co., Ltd.) was continuously introduced into a single-screw extruder having an axial diameter of 65mm, and the mixture was extruded at a cylinder temperature of 280 ℃ and a discharge rate of 83.0 kg/h.

The extruded high hardness resin and polycarbonate resin were introduced into a feedblock having 2 kinds of 2-layer distribution pins, and the high hardness resin and polycarbonate resin were laminated at a temperature of 280 ℃. Then, the sheet was introduced into a T die having a temperature of 280 ℃ and extruded into a sheet form, and the sheet was cooled while transferring the mirror surface by 3 mirror-finishing rolls having a temperature of 120 ℃ to 130 ℃ to 190 ℃ from the upstream side, to obtain a laminate of a high-hardness resin layer and a polycarbonate resin layer (base material layer). The thickness of the laminate was 2mm, and the thickness of the high-hardness resin layer was 60 μm in the vicinity of the center.

The hard coating antiglare layer was formed in the same manner as in example 1.

The first protective film and the second protective film were bonded in the same manner as in example 5.

Example 7: PM-120N (Tg120 ℃ C.)/low TgPC (Tg125 ℃ C.)/1.5 mmt

A laminate composed of a base material layer and a high-hardness resin layer was formed using the same multilayer extrusion apparatus as in example 1. Specifically, a high-hardness resin (B4) (a copolymer comprising 7% by mass of a styrene structural unit, 86% by mass of a methyl methacrylate structural unit and 7% by mass of an N-phenylmaleimide structural unit; DELPET PM120N (manufactured by Asahi Kasei-Kasei Co., Ltd.) was continuously introduced into a single-screw extruder having an axial diameter of 35mm, and extruded at a cylinder temperature of 230 ℃ and an extrusion rate of 2.6 kg/h. Then, a polycarbonate resin (Ipipzeta T-1380; manufactured by Mitsubishi gas chemical) was continuously introduced into a single-screw extruder having an axial diameter of 65mm, and extruded at a cylinder temperature of 240 ℃ and a discharge rate of 62.0 kg/h.

Then, a laminate of a high-hardness resin layer and a polycarbonate resin layer (base material layer) was obtained by T-die extrusion in the same manner as in example 1. The thickness of the laminate was 1.5mm, and the thickness of the high-hardness resin layer was 60 μm in the vicinity of the center.

The hard coating antiglare layer was formed in the same manner as in example 1.

The resin sheet was covered on both sides with E made by Nitto electricianMASK 100 (melting point: 109 ℃ C.), and pressure bonding was performed between 2 rubber rolls at room temperature (load 5 kg/cm)²) And adhering the first protective film. Thereafter, a resin sheet for molding was prepared by laminating a second protective film on both sides of a # 40-R200A (melting point: 148 ℃ C.) manufactured by Toray film processing Co., Ltd, by pressure bonding between rubber rolls in the same manner.

Example 8: r200(Tg126 ℃ C.)/low TgPC (Tg125 ℃ C.)/2 mmt

A laminate composed of a base material layer and a high-hardness resin layer was formed using the same multilayer extrusion apparatus as in example 1. Specifically, a high-hardness resin (B2) (a copolymer comprising 26 mass% of a methyl methacrylate structural unit, 55 mass% of a styrene structural unit and 19 mass% of a maleic anhydride structural unit; RESISFY R200 (manufactured by DENKA Co., Ltd.)) was continuously introduced into a single-screw extruder having an axial diameter of 35mm, and the mixture was extruded at a cylinder temperature of 230 ℃ and an extrusion rate of 2.6 kg/h. Then, a polycarbonate resin (Ipipzeta T-1380; manufactured by Mitsubishi gas chemical) was continuously introduced into a single-screw extruder having an axial diameter of 65mm, and extruded at a cylinder temperature of 240 ℃ and a discharge rate of 83.0 kg/h.

Then, a laminate of a high-hardness resin layer and a polycarbonate resin layer (base material layer) was obtained by T-die extrusion in the same manner as in example 1. The thickness of the laminate was 2mm, and the thickness of the high-hardness resin layer was 60 μm in the vicinity of the center.

The hard-coated antiglare layer was applied to the laminate by a bar coater in the same manner as in example 1, and the uneven surface of a 2mm thick ground glass plate having a haze of 30% was covered with the laminate, and a 5-second metal halide lamp (20 mW/cm) was irradiated from the glass plate²) After the hard coat layer was cured and the hard coat antiglare layer was adhered, the ground glass plate was peeled off to prepare a resin sheet. The film thickness of the hard coating antiglare layer was 6 μm. The haze of the resin sheet was 29%.

The first protective film and the second protective film were bonded in the same manner as in example 7.

Example 9: C-PC (KH3410UR) (Tg118 deg.C)/Low TgPC (Tg125 deg.C)/2 mmt

A laminate composed of a base material layer and a high-hardness resin layer was formed using the same multilayer extrusion apparatus as in example 1. Specifically, a high-hardness resin (B3) (polycarbonate resin; Ifpilon KH3410UR (manufactured by Mitsubishi engineering plastics Co., Ltd.)) was continuously introduced, and the mixture was extruded at a cylinder temperature of 270 ℃ and a discharge rate of 2.6 kg/hr. Then, a polycarbonate resin (Ipipzeta T-1380; manufactured by Mitsubishi gas chemical) was continuously introduced into a single-screw extruder having an axial diameter of 65mm, and extruded at a cylinder temperature of 240 ℃ and a discharge rate of 83.0 kg/h.

Then, a laminate of a high-hardness resin layer and a polycarbonate resin layer (base material layer) was obtained by T-die extrusion in the same manner as in example 1. The thickness of the laminate was 2mm, and the thickness of the high-hardness resin layer was 60 μm in the vicinity of the center.

The hard coating antiglare layer was formed in the same manner as in example 8.

The first protective film and the second protective film were bonded in the same manner as in example 7.

Example 10: alloy of R100 and PM120N (Tg123 deg.C)/Low TgPC (Tg125 deg.C)/1.2 mmt

A copolymer (RESISFY R100(DENKA corporation)) of 21 mass% of a methyl methacrylate structural unit, 64 mass% of a styrene structural unit and 15 mass% of a maleic anhydride structural unit was 75 mass%, and a copolymer (DELPET PM 120N; manufactured by Asahi Kasei Co., Ltd.) of 7 mass% of a styrene structural unit, 86 mass% of a methyl methacrylate structural unit and 7 mass% of an N-phenyl maleimide structural unit was 25 mass% introduced into an extruder (TEM-26 SS, L/D. apprxeq.40; Toshiba machine Co., Ltd.) having a screw diameter of 26mm, and the mixture was melt-kneaded at 240 ℃ to obtain a high-hardness resin (B4).

A laminate composed of a base material layer and a high-hardness resin layer was formed using the same multilayer extrusion apparatus as in example 1. Specifically, the high-hardness resin (B4) was continuously introduced into a single-screw extruder having an axial diameter of 35mm, and extruded at a cylinder temperature of 230 ℃ and a discharge rate of 2.6 kg/h. Then, a polycarbonate resin (Ipipzeta T-1380; manufactured by Mitsubishi gas chemical) was continuously introduced into a single-screw extruder having an axial diameter of 65mm, and extruded at a cylinder temperature of 240 ℃ and a discharge rate of 50.0 kg/h.

Then, a laminate of a high-hardness resin layer and a polycarbonate resin layer (base material layer) was obtained by T-die extrusion in the same manner as in example 1. The thickness of the laminate was 1.2mm, and the thickness of the high-hardness resin layer was 60 μm in the vicinity of the center.

The hard coating antiglare layer was formed in the same manner as in example 8.

The first protective film and the second protective film were bonded in the same manner as in example 7.

Example 11: r310(Tg141 ℃ C.)/low TgPC (Tg125 ℃ C.)/0.5 mmt

A laminate composed of a base material layer and a high-hardness resin layer was formed using the same multilayer extrusion apparatus as in example 1. Specifically, a high-hardness resin (B2) (a copolymer comprising 6 mass% of methyl methacrylate structural units, 71 mass% of styrene structural units and 23 mass% of maleic anhydride structural units; RESISFY R310 (manufactured by DENKA) was continuously introduced into a single-screw extruder having an axial diameter of 35mm, and extruded at a cylinder temperature of 230 ℃ and an extrusion rate of 8 kg/h. Then, a polycarbonate resin (Ipipzeta T-1380; manufactured by Mitsubishi gas chemical) was continuously introduced into a single-screw extruder having an axial diameter of 65mm, and extruded at a cylinder temperature of 240 ℃ and a discharge rate of 35.0 kg/h.

Then, a laminate of a high-hardness resin layer and a polycarbonate resin layer (base material layer) was obtained by T-die extrusion in the same manner as in example 1. The thickness of the laminate (Y2) was 0.5mm, and the thickness of the high-hardness resin layer was 100 μm in the vicinity of the center.

The hard-coated antiglare layer was applied to the laminate by a bar coater in the same manner as in example 1, and the uneven surface of a 2mm thick ground glass plate having a haze of 4% was covered with the laminate, and a 5-second metal halide lamp (20 mW/cm) was irradiated from the glass plate²) After the hard coat layer was cured and the hard coat antiglare layer was adhered, the ground glass plate was peeled off to prepare a resin sheet. The film thickness of the hard coating antiglare layer was 6 μm. The haze of the resin sheet was 2%.

The first protective film and the second protective film were bonded in the same manner as in example 1.

Example 12: FPC0220(Tg184 ℃)/E2000(147 ℃)/1.2mmt

A laminate composed of a base material layer and a high-hardness resin layer was formed using the same multilayer extrusion apparatus as in example 1. Specifically, a high-hardness resin (B5) (polycarbonate resin represented by general formula (8); Iupizeta FPC0220 (manufactured by Mitsubishi gas chemical Co., Ltd.)) was continuously introduced into a single-screw extruder having an axial diameter of 35mm, and the mixture was extruded at a cylinder temperature of 300 ℃ and an extrusion rate of 2.6 kg/h. Then, a polycarbonate resin (Ipiplon E2000; manufactured by Mitsubishi gas chemical Co., Ltd.) was continuously introduced into a single-screw extruder having an axial diameter of 65mm, and the mixture was extruded at a cylinder temperature of 280 ℃ and a discharge rate of 50.0 kg/h.

The extruded high hardness resin and polycarbonate resin were introduced into a feedblock having 2 kinds of 2-layer distribution pins, and the high hardness resin and polycarbonate resin were laminated at a temperature of 280 ℃. Then, the sheet was extruded into a sheet by a T die at a temperature of 280 ℃ and cooled by 3 mirror finishing rolls set at temperatures of 120 ℃, 130 ℃ and 190 ℃ from the upstream side while transferring the mirror surface, thereby obtaining a laminate of a high-hardness resin layer and a polycarbonate resin layer (base material layer). The thickness of the laminate was 1.2mm, and the thickness of the high-hardness resin layer was 60 μm in the vicinity of the center.

The hard coating antiglare layer was formed in the same manner as in example 11.

The first protective film and the second protective film were bonded in the same manner as in example 1.

Example 13: MS-H (Tg115 ℃ C.)/Low TgPC (Tg125 ℃ C.)/1.2 mmt

A laminate composed of a base material layer and a high-hardness resin layer was formed using the same multilayer extrusion apparatus as in example 1. A high-hardness resin (B1) (a resin in which both R1 and R2 in the general formula (1) are methyl groups, R3 in the general formula (2) is a hydrogen atom, and R4 is a cyclohexyl group; and which comprises 75 mol% of a (meth) acrylate structural unit and 25 mol% of an aliphatic vinyl structural unit and has a weight average molecular weight of 120,000) was continuously introduced into a single-screw extruder having an axial diameter of 35mm, and extruded at a cylinder temperature of 240 ℃ and an extrusion rate of 2.6 kg/h. Then, a polycarbonate resin (Ipipzeta T-1380; manufactured by Mitsubishi gas chemical) was continuously introduced into a single-screw extruder having an axial diameter of 65mm, and extruded at a cylinder temperature of 240 ℃ and a discharge rate of 50.0 kg/h.

Then, a laminate of a high-hardness resin layer and a polycarbonate resin layer (base material layer) was obtained by T-die extrusion in the same manner as in example 1. The thickness of the laminate was 1.2mm, and the thickness of the high-hardness resin layer was 60 μm in the vicinity of the center.

The hard coating antiglare layer was formed in the same manner as in example 11.

The first protective film and the second protective film were bonded in the same manner as in example 1.

Comparative example 1: MS-H (Tg115 ℃ C.)/low TgPC (125 ℃ C.)/0.5 mmt

A laminate was produced in the same manner as in example 13 except that the conditions for extruding the high-hardness resin (B1) by the single-shaft extruder were set to a cylinder temperature of 230 ℃ and a discharge rate of 8.0kg/h, the discharge rate for extruding the polycarbonate resin by the single-shaft extruder was set to 35.0kg/h, and the thickness of the laminate of the high-hardness resin layer and the polycarbonate resin layer (base material layer) was set to 0.5mm (the thickness of the high-hardness resin layer was 60 μm in the vicinity of the center).

The hard coating antiglare layer was formed in the same manner as in example 1.

The first protective film and the second protective film are not bonded.

Comparative example 2: R100-PMMA alloy (Tg115 ℃ C.)/low TgPC (Tg125 ℃ C.)/1.2 mmt

75% by mass of a copolymer (RESISFY R100; manufactured by DENKA K.K.) composed of 21% by mass of methyl methacrylate structural units, 64% by mass of styrene structural units and 15% by mass of maleic anhydride structural units and 25% by mass of an acrylic resin (PARAPET HR-1000L (PMMA; manufactured by Coly corporation) were introduced into an extruder (TEM-26 SS, L/D. apprxeq.40; manufactured by Toshiba machine) having a screw diameter of 26mm, and melt-kneaded at 240 ℃ to obtain a high-hardness resin (B2).

A laminate composed of a base material layer and a high-hardness resin layer was formed using the same multilayer extrusion apparatus as in example 1. Specifically, the high-hardness resin was continuously introduced into a single-screw extruder having an axial diameter of 35mm, and extruded at a cylinder temperature of 230 ℃ and an extrusion rate of 2.6 kg/h. Then, a polycarbonate resin (Ipipzeta T-1380; manufactured by Mitsubishi gas chemical) was continuously introduced into a single-screw extruder having an axial diameter of 65mm, and extruded at a cylinder temperature of 240 ℃ and a discharge rate of 50.0 kg/h.

Then, a laminate of a high-hardness resin layer and a polycarbonate resin layer (base material layer) was obtained by T-die extrusion in the same manner as in example 1. The thickness of the laminate was 1.2mm, and the thickness of the high-hardness resin layer was 60 μm in the vicinity of the center.

The hard coating antiglare layer was formed in the same manner as in example 1.

The resin sheet was covered on both sides with E MASK 100 (melting point: 109 ℃) manufactured by Nitto electric engineering, and pressure-bonded between 2 rubber rollers (load 5kg/cm2) at room temperature, and a first protective film was attached. The second protective film is not attached.

Comparative example 3

A laminate of a high-hardness resin layer and a polycarbonate resin layer (base material layer) was obtained in the same manner as in example 1.

The hard coating antiglare layer was formed in the same manner as in example 1.

The resin sheet was covered on both sides with a No. 40-R200A (melting point: 148 ℃ C.) made by Toray film processing Co., Ltd., and pressure-bonded between 2 rubber rollers at room temperature (load 5 kg/cm)²) And attaching the first protective film. The second protective film is not attached.

Comparative example 4: MS-H (Tg115 ℃ C.)/S1000 (Tg147 ℃ C.)/1.2 mmt

A laminate composed of a base material layer and a high-hardness resin layer was formed using the same multilayer extrusion apparatus as in example 1. Specifically, a high-hardness resin (B1) (a resin in which both R1 and R2 in the general formula (1) are methyl groups, R3 in the general formula (2) is a hydrogen atom, and R4 is a cyclohexyl group; and which is composed of 75 mol% of a (meth) acrylate structural unit and 25 mol% of an aliphatic vinyl structural unit and has a weight-average molecular weight of 120,000) was continuously introduced into a single-screw extruder having an axial diameter of 35mm, and extruded at a cylinder temperature of 240 ℃ and an extrusion rate of 2.6 kg/h. Polycarbonate resin (Ipiplon S-1000; manufactured by Mitsubishi engineering plastics Co., Ltd.) was continuously introduced into a single-screw extruder having an axial diameter of 65mm, and the mixture was extruded at a cylinder temperature of 280 ℃ and a discharge rate of 50.0 kg/hr.

The extruded high hardness resin and polycarbonate resin were introduced into a feedblock having 2 kinds of 2-layer distribution pins, and the high hardness resin and polycarbonate resin were laminated at a temperature of 270 ℃. The sheet was extruded into a sheet by a T die at a temperature of 270 ℃ and cooled while transferring the mirror surface by 3 mirror-finishing rolls set at temperatures of 120 ℃, 130 ℃ and 190 ℃ from the upstream side, to obtain a laminate of a high-hardness resin layer and a polycarbonate resin layer (base material layer). The thickness of the laminate was 1.2mm, and the thickness of the high-hardness resin layer was 60 μm in the vicinity of the center.

The hard coating antiglare layer was formed in the same manner as in example 1.

The first protective film and the second protective film were bonded in the same manner as in example 1.

Comparative example 5: MS-H (Tg115 ℃ C.)/S1000 (Tg147 ℃ C.)/2 mmt

A molding resin sheet was produced in the same manner as in comparative example 4, except that the discharge speed when the polycarbonate resin was extruded by a uniaxial extruder was 83.0kg/h, and the thickness of the laminate of the high-hardness resin layer and the polycarbonate resin layer (base material layer) was 2mm (the thickness of the high-hardness resin layer was 60 μm in the vicinity of the center).

Comparative example 6: MS-H (Tg115 ℃ C.)/S1000 (Tg147 ℃ C.)/3.5 mmt

A molding resin sheet was produced in the same manner as in comparative example 4, except that the discharge rates of the high-hardness resin (B1) and the polycarbonate resin extruded by the uniaxial extruder were 1.3kg/h and 72.0kg/h, respectively, and the thickness of the laminate of the high-hardness resin layer and the polycarbonate resin layer (base material layer) was 3.5mm (the thickness of the high-hardness resin layer was 60 μm in the vicinity of the center).

Comparative example 7: MS-H (Tg115 ℃ C.)/S1000 (Tg147 ℃ C.)/0.5 mmt

A molding resin sheet was produced in the same manner as in comparative example 4, except that the discharge speeds when the high-hardness resin (B1) and the polycarbonate resin were extruded by a single-shaft extruder were set to 4.8kg/h and 35.0kg/h, respectively, and the thickness of the laminate of the high-hardness resin layer and the polycarbonate resin layer (substrate layer) was set to 0.5mm (the thickness of the high-hardness resin layer was 60 μm in the vicinity of the center). Comparative example 8: PMMA (Tg105 ℃ C.)/low TgPC (Tg125 ℃ C.)/0.8 mmt

A multilayer extrusion apparatus having a single-screw extruder with an axial diameter of 32mm, a single-screw extruder with an axial diameter of 65mm, a feed block connected to each extruder, and a T die connected to the feed block was used to mold a laminate composed of a base material layer and a high-hardness resin layer. Specifically, a high-hardness resin (acrylic resin; PARAPET HR-1000L (PMMA); manufactured by Coly corporation) was continuously introduced into a single-screw extruder having an axial diameter of 32mm, and the mixture was extruded at a cylinder temperature of 250 ℃ and a discharge rate of 2.6 kg/h. Then, a polycarbonate resin (Ipipzeta T-1380; manufactured by Mitsubishi gas chemical) was continuously introduced into a single-screw extruder having an axial diameter of 65mm, and extruded at a cylinder temperature of 240 ℃ and a discharge rate of 32.0 kg/h.

The extruded high hardness resin and polycarbonate resin were introduced into a feedblock having 2 kinds of 2-layer distribution pins, and the high hardness resin and polycarbonate resin were laminated at a temperature of 240 ℃. Then, the sheet was introduced into a T die having a temperature of 240 ℃ and extruded into a sheet form, and the sheet was cooled while transferring the mirror surface by 3 mirror-finishing rolls having a temperature of 110 ℃ to 140 ℃ to 185 ℃ from the upstream side, to obtain a laminate of a high-hardness resin layer and a polycarbonate resin layer (base material layer). The thickness of the laminate was 0.8mm, and the thickness of the high-hardness resin layer was 60 μm in the vicinity of the center.

The hard coating antiglare layer was formed in the same manner as in example 1.

The first protective film and the second protective film were bonded in the same manner as in example 1.

Comparative example 9: FPC0220(Tg184 ℃)/T1380(125 ℃)/1.2mmt

A laminate composed of a base material layer and a high-hardness resin layer was formed using the same multilayer extrusion apparatus as in example 1. Specifically, a high-hardness resin (B5) (polycarbonate resin represented by general formula (8); Iupizeta FPC0220 (manufactured by Mitsubishi gas chemical Co., Ltd.)) was continuously introduced into a single-screw extruder having an axial diameter of 35mm, and the mixture was extruded at a cylinder temperature of 300 ℃ and an extrusion rate of 2.6 kg/h. Then, a polycarbonate resin (Ipipzeta T1380; manufactured by Mitsubishi gas chemical) was continuously introduced into a single-screw extruder having an axial diameter of 65mm, and extruded at a cylinder temperature of 240 ℃ and a discharge rate of 50.0 kg/h.

The extruded high hardness resin and polycarbonate resin were introduced into a feedblock having 2 kinds of 2-layer distribution pins, and the high hardness resin and polycarbonate resin were laminated at a temperature of 280 ℃. Then, the sheet was extruded into a sheet by a T die at a temperature of 280 ℃ and cooled by 3 mirror finishing rolls set at temperatures of 120 ℃, 130 ℃ and 190 ℃ from the upstream side while transferring the mirror surface, thereby obtaining a laminate of a high-hardness resin layer and a polycarbonate resin layer (base material layer). The thickness of the laminate was 1.2mm, and the thickness of the high-hardness resin layer was 60 μm in the vicinity of the center.

The hard coating antiglare layer was formed in the same manner as in example 1.

The first protective film and the second protective film were bonded in the same manner as in example 1.

Comparative example 10: s-1000 (Tg147 ℃ C.) alone/2 mmt

As an alternative to the high-hardness resin, a laminate is formed using the same polycarbonate resin as the resin contained in the base layer. As the extrusion apparatus, the same multilayer extrusion apparatus as in example 1 was used. Specifically, a polycarbonate resin (Ipiplon S-1000 (manufactured by Mitsubishi engineering plastics Co., Ltd.; pencil hardness: 3B) was continuously introduced into a single-shaft extruder having an axial diameter of 35mm, and the mixture was extruded at a cylinder temperature of 280 ℃ and a discharge rate of 2.6 kg/h. Polycarbonate resin (Ipiplon S-1000; manufactured by Mitsubishi engineering plastics Co., Ltd.) was continuously introduced into a single-screw extruder having an axial diameter of 65mm, and the mixture was extruded at a cylinder temperature of 280 ℃ and a discharge rate of 83.0 kg/h.

The extruded polycarbonate resin was introduced into a feedblock having 2 kinds of 2-layer distribution pins and laminated at a temperature of 280 ℃. Then, the sheet was introduced into a T die having a temperature of 280 ℃ and extruded into a sheet form, and the sheet was cooled while transferring the mirror surface by 3 mirror-finishing rolls having a temperature of 120 ℃ to 130 ℃ to 190 ℃ from the upstream side to obtain a polycarbonate resin laminate. The thickness of the laminate obtained was 2 mm.

The hard coating antiglare layer was formed in the same manner as in example 1.

The first protective film and the second protective film were bonded in the same manner as in example 1.

The resin sheets produced in examples and comparative examples were evaluated for hardness, presence or absence of cracks after molding, flow marks, mold scratch transfer, and presence or absence of fusion of the protective film. The results are shown in table 1 below.

[ Table 1]

The resin sheet of the present invention was found to have excellent hardness, no flow mark, and no appearance abnormality such as cracking after thermoforming.

Several embodiments of the present invention have been described, but these embodiments are merely provided as examples and are not intended to limit the scope of the present invention. These novel embodiments can be implemented in other various forms, and various omissions, substitutions, and changes can be made without departing from the spirit of the present invention. These embodiments and modifications thereof are included in the scope and spirit of the present invention, and are also included in the inventions described in the claims and the scope equivalent thereto.