JP6530583B2 - Resin laminate and scratch resistant resin laminate using the same - Google Patents

Description

  The present invention relates to a resin laminate and an abrasion resistant resin laminate using the same.

  As a protective plate, a resin plate or a scratch-resistant resin plate provided with a cured film on the surface of the resin plate is used as a display, a touch panel, and a display window of a portable information terminal.

  The display, the touch panel, the display window of the portable information terminal, and the like may be touched by the user. In addition, in devices such as displays, touch panels, and portable information terminals, the temperature inside the device may increase significantly due to the heat generation of the light source provided in the device. Therefore, the resin plate and the scratch-resistant resin plate used as the protective plate are required to be excellent in surface hardness and excellent in warpage resistance deformation under high temperature and high humidity environment. In addition, the scratch-resistant resin plate is required to have good adhesion between the resin laminate and the cured film. Patent Document 1 discloses a resin laminate in which a methyl methacrylate-styrene copolymer resin layer is laminated on one side of a polycarbonate resin layer and which is excellent in warpage deformation resistance under the environment of temperature 40 ° C. and humidity 90%. It is done.

Japanese Patent Application Laid-Open No. 2010-167659

  The temperature inside the above-mentioned device may rise significantly over 40 ° C, and the resin plate used as a protective plate is more severe under high temperature and high humidity environment such as 85 ° C temperature and 85% humidity environment. It is desired to be excellent in warpage resistance deformation in

  An object of the present invention is to provide a resin laminate excellent in surface hardness and excellent in warpage deformation resistance under a severe high temperature and high humidity environment of 85 ° C. and 85% humidity environment. Then, a cured film is provided on at least one surface of this resin laminate, and an object of the present invention is to provide a scratch-resistant resin plate which is excellent in the adhesion between the resin laminate and the cured film.

［式中：Ｒ^１、Ｒ^２は、それぞれ同一でも、異なっていてもよく、水素、ハロゲン、水酸基、アルコキシ基、ニトロ基、直鎖状または分岐状の炭素数１〜１２のアルキル基を表す。ｎは１〜３の整数を示す。ｎが２または３であるとき、Ｒ^２は、それぞれ同一でも、異なっていてもよい。］

［式中：Ｒ^３、Ｒ^４は、それぞれ同一でも、異なっていてもよく、水素、直鎖状または分岐状の炭素数１〜１２のアルキル基を表す。］
下記（Ａ）および（Ｂ）のうち少なくとも一方の条件を満たすことを特徴とする樹脂積層板。
（Ａ）熱可塑性樹脂層が、さらに、メタクリル酸エステル単量体単位を主成分として含むメタクリル樹脂を含有する。
（Ｂ）樹脂積層板の総厚に対するポリカーボネート樹脂層の厚みの割合が７０％以下である。
＜２＞ 熱可塑性樹脂層における共重合体とメタクリル樹脂の含有量が、共重合体とメタクリル樹脂との合計１００重量部を基準として、共重合体は２０〜７０重量部であり、メタクリル樹脂は８０〜３０重量部である前記＜１＞に記載の樹脂積層板。
＜３＞ 前記共重合体に含まれるメタクリル酸エステル単量体単位、ビニル芳香族単量体単位、および環状酸無水物単量体単位の重量割合が、ビニル芳香族単量体単位、メタクリル酸エステル単量体単位、および環状酸無水物単量体単位の合計１００重量％を基準として、ビニル芳香族単量体単位が５０〜８０重量％、メタクリル酸エステル単量体単位が５〜３５重量％、環状酸無水物単量体単位が５〜３０重量％である前記＜１＞または＜２＞に記載の樹脂積層板。
＜４＞ 前記ビニル芳香族単量体が、スチレン単量体である前記＜１＞〜＜３＞のいずれかに記載の樹脂積層板。
＜５＞ 前記環状酸無水物単量体が、無水マレイン酸である前記＜１＞〜＜４＞のいずれかに記載の樹脂積層板。
＜６＞ ポリカーボネート樹脂層と、熱可塑性樹脂層が、溶融共押出成形により積層されてなるものである前記＜１＞〜＜５＞のいずれかに記載の樹脂積層板。
＜７＞ 前記＜１＞〜＜６＞のいずれかに記載の樹脂積層板の少なくとも一方の面に硬化被膜を備えてなる耐擦傷性樹脂積層板。
＜８＞ 前記＜７＞に記載の耐擦傷性樹脂積層板からなるディスプレイ用保護板。
＜９＞ 前記＜７＞に記載の耐擦傷性樹脂積層板からなるタッチパネル用保護板。
＜１０＞ 前記＜７＞に記載の耐擦傷性樹脂積層板からなる携帯型情報端末の表示窓用保護板。
＜１１＞ ポリカーボネート樹脂層の少なくとも一方の面に、熱可塑性樹脂層が積層されてなり、前記熱可塑性樹脂層が、メタクリル酸エステル単量体単位、下記一般式（１）で表されるビニル芳香族単量体単位、および下記一般式（２）で表される環状酸無水物単量体単位を含む共重合体を含有する樹脂積層板の、高温高湿環境下での耐反り変形性を向上させる方法であって、
前記熱可塑性樹脂層に、メタクリル酸エステル単量体単位を主成分として含むメタクリル樹脂とを含有させることを特徴とする方法。

［式中：Ｒ^１、Ｒ^２は、それぞれ同一でも、異なっていてもよく、水素、ハロゲン、水酸基、アルコキシ基、ニトロ基、直鎖状または分岐状の炭素数１〜１２のアルキル基を表す。ｎは１〜３の整数を示す。ｎが２または３であるとき、Ｒ^２は、それぞれ同一でも、異なっていてもよい。］

［式中：Ｒ^３、Ｒ^４は、それぞれ同一でも、異なっていてもよく、水素、直鎖状または分岐状の炭素数１〜１２のアルキル基を表す。］
＜１２＞ ポリカーボネート樹脂層の少なくとも一方の面に、熱可塑性樹脂層が積層されてなり、前記熱可塑性樹脂層が、メタクリル酸エステル単量体単位、下記一般式（１）で表されるビニル芳香族単量体単位、および下記一般式（２）で表される環状酸無水物単量体単位を含む共重合体を含有する樹脂積層板の、高温高湿環境下での耐反り変形性を向上させる方法であって、
前記樹脂積層板の総厚に対する前記ポリカーボネート樹脂層の厚みの割合を７０％以下とすることを特徴とする方法。

［式中：Ｒ^１、Ｒ^２は、それぞれ同一でも、異なっていてもよく、水素、ハロゲン、水酸基、アルコキシ基、ニトロ基、直鎖状または分岐状の炭素数１〜１２のアルキル基を表す。ｎは１〜３の整数を示す。ｎが２または３であるとき、Ｒ^２は、それぞれ同一でも、異なっていてもよい。］

［式中：Ｒ^３、Ｒ^４は、それぞれ同一でも、異なっていてもよく、水素、直鎖状または分岐状の炭素数１〜１２のアルキル基を表す。］ MEANS TO SOLVE THE PROBLEM As a result of earnestly examining that the present inventors might solve the said subject, they found the solution means which consists of the following structures, and came to complete this invention.
The thermoplastic resin layer is laminated | stacked on the at least one surface of a <1> polycarbonate resin layer, and the said thermoplastic resin layer is a methacrylic acid ester monomer unit, The vinyl aromatic represented by following General formula (1) A resin laminate containing a copolymer including a group monomer unit and a cyclic acid anhydride monomer unit represented by the following general formula (2),

[Wherein, R ¹ and R ² may be the same or different, and represent hydrogen, halogen, a hydroxyl group, an alkoxy group, a nitro group, a linear or branched alkyl group having 1 to 12 carbon atoms] . n is an integer of 1 to 3; When n is 2 or 3, each R ² may be the same or different. ]

[In the Formula: R ³ and R ^{4, which} may be the same or different, each represents hydrogen, a linear or branched alkyl group having 1 to 12 carbon atoms, and ]
A resin laminate characterized by satisfying at least one of the following (A) and (B):
(A) The thermoplastic resin layer further contains a methacrylic resin containing a methacrylic acid ester monomer unit as a main component.
(B) The ratio of the thickness of the polycarbonate resin layer to the total thickness of the resin laminate is 70% or less.
The content of the copolymer and the methacrylic resin in the <2> thermoplastic resin layer is 20 to 70 parts by weight of the copolymer based on 100 parts by weight in total of the copolymer and the methacrylic resin, and the methacrylic resin is The resin laminated board as described in said <1> which is 80-30 weight part.
The weight ratio of the methacrylic acid ester monomer unit, the vinyl aromatic monomer unit, and the cyclic acid anhydride monomer unit contained in the <3> copolymer is a vinyl aromatic monomer unit, methacrylic acid 50 to 80% by weight of vinyl aromatic monomer units and 5 to 35% by weight of methacrylic acid ester monomer units based on 100% by weight in total of ester monomer units and cyclic acid anhydride monomer units The resin laminated board as described in said <1> or <2> which is 5-30 weight% of cyclic | annular acid anhydride monomer units.
The resin laminated board in any one of said <1>-<3> whose <4> above-mentioned vinyl aromatic monomer is a styrene monomer.
<5> The resin laminate according to any one of <1> to <4>, wherein the cyclic acid anhydride monomer is maleic anhydride.
The resin laminated board in any one of said <1>-<5> which a <6> polycarbonate resin layer and a thermoplastic resin layer are laminated | stacked by melt co-extrusion molding.
The abrasion resistant resin laminated board formed by equipping the at least one surface of the resin laminated board in any one of <7> said <1>-<6> with a cured film.
<8> A protective plate for a display, comprising the scratch-resistant resin laminate according to <7>.
<9> A protective plate for a touch panel, comprising the scratch-resistant resin laminate according to <7>.
<10> A protective plate for a display window of a portable information terminal comprising the scratch-resistant resin laminate as described in <7>.
<11> A thermoplastic resin layer is laminated on at least one surface of a polycarbonate resin layer, and the thermoplastic resin layer is a methacrylic acid ester monomer unit, a vinyl aroma represented by the following general formula (1) -Warpage deformation resistance of a resin laminate containing a copolymer containing a cyclic acid anhydride monomer unit represented by the following general formula (2) and a group monomer unit, under high temperature and high humidity environment A way to improve
A method characterized in that the thermoplastic resin layer contains a methacrylic resin containing a methacrylic acid ester monomer unit as a main component.

[Wherein, R ¹ and R ² may be the same or different, and represent hydrogen, halogen, a hydroxyl group, an alkoxy group, a nitro group, a linear or branched alkyl group having 1 to 12 carbon atoms] . n is an integer of 1 to 3; When n is 2 or 3, each R ² may be the same or different. ]

[In the Formula: R ³ and R ^{4, which} may be the same or different, each represents hydrogen, a linear or branched alkyl group having 1 to 12 carbon atoms, and ]
The thermoplastic resin layer is laminated | stacked on the at least one surface of a <12> polycarbonate resin layer, and the said thermoplastic resin layer is a methacrylic acid ester monomer unit, The vinyl aromatic represented by following General formula (1) -Warpage deformation resistance of a resin laminate containing a copolymer containing a cyclic acid anhydride monomer unit represented by the following general formula (2) and a group monomer unit, under high temperature and high humidity environment A way to improve
A method, wherein the ratio of the thickness of the polycarbonate resin layer to the total thickness of the resin laminate is 70% or less.

[Wherein, R ¹ and R ² may be the same or different, and represent hydrogen, halogen, a hydroxyl group, an alkoxy group, a nitro group, a linear or branched alkyl group having 1 to 12 carbon atoms] . n is an integer of 1 to 3; When n is 2 or 3, each R ² may be the same or different. ]

[In the Formula: R ³ and R ^{4, which} may be the same or different, each represents hydrogen, a linear or branched alkyl group having 1 to 12 carbon atoms, and ]

  According to the present invention, it is possible to provide a resin laminate excellent in surface hardness and excellent in warpage deformation resistance under a severe high temperature and high humidity environment of 85 ° C. and 85% humidity environment. Then, a cured film is provided on at least one surface of the resin laminate, and a scratch-resistant resin plate excellent in the adhesion between the resin laminate and the cured film can be provided.

It is a schematic explanatory drawing which shows the manufacturing method of the resin laminated board which concerns on one Embodiment of this invention.

In the resin laminate of the present invention, a thermoplastic resin layer is laminated on at least one surface of a polycarbonate resin layer, and the thermoplastic resin layer is a methacrylic acid ester monomer unit, a vinyl aromatic monomer unit, And a resin laminate containing a copolymer containing a cyclic acid anhydride monomer unit, which satisfies at least one of the following (A) and (B).
(A) The thermoplastic resin layer further contains a methacrylic resin containing a methacrylic acid ester monomer unit as a main component.
(B) The ratio of the thickness of the polycarbonate resin layer to the total thickness of the resin laminate is 70% or less.

  By satisfying at least one of the above (A) and (B), the resin laminate is excellent in surface hardness and excellent in warpage and deformation resistance under high temperature and high humidity environment, for example, temperature 85 Excellent warpage resistance even under severe high temperature and high humidity environment with 85% humidity.

  As (A), a thermoplastic resin layer is made to contain a copolymer and a methacrylic resin which has a methacrylic acid ester monomer unit as a main component.

  In the case where the resin laminate has a three-layer structure in which the thermoplastic resin layer is laminated on both sides of the polycarbonate resin layer, at least one of the heat from the viewpoint of warpage and deformation resistance under a high temperature and high humidity environment. Although a predetermined methacrylic resin may be contained in the plastic resin layer, it is preferable to contain the predetermined methacrylic resin in both thermoplastic resin layers.

  As (B), the ratio of the thickness of the polycarbonate resin layer to the total thickness of the resin laminate is 70% or less, preferably 60% or less, more preferably 55% or less. The ratio of the thickness of the polycarbonate resin layer satisfies the above, and is preferably 20% or more, more preferably 30% or more, and more preferably 40% or more with respect to the total thickness of the resin laminate. Is more preferred.

  The resin laminate has a three-layer structure in which a thermoplastic resin layer is laminated on both sides of a polycarbonate resin layer, and the thicknesses of the respective thermoplastic resin layers are different from each other under a high temperature and high humidity environment. From the viewpoint of warpage deformation resistance, the ratio of the thickness of the polycarbonate resin layer is within the above predetermined range with respect to the total thickness of the resin laminate and 50 with respect to the thickness of the larger thickness thermoplastic resin layer. It is preferable to make it% or more.

  The resin laminate may satisfy at least one of the conditions of (A) and (B), and may satisfy only one of the conditions or may satisfy both of the conditions. It is preferable to satisfy at least (A) from the viewpoint of warpage resistance under high temperature and high humidity environment.

  When the resin laminate of the present invention has a three-layer structure in which a thermoplastic resin layer is laminated on both sides of a polycarbonate resin layer, the thickness and composition of each thermoplastic resin layer may be the same as each other. May be different.

  The thickness of the resin laminate is preferably 100 to 3000 μm, more preferably 150 to 2000 μm, and still more preferably 200 to 1500 μm. When the resin laminate satisfies (A), the thickness of the polycarbonate resin layer is preferably 50 to 2970 μm, more preferably 70 to 1950 μm, from the viewpoint of surface hardness and warp deformation resistance under a high temperature and high humidity environment. More preferably, the thickness is 100 to 1430 μm, and the thickness of the thermoplastic resin layer is preferably 20 to 200 μm, more preferably 40 to 150 μm, and still more preferably 50 to 100 μm. When the resin laminate satisfies (B), the thickness of the polycarbonate resin layer is preferably 20 to 2100 μm, more preferably 50 to 1200 μm, from the viewpoint of surface hardness and warp deformation resistance under a high temperature and high humidity environment. The thickness is more preferably 80 to 800 μm, and the thickness of the thermoplastic resin layer is preferably 50 to 900 μm, more preferably 70 to 800 μm, and still more preferably 90 to 700 μm.

(Polycarbonate resin layer)
As polycarbonate resin which forms a polycarbonate resin layer, resin obtained by making dihydric phenol and a carbonylation agent react by the interfacial polycondensation method, the melt transesterification method etc., for example, a carbonate prepolymer is made to solid phase transesterification method For example, a resin obtained by polymerizing with a resin, a resin obtained by polymerizing a cyclic carbonate compound by a ring opening polymerization method, and the like can be mentioned.

  Examples of dihydric phenols include hydroquinone, resorcinol, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis {(4-hydroxy-3,5-dimethyl) phenyl} methane, 1,1- Bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane (generally called bisphenol A), 2,2-bis { (4-hydroxy-3-methyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dibromo) ) Phenyl} propane, 2,2-bis {(3-isopropyl-4-hydroxy) phenyl} propane, 2,2-bis {(4 Hydroxy-3-phenyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-Dimethylbutane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4 -Methylpentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,3 5-trimethylcyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis {(4-hydroxy) 3-Methyl) phenyl} fluorene, α, α′-bis (4-hydroxyphenyl) -o-diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ester and the like, and two or more of them may be used if necessary It is also good.

  Among them, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3 -Methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) It is preferable to use one or two or more dihydric phenols selected from the group consisting of -3,3,5-trimethylcyclohexane and α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene, particularly preferably And bisphenol A alone; and bisphenol A and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylsilane 1 selected from the group consisting of chlorohexane, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane and α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene 1 The combined use with a species or more of dihydric phenol is preferred.

  Examples of the carbonylating agent include carbonyl halides such as phosgene; carbonate esters such as diphenyl carbonate; haloformates such as dihaloformates of dihydric phenol; and the like, and two or more of them may be used if necessary.

  The polycarbonate resin is, if necessary, an additive such as a light diffusing agent, a matting agent, a dye, a light stabilizer, an ultraviolet absorber, an antioxidant, a releasing agent, a flame retardant, an antistatic agent, etc. Or you may contain 2 or more types.

  The polycarbonate resin layer may contain other resin components other than the polycarbonate resin. The content of the other resin component in the polycarbonate resin layer is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, based on 100 parts by weight in total of the polycarbonate resin and the other resin component. More preferably, it is 10 parts by weight or less.

(Thermoplastic resin layer)
The thermoplastic resin layer comprises a methacrylic acid ester monomer unit, a vinyl aromatic monomer unit represented by the following general formula (1), and a cyclic acid anhydride monomer represented by the following general formula (2) It contains a copolymer containing units. The thermoplastic resin layer can be formed from a thermoplastic resin composition containing a copolymer.

［式中：Ｒ^１、Ｒ^２は、それぞれ同一でも、異なっていてもよく、水素、ハロゲン、水酸基、アルコキシ基、ニトロ基、直鎖状または分岐状の炭素数１〜１２のアルキル基を表す。ｎは１〜３の整数を示す。ｎが２または３であるとき、Ｒ^２は、それぞれ同一でも、異なっていてもよい。］

[Wherein, R ¹ and R ² may be the same or different, and represent hydrogen, halogen, a hydroxyl group, an alkoxy group, a nitro group, a linear or branched alkyl group having 1 to 12 carbon atoms] . n is an integer of 1 to 3; When n is 2 or 3, each R ² may be the same or different. ]

［式中：Ｒ^３、Ｒ^４は、それぞれ同一でも、異なっていてもよく、水素、直鎖状または分岐状の炭素数１〜１２のアルキル基を表す。］

[In the Formula: R ³ and R ^{4, which} may be the same or different, each represents hydrogen, a linear or branched alkyl group having 1 to 12 carbon atoms, and ]

  As a monomer used as a methacrylate ester monomer unit, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate And 2-ethylhexyl methacrylate and cyclohexyl methacrylate. These methacrylic acid ester monomers may be used alone or in combination of two or more. Among these monomers, methacrylic acid alkyl esters in which the carbon number of the alkyl group is 1 to 7 are preferable, and methyl methacrylate is particularly preferable because the heat resistance and transparency of the resulting copolymer are excellent.

  The vinyl aromatic monomer unit represented by the general formula (1) (hereinafter sometimes referred to as a vinyl aromatic monomer unit) is derived from an aromatic vinyl monomer. As a monomer to be used, for example, styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 2-methyl-4-chlorostyrene 2,4,6-trimethylstyrene, α-methylstyrene, cis-β-methylstyrene, trans-β-methylstyrene, 4-methyl-α-methylstyrene, 4-fluoro-α-methylstyrene, 4-chloro -Α-methylstyrene, 4-bromo-α-methylstyrene, 4-t-butylstyrene, 2-fluorostyrene, 3-fluorostyrene, 4-fluorostyrene, 2,4-difluorostyrene, 2-chlorostyrene, 3 -Chlorostyrene, 4-chlorostyrene, 2,4-dichlorostyrene, 2,6-dichlorostyrene, 2-bromo Styrene, 3-bromostyrene, 4-bromostyrene, 2,4-dibromostyrene, alpha-bromostyrene, beta-bromostyrene, 2-hydroxystyrene, 4-hydroxy styrene. These aromatic vinyl monomers may be used alone or in combination of two or more. Among these monomers, styrene and α-methylstyrene are preferred because of easy copolymerization.

  The cyclic acid anhydride monomer unit (hereinafter sometimes referred to as a cyclic acid anhydride monomer unit) represented by the general formula (2) is derived from unsubstituted and / or substituted maleic anhydride. As a monomer to be used, for example, maleic anhydride, citraconic anhydride, dimethyl maleic anhydride, dichloromaleic anhydride, bromomaleic anhydride, dibromomaleic anhydride, phenyl maleic anhydride, diphenyl maleic anhydride, etc. It can be mentioned. These cyclic acid anhydride monomer units may be used alone or in combination of two or more. Among these monomers, maleic anhydride is preferred because of easy copolymerization.

The weight ratio of the methacrylic acid ester monomer unit, the vinyl aromatic monomer unit, and the cyclic acid anhydride monomer unit contained in the copolymer was the methacrylic acid ester monomer unit, the vinyl aromatic monomer 5 to 35% by weight of methacrylic acid ester monomer units, 50 to 80% by weight of vinyl aromatic monomer units, based on 100% by weight of the total of units and cyclic anhydride monomer units, cyclic acid It is preferable that an anhydride monomer unit is 5 to 30 weight%.
From the viewpoint of transparency, the weight ratio of the methacrylic acid ester monomer is preferably 5 to 35% by weight, more preferably 10 to 30% by weight, and still more preferably 15 to 25% by weight.
The weight ratio of the vinyl aromatic monomer unit is preferably 50 to 80% by weight, more preferably 55 to 75% by weight, and further preferably 60 to 70% by weight from the viewpoint of transparency, heat resistance, and dimensional stability. preferable.
From the viewpoints of transparency and heat resistance, the weight ratio of the cyclic acid anhydride monomer unit is preferably 5 to 30% by weight, more preferably 10 to 25% by weight, and still more preferably 10 to 20% by weight.

  The copolymer contains, in addition to the methacrylic acid ester monomer unit, the vinyl aromatic monomer unit, and the cyclic acid anhydride monomer unit, other monomer units other than these monomer units It may be The other monomer unit may be copolymerized with at least one monomer unit of a methacrylic acid ester monomer unit, a vinyl aromatic monomer unit, and a cyclic acid anhydride monomer unit. What is necessary is that it is possible to copolymerize with all three types of monomer units. The weight ratio of the other monomer units in the copolymer is a total of 100 of methacrylic acid ester monomer units, vinyl aromatic monomer units, cyclic acid anhydride monomer units, and other monomer units. The content is preferably 50% by weight or less, more preferably 30% by weight or less, and still more preferably 10% by weight or less, based on the weight%.

  The copolymer is added, if necessary, with, for example, rubber particles, light diffusing agents, matting agents, dyes, light stabilizers, ultraviolet light absorbers, antioxidants, releasing agents, flame retardants, antistatic agents, etc. One or more agents may be added.

The thermoplastic resin layer may further contain, in addition to the copolymer, a methacrylic resin (hereinafter sometimes referred to as a methacrylic resin) containing a methacrylic acid ester monomer unit as a main component. The condition (A) described above is satisfied by the thermoplastic resin layer containing the copolymer and the methacrylic resin. The methacrylic resin contains a methacrylic acid ester monomer unit as a main component, and a vinyl aromatic monomer unit represented by the general formula (1) and a cyclic acid anhydride represented by the general formula (2) It is a methacrylic resin which does not simultaneously contain a monomer unit. That is, the copolymer is not included in the methacrylic resin. The methacrylic resin may be any one of a vinyl aromatic monomer unit represented by the general formula (1) and a cyclic acid anhydride monomer unit represented by the general formula (2). It may contain a monomeric unit. As a methacrylic acid ester monomer, the same thing as what was illustrated as a methacrylic acid ester monomer contained in said copolymer is mentioned.
The methacrylic resin may be a homopolymer consisting of only one methacrylic acid ester monomer, or may be copolymerized with two or more methacrylic acid esters, or one or more methacrylic acid esters and the methacrylic acid ester. It may be a copolymer with other monomers that may be used. When the methacrylic resin is a copolymer, the weight ratio of the methacrylic acid ester monomer unit is more than 50% by weight, preferably 70% by weight or more, and preferably 90% by weight or more based on 100% by weight of the methacrylic resin. It is more preferable that

  As other monomers copolymerizable with methacrylic acid ester, for example, methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, acrylic acid Acrylic esters such as 2-hydroxyethyl; styrene; halogenated styrenes such as chlorostyrene and bromostyrene; substituted styrenes such as alkylstyrenes such as vinyltoluene and α-methylstyrene; methacrylic acid, acrylic acid and the like Unsaturated acids; acrylonitrile, methacrylonitrile, maleic anhydride, phenyl maleimide, cyclohexyl maleimide and the like. These other monomers copolymerizable with methyl methacrylate may be used alone or in combination of two or more.

  The methacrylic resin is, if necessary, additives such as, for example, rubber particles, light diffusing agents, matting agents, dyes, light stabilizers, ultraviolet light absorbers, antioxidants, releasing agents, flame retardants, antistatic agents, etc. May be added alone or in combination of two or more.

  When the thermoplastic resin layer contains a copolymer and a methacrylic resin, the content thereof is 20 to 70 parts by weight based on a total of 100 parts by weight of the copolymer and the methacrylic resin. Preferably, the methacrylic resin is 80 to 30 parts by weight.

  In the thermoplastic resin layer, as required, for example, rubber particles, light diffusing agents, matting agents, dyes, light stabilizers, ultraviolet light absorbers, antioxidants, mold release agents, flame retardants, antistatic agents, etc. The additive of (1) may be contained alone or in combination of two or more.

  The thermoplastic resin layer may contain other resin components other than the copolymer and the methacrylic resin. The content of the other resin component in the thermoplastic resin layer is the total of the other resin component and the copolymer, and in the case of containing a methacrylic resin, the total 100 weight of the other resin component, the copolymer and the methacrylic resin The content is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, and still more preferably 10 parts by weight or less, based on parts.

(Method of manufacturing resin laminates)
As a method of producing a resin laminate, for example, a method of laminating and integrating a polycarbonate resin layer and a thermoplastic resin layer by melt co-extrusion molding, a polycarbonate resin layer and a thermoplastic resin layer, an adhesive or an adhesive The method of bonding through an agent is mentioned. Among them, melt coextrusion is preferred. A resin laminate produced by melt coextrusion molding is easier to perform secondary molding compared to a resin laminate produced by laminating a polycarbonate resin layer and a thermoplastic resin layer via an adhesive or an adhesive. .

  Hereinafter, an embodiment of a method of producing a resin laminate of the present invention will be described in detail with reference to FIG. 1 by taking a case of production by melt coextrusion as an example.

  As shown in FIG. 1, a thermoplastic resin composition containing a polycarbonate resin layer forming a polycarbonate resin layer, a copolymer forming a thermoplastic resin layer, and, if necessary, a methacrylic resin, is separately extruded. Two-layer construction in which the thermoplastic resin layer is laminated on one side of the polycarbonate resin layer, or both of the polycarbonate resin layer. The three-layer structure in which the thermoplastic resin layer is laminated on the surface is integrally laminated and extruded. When the thermoplastic resin composition contains a copolymer and a methacrylic resin, these can be mixed by a conventionally known method. The copolymer and the methacrylic resin may be respectively supplied to the above extruder, and both may be mixed in the extruder, or both may be mixed beforehand to obtain a mixture, and this mixture is extruded as the above. It may be supplied to the machine. The feed block and the die may be combined and used instead of the multi-manifold die.

Next, the sheet-like or film-like molten resin 4 extruded from the multi-manifold die 3 is sandwiched between the first cooling roll 5 and the second cooling roll 6 which are disposed to face each other in the substantially horizontal direction. At least one of the first cooling roll 5 and the second cooling roll 6 is connected to a rotational drive means such as a motor, and both rolls are configured to rotate at a predetermined circumferential speed. Of the two rolls, the second cooling roll 6 is a winding roll on which the sheet-like or film-like molten resin 4 after being held between the two rolls is wound.
The first cooling roll 5 and the second cooling roll 6 may be formed of a metal roll or a metal elastic roll, or may be formed by combining a metal roll and a metal elastic roll.

In order to obtain the resin laminate 8 having a reduced retardation value, it is preferable to configure the first cooling roll 5 and the second cooling roll 6 by a combination of a metal roll and a metal elastic roll. That is, when the molten resin is sandwiched between the metal roll and the metal elastic roll, the metal elastic roll is elastically deformed concavely along the outer peripheral surface of the metal roll via the molten resin, and the metal elastic roll and the metal roll are melted. Contact with a predetermined contact length through the resin. As a result, the metal roll and the metal elastic roll come into pressure contact with the molten resin in surface contact, and the molten resin sandwiched between the rolls is formed into a film while being uniformly pressurized in a surface state. As a result, distortion at the time of film formation is reduced, and a resin laminate 8 having a reduced retardation value is obtained.
When combining a metal roll and a metal elastic roll, it is preferable to use a metal elastic roll as the first cooling roll 5 and a metal roll as the second cooling roll 6. Thereby, the retardation value of the resin laminated board 8 obtained can be reduced more.

  The molten resin 4 sandwiched between the first cooling roll 5 and the second cooling roll 6 described above is wound in the order of the second cooling roll 6 and the third cooling roll 7. Specifically, the molten resin 4 wound around the second cooling roll 6 is passed between the second cooling roll 6 and the third cooling roll 7 and wound around the third cooling roll 7. Thereby, since molten resin 4 is cooled gently, the retardation value of resin laminated board 8 obtained can be reduced. A predetermined distance may be provided between the second cooling roll 6 and the third cooling roll 7 to be in an open state, and the molten resin 4 is sandwiched between the two rolls without providing the predetermined distance. May be

  The third cooling roll 7 is not particularly limited, and a conventional metal roll conventionally used in extrusion molding can be adopted. Specific examples thereof include drilled rolls and spiral rolls. The surface state of the third cooling roll 7 is preferably a mirror surface. In addition, a fourth cooling roll, a fifth cooling roll, ... and a plurality of cooling rolls are provided after the third cooling roll 7, and the sheet-like or film-like resin laminated plate 8 is wound around the third cooling roll 7. May be sequentially wound on the next cooling roll.

  The resin laminate plate 8 wound around the third cooling roll 7 and gently cooled is taken up by a take-up roll (not shown) and taken up to obtain the resin laminate plate 8 of the present invention. The thickness of the entire resin laminate plate 8 can be arbitrarily adjusted by adjusting the thickness of the entire molten resin 4 in a molten state, the distance between cooling rolls and belts provided in the cooling unit, the circumferential speed, and the like.

  The thicknesses of the polycarbonate resin layer and the thermoplastic resin layer can be arbitrarily adjusted by adjusting the amount of supply from the extruder, and the like.

(Abrasion resistant resin laminates)
In the resin laminate of the present invention, a cured film may be formed on at least one surface. By providing the cured film on at least one surface of the resin laminate, the surface hardness is further improved, and the resin laminate can be used as a scratch-resistant resin plate.

The following (i) to (v) may be mentioned as the layer configuration of the scratch resistant resin laminate. The polycarbonate resin layer is abbreviated as PC layer, and the thermoplastic resin layer is abbreviated as TR layer.
(I) TR layer / PC layer / cured film (ii) cured film / TR layer / PC layer (iii) cured film / TR layer / PC layer / cured film (iv) TR layer / PC layer / TR layer / cured film (V) Hardened film / TR layer / PC layer / TR layer / hardened film When forming a hardened film on both sides of a resin laminate, the composition and thickness of the hardened film on both sides are the same. It may be or may be different. Moreover, when forming a cured film only in one side of a resin laminated board, it is preferable to form a cured film in TR layer.

  The thickness of the cured film is preferably 0.5 to 50 μm, more preferably 1 to 20 μm. The smaller the thickness of the cured film, the less the tendency for cracking to occur. However, if the thickness of the cured film is too thin, the abrasion resistance becomes insufficient, which is not preferable.

  The surface of the scratch resistant resin laminate may be subjected to an antireflective treatment by a coating method, a sputtering method, a vacuum evaporation method or the like, as necessary. In addition, an antireflective sheet produced separately may be bonded to at least one surface of the scratch resistant resin laminate for the purpose of imparting an antireflective effect.

(Method of manufacturing scratch resistant resin laminate)
As a method for producing a scratch-resistant resin laminate, for example, a curable coating composition is applied to at least one surface of the resin laminate to form a curable coating film, and then the curable coating film is cured. And a method of forming a cured film.

(Curable coating composition)
The curable coating composition contains, as an essential component, a curable compound that provides scratch resistance, and optionally contains a curing catalyst, conductive particles, a solvent, a leveling agent, a stabilizer, an antioxidant, a colorant, and the like. Do.

(Curable compound)
As a curable compound, for example, an acrylate compound, a urethane acrylate compound, an epoxy acrylate compound, a carboxyl group-modified epoxy acrylate compound, a polyester acrylate compound, a copolymer acrylate compound, an alicyclic epoxy resin, a glycidyl ether epoxy resin, a vinyl ether compound, An oxetane compound etc. are mentioned. Among them, radical curable compounds such as polyfunctional acrylate compounds, polyfunctional urethane acrylate compounds, polyfunctional epoxy acrylate compounds and the like, and thermal polymerization systems such as alkoxysilanes and alkylalkoxysilanes from the viewpoint of the scratch resistance of the cured film. And the like. These curable compounds may be cured by irradiation with energy rays such as electron beams, radiation, and ultraviolet rays, or may be cured by heating. Each of these curable compounds may be used alone, or a plurality of compounds may be used in combination.

  Particularly preferred curable compounds are compounds having at least three (meth) acryloyloxy groups in the molecule. Here, the (meth) acryloyloxy group means an acryloyloxy group or a methacryloyloxy group, and in addition, in the present specification, “(meth)” when referring to (meth) acrylate and the like has the same meaning.

  Examples of the compound having at least three (meth) acryloyloxy groups in the molecule, which is an example of a curable compound, include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, and glycerin tri (meth) acrylate. ) Acrylate, pentaglycerol tri (meth) acrylate, pentaerythritol tri- or tetra- (meth) acrylate, dipentaerythritol tri-, tetra-, penta- or hexa- (meth) acrylate, tripentaerythritol tetra-, penta- And poly (meth) acrylates of trivalent or higher polyhydric alcohols such as hexa- or hepta- (meth) acrylates; compounds having at least two isocyanato groups in the molecule, (meth) acrylates having hydroxyl groups, Urethane (meth) acrylates obtained by reacting at a ratio such that the hydroxyl group is equimolar or more to the socyanato group and the number of (meth) acryloyloxy groups in the molecule is 3 or more [eg, diisocyanate and pentaerythritol The reaction of tri (meth) acrylate gives a hexafunctional urethane (meth) acrylate]; and tri (meth) acrylate of tris (2-hydroxyethyl) isocyanuric acid. In addition, although the monomer was illustrated here, you may use as these monomers as it is, for example, you may use what became the form of oligomers, such as a dimer and a trimer. Also, a monomer and an oligomer may be used in combination. These (meth) acrylate compounds may be used alone or in combination of two or more.

  As a compound which has at least three (meth) acryloyloxy groups in the molecule | numerator which is an example of a curable compound, a commercially available thing can be used. Specific examples thereof include “U-6 HA” (urethane acrylate oligomer), “NK card M101” (urethane acrylate type), “NK ester A-TMM-3L”, all manufactured by Shin-Nakamura Chemical Co., Ltd. (Pentaerythritol triacrylate), "NK ester A-TMMT" (pentaerythritol tetraacrylate), "NK ester A-9530" (dipentaerythritol pentaacrylate) and "NK ester A-DPH" (dipentaerythritol hexaacrylate) “KAYARAD DPCA” (dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd., “Nopcocure 200” series manufactured by San Nopco Co., Ltd., “Unidic” series manufactured by Dainippon Ink and Chemicals, Inc. It can be mentioned.

(Other curable compounds)
When a compound having at least three (meth) acryloyloxy groups in the molecule is used as the curable compound, if necessary, another curable compound such as ethylene glycol di (meth) acrylate or diethylene glycol is used. A compound having two (meth) acryloyloxy groups in the molecule, such as di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, may be used in combination . The amount used is usually up to 20 parts by weight per 100 parts by weight of the compound having at least 3 (meth) acryloyloxy groups in the molecule.

(Photopolymerization initiator)
When the curable coating film is cured by ultraviolet light, the curable coating composition may contain a photopolymerization initiator as a curing catalyst. Examples of the photopolymerization initiator include benzyl, benzophenone and derivatives thereof, thioxanthones, benzyldimethyl ketals, α-hydroxyalkylphenones, hydroxyketones, aminoalkylphenones, acyl phosphine oxides, etc. A mixture of two or more of these can also be used depending on the situation. The amount of the photopolymerization initiator used is usually 0.1 to 5 parts by weight with respect to 100 parts by weight of the curable compound.

  As the photopolymerization initiator, a commercially available product can be used, and as a specific example, all of them are "IRGACURE 651", "IRGACURE 184", "IRGACURE 500", "IRGACURE 1000" manufactured by Ciba Specialty Chemicals Inc. IRGACURE (IRGACURE) series and "IRGACURE 2959", "DAROCUR 1173", "IRGACURE 907", "IRGACURE 369", "IRGACURE 1700", "IRGACURE 1800", "IRGACURE 819", "IRGACURE 784" etc. DAROCUR (Darocure) series, all manufactured by Nippon Kayaku Co., Ltd. "KAYACURE ITX", "KAYACURE DETX-S", "KAYACURE BP-100", "KAYACUREBMS", "KA ACURE 2-EAQ "such as, KAYACURE (Kayacure) series, and the like.

(Conductive particles)
The curable coating composition may contain conductive particles. Thereby, antistatic property can be provided to a cured film. As the conductive particles, for example, antimony-tin complex oxide, tin oxide containing phosphorus, antimony oxide such as antimony pentoxide, antimony-zinc complex oxide, titanium oxide, indium-tin complex oxide (ITO), etc. Inorganic particles are preferably used. The conductive particles can also be used in the form of a sol having a solid content concentration of about 10 to 30% by weight.

  The particle size of the conductive particles is usually 0.5 μm or less, and in terms of the antistatic property and transparency of the cured film, it is preferably 0.001 μm or more in terms of the average particle size, and preferably 0. .1 μm or less, more preferably 0.05 μm or less. The smaller the average particle diameter of the conductive particles, the lower the haze of the scratch-resistant resin laminate, and the higher the transparency.

  The amount of the conductive particles used is usually 2 to 50 parts by weight, preferably 3 to 20 parts by weight, per 100 parts by weight of the curable compound. The larger the amount of the conductive particles used, the more the antistatic property of the cured film tends to be improved. However, if the amount of the conductive particles used is too large, the transparency of the cured film is unfavorably reduced.

  The conductive particles can be produced, for example, by a vapor phase decomposition method, a plasma evaporation method, an alkoxide decomposition method, a coprecipitation method, a hydrothermal method or the like. In addition, the surface of the conductive particles may be surface-treated with, for example, a nonionic surfactant, a cationic surfactant, an anionic surfactant, a silicon coupling agent, an aluminum coupling agent, or the like.

(solvent)
The curable coating composition may contain a solvent for the purpose of adjusting its viscosity and the like. In particular, when the curable coating composition contains conductive particles, it is preferable to contain a solvent for the dispersion. When preparing a curable coating composition containing conductive particles and a solvent, for example, the conductive particles and the solvent are mixed to disperse the conductive particles in the solvent, and then the dispersion is a curable compound. The conductive particles may be dispersed in the liquid mixture after the curable compound and the solvent are mixed.

  The solvent should be one which can dissolve the curable compound and can be easily volatilized after application, and in the case where conductive particles are used as a paint component, it can be dispersed. Good to have. As such solvent, for example, alcohols such as diacetone alcohol, methanol, ethanol, isopropyl alcohol, isobutyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 1-methoxy-2-propanol and the like; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and diacetone alcohol; aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; water and the like. The amount of the solvent used may be appropriately adjusted in accordance with the properties and the like of the curable compound.

(Leveling agent)
When the curable coating composition contains a leveling agent, silicone oil is preferably used. Specific examples thereof include dimethyl silicone oil, phenyl methyl silicone oil, alkyl / aralkyl modified silicone oil, fluoro silicone oil, polyether modified silicone oil, fatty acid ester modified silicone oil, methyl hydrogen silicone oil, silanol group-containing silicone oil, alkoxy Group containing silicone oil, phenol group containing silicone oil, methacryl modified silicone oil, amino modified silicone oil, carboxylic acid modified silicone oil, carbinol modified silicone oil, epoxy modified silicone oil, mercapto modified silicone oil, fluorine modified silicone oil, polyether Modified silicone oil etc. may be mentioned. These leveling agents may be used alone or in combination of two or more. The amount of the leveling agent used is usually 0.01 to 5 parts by weight with respect to 100 parts by weight of the curable compound.

  A commercially available thing can be used for a leveling agent, and, as for the specific example, all are "SH200-100cs", "SH28PA", "SH29PA", "SH30PA", "Toray * Dow Corning silicone KK-made". ST83PA "," ST80PA "," ST97PA "and" ST86PA ", all of" BYK-302 "," BYK-307 "," BYK-320 "and" BYK-330 "manufactured by Big Chemie Japan Ltd. Etc.

(Method of applying a curable coating composition)
As a method of applying the curable coating composition to at least one surface of a resin laminate, for example, a bar coating method, a microgravure coating method, a roll coating method, a flow coating method, a dip coating method, a spin coating method, a die coating method And spray coating methods.

(Curing method of curable coating)
In order to cure the curable coating film, energy rays may be irradiated, heating or the like depending on the type of the curable coating composition.

As an energy ray in the case of hardening a curable coating film by irradiation of an energy ray, an ultraviolet ray, an electron beam, radiation etc. are mentioned, for example. The conditions such as the strength and the irradiation time are appropriately selected according to the type of the curable coating composition.
In addition, when curing the curable coating film by heating, the conditions such as temperature and time are appropriately selected according to the type of the curable coating composition, and the heating temperature is such that the resin substrate is not deformed. In general, the temperature is preferably 100 ° C. or less. When the curable coating composition contains a solvent, after coating, the curable coating may be cured after evaporating the solvent, or the volatilization of the solvent and the curing of the curable coating may be simultaneously performed. It is also good.

(Use)
Resin laminates have excellent surface hardness and excellent resistance to warping deformation under severe high temperature and humidity conditions of 85 ° C. and 85% humidity environment, so they can be used in exterior applications, billboard applications, lighting applications, and displays. It can be used suitably for a face plate application etc., and can be used more suitably as a front plate in a display. Furthermore, the resin laminate can be suitably used as a resin substrate of a scratch-resistant resin laminate by having excellent adhesion to a cured film. The scratch-resistant resin laminate having a cured film on at least one surface of the resin laminate can be particularly suitably used as a display protection plate, a touch panel protection plate, and a display window protection plate for a portable information terminal.

  Examples of the type of display protected include a cathode ray tube (CRT) display, a liquid crystal display, a plasma display, an EL display and the like. In addition, as the application of the protected display, for example, a monitor of a television or computer, a tablet, a smartphone, a mobile phone, a display window of a portable information terminal such as PHS (Personal Handy-phone System), PDA (Personal Digital Assistant), Examples include a finder unit of a digital camera or a hand-held video camera, a display window of a portable game machine, and the like.

  The application of the protected touch panel includes, for example, car navigation systems, portable information terminals, automatic teller machines (ATMs) of banks, operation panels of industrial machines, etc., screens of personal computers, touch panels such as portable game machines, etc. Etc.

  In order to produce a display protection plate and a touch panel protection plate, processing such as printing, drilling, etc. may first be performed on a scratch-resistant resin laminated plate as necessary, and cutting processing to a necessary size may be performed. After that, if the display or the touch panel is set, the display and the touch panel can be effectively protected. At that time, when a cured film is formed on one surface of the resin laminate, it is preferable that the surface on which the cured film is formed be on the front side (viewer side). When the thermoplastic resin layer is laminated on one surface of the polycarbonate resin layer, the resin laminate is preferably placed so that the thermoplastic resin layer is on the front side (viewer side).

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to these examples.

The extrusion apparatus used in Examples and Comparative Examples is the apparatus shown in FIG. 1, and the configuration is as follows.
Extruder 1: Screw diameter 65 mm, uniaxial, vented extruder (manufactured by Toshiba Machine Co., Ltd.).
Extruder 2: Screw diameter 45 mm, uniaxial, vented extruder (manufactured by Hitachi Zosen Co., Ltd.).
Multi-manifold type die 3: multi-manifold type die of two kinds and two-layer distribution type (manufactured by Hitachi Zosen Co., Ltd.).
1st cooling roll 5: metal elastic roll 2nd cooling roll 6: metal roll 3rd cooling roll 7: metal roll

  The metal elastic roll has a stainless steel thin film with a thickness of 2 mm, one side of which is mirror-polished, arranged so that the mirror-finished surface is the outer surface of the roll so as to cover the outer peripheral portion of the shaft roll made of stainless steel. It is a metal elastic roll having an outer diameter of 250 mm in which a fluid consisting of a heat transfer oil is sealed between the metal thin film. The metal roll is a spiral roll made of stainless steel whose surface is mirror finished and having an outer diameter of 250 mm.

Resins used in Examples and Comparative Examples are the following three types.
Polycarbonate resin: "Karibar 301-10" manufactured by Sumika Styron Polycarbonate Co., Ltd. was used.
Copolymer: consisting of methyl methacrylate monomer unit, styrene monomer unit, and maleic anhydride monomer unit, methyl methacrylate monomer unit, styrene monomer unit, and maleic anhydride monomer Use a copolymer having 20% by weight of methyl methacrylate monomer units, 65% by weight of styrene monomer units, and 15% by weight of maleic anhydride monomer units, based on 100% by weight of the total units. It was.
Methacrylic resin: Methyl methacrylate consisting of methyl methacrylate monomer units and methyl acrylate monomer units, based on a total of 100% by weight of methyl methacrylate monomer units and methyl acrylate monomer units A methacrylic resin having 97.8% by weight of monomer units and 2.2% by weight of methyl acrylate monomer units was used.

(Examples 1 to 5 and Comparative Examples 1 to 4)
(Production of laminated board)
First, the extruders 1 and 2, the multi-manifold die 3 and the first to third cooling rolls 5 to 7 were arranged as shown in FIG. Subsequently, a polycarbonate resin is melt-kneaded by the extruder 1 as a resin for forming a polycarbonate resin layer, and heat is formed by mixing a copolymer and a methacrylic resin at a ratio shown in Table 1 as a resin for forming a thermoplastic resin layer. The plastic resin composition was melt-kneaded with an extruder 2 and each was supplied to a multi-manifold die 3 with a set temperature of 260 ° C.
Then, the film-like melt is formed by laminating the thermoplastic resin layer supplied from the extruder 2 to the multi-manifold die 3 on one surface of the polycarbonate resin layer supplied from the extruder 1 to the multi-manifold die 3 The resin 4 was extruded from a multi-manifold die 3.

Next, the film-like molten resin 4 extruded from the multi-manifold die 3 is sandwiched between the first cooling roll 5 and the second cooling roll 6 disposed opposite to each other, and wound around the third cooling roll 7 for forming and cooling A two-layered resin laminate having a thickness shown in Table 1 and a thermoplastic resin layer laminated on one surface of a polycarbonate resin layer was obtained.
The surface temperature of the first cooling roll 5 was 110 ° C., the surface temperature of the second cooling roll 6 was 125 ° C., and the surface temperature of the third cooling roll 7 was 120 ° C. These temperatures are values obtained by measuring the surface temperatures of the respective cooling rolls.

  The pencil hardness of each of the obtained resin laminates (Examples 1 to 5 and Comparative Examples 1 to 4) was measured by the following method in order to evaluate the surface hardness. Furthermore, in order to evaluate the warpage deformation resistance under high temperature and high humidity environment of each resin laminate, the amount of warpage was measured by the following method. The results are shown in Table 1.

<Pencil hardness>
The thermoplastic resin layer surface of the obtained resin laminate was measured according to JIS K5600.

Warpage amount
The resin laminate was cut into a square in a size of 200 mm in the extrusion direction and 200 mm in the direction orthogonal to the extrusion direction to prepare a test piece. The obtained test piece is placed on the surface plate with the convexly curved surface as the ground contact side, and the amount of floating of the four corners of the test piece from the surface of the plate on which the test piece is placed is measured using a position sensor. The average value was measured to calculate an average value, and this average value was defined as the warpage amount A. Next, while the test piece is suspended, the test piece is placed in a constant temperature and humidity chamber at a temperature of 85 ° C. and a humidity of 85% and allowed to stand for 72 hours, and then the test piece is removed from the temperature and humidity control chamber and suspended in temperature After leaving still for 4 hours in an environment of 25 ° C. and 50% humidity, the average value of the floating amounts at the four corners of the test piece was calculated in the same manner as the warpage A, and this average was taken as the warpage B. Then, the warpage amount A was determined by subtracting the warpage amount A from the warpage amount B. The smaller the value of the warpage amount, the more excellent the resin laminate is in the warpage deformation resistance under high temperature and high humidity environment.

(Preparation of scratch-resistant resin plate)
25 parts of urethane acrylate oligomer ("U-6HA" manufactured by Shin-Nakamura Chemical Co., Ltd.), 1 part of a photopolymerization initiator ("IRGACURE 184" manufactured by Ciba Specialty Chemicals Co., Ltd.), 1-methoxy as a solvent A curable coating was prepared by mixing 37 parts of -2-propanol and 37 parts of isobutyl alcohol.

  Each resin laminate obtained in Examples 1 to 5 and Comparative Examples 1 to 4 is cut into a size of 100 mm in the extrusion direction and 80 mm in the direction orthogonal to the extrusion direction, and both resin laminates are dipped by dipping. The coating film of the curable paint prepared above was formed on the surface of. Next, each resin laminate on which the coating film is formed is dried at room temperature for 1 minute, and further dried in a hot air oven at 50 ° C. for 3 minutes to volatilize the solvent, and 120 W of high pressure mercury is applied to the coating film. Using a lamp, ultraviolet rays of 0.5 J / cm 2 were irradiated and cured to obtain each scratch resistant resin laminate in which a cured film having a thickness of 3.5 μm was formed on both sides.

  About each obtained abrasion resistant resin laminated board, in order to evaluate the adhesiveness of a resin laminated board and a cured film, adhesiveness was evaluated by the following method. The results are shown in Table 1.

<Adhesiveness>
After inserting 100 pieces of 2 mm × 2 mm cross hatch with a cutter on the surface of the cured film formed on the thermoplastic resin layer side of the scratch resistant resin laminate, and after pasting cellophane tape (manufactured by Nichiban Co., Ltd.) , The cellophane tape was peeled off. After affixing the cellophane tape, the operation of peeling off the cellophane tape was further repeated twice, and this operation was repeated a total of three times, and the number of squares of the cured film peeled off from the resin laminate was measured. Those with no peeled squares were evaluated as “○”, and those with peeled squares were rated “X”.

1, 2 Extruder 3 Multi-manifold type die 4 Molten resin 5 1st cooling roll 6 2nd cooling roll 7 3rd cooling roll 8 resin laminate

Claims (11)

A thermoplastic resin layer is laminated on at least one surface of a polycarbonate resin layer, and the thermoplastic resin layer is a methacrylic acid ester monomer unit, a vinyl aromatic unit represented by the following general formula (1) And a copolymer containing a cyclic acid anhydride monomer unit represented by the following general formula (2):
The weight ratio of the methacrylic acid ester monomer unit, the vinyl aromatic monomer unit, and the cyclic acid anhydride monomer unit contained in the copolymer is the vinyl aromatic monomer unit, methacrylic acid unit amount 50 to 80% by weight of vinyl aromatic monomer units, 5 to 35% by weight of methacrylic acid ester monomer units, cyclic, based on 100% by weight in total of the unit and cyclic acid anhydride monomer units A resin laminate wherein the acid anhydride monomer unit is 5 to 30% by weight,

[Wherein, R ¹ and R ² may be the same or different, and represent hydrogen, halogen, a hydroxyl group, an alkoxy group, a nitro group, a linear or branched alkyl group having 1 to 12 carbon atoms] . n is an integer of 1 to 3; When n is 2 or 3, each R ² may be the same or different. ]

[In the Formula: R ³ and R ^{4, which} may be the same or different, each represents hydrogen, a linear or branched alkyl group having 1 to 12 carbon atoms, and ]
It meets the following conditions (A),
The content of the copolymer and the methacrylic resin in the thermoplastic resin layer is 20 to 70 parts by weight of the copolymer, based on 100 parts by weight of the total of the copolymer and the methacrylic resin, and the methacrylic resin is 80 to The resin laminated board characterized by being 30 parts by weight .
(A) The thermoplastic resin layer further contains a methacrylic acid ester monomer unit as a main component, and is represented by the vinyl aromatic monomer unit represented by the general formula (1) and the general formula (2) It contains a methacrylic resin which does not simultaneously contain cyclic anhydride monomer units. The resin laminate according to claim 1, wherein the vinyl aromatic monomer is a styrene monomer. The resin laminate according to claim 1, wherein the cyclic acid anhydride monomer is maleic anhydride. The resin laminate according to any one of claims 1 to 3 , wherein the polycarbonate resin layer and the thermoplastic resin layer are integrally laminated. The resin laminate according to any one of claims 1 to 4 , wherein the polycarbonate resin layer and the thermoplastic resin layer are laminated by melt coextrusion molding. An abrasion resistant resin laminate comprising a cured film on at least one surface of the resin laminate according to any one of claims 1 to 5 . A protective plate for a display, comprising the scratch-resistant resin laminate according to claim 6 . A protective plate for a touch panel, comprising the scratch-resistant resin laminate according to claim 6 . A protective plate for a display window of a portable information terminal, comprising the scratch-resistant resin laminate according to claim 6 . A thermoplastic resin layer is laminated on at least one surface of a polycarbonate resin layer, and the thermoplastic resin layer is a methacrylic acid ester monomer unit, a vinyl aromatic unit represented by the following general formula (1) And a copolymer containing a cyclic acid anhydride monomer unit represented by the following general formula (2):
The weight ratio of the methacrylic acid ester monomer unit, the vinyl aromatic monomer unit, and the cyclic acid anhydride monomer unit contained in the copolymer is the vinyl aromatic monomer unit, methacrylic acid unit amount 50 to 80% by weight of vinyl aromatic monomer units, 5 to 35% by weight of methacrylic acid ester monomer units, cyclic, based on 100% by weight in total of the unit and cyclic acid anhydride monomer units A method for improving the warpage resistance of a resin laminate having 5 to 30% by weight of an acid anhydride monomer unit in a high temperature and high humidity environment,
The thermoplastic resin layer contains a methacrylic acid ester monomer unit as a main component, and a vinyl aromatic monomer unit represented by the following general formula (1) and a cyclic acid anhydride represented by the following general formula (2) Containing a methacrylic resin that does not simultaneously contain a monomer unit ,
The content of the copolymer and the methacrylic resin in the thermoplastic resin layer is 20 to 70 parts by weight of the copolymer, based on 100 parts by weight of the total of the copolymer and the methacrylic resin, and the methacrylic resin is 80 to wherein 30 parts by weight der Rukoto.

[Wherein, R ¹ and R ² may be the same or different, and represent hydrogen, halogen, a hydroxyl group, an alkoxy group, a nitro group, a linear or branched alkyl group having 1 to 12 carbon atoms] . n is an integer of 1 to 3; When n is 2 or 3, each R ² may be the same or different. ]

[In the Formula: R ³ and R ^{4, which} may be the same or different, each represents hydrogen, a linear or branched alkyl group having 1 to 12 carbon atoms, and ] A thermoplastic resin layer is laminated on at least one surface of a polycarbonate resin layer, and the thermoplastic resin layer is a methacrylic acid ester monomer unit, a vinyl aromatic unit represented by the following general formula (1) And a copolymer containing a cyclic acid anhydride monomer unit represented by the following general formula (2):
The weight ratio of the methacrylic acid ester monomer unit, the vinyl aromatic monomer unit, and the cyclic acid anhydride monomer unit contained in the copolymer is the vinyl aromatic monomer unit, methacrylic acid unit amount 50 to 80% by weight of vinyl aromatic monomer units, 5 to 35% by weight of methacrylic acid ester monomer units, cyclic, based on 100% by weight in total of the unit and cyclic acid anhydride monomer units A resin laminate wherein the acid anhydride monomer unit is 5 to 30% by weight,

[Wherein, R ¹ and R ² may be the same or different, and represent hydrogen, halogen, a hydroxyl group, an alkoxy group, a nitro group, a linear or branched alkyl group having 1 to 12 carbon atoms] . n is an integer of 1 to 3; When n is 2 or 3, each R ² may be the same or different. ]

[In the Formula: R ³ and R ^{4, which} may be the same or different, each represents hydrogen, a linear or branched alkyl group having 1 to 12 carbon atoms, and ]
It meets the following conditions (A),
The content of the copolymer and the methacrylic resin in the thermoplastic resin layer is 20 to 70 parts by weight of the copolymer, based on 100 parts by weight of the total of the copolymer and the methacrylic resin, and the methacrylic resin is 80 to It is a method of manufacturing a resin laminate which is 30 parts by weight ,
The method for producing the resin laminate, wherein the polycarbonate resin and the thermoplastic resin layer are integrally laminated by melt coextrusion molding.
(A) The thermoplastic resin layer further contains a methacrylic acid ester monomer unit as a main component, and is represented by the vinyl aromatic monomer unit represented by the general formula (1) and the general formula (2) It contains a methacrylic resin which does not simultaneously contain cyclic anhydride monomer units.

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