JP2017164969A - Thermoplastic resin laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin laminate which is suitably used for a transparent substrate material or a transparent protective material and is excellent in transparency, smoothness, scratch resistance, impact resistance and shape stability in an environment of high temperature and high humidity or the like.SOLUTION: There is provided a thermoplastic resin laminate which has a vinyl copolymer resin (A) on both surfaces of a thermoplastic resin composition (B) layer containing a polycarbonate resin and an amorphous copolyester resin, where the difference in glass transition temperature between the thermoplastic resin composition (B) and the vinyl copolymer resin (A) is 15°C or less, the vinyl copolymer resin (A) contains a specific (meth)acrylic acid ester constituent unit (a) and a specific aliphatic vinyl constituent unit (b), the total ratio of the (meth)acrylic acid ester constituent unit (a) and the aliphatic vinyl constituent unit (b) is 80 to 100 mol% based on the total constituent units in the vinyl copolymer resin (A) and the molar ratio between the (meth)acrylic acid ester constituent unit (a) and the aliphatic vinyl constituent unit (b) is 55:45 to 85:15.SELECTED DRAWING: None

Description

The present invention relates to a thermoplastic resin laminate suitable for optical applications such as a transparent substrate material and a protective material.

Polycarbonate resin plates are excellent in transparency, impact resistance, and heat resistance, and are used for soundproofing partitions, carports, signboards, glazing materials, lighting equipment, etc., but they have the disadvantage of being easily damaged due to their low surface hardness. Yes, usage is limited. In order to remedy this defect, Patent Document 1 proposes a method of coating the surface with an ultraviolet curable resin or the like, and a method of applying a hard coat to a substrate in which a polycarbonate resin and an acrylic resin are coextruded. However, when a hard coat is applied to the surface of the polycarbonate resin, the required pencil hardness cannot be satisfied, and it may not be used for applications requiring the surface hardness. In addition, since the surface hardness is improved to some extent by the method of applying the acrylic resin to the surface layer, the application is extended to the front panel of the information display device, etc., but in this method, the acrylic resin and the polycarbonate resin are made of two layers of different materials. Due to the large difference in glass transition temperature and the difference in water absorption characteristics, warpage occurs in a high-temperature and high-humidity environment.

Patent Document 3 discloses a method of applying a surface layer made of a specific vinyl copolymer resin on both surfaces of a polycarbonate resin as a method of suppressing warpage in a high temperature and high humidity environment. However, in the method of Patent Document 3, since there is a certain difference in the glass transition temperature between the vinyl copolymer resin and the polycarbonate resin, a laminate having good smoothness can be obtained particularly in a laminate having a thickness of 800 μm or less. In addition to the difficulty, there is a tendency that residual strain during molding tends to increase, and there is a problem that warpage is likely to occur as the environment changes.

JP 2006-103169 A JP 2010-167659 A JP 2009-196125 A

  From the above situation, the present invention is suitable for transparent substrate materials and protective materials, and has transparency, smoothness, scratch resistance, impact resistance, and shape stability in a high temperature and high humidity environment. An object is to provide an excellent thermoplastic resin laminate.

  As a result of intensive studies to solve the above problems, the present inventors have found that a vinyl copolymer resin (A) is formed on both surfaces of a thermoplastic resin composition (B) layer containing a polycarbonate and an amorphous copolymer polyester resin. ) A thermoplastic resin laminate in which layers are laminated, and the glass transition temperature difference between the thermoplastic resin composition (B) and the vinyl copolymer resin (A) is 15 ° C. or less, so that the transparency The present inventors have found that a thermoplastic resin laminate having both smoothness, scratch resistance, impact resistance, and shape stability in a high-temperature and high-humidity environment can be obtained, and the present invention has been achieved. That is, the present invention provides the following thermoplastic resin laminate.

In the present specification, “(meth) acrylic acid” means acrylic acid or methacrylic acid. Further, in this specification, the glass transition temperature is a temperature when measured using a differential scanning calorimetry apparatus with a sample of 10 mg, a heating rate of 10 ° C./min, and calculated by the second heating midpoint method. .

（式中、Ｒ１は水素原子またはメチル基であり、Ｒ２は炭素数１〜１６の基である。）

（式中、Ｒ３は水素原子またはメチル基であり、Ｒ４はシクロヘキシル基または炭素数１〜４の炭化水素置換基を有するシクロヘキシル基である。）
［２］ 一般式（１）のＲ１及びＲ２がメチル基である［１］に記載の熱可塑性樹脂積層体。
［３］ 一般式（２）のＲ４がシクロヘキシル基である［１］または［２］のいずれかに記載の熱可塑性樹脂積層体。
［４］ 前記熱可塑性樹脂組成物（Ｂ）中のポリカーボネート樹脂と非晶性共重合ポリエステル樹脂の合計に対するポリカーボネート樹脂の割合が５０〜９５重量％であり、かつ熱可塑性樹脂組成物（Ｂ）のガラス転移温度が１１０〜１４５℃の範囲である［１］〜［３］のいずれかに記載の熱可塑性樹脂積層体。
［５］ 前記熱可塑性樹脂組成物（Ｂ）中の非晶性共重合ポリエステル樹脂がジオール構成単位中に１，４−シクロヘキサンジメタノールに由来する構成単位を有する［１］〜［４］のいずれかに記載の熱可塑性樹脂積層体。
［６］ 前記熱可塑性樹脂組成物（Ｂ）中の非晶性共重合ポリエステル樹脂の全ジオール構成単位中の１，４−シクロヘキサンジメタノールに由来する構成単位の割合が３０〜９０モル％である［５］に記載の熱可塑性樹脂積層体。
［７］ 前記熱可塑性樹脂組成物（Ｂ）中の非晶性共重合ポリエステル樹脂がジオール構成単位中に３，９−ビス（１，１−ジメチル−２−ヒドロキシエチル）−２，４，８，１０−テトラオキサスピロ〔５．５〕ウンデカンに由来する構成単位を有する［１］〜［４］のいずれかに記載の熱可塑性樹脂積層体。
［８］ 前記熱可塑性樹脂組成物（Ｂ）中の非晶性共重合ポリエステル樹脂の全ジオール構成単位中の３，９−ビス（１，１−ジメチル−２−ヒドロキシエチル）−２，４，８，１０−テトラオキサスピロ〔５．５〕ウンデカンに由来する構成単位の割合が１０〜８０モル％である［７］に記載の熱可塑性樹脂積層体。
［９］ 前記熱可塑性樹脂組成物（Ｂ）層にゴム系材料を含む［１］〜［８］のいずれかに記載の熱可塑性樹脂積層体。
［１０］ 片面または両面にハードコート処理を施したものである［１］〜［９］のいずれかに記載の熱可塑性樹脂積層体。
［１１］ 片面または両面に反射防止処理、防汚処理、帯電防止処理、耐候性処理および防眩処理から選択されるいずれか一つ以上の処理を施したものである［１］〜［１０］のいずれかに記載の熱可塑性樹脂積層体。
［１２］ ［１］〜［１１］のいずれかに記載の熱可塑性樹脂積層体から成る透明性基板材料。
［１３］ ［１］〜［１１］のいずれかに記載の熱可塑性樹脂積層体から成る透明性保護材料。 [1] A thermoplastic resin laminate having a vinyl copolymer resin (A) layer on both sides of a thermoplastic resin composition (B) layer containing a polycarbonate resin and an amorphous copolymer polyester resin, wherein the thermoplastic The difference in glass transition temperature between the resin composition (B) and the vinyl copolymer resin (A) is 15 ° C. or less, and the vinyl copolymer resin (A) is represented by the following general formula (1) (meth) acrylic An acid ester structural unit (a) and an aliphatic vinyl structural unit (b) represented by the following general formula (2), the (meth) acrylic acid ester structural unit (a) and the aliphatic vinyl structural unit (B) is 80-100 mol% with respect to the sum total of all the structural units in the said vinyl copolymer resin (A), the said (meth) acrylate structural unit (a) and the said aliphatic Mole with vinyl structural unit (b) A thermoplastic resin laminate characterized by being a thermoplastic resin having a ratio of 55:45 to 85:15.

(In the formula, R1 is a hydrogen atom or a methyl group, and R2 is a group having 1 to 16 carbon atoms.)

(In the formula, R 3 is a hydrogen atom or a methyl group, and R 4 is a cyclohexyl group or a cyclohexyl group having a hydrocarbon substituent having 1 to 4 carbon atoms.)
[2] The thermoplastic resin laminate according to [1], wherein R1 and R2 in the general formula (1) are methyl groups.
[3] The thermoplastic resin laminate according to any one of [1] or [2], wherein R4 in the general formula (2) is a cyclohexyl group.
[4] The ratio of the polycarbonate resin to the total of the polycarbonate resin and the amorphous copolyester resin in the thermoplastic resin composition (B) is 50 to 95% by weight, and the thermoplastic resin composition (B) The thermoplastic resin laminate according to any one of [1] to [3], wherein the glass transition temperature is in the range of 110 to 145 ° C.
[5] Any of [1] to [4], wherein the amorphous copolymer polyester resin in the thermoplastic resin composition (B) has a structural unit derived from 1,4-cyclohexanedimethanol in a diol structural unit. A thermoplastic resin laminate according to any one of the above.
[6] The proportion of structural units derived from 1,4-cyclohexanedimethanol in all diol structural units of the amorphous copolymer polyester resin in the thermoplastic resin composition (B) is 30 to 90 mol%. The thermoplastic resin laminate according to [5].
[7] The amorphous copolymer polyester resin in the thermoplastic resin composition (B) is 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8 in the diol structural unit. , 10-tetraoxaspiro [5.5] The thermoplastic resin laminate according to any one of [1] to [4], which has a structural unit derived from undecane.
[8] 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4 in all diol constituent units of the amorphous copolymer polyester resin in the thermoplastic resin composition (B) The thermoplastic resin laminate according to [7], wherein the proportion of structural units derived from 8,10-tetraoxaspiro [5.5] undecane is 10 to 80 mol%.
[9] The thermoplastic resin laminate according to any one of [1] to [8], wherein the thermoplastic resin composition (B) layer includes a rubber-based material.
[10] The thermoplastic resin laminate according to any one of [1] to [9], wherein one side or both sides are hard-coated.
[11] One or both surfaces are subjected to any one or more treatments selected from antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment and antiglare treatment [1] to [10] The thermoplastic resin laminate according to any one of the above.
[12] A transparent substrate material comprising the thermoplastic resin laminate according to any one of [1] to [11].
[13] A transparent protective material comprising the thermoplastic resin laminate according to any one of [1] to [11].

The thermoplastic resin laminate obtained by the present invention has transparency, smoothness, scratch resistance, impact resistance, and shape stability in a high temperature and high humidity environment. It can be suitably used for optical applications such as materials.

The present invention will be described in detail below, but the present invention is not limited to the illustrated production examples and examples, and can be changed to any method as long as it does not significantly depart from the contents of the present invention. You can also do it.

The thermoplastic resin laminate of the present invention is a thermoplastic resin laminate having a vinyl copolymer resin (A) layer on both sides of a thermoplastic resin composition (B) layer containing a polycarbonate resin and an amorphous copolymer polyester resin. The difference in glass transition temperature between the thermoplastic resin composition (B) and the vinyl copolymer resin (A) is 15 ° C. or less, and the vinyl copolymer resin (A) is represented by the general formula (1). The (meth) acrylic acid ester structural unit (a) including the (meth) acrylic acid ester structural unit (a) and the aliphatic vinyl structural unit (b) represented by the general formula (2) And the aliphatic vinyl structural unit (b) is 80 to 100 mol% based on the total of all structural units in the vinyl copolymer resin (A), and the (meth) acrylic acid ester structural unit (A) and said aliphatic vinyl The molar ratio of the structural unit (b) is 55: 45 to 85: A thermoplastic resin laminate, characterized in that the thermoplastic resin is 15.

（式中、Ｒ５は水素原子またはメチル基であり、Ｒ６はフェニル基または炭素数１〜４の炭化水素置換基を有するフェニル基である。）
すなわち、ビニル共重合樹脂（Ａ’）は、ビニル共重合樹脂（Ａ）の芳香族二重結合を水素化する前の熱可塑性樹脂である。ビニル共重合樹脂（Ａ）において、前記一般式（１）で表される（メタ）アクリル酸エステル構成単位（ａ）と、前記一般式（２）で表される脂肪族ビニル構成単位（ｂ）とのモル比は、５５：４５〜８５：１５の範囲であり、６０：４０〜８０：２０の範囲であるとより好ましい。（メタ）アクリル酸エステル構成単位（ａ）と脂肪族ビニル構成単位（ｂ）との合計に対する（メタ）アクリル酸エステル構成単位（ａ）のモル比が５５％未満であると、熱可塑性樹脂組成物（Ｂ）層との密着性が低くなる場合があるので好ましくない。また、該モル比が８５％を超える範囲であると、得られる熱可塑性樹脂積層体の高温高湿環境での形状安定性が乏しくなるため、好ましくない。 The vinyl copolymer resin (A) used for the thermoplastic resin laminate of the present invention is represented by the structural unit (a) derived from the (meth) acrylate monomer represented by the formula (1) and the following formula (3). The thermoplastic resin containing the structural unit (b) derived from the aromatic vinyl monomer, wherein the proportion of the structural unit (a) to the total of the structural unit (a) and the structural unit (b) is 55 to 85 mol%. Is a thermoplastic resin obtained by hydrogenating 70% or more of the aromatic double bond in the structural unit (b) derived from the aromatic vinyl monomer in the vinyl copolymer resin (A ′).

(In the formula, R5 is a hydrogen atom or a methyl group, and R6 is a phenyl group or a phenyl group having a hydrocarbon substituent having 1 to 4 carbon atoms.)
That is, the vinyl copolymer resin (A ′) is a thermoplastic resin before hydrogenating the aromatic double bond of the vinyl copolymer resin (A). In the vinyl copolymer resin (A), the (meth) acrylate structural unit (a) represented by the general formula (1) and the aliphatic vinyl structural unit (b) represented by the general formula (2) Is in the range of 55:45 to 85:15, and more preferably in the range of 60:40 to 80:20. When the molar ratio of the (meth) acrylate structural unit (a) to the total of the (meth) acrylate structural unit (a) and the aliphatic vinyl structural unit (b) is less than 55%, the thermoplastic resin composition This is not preferable because the adhesion to the product (B) layer may be lowered. Further, if the molar ratio is in a range exceeding 85%, the resulting thermoplastic resin laminate is not preferred because the shape stability in a high temperature and high humidity environment becomes poor.

In the structural unit (a) derived from the (meth) acrylic acid ester monomer represented by the formula (1) constituting the vinyl copolymer resin (A ′), R1 is a hydrogen atom or a methyl group, and R2 is the number of carbon atoms. 1 to 18 hydrocarbon groups. When there are a plurality of structural units (a), the plurality of R1 and R2 may be the same or different. As the (meth) acrylic acid ester monomer, in the structural unit (a), R2 is at least one selected from a methyl group, an ethyl group, a butyl group, a lauryl group, a stearyl group, a cyclohexyl group, and an isobornyl group (meta ) It is preferably a structural unit derived from an acrylate monomer. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, (meth And (meth) acrylic acid alkyl esters such as stearyl acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate. The structural unit (a) is more preferably a structural unit derived from at least one selected from methyl methacrylate and methyl acrylate. Vinyl used for the thermoplastic resin laminate of the present invention by making the structural unit (a) of the vinyl copolymer resin (A ′) a structural unit derived from at least one selected from methyl methacrylate and methyl acrylate. The copolymer resin (A) is excellent in transparency.

In the structural unit (b) derived from the aromatic vinyl monomer represented by the formula (3), R5 is a hydrogen atom or a methyl group, and R6 is a phenyl group or a phenyl having a hydrocarbon substituent having 1 to 4 carbon atoms. It is a group. When there are a plurality of structural units (b), the plurality of R5 and R6 may be the same or different. Examples of the aromatic vinyl monomer include at least one selected from styrene, α-methylstyrene, o-methylstyrene, and p-methylstyrene. More preferably, it is a structural unit derived from styrene in which R5 is a hydrogen atom and R6 is a phenyl group. By using the structural unit (b) as a structural unit derived from styrene, the vinyl copolymer resin (A) used in the thermoplastic resin laminate of the present invention has excellent shape stability in a high-temperature and high-humidity environment. .

The vinyl copolymer resin (A) used for the thermoplastic resin laminate of the present invention is obtained by a method described later, and the wholly aromatic compound in the structural unit (b) derived from the aromatic vinyl monomer of the vinyl copolymer resin (A ′). It can be obtained by hydrogenating 70% or more of the heavy bonds. In the vinyl copolymer resin (A), a part of the aromatic double bond of the phenyl group of R4 (the phenyl group which may have a hydrocarbon substituent having 1 to 4 carbon atoms) in the structural unit (b) is hydrogenated. And a structural unit in which R4 is a phenyl group (that is, a structural unit in which the aromatic double bond of the phenyl group is not hydrogenated). Specific examples of the structural unit in which a part of the aromatic double bond of the phenyl group of R4 is hydrogenated include cyclohexane, cyclohexene, cyclohexadiene, α-methylcyclohexane, α-methylcyclohexene, α-methylcyclohexadiene. , O-methylcyclohexane, o-methylcyclohexene, o-methylcyclohexadiene, p-methylcyclohexane, p-methylcyclohexene, p-methylcyclohexadiene, and at least one component selected therefrom Units may be included. Among them, it is preferable to include a structural unit derived from at least one selected from cyclohexane and α-methylcyclohexane.

The vinyl copolymer resin (A ′) before hydrogenation of the vinyl copolymer resin (A) used in the thermoplastic resin laminate of the present invention is obtained by polymerizing the (meth) acrylate monomer and the aromatic vinyl monomer. Can be manufactured. A known method can be used for the polymerization. For example, it can be produced by a bulk polymerization method, a solution polymerization method or the like. The bulk polymerization method is carried out by a method in which a monomer composition containing the monomer and the polymerization initiator is continuously supplied to a complete mixing tank and continuously polymerized at 100 to 180 ° C. The monomer composition may contain a chain transfer agent as necessary.

The polymerization initiator is not particularly limited, but t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, t-hexylperoxyisopropyl monocarbonate, t-amylperoxynormal Organic peroxides such as octoate, t-butylperoxyisopropyl monocarbonate, di-t-butyl peroxide, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile) ), 2,2′-azobis (2,4-dimethylvaleronitrile) Can be mentioned. These can be used alone or in combination of two or more.

A chain transfer agent is used as necessary, and examples thereof include α-methylstyrene dimer.

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, tetrahydrofuran, Examples include ether solvents such as dioxane and alcohol solvents such as methanol and isopropanol.

The vinyl copolymer resin (A) used for the thermoplastic resin laminate of the present invention is obtained by polymerizing a (meth) acrylic acid ester monomer and an aromatic vinyl monomer to obtain a vinyl copolymer resin (A ′). It is obtained by hydrogenating 70% or more of the aromatic double bond in the structural unit derived from the aromatic vinyl monomer in the copolymer resin (A ′). The solvent used for the hydrogenation reaction may be the same as or different from the polymerization solvent. For example, 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, alcohol solvents such as methanol and isopropanol A solvent can be mentioned.

The method for hydrogenation is not particularly limited, and a known method can be used. For example, it can be carried out in a batch system or a continuous flow system at a hydrogen pressure of 3 to 30 MPa and a reaction temperature of 60 to 250 ° C. By setting the temperature to 60 ° C. or higher, the reaction time does not take too long, and by setting the temperature to 250 ° C. or lower, there are few occurrences of molecular chain scission or ester site hydrogenation.

Examples of the catalyst used in the hydrogenation reaction include metals such as nickel, palladium, platinum, cobalt, ruthenium, and rhodium or oxides or salts or complex compounds of these metals, carbon, alumina, silica, silica / alumina, and diatomaceous earth. And a solid catalyst supported on a porous carrier.

The vinyl copolymer resin (A) used in the thermoplastic resin laminate of the present invention is such that in the vinyl copolymer resin (A ′), 70% or more of the aromatic double bond in the structural unit derived from the aromatic vinyl monomer is contained. It was obtained by hydrogenation. That is, the ratio of the aromatic double bond remaining in the structural unit derived from the aromatic vinyl monomer is 30% or less. If it is in the range exceeding 30%, the transparency of the vinyl copolymer resin (A) is lowered, and as a result, the transparency of the thermoplastic resin laminate of the present invention may be lowered. The ratio of the aromatic double bond remaining in the structural unit derived from the aromatic vinyl monomer is preferably less than 10%, more preferably less than 5%. The vinyl copolymer resin (A) is a commonly used additive such as an antioxidant, an anti-coloring agent, an ultraviolet absorber, a light diffusing agent, a flame retardant, a release agent, a lubricant, an antistatic agent, and a dye / pigment. May be included.

The weight average molecular weight of the vinyl copolymer resin (A) is not particularly limited, but is preferably 40,000 to 500,000, and preferably 50,000 to 300,000 from the viewpoint of strength and moldability. Is more preferable. The said weight average molecular weight is a weight average molecular weight of standard polystyrene conversion measured by gel permeation chromatography (GPC).

The glass transition temperature of the vinyl copolymer resin (A) is preferably in the range of 110 to 160 ° C. More preferably, it is 120-145 degreeC. When the glass transition temperature of the vinyl copolymer resin (A) is less than 110 ° C., the thermoplastic resin laminate provided in the present invention may cause dimensional change or warpage in a high temperature and high humidity environment, and the thermoplastic resin. It becomes difficult to set the glass transition temperature difference with the composition (B) layer to 15 ° C. or less. As a result, it is difficult to obtain a laminate having good smoothness, and there is a tendency that residual strain during molding tends to increase, and warpage tends to occur in a high temperature and high humidity environment, which is not preferable. Moreover, since the glass transition temperature difference with a thermoplastic resin composition (B) layer exceeds 15 degreeC as the glass transition temperature of vinyl copolymer resin (A) is higher than 160 degreeC, at the time of peeling from a forming roll. Appearance defects tend to occur, which is not preferable.

The proportion of the vinyl copolymer resin (A) in the vinyl copolymer resin (A) layer used in the thermoplastic resin laminate of the present invention is preferably 70% by weight or more, more preferably 80% by weight, and particularly preferably 90% by weight or more. In addition to the vinyl copolymer resin (A), other resins can be blended in the vinyl copolymer resin (A) layer used in the thermoplastic resin laminate of the present invention as long as the transparency is not impaired. Examples of other resins include polystyrene, methyl methacrylate-styrene copolymer resin, acrylonitrile-styrene copolymer resin, polymethyl methacrylate, polycarbonate, polyester, and the like. Specifically, trade names: Estyrene MS200 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Regis Phi R-100 (manufactured by Denki Kagaku Kogyo Co., Ltd.), XIRAN SZ15170 (manufactured by Polyscope), Toyostyrene T080 (Toyostyrene Co., Ltd.) )) And the like. In addition, the vinyl copolymer resin (A) is an antioxidant, a coloring inhibitor, an ultraviolet absorber, a light diffusing agent, a flame retardant, a mold release agent, a lubricant, an antistatic agent, a dye / pigment and the like. An additive may be included.

The thermoplastic resin composition (B) used for the thermoplastic resin laminate of the present invention is characterized by containing a polycarbonate resin and an amorphous copolymer polyester resin.

The polycarbonate resin used in the thermoplastic resin composition (B) of the present invention can be obtained by interfacial polymerization of an aromatic dihydroxy compound or a small amount thereof and a polyhydroxy compound and phosgene, or the above aromatic dihydroxy compound and carbonic acid. This is a thermoplastic polycarbonate polymer which may be branched by a transesterification reaction with a diester. For example, a carbonate polymer containing bisphenol A as a main raw material is used. The molecular weight of the polycarbonate resin to be used is preferably such that a sheet can be produced by ordinary extrusion molding, and the weight average molecular weight in terms of polystyrene is preferably 45,000 to 70,000.

The amorphous copolymer polyester resin used in the thermoplastic resin composition (B) of the present invention is composed of at least three or more structural units selected from the following structural units having a dicarboxylic acid skeleton and structural units having a diol skeleton. Is a polycondensate. The dicarboxylic acid structural unit is not particularly limited, but succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, decanedicarboxylic acid, norbornane dicarboxylic acid, Aliphatic dicarboxylic acids such as tricyclodecanedicarboxylic acid and pentacyclododecanedicarboxylic acid and ester-forming derivatives thereof; terephthalic acid (hereinafter referred to as PTA), isophthalic acid, phthalic acid, 2-methylterephthalic acid, naphthalenedicarboxylic acid And dicarboxylic acid structural units derived from aromatic dicarboxylic acids such as biphenyldicarboxylic acid and tetralindicarboxylic acid, and ester-forming derivatives thereof. The diol structural unit is not particularly limited, but ethylene glycol (hereinafter referred to as EG), trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, propylene Aliphatic diols such as glycol and neopentyl glycol; polyether compounds such as polyethylene glycol, polypropylene glycol and polybutylene glycol; 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol (hereinafter referred to as CHDM) 1,2-decahydronaphthalene diethanol, 1,3-decahydronaphthalene diethanol, 1,4-decahydronaphthalene diethanol, 1,5-decahydronaphthalene diethanol, 1,6-decahydronaphtha Cycloaliphatic diols such as 1,7-decahydronaphthalene diethanol, tetralin dimethanol, norbornene dimethanol, tricyclodecane dimethanol, pentacyclododecane dimethanol; 3,9-bis (1,1- Dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane (hereinafter referred to as SPG), 5-methylol-5-ethyl-2- (1,1-dimethyl- Cyclic acetals such as 2-hydroxyethyl) -1,3-dioxane; 4,4 ′-(1-methylethylidene) bisphenol, methylenebisphenol (bisphenol F), 4,4′-cyclohexylidenebisphenol (bisphenol Z) , 4,4′-sulfonylbisphenol (bisphenol S), etc. Phenols; alkylene oxide adducts of the bisphenols; aromatic dihydroxy compounds such as hydroquinone, resorcin, 4,4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenylbenzophenone; and the fragrance A diol structural unit derived from an alkylene oxide adduct of a group dihydroxy compound can be exemplified.

The amorphous copolymer polyester resin used in the thermoplastic resin composition (B) of the present invention has transparency, impact resistance, compatibility with polycarbonate, and a glass transition temperature of 110 ° C. or lower. preferable. As a composition satisfying the above, it is preferable to select PTA as the dicarboxylic acid structural unit, and it is preferable to select a combination of EG and CHDM or a combination of EG and SPG as the diol structural unit.

When PTA is selected as the dicarboxylic acid structural unit, and EG and CHDM are selected as the diol structural unit, the ratio of the diol structural unit derived from CHDM in the total diol structural unit in the amorphous copolymer polyester resin used in the present invention is: It is preferable that it is 30-90 mol%, More preferably, it is 50-80 mol%. When the said ratio is smaller than 30 mol%, compatibility with a polycarbonate is bad and sufficient transparency may not be obtained, and it is not preferable. Moreover, when larger than 90 mol%, crystallinity may be shown and it is not preferable. When PTA is selected as the dicarboxylic acid structural unit, and EG and SPG are selected as the diol structural unit, the ratio of the diol structural unit derived from SPG in the total diol structural unit in the amorphous copolymer polyester resin used in the present invention is: It is preferable that it is 10-80 mol%, More preferably, it is 20-60 mol%. When the said ratio is smaller than 10 mol%, compatibility with a polycarbonate is bad and sufficient transparency may not be obtained, and it is not preferable. Moreover, when larger than 80 mol%, crystallinity may be shown and it is not preferable. In the amorphous copolyester resin used in the present invention, the proportion of dicarboxylic acid structural units derived from PTA in all dicarboxylic acid structural units is preferably 70 mol% or more. When the amorphous copolymer polyester resin has the diol constituent unit and the dicarboxylic acid constituent unit, an amorphous copolymer polyester resin having a glass transition temperature of 95 ° C. or lower is obtained, and the glass of the thermoplastic resin composition (B) layer is obtained. This is preferable because the transition temperature lowering effect is high. The thermoplastic resin laminate of the present invention is excellent in transparency, impact resistance, shape stability in a high temperature and high humidity environment, and economy.

The amorphous copolymer polyester resin used for the thermoplastic resin laminate of the present invention preferably contains 5 to 25 ppm of titanium atoms. When the amorphous copolymerized polyester resin contains titanium atoms in the above range, the amorphous copolymerized polyester resin has excellent moldability, mechanical strength, and thermal stability. The titanium atom is preferably contained as a titanate compound in the amorphous copolymerized polyester resin. The titanate ester compound is preferably added as a catalyst during the production of the amorphous copolymer polyester resin. As titanate ester, tetra-n-butyl titanate, tetra-n-butyl titanate dimer, tetra-n-butyl titanate trimer, tetra-n-butyl titanate tetramer, tetra-t-butyl titanate, tetra-n-propyl titanate , Tetraisopropyl titanate, tetraphenyl titanate, tetracyclohexyl titanate, and tetrabenzyl titanate. Of these, tetra-n-butyl titanate is particularly preferred. The titanic acid ester compound needs to be added so as to contain titanium atoms in the above range in consideration of loss due to scattering during the production of the amorphous copolymer polyester resin, particularly during polycondensation.

Moreover, it is preferable that the amorphous copolymerization polyester resin used for the thermoplastic resin laminated body of this invention contains 20-150 ppm of phosphorus atoms. When the amorphous copolymer polyester resin contains a phosphorus atom in the above range, the color tone, thermal stability, moldability, and mechanical strength of the amorphous copolymer polyester resin are excellent. The phosphorus atom needs to be contained as a monophosphate ester and / or a monophosphite compound in the amorphous copolyester resin. The monophosphate ester and / or the monophosphite compound needs to be added as an additive during the polymerization of the amorphous copolymer polyester resin. Monophosphate compounds include methyl phosphate, ethyl phosphate, butyl phosphate, phenyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, diphenyl phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate And phosphoric acid esters such as triphenyl phosphate, and monophosphorous acid ester compounds include methyl phosphite, ethyl phosphite, butyl phosphite, phenyl phosphite, dimethyl phosphite, phosphorous acid Examples include diethyl acid, dibutyl phosphite, diphenyl phosphite, trimethyl phosphite, triethyl phosphite, tributyl phosphite, triphenyl phosphite. Among these, trimethyl phosphate and triethyl phosphate are particularly preferable. The monophosphate ester and / or the monophosphite compound should be added so as to contain phosphorus atoms in the above range in consideration of loss due to scattering during polymerization of the amorphous copolymer polyester resin, particularly during polycondensation. is there. When the phosphorus atom contained in the amorphous copolyester resin used in the present invention is derived from a compound other than a monophosphate ester and / or a monophosphite compound, for example, from a diphosphate ester, more Specifically, when it is derived from 1,3-phenylenebis (dixylenyl phosphate), it is not preferable because sufficient molding stability cannot be obtained such as foaming during molding of the thermoplastic resin composition. The thermoplastic resin composition can also be used when the amorphous copolymer polyester resin used in the present invention is melt-kneaded with a mono- or twin-screw extruder or the like so that the amount of phosphorus atoms is a predetermined amount. It is not preferable because sufficient molding stability cannot be obtained such as foaming during molding of the product.

In the amorphous copolymer polyester resin used for the thermoplastic resin laminate of the present invention, the weight ratio (P / Ti) of phosphorus atoms to titanium atoms is preferably 2.5 to 20.0. P / Ti is preferably 3.0 to 15.0, more preferably 3.5 to 10.0. When P / Ti is in the above range, the color tone, thermal stability, moldability, and mechanical strength of the amorphous copolymer polyester resin are excellent. Furthermore, the thermal stability during molding of a thermoplastic resin composition comprising a polycarbonate resin and an amorphous copolyester resin is excellent. When P / Ti is 2.5 or less, the color tone and thermal stability of the amorphous copolymer polyester resin are inferior, and the thermoplastic resin composition comprises a polycarbonate resin and an amorphous copolymer polyester resin. The thermal stability during the molding of (B) is inferior. As a result, an abnormal increase in molecular weight, poor appearance due to foaming, bubbles, and the like occur during molding of the thermoplastic resin composition (B). Moreover, since the conditions at the time of shaping | molding a thermoplastic resin composition (B) will receive restrictions, for example in terms of temperature and a residence time, it is unpreferable.

The method for producing the amorphous copolyester resin used in the thermoplastic resin laminate of the present invention is not particularly limited, and conventionally known methods can be applied. Examples thereof include a melt polymerization method such as a transesterification method and a direct esterification method, or a solution polymerization method. Various kinds of commonly used additives may be added to the amorphous copolyester resin. Examples of the additives include transesterification catalyst, esterification catalyst, etherification inhibitor, heat stabilizer, light stabilizer, etc. And various stabilizers, polymerization regulators and the like.

The ratio of the polycarbonate resin and the amorphous copolymer polyester resin in the thermoplastic resin composition (B) used in the thermoplastic resin laminate of the present invention is the polycarbonate resin relative to the total of the polycarbonate resin and the amorphous copolymer polyester resin. And the glass transition temperature is preferably in the range of 110 to 145 ° C, more preferably in the range of 120 to 135 ° C. If the ratio of the polycarbonate resin is less than 50% by weight, the impact resistance becomes poor, which is not preferable. Further, when the proportion of the polycarbonate resin exceeds 95% by weight, the glass transition temperature of the thermoplastic resin composition (B) increases, and the glass transition temperature difference with the vinyl copolymer resin (A) layer tends to increase. It becomes difficult to form a laminate having good smoothness. By setting the ratio of the polycarbonate resin and the amorphous copolyester resin in the thermoplastic resin composition within the above range, the thermoplastic resin laminate of the present invention can be easily molded into a laminate having good smoothness. It has the advantages of excellent impact resistance and dimensional stability in high temperature and high humidity environments.

The thermoplastic resin composition (B) used for the thermoplastic resin laminate of the present invention may contain a rubber-based material other than polycarbonate resin and amorphous copolymer polyester resin as long as transparency is not impaired. Examples of rubber materials include butadiene-acrylonitrile-styrene core-shell rubber, methyl methacrylate-butadiene-styrene core-shell rubber, methyl methacrylate-butyl acrylate-styrene core-shell rubber, octyl acrylate-butadiene-styrene core-shell rubber, Examples include alkyl acrylate-butadiene-acrylonitrile-styrene core-shell type rubber, butadiene-styrene core-shell type rubber, methyl methacrylate-butyl acrylate type core-shell type rubber, and the like. These can be used alone or in combination. You can also The average particle diameter of the rubber material is 1 μm or less, preferably 0.8 μm or less, and more preferably 0.7 μm or less. If the average particle diameter of the rubber-based material exceeds 1 μm, the probability that light is scattered on the rubber-based material and scattered increases, so that the transparency tends to decrease. The refractive index of the rubber material is 0.020 or less, preferably 0.018 or less, more preferably 0.015 or less, in absolute value difference with the refractive index of the thermoplastic resin composition (B). When the absolute value difference of the refractive index exceeds 0.020, light tends to be scattered at the interface between the thermoplastic resin composition (B) and the rubber-based material, and transparency is deteriorated. By adding a rubber-based material within a range that does not impair transparency, impact resistance can be further imparted to the thermoplastic resin laminate of the present invention.

The total ratio of the polycarbonate resin and the amorphous copolymer polyester resin in the thermoplastic resin composition (B) used in the thermoplastic resin laminate of the present invention is preferably 70% by weight or more, more preferably 80% by weight, and more preferably 90% by weight or more. Is particularly preferred. The thermoplastic resin composition (B) used in the thermoplastic resin laminate of the present invention may contain a resin other than a polycarbonate resin and an amorphous copolymer polyester resin, and the polycarbonate resin and the amorphous copolymer polyester resin. Examples of other resins include polyester resins other than amorphous copolymer polyester resins such as polyethylene terephthalate, polyethylene naphthalate, and polyarylate.

In addition, various commonly used additives may be added to the thermoplastic resin composition (B) used in the thermoplastic resin laminate of the present invention. Examples of the additives include antioxidants and anti-coloring agents. UV absorbers, light diffusing agents, flame retardants, mold release agents, lubricants, antistatic agents, dyes and pigments, and the like. The method of mixing is not particularly limited, and a method of compounding the whole amount, a method of dry blending the master batch, a method of dry blending the whole amount, and the like can be used.

Further, the thermoplastic resin composition (B) used for the thermoplastic resin laminate of the present invention is produced by a known technique. Although it does not specifically limit, For example, it obtains by melt-kneading, after dry-mixing the component containing a polycarbonate resin and an amorphous copolyester resin.

The thermoplastic resin laminate of the present invention comprises a layer comprising a thermoplastic resin composition (B) and a vinyl copolymer resin (A) layer provided on both sides of the layer (B).

As a method for producing the thermoplastic resin laminate of the present invention, a known laminating technique such as a multicolor injection molding method, a film insert method, a melt extrusion method, an extrusion laminating method, a hot pressing method, or a solution casting method is used. I can do it. Moreover, you may use the adhesive agent suitable between resin for these lamination | stacking, or adhesive resin.

The production of the thermoplastic resin laminate by the melt extrusion method will be further described in detail. For production of the thermoplastic resin laminate of the present invention, a known melt extrusion method such as a T-die extrusion method or an inflation method can be used. From the viewpoint of obtaining a laminate with little thickness unevenness, It is desirable to select an extrusion method. A generally used extruder may be used as an apparatus for melting the resin, and a single-screw extruder or a multi-screw extruder may be used. The extruder may have one or more vents, and may remove moisture, low-molecular substances, and the like from the melted resin by reducing the vents. Moreover, you may provide a wire-mesh filter, a sintered filter, a gear pump, etc. as needed at the front-end | tip or downstream side of an extruder. As a method of laminating the resin, a known method such as a feed block method or a multi-manifold method can be used. There are various types of T-die, such as a coat hanger die, a fish tail die, and a stack plate die, and any of them can be selected.

The resin temperature during extrusion is preferably 200 to 320 ° C. If it is less than 200 ° C., the fluidity of the resin is insufficient, and the shape of the surface of the transfer roll is not transferred, so that the resulting thermoplastic resin laminate may have poor smoothness. On the other hand, when the temperature exceeds 320 ° C., the resin is decomposed, and this causes undesirable appearance, coloring, deterioration of heat distortion resistance, deterioration of working environment due to odor, and the like, which is not preferable. More preferably, the resin temperature during extrusion is 220 to 300 ° C. When the extrusion temperature is in the above range, the smoothness and transparency of the resulting thermoplastic resin laminate are excellent.

Although the conventionally well-known method can be used for the cooling method of the molten resin extruded from T-die, generally it cools with a cooling roll. Since the vinyl copolymer resin (A) and the thermoplastic resin composition (B) used in the present invention are substantially amorphous resins, the temperature of the cooling roll can be set widely. In the case of obtaining a sheet molded product having no appearance defect at the time of peeling from the roll and having good smoothness, the temperature of the cooling roll should be not less than the glass transition temperature TgA and not more than TgA + 20 ° C. of the vinyl copolymer resin (A). It is preferably TgA or more and TgA + 10 ° C. or less. It is preferable to set the cooling roll temperature within the above range and to control the discharge speed and the take-up speed according to the apparatus. When the temperature of a cooling roll exists in the said range, the thermoplastic resin laminated body obtained becomes the thing excellent in smoothness.

  The thickness of the thermoplastic resin laminate in the present invention is preferably in the range of 0.1 to 10.0 mm. If the thickness is less than 0.1 mm, transfer failure or thickness accuracy failure may occur due to bank omission. In addition, when the thickness exceeds 10.0 mm, a thickness accuracy defect or an appearance defect due to uneven cooling after molding may occur. More preferably, it is the range of 0.3-5.0 mm, More preferably, it is the range of 0.3-3.0 mm.

The thickness (one side) of the vinyl copolymer resin (A) layer of the thermoplastic resin laminate in the present invention is preferably 25% or less of the total thickness of the thermoplastic resin laminate, and is in the range of 10 to 500 μm. Is preferred. If the thickness (one side) of the vinyl copolymer resin (A) layer exceeds 25% of the total thickness of the thermoplastic resin laminate, warping may occur in a high temperature and high humidity environment, and sufficient impact resistance will be obtained. It may not be possible. If the thickness is less than 10 μm, scratch resistance and weather resistance may be insufficient, and if it exceeds 500 μm, warping may occur in a high-temperature and high-humidity environment, and sufficient impact resistance may be obtained. It may not be possible. More preferably, it is the range of 30-200 micrometers.

The thermoplastic resin laminate of the present invention can be subjected to any one or more of hard coat treatment, antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment and antiglare treatment on one or both sides thereof. . The method for these treatments is not particularly limited, and a known method can be used. For example, a method of applying a thermosetting or photocurable film, a method of applying a reflection reducing coating, a method of depositing a dielectric thin film, a method of applying an antistatic coating, and the like can be mentioned. Known coating agents can be used, for example, organic coating agents such as melamine resin, urethane resin, acrylic resin and ultraviolet curable acrylic resin, silicon coating agents such as silane compounds, and inorganic such as metal oxides. -Based coating agents and organic-inorganic hybrid coating agents.

The thermoplastic resin laminate of the present invention is characterized by excellent transparency, impact resistance, surface hardness, and shape stability in a high humidity environment. The thermoplastic resin laminate is a transparent substrate material, transparent It is used as a protective material, and is suitably used for a front panel of a display device that requires high shape stability particularly in a high temperature and high humidity environment.

  Hereinafter, the present invention will be described specifically by way of examples. However, the present invention is not limited to these examples and comparative examples. The thermoplastic resin laminates obtained in the examples and comparative examples were evaluated as follows.

<Hydrogenation rate of copolymer>
About the vinyl copolymer resin obtained in the following synthesis examples, it calculated | required by the decreasing rate of the absorption of 260 nm in the UV spectrum measurement before and behind hydrogenation reaction. From the absorbance (A1) at the concentration (C1) of the resin before the hydrogenation reaction and the absorbance (A2) at the concentration (C2) of the resin after the hydrogenation reaction, the following formula was used.
Hydrogenation rate (%) = [1- (A2 × C1) / (A1 × C2)] × 100

<Concentration of phosphorus atom and titanium atom>
Regarding the amorphous copolyester resin obtained in the following synthesis examples, the concentration of phosphorus atoms and titanium atoms in the noncrystalline copolyester resin was determined by an ICP emission analyzer (manufactured by Shimadzu Corporation: ICPE-9000). ).

<Thickness measurement>
The thermoplastic resin laminates obtained in the following examples and comparative examples were measured using a digital micrometer (manufactured by Sony Magnescale Co., Ltd .: M-30), and the obtained thermoplastic resin laminates were measured. The average of 10 points was taken as the thickness of the thermoplastic resin laminate.

<Transparency evaluation>
For the thermoplastic resin laminates obtained in the following examples and comparative examples, the total light transmittance is a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd .: COH-400) in accordance with JIS K 7105 and ASTM D1003. Measured with The thing with 90% or more of total light transmittance in thickness 0.6mm was set as the pass.

<Smoothness evaluation>
About the thermoplastic resin laminates obtained in the following examples and comparative examples, from a 0.6 mm thick thermoplastic resin laminate, a rectangular test of 90 mm in length and 60 mm in width, with the extrusion direction as the length and the width direction as the width. Cut out the piece and place it on a horizontal surface so that the test piece is concave upward. Place a weight of φ38mm and weight 300g on the center of the test piece and fix it, and measure the gap length between the four corners of the test piece and the horizontal plane. And what the average value does not exceed 1.0 mm was set as the pass.

<Adhesion evaluation>
For the thermoplastic resin laminates obtained in the following examples and comparative examples, a test piece was cut out to 100 mm × 300 mm, and the test piece was pressed into a cylinder with a diameter of 80 mm so that the long side was in the circumferential direction, and the laminated resin The presence or absence of peeling at the interface was evaluated. The number of sheets where peeling occurred was 2 or less out of 10 sheets.

<Abrasion resistance evaluation>
For the thermoplastic resin laminates obtained in the following examples and comparative examples, the pencil hardness is vinyl according to JIS K 5600-5-4 using pencils of various hardness (Uni, manufactured by Mitsubishi Pencil Co., Ltd.). The pencil hardness of the copolymer resin (A) layer was measured. Those having a pencil hardness of 3H or more were accepted.

<Impact resistance evaluation>
The thermoplastic resin laminates obtained in the following Examples and Comparative Examples were evaluated by a falling ball test with the vinyl copolymer resin (A) layer on the upper side and the thermoplastic resin composition (B) layer on the lower side. . The falling ball test is performed by fixing the sample between φ50 flanges, dropping a φ15mm, 30.0g metal ball, and measuring the height when the test piece mounted on the bottom breaks at 10cm intervals. A value up to 100 cm in height at the time of breaking was measured. The thing with the height at the time of a fracture | rupture of 50 cm or more was set as the pass.

<Shape stability evaluation in high temperature and high humidity environment>
About the thermoplastic resin laminates obtained in the following examples and comparative examples, from a 0.6 mm thick thermoplastic resin laminate, a rectangular test of 90 mm in length and 60 mm in width, with the extrusion direction as the length and the width direction as the width. The piece was cut out, fastened to a short side central portion of 5 mm with a clip having a width of 13 mm, suspended so that the test piece was vertical, and allowed to stand for 16 hours in a constant temperature and humidity chamber set at a temperature of 85 ° C. and a humidity of 85%. The test piece after the test is placed on a horizontal surface so as to be concave upward, and a weight of φ38 mm and a weight of 300 g is placed on the center of the test piece and fixed, and the gap length between the four corners of the test piece and the horizontal surface is measured. The average deformation amount from before the test did not exceed 1.0 mm.

Synthesis Example 1 [Production of Vinyl Copolymer Resin (A1)]
Purified methyl methacrylate (Mitsubishi Gas Chemical Co., Ltd.) 77.0 mol%, purified styrene (Wako Pure Chemical Industries, Ltd.) 23.0 mol%, and t-amylperoxy as a polymerization initiator A monomer composition comprising 2-ethylhexanoate (produced by Arkema Yoshitomi Co., Ltd., trade name: Luperox 575) 0.002 mol% is continuously supplied at a rate of 1 kg / h to a 10 L complete mixing tank with a helical ribbon blade. Then, continuous polymerization was carried out at an average residence time of 2.5 hours and a polymerization temperature of 150 ° C. It extracted continuously from the bottom part so that the liquid level of a polymerization tank might become constant, and it introduced into the solvent removal apparatus, and obtained the pellet-like vinyl copolymer resin (A1 ').
The obtained vinyl copolymer resin (A1 ′) was dissolved in methyl isobutyrate (manufactured by Kanto Chemical Co., Inc.) to prepare a 10 wt% methyl isobutyrate solution. A 1000 mL autoclave apparatus was charged with 500 parts by weight of a 10% by weight methyl isobutyrate solution of (A1 ′) and 1 part by weight of 10% by weight Pd / C (manufactured by NE Chemcat Co., Ltd.) at a hydrogen pressure of 9 MPa and 200 ° C. for 15 hours. Retained and hydrogenated the benzene ring site. The catalyst was removed by a filter and introduced into a solvent removal apparatus to obtain a pellet-like vinyl copolymer resin (A1). As a result of measurement by ¹ H-NMR, the proportion of the methyl methacrylate structural unit was 75 mol%, and as a result of the absorbance measurement at a wavelength of 260 nm, the hydrogenation reaction rate at the benzene ring site was 99%. The resulting vinyl copolymer resin (A1) had a glass transition temperature of 120 ° C.

Synthesis Example 2 [Production of vinyl copolymer resin (A2)]
A vinyl copolymer resin (A2) was prepared in the same manner as in Synthesis Example 1 except that the amount of methyl methacrylate used in Synthesis Example 1 was 62.0 mol% and the amount of styrene was 38.0 mol%. Obtained. As a result of the measurement by ¹ H-NMR, the proportion of the methyl methacrylate structural unit was 60 mol%, and as a result of the absorbance measurement at a wavelength of 260 nm, the hydrogenation reaction rate at the benzene ring site was 99%. The vinyl copolymer resin (A2) obtained had a glass transition temperature of 120 ° C.

Synthesis Example 3 [Production of vinyl copolymer resin (A3)]
A vinyl copolymer resin (A3) was prepared in the same manner as in Synthesis Example 1 except that the amount of methyl methacrylate used in Synthesis Example 1 was 92.0 mol% and the amount of styrene was 8.0 mol%. Obtained. As a result of measurement by ¹ H-NMR, the proportion of the methyl methacrylate structural unit was 90 mol%, and as a result of absorbance measurement at a wavelength of 260 nm, the hydrogenation reaction rate at the benzene ring site was 99%. The obtained vinyl copolymer resin (A3) had a glass transition temperature of 112 ° C.

Synthesis Example 4 [Production of vinyl copolymer resin (A4)]
A vinyl copolymer resin (A4) was prepared in the same manner as in Synthesis Example 1 except that the amount of methyl methacrylate used in Synthesis Example 1 was 32.0 mol% and the amount of styrene was 68.0 mol%. Obtained. As a result of measurement by ¹ H-NMR, the proportion of the methyl methacrylate structural unit was 30 mol%, and as a result of the absorbance measurement at a wavelength of 260 nm, the hydrogenation reaction rate at the benzene ring site was 99%. The obtained vinyl copolymer resin (A4) had a glass transition temperature of 123 ° C.

Synthesis Example 5 [Production of Amorphous Copolyester Resin]
A 150-liter polyester resin production system equipped with a packed-column rectification column, a partial condenser, a full condenser, a cold trap, a stirrer, a heating device, and a nitrogen introduction tube is charged with 36.4 kg of terephthalic acid and 17.0 kg of ethylene glycol. The esterification reaction was carried out by a conventional method. To the obtained ester, 10.2 kg of ethylene glycol for depolymerization and 5.7 g of germanium dioxide were added, and depolymerization was performed at 225 ° C. under a nitrogen stream. After reacting for 3 hours while distilling off the water produced, ethylene glycol was distilled off at 215 ° C. and 13.3 kPa. Tetra-n-butyl titanate 3.7 g, potassium acetate 4.3 g, triethyl phosphate 19.9 g, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4, 20.6 kg of 8,10-tetraoxaspiro [5.5] undecane (SPG) was added, and the reaction was performed at 225 ° C. and 13.3 kPa for 3 hours. The resulting ester was heated and depressurized, and finally subjected to a polycondensation reaction at 270 ° C. under a high vacuum (130 Pa or less). When the melt viscosity reached 1400 Pa · s, the reaction was terminated. A polymerized polyester resin was obtained. As a result of measurement by ¹ H-NMR, the ratio of the SPG structural unit to the total diol structural unit was 30 mol%, and the glass transition temperature was 95 ° C. Moreover, the density | concentrations of the phosphorus atom and titanium atom in the obtained amorphous copolymer polyester are 24.1 ppm and 8.9 ppm, respectively, and the weight ratio (P / Ti) of a phosphorus atom and a titanium atom is 2.7. Met.

Production Example 1 [Production of Thermoplastic Resin Composition (B1)]
Polycarbonate resin (Mitsubishi Engineering Plastics Co., Ltd. Iupilon S-1000, glass transition temperature: 143 ° C.) and amorphous copolymer polyester resin (Eastman Chemical Co., Ltd. Eastar DN011 (dicarboxylic acid structural unit PTA: 100 mol%, diol) Structural unit EG: CHDM = 39: 61 (molar ratio)), glass transition temperature: 83 ° C., phosphorus atom concentration: 64 ppm, titanium atom concentration: 14 ppm, weight ratio of phosphorus atom to titanium atom (P / Ti): 4. 6) is continuously introduced into a twin-screw extruder having a shaft diameter of 30 mm and extruded under conditions of a cylinder temperature of 270 ° C. and a discharge speed of 25 kg / h. A thermoplastic resin composition (B1) was obtained. The glass transition temperature of the obtained thermoplastic resin composition (B1) was 134 ° C.

Production Example 2 [Production of Thermoplastic Resin Composition (B2)]
A thermoplastic resin mixture obtained by dry-mixing a polycarbonate resin (Iupilon S-1000 manufactured by Mitsubishi Engineering Plastics Co., Ltd.) and an amorphous copolyester resin (Eastman DN011 manufactured by Eastman Chemical Co., Ltd.) in a weight ratio of 70:30. A thermoplastic resin composition (B2) was obtained in the same manner as in Production Example 1 except that was used. The thermoplastic resin composition (B2) obtained had a glass transition temperature of 125 ° C.

Production Example 3 [Production of Thermoplastic Resin Composition (B3)]
A thermoplastic resin mixture obtained by dry-mixing a polycarbonate resin (Iupilon S-1000 manufactured by Mitsubishi Engineering Plastics Co., Ltd.) and an amorphous copolymer polyester resin (Eastman Chemical Co. Eastal DN011) to a weight ratio of 55:45, respectively. A thermoplastic resin composition (B3) was obtained in the same manner as in Production Example 1 except that was used. The thermoplastic resin composition (B3) obtained had a glass transition temperature of 116 ° C.

Production Example 4 [Production of thermoplastic resin composition (B4)]
A thermoplastic resin mixture obtained by dry-mixing a polycarbonate resin (Iupilon S-1000 manufactured by Mitsubishi Engineering Plastics Co., Ltd.) and an amorphous copolyester resin (Eastman DN011 manufactured by Eastman Chemical Co., Ltd.) in a weight ratio of 70:30. (Refractive index 1.57 (calculated value)) 100 parts by weight of methyl methacrylate-butadiene-styrene core-shell type rubber (Kaneka Corporation Kane Ace M-300 (refractive index 1.56) 5 parts by weight) A thermoplastic resin composition (B4) was obtained in the same manner as in Production Example 1, except that it was continuously introduced into a twin-screw extruder having a shaft diameter of 30 mm, and the glass of the obtained thermoplastic resin composition (B4) was obtained. The transition temperature was 120 ° C.

Production Example 5 [Production of thermoplastic resin composition (B5)]
A thermoplastic resin mixture obtained by dry-mixing polycarbonate resin (Iupilon S-1000 manufactured by Mitsubishi Engineering Plastics Co., Ltd.) and the amorphous copolymer polyester resin obtained in Synthesis Example 5 to a weight ratio of 70:30, respectively. A thermoplastic resin composition (B5) was obtained in the same manner as in Production Example 1 except that it was used. The resulting thermoplastic resin composition (B5) had a glass transition temperature of 129 ° C.

Production Example 6 [Production of thermoplastic resin composition (B6)]
A thermoplastic resin mixture obtained by dry-mixing a polycarbonate resin (Iupilon S-1000 manufactured by Mitsubishi Engineering Plastics Co., Ltd.) and an amorphous copolymer polyester resin (Eastman DN011 manufactured by Eastman Chemical Co., Ltd.) in a weight ratio of 30:70, respectively. A thermoplastic resin composition (B6) was obtained in the same manner as in Production Example 1 except that was used. The glass transition temperature of the obtained thermoplastic resin composition (B6) was 101 ° C.

Example 1 [resin (A1) / resin (B1) / resin (A1)]
Thermoplastic using a multilayer extruder having a single screw extruder with a shaft diameter of 32 mm, a single screw extruder with a shaft diameter of 65 mm, a feed block connected to the full extruder, and a T-die connected to the feed block. The resin laminate was coextruded. The vinyl copolymer resin (A1) obtained in Synthesis Example 1 was continuously introduced into a single-screw extruder having a shaft diameter of 32 mm and extruded under conditions of a cylinder temperature of 250 ° C. and a discharge speed of 20.0 kg / h. Further, the thermoplastic resin composition (B1) obtained in Production Example 1 was continuously introduced into a single-screw extruder having a shaft diameter of 65 mm and extruded at a cylinder temperature of 270 ° C. and a discharge speed of 66.0 kg / h. The feed block connected to the entire extruder was provided with two types and three layers of distribution pins, and the vinyl copolymer resin (A1) and the thermoplastic resin composition (B1) were introduced and laminated at a temperature of 270 ° C. Extruded into a sheet form with a T die having a temperature of 270 ° C. connected to the tip, cooled with three mirror rolls having a temperature of 125 ° C., 120 ° C., and 120 ° C. from the upstream side, and the thermoplastic resin composition (B1) A thermoplastic resin laminate in which vinyl copolymer resin (A1) was laminated on both sides was obtained. The glass transition temperature difference between the thermoplastic resin composition (B1) and the vinyl copolymer resin (A1) was 14 ° C. The thickness of the obtained thermoplastic resin laminate was 0.6 mm, and the thickness of each layer was (A1) / (B1) / (A1) = 70 μm / 460 μm / 70 μm near the center. The results of transparency evaluation, smoothness evaluation, adhesion evaluation, scratch resistance evaluation, impact resistance evaluation, and shape stability evaluation in a high temperature and high humidity environment were all good, and the overall judgment was acceptable.

Example 2 [Resin (A1) / Resin (B2) / Resin (A1)]
In the same manner as in Example 1, except that the thermoplastic resin composition (B2) obtained in Production Example 2 was introduced instead of the thermoplastic resin composition (B1) used in Example 1, a thermoplastic resin composition ( A thermoplastic resin laminate in which vinyl copolymer resin (A1) was laminated on both sides of B2) was obtained. The glass transition temperature difference between the thermoplastic resin composition (B2) and the vinyl copolymer resin (A1) was 5 ° C. The thickness of the obtained thermoplastic resin laminate was 0.6 mm, and the thickness of each layer was (A1) / (B2) / (A1) = 70 μm / 460 μm / 70 μm near the center. The results of transparency evaluation, smoothness evaluation, adhesion evaluation, scratch resistance evaluation, impact resistance evaluation, and shape stability evaluation in a high temperature and high humidity environment were all good, and the overall judgment was acceptable.

Example 3 [Resin (A1) / Resin (B3) / Resin (A1)]
In the same manner as in Example 1 except that the thermoplastic resin composition (B3) obtained in Production Example 3 was introduced instead of the thermoplastic resin composition (B1) used in Example 1, a thermoplastic resin composition ( A thermoplastic resin laminate in which vinyl copolymer resin (A1) was laminated on both sides of B3) was obtained. The glass transition temperature difference between the thermoplastic resin composition (B3) and the vinyl copolymer resin (A1) was 4 ° C. The thickness of the obtained thermoplastic resin laminate was 0.6 mm, and the thickness of each layer was (A1) / (B3) / (A1) = 70 μm / 460 μm / 70 μm near the center. The results of transparency evaluation, smoothness evaluation, adhesion evaluation, scratch resistance evaluation, impact resistance evaluation, and shape stability evaluation in a high temperature and high humidity environment were all good, and the overall judgment was acceptable.

Example 4 [Resin (A1) / Resin (B4) / Resin (A1)]
In the same manner as in Example 1 except that the thermoplastic resin composition (B4) obtained in Production Example 4 was introduced instead of the thermoplastic resin composition (B1) used in Example 1, a thermoplastic resin composition ( A thermoplastic resin laminate in which vinyl copolymer resin (A1) was laminated on both sides of B4) was obtained. The glass transition temperature difference between the thermoplastic resin composition (B4) and the vinyl copolymer resin (A1) was 0 ° C. The thickness of the obtained thermoplastic resin laminate was 0.6 mm, and the thickness of each layer was (A1) / (B4) / (A1) = 70 μm / 460 μm / 70 μm near the center. The results of transparency evaluation, smoothness evaluation, adhesion evaluation, scratch resistance evaluation, impact resistance evaluation, and shape stability evaluation in a high temperature and high humidity environment were all good, and the overall judgment was acceptable.

Example 5 [Resin (A2) / Resin (B2) / Resin (A2)]
The thermoplastic resin composition (B2) is the same as in Example 2 except that the vinyl copolymer resin (A2) obtained in Synthesis Example 2 is introduced instead of the vinyl copolymer resin (A1) used in Example 2. A thermoplastic resin laminate in which a vinyl copolymer resin (A2) was laminated on both sides was obtained. The glass transition temperature difference between the thermoplastic resin composition (B2) and the vinyl copolymer resin (A2) was 5 ° C. The thickness of the obtained thermoplastic resin laminate was 0.6 mm, and the thickness of each layer was (A2) / (B2) / (A2) = 70 μm / 460 μm / 70 μm near the center. The results of transparency evaluation, smoothness evaluation, adhesion evaluation, scratch resistance evaluation, impact resistance evaluation, and shape stability evaluation in a high temperature and high humidity environment were all good, and the overall judgment was acceptable.

Example 6 [Resin (A1) / Resin (B5) / Resin (A1)]
A thermoplastic resin composition (in the same manner as in Example 1 except that the thermoplastic resin composition (B5) obtained in Production Example 5 was introduced instead of the thermoplastic resin composition (B1) used in Example 1. A thermoplastic resin laminate in which vinyl copolymer resin (A1) was laminated on both sides of B5) was obtained. The glass transition temperature difference between the thermoplastic resin composition (B5) and the vinyl copolymer resin (A1) was 9 ° C. The thickness of the obtained thermoplastic resin laminate was 0.6 mm, and the thickness of each layer was (A1) / (B5) / (A1) = 70 μm / 460 μm / 70 μm near the center. The results of transparency evaluation, smoothness evaluation, adhesion evaluation, scratch resistance evaluation, impact resistance evaluation, and shape stability evaluation in a high temperature and high humidity environment were all good, and the overall judgment was acceptable.

Comparative Example 1 [Resin (A3) / Resin (B2) / Resin (A3)]
The vinyl copolymer resin (A3) obtained in Synthesis Example 3 was introduced instead of the vinyl copolymer resin (A1) used in Example 2, and the temperatures of the three mirror rolls were 117 ° C. and 112 ° C. from the upstream side. The thermoplastic resin laminate in which the vinyl copolymer resin (A3) was laminated on both sides of the thermoplastic resin composition (B2) was obtained in the same manner as in Example 2 except that the temperature was 112 ° C. The glass transition temperature difference between the thermoplastic resin composition (B2) and the vinyl copolymer resin (A3) was 13 ° C. The thickness of the obtained thermoplastic resin laminate was 0.6 mm, and the thickness of each layer was (A3) / (B2) / (A3) = 70 μm / 460 μm / 70 μm near the center. Although the results of transparency evaluation, smoothness evaluation, adhesion evaluation, scratch resistance evaluation, and impact resistance evaluation were all good, the results of shape stability evaluation in a high temperature and high humidity environment were poor. The judgment was unacceptable.

Comparative Example 2 [Resin (A4) / Resin (B2) / Resin (A4)]
The vinyl copolymer resin (A4) obtained in Synthesis Example 4 was introduced in place of the vinyl copolymer resin (A1) used in Example 2, and the temperatures of the three mirror rolls were set to 128 ° C and 123 ° C from the upstream side. A thermoplastic resin laminate in which the vinyl copolymer resin (A4) was laminated on both sides of the thermoplastic resin composition (B2) was obtained in the same manner as in Example 2 except that the temperature was 123 ° C. The glass transition temperature difference between the thermoplastic resin composition (B2) and the vinyl copolymer resin (A4) was 2 ° C. The thickness of the obtained thermoplastic resin laminate was 0.6 mm, and the thickness of each layer was (A4) / (B2) / (A4) = 70 μm / 460 μm / 70 μm near the center. The adhesion evaluation was poor, and other evaluations could not be performed. The overall judgment was unacceptable.

Comparative Example 3 [resin (A1) / polycarbonate resin / resin (A1)]
Similar to Example 1 except that a polycarbonate resin (Iupilon S-1000 manufactured by Mitsubishi Engineering Plastics Co., Ltd., glass transition temperature: 143 ° C.) was introduced instead of the thermoplastic resin composition (B1) used in Example 1. Thus, a thermoplastic resin laminate in which the vinyl copolymer resin (A1) was laminated on both sides of the polycarbonate resin was obtained. The glass transition temperature difference between the thermoplastic resin composition (B2) and the vinyl copolymer resin (A4) was 23 ° C. The thickness of the obtained thermoplastic resin laminate was 0.6 mm, and the thickness of each layer was (A1) / polycarbonate resin / (A1) = 70 μm / 460 μm / 70 μm near the center. Although the results of transparency evaluation, adhesion evaluation, scratch resistance evaluation, and impact resistance evaluation were all good, the results of smoothness evaluation and shape stability evaluation in a high temperature and high humidity environment were poor. The judgment was unacceptable.

Comparative Example 4 [Resin (A1) / Resin (B6) / Resin (A1)]
In the same manner as in Example 1, except that the thermoplastic resin composition (B6) obtained in Production Example 6 was introduced instead of the thermoplastic resin composition (B1) used in Example 1, a thermoplastic resin composition ( A thermoplastic resin laminate in which vinyl copolymer resin (A1) was laminated on both sides of B6) was obtained. The glass transition temperature difference between the thermoplastic resin composition (B6) and the vinyl copolymer resin (A1) was 19 ° C. The thickness of the obtained thermoplastic resin laminate was 0.6 mm, and the thickness of each layer was (A1) / (B6) / (A1) = 70 μm / 460 μm / 70 μm near the center. Although the results of transparency evaluation, adhesion evaluation, and scratch resistance evaluation were all good, the results of smoothness evaluation, impact resistance, and shape stability evaluation in a high-temperature and high-humidity environment were poor, and overall judgment Was rejected.

Comparative Example 5 [methacrylic resin / polycarbonate resin / methacrylic resin]
In place of the vinyl copolymer resin (A1) used in Comparative Example 3, a methacrylic resin (Delpet 80N (glass transition temperature 105 ° C.) manufactured by Asahi Kasei Chemicals Corporation) was introduced, and the temperature of the three mirror rolls was set upstream. To a temperature of 110 ° C., 105 ° C., and 105 ° C., a thermoplastic resin laminate in which a methacrylic resin was laminated on both sides of a polycarbonate resin was obtained in the same manner as in Example 1. The glass transition temperature difference between the polycarbonate resin and the methacrylic resin was 38 ° C. The thickness of the obtained thermoplastic resin laminate was 0.6 mm, and the thickness of each layer was about methacrylic resin / polycarbonate resin / methacrylic resin = 70 μm / 460 μm / 70 μm near the center. Although the results of transparency evaluation, adhesion evaluation, scratch resistance evaluation, and impact resistance evaluation were all good, the results of smoothness evaluation and shape stability evaluation in a high temperature and high humidity environment were poor. The judgment was unacceptable.

Comparative Example 6 [Polycarbonate resin]
A polycarbonate resin monolayer was molded using a monolayer extruder having a single screw extruder having a shaft diameter of 65 mm and a T die connected to the extruder. Polycarbonate resin (Iupilon S-1000 manufactured by Mitsubishi Engineering Plastics Co., Ltd., glass transition temperature: 143 ° C.) was continuously introduced into the single screw extruder and extruded at a cylinder temperature of 270 ° C. and a discharge speed of 86.0 kg / h. . It was extruded into a sheet shape with a T-die having a temperature of 270 ° C. connected to the tip, and cooled with three mirror rolls having a temperature of 148 ° C., 143 ° C., and 143 ° C. from the upstream side to obtain a polycarbonate resin monolayer. The thickness of the obtained single layer body was 0.6 mm. Although the results of transparency evaluation, smoothness evaluation, adhesion evaluation, scratch resistance evaluation, impact resistance evaluation, and shape stability evaluation in a high temperature and high humidity environment were all good, the results of the scratch resistance evaluation were It was bad and the comprehensive judgment was unacceptable.

Claims (13)

A thermoplastic resin laminate having a vinyl copolymer resin (A) layer on both sides of a thermoplastic resin composition (B) layer comprising a polycarbonate resin and an amorphous copolymer polyester resin, wherein the thermoplastic resin composition (B) and vinyl copolymer resin (A) have a glass transition temperature difference of 15 ° C. or less, and the vinyl copolymer resin (A) is represented by the following general formula (1) A unit (a) and an aliphatic vinyl structural unit (b) represented by the following general formula (2), the (meth) acrylic ester structural unit (a) and the aliphatic vinyl structural unit (b) And the total proportion of all structural units in the vinyl copolymer resin (A) is 80 to 100 mol%, the (meth) acrylic ester structural unit (a) and the aliphatic vinyl structural unit The molar ratio with (b) is 5 : 45 to 85: The thermoplastic resin laminate, characterized in that the thermoplastic resin is 15.

(In the formula, R1 is a hydrogen atom or a methyl group, and R2 is a group having 1 to 16 carbon atoms.)

(In the formula, R 3 is a hydrogen atom or a methyl group, and R 4 is a cyclohexyl group or a cyclohexyl group having a hydrocarbon substituent having 1 to 4 carbon atoms.) The thermoplastic resin laminate according to claim 1, wherein R1 and R2 in the general formula (1) are methyl groups. The thermoplastic resin laminate according to claim 1, wherein R 4 in the general formula (2) is a cyclohexyl group. The ratio of the polycarbonate resin to the total of the polycarbonate resin and the amorphous copolymer polyester resin in the thermoplastic resin composition (B) is 50 to 95% by weight, and the glass transition temperature of the thermoplastic resin composition (B). Is a range of 110-145 degreeC, The thermoplastic resin laminated body in any one of Claims 1-3. The heat according to any one of claims 1 to 4, wherein the amorphous copolyester resin in the thermoplastic resin composition (B) has a structural unit derived from 1,4-cyclohexanedimethanol in the diol structural unit. Plastic resin laminate. The proportion of structural units derived from 1,4-cyclohexanedimethanol in all diol structural units of the amorphous copolymer polyester resin in the thermoplastic resin composition (B) is 30 to 90 mol%. The thermoplastic resin laminate described in 1. The amorphous copolymer polyester resin in the thermoplastic resin composition (B) is 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10- in the diol constituent unit. The thermoplastic resin laminate according to any one of claims 1 to 4, comprising a structural unit derived from tetraoxaspiro [5.5] undecane. 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10 in all diol constituent units of the amorphous copolyester resin in the thermoplastic resin composition (B) The thermoplastic resin laminate according to claim 7, wherein the proportion of structural units derived from tetraoxaspiro [5.5] undecane is 10 to 80 mol%. The thermoplastic resin laminate according to any one of claims 1 to 8, wherein the thermoplastic resin composition (B) layer contains a rubber-based material. The thermoplastic resin laminate according to any one of claims 1 to 9, wherein a hard coat treatment is applied to one side or both sides. 11. One or more treatments selected from antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment and antiglare treatment are applied to one or both sides. Thermoplastic resin laminate. The transparent substrate material which consists of a thermoplastic resin laminated body in any one of Claims 1-11. The transparency protective material which consists of a thermoplastic resin laminated body in any one of Claims 1-11.