TW202222581A

TW202222581A - Layered resin product, and transparent substrate material and transparent protective material using same

Info

Publication number: TW202222581A
Application number: TW110128686A
Authority: TW
Inventors: 平林正樹
Original assignee: 日商三菱瓦斯化學股份有限公司; 日商Ｍｇｃ菲爾須特股份有限公司
Priority date: 2020-08-11
Filing date: 2021-08-04
Publication date: 2022-06-16
Also published as: CN116034032A; JPWO2022034837A1; WO2022034837A1

Abstract

The present invention is capable of providing a layered resin product which has a layer containing a thermoplastic resin (B) on at least one surface of a layer containing a polycarbonate-based resin (A), and in which a hard coat layer is present on at least one surface of the layer containing a thermoplastic resin (B). The polycarbonate-based resin layer (A) has a glass transition temperature of 115-140 DEG C. The thermoplastic resin (B) contains a methacrylic resin (C) and a styrene copolymer (D). Relative to a total of 100 parts by mass of the methacrylic resin (C) and the styrene copolymer (D), the content of the methacrylic resin (C) is 15-70 parts by mass and the content of the styrene copolymer (D) is 85-30 parts by mass. The styrene copolymer (D) is a copolymer which contains 68-84 mass% of a vinyl aromatic monomer unit (d1) and 16-32 mass% of a cyclic acid anhydride monomer unit (d2) and which has a weight average molecular weight of 50,000-130,000. After carrying out heat molding to a size of 50 mmR using a hot pressing machine at a mold temperature of 120 DEG C, cracking and spring back do not occur in a curved portion.

Description

樹脂積層體及使用其之透明基板材料及透明保護材料Resin laminate and transparent substrate material and transparent protective material using the same

本發明係有關透明基板材料或保護材料所使用的樹脂積層體。更詳細係有關在低溫之熱成形性優異，且抑制干涉條紋之發生之外觀良好的樹脂積層體。The present invention relates to a resin laminate used for a transparent substrate material or a protective material. More specifically, it relates to a resin laminate having excellent thermal formability at low temperature and suppressing the occurrence of interference fringes and having a good appearance.

丙烯酸樹脂係表面硬度、透明性、耐擦傷性及耐候性等優異。此外，聚碳酸酯樹脂為耐衝撃性等優異。因此，具有丙烯酸樹脂層與聚碳酸酯樹脂層的積層體係表面硬度、透明性、耐擦傷性、耐候性及耐衝撃性等優異，可用於汽車零件、家電製品、電子機器及携帶型資訊終端之顯示窗。Acrylic resins are excellent in surface hardness, transparency, scratch resistance and weather resistance. In addition, polycarbonate resin is excellent in shock resistance and the like. Therefore, the laminate system with the acrylic resin layer and the polycarbonate resin layer is excellent in surface hardness, transparency, scratch resistance, weather resistance and shock resistance, and can be used in automotive parts, home appliances, electronic equipment and portable information terminals. display window.

近年，伴隨設計需求之多樣化，對於顯示器裝置之前面板等，也要求藉由真空成形或加壓成形等之熱成形，提高設計性的製品。具有丙烯酸樹脂層與聚碳酸酯樹脂層的積層體，由於如上述優異的性能面，而嘗試用於前面板。但是將具有丙烯酸樹脂層與聚碳酸酯樹脂層之積層體進行熱成形時，聚碳酸酯樹脂必須將薄片加熱至充分地延伸的溫度，對丙烯酸樹脂施加過剩的熱，故在丙烯酸樹脂層與聚碳酸酯樹脂層之界面產生剝離，表面白化，或有產生龜裂的情形。而為了抑制白化･龜裂之發生，而降低成形溫度時，會產生無法再現模具形狀之「回彈」的情形。In recent years, with the diversification of design demands, products with improved design properties by thermoforming such as vacuum forming or press forming are also required for display device front panels and the like. A laminate having an acrylic resin layer and a polycarbonate resin layer is attempted to be used for a front panel due to the above-mentioned excellent performance. However, when thermoforming a laminate having an acrylic resin layer and a polycarbonate resin layer, the polycarbonate resin must be heated to a temperature at which the sheet is sufficiently stretched, and excessive heat is applied to the acrylic resin. The interface of the carbonate resin layer may be peeled off, the surface may be whitened, or cracks may be generated. In order to suppress the occurrence of whitening and cracking, when the molding temperature is lowered, the "springback" of the mold shape cannot be reproduced.

專利文獻1揭示具有特定末端基之聚碳酸酯樹脂與丙烯酸系樹脂之成形用樹脂薄片，作為適合真空成形或加壓成形等熱成形之成形用樹脂薄片。此樹脂薄片在熱成形之彎曲加工時，抑制白化･龜裂之發生。但是此樹脂薄片之丙烯酸系樹脂層表面進行表面硬化(Hard Coat)時，在熱成形之彎曲加工時，有發生龜裂的問題。Patent Document 1 discloses a resin sheet for molding of a polycarbonate resin and an acrylic resin having specific terminal groups, as a resin sheet for molding suitable for thermoforming such as vacuum molding and press molding. This resin sheet suppresses the occurrence of whitening and cracking during the bending process of thermoforming. However, when the surface of the acrylic resin layer of the resin sheet is hard coated, there is a problem that cracks occur during bending during thermoforming.

專利文獻2揭示為了在160℃溫度下進行熱成形，苯乙烯-馬來酸酐共聚物與甲基丙烯酸樹脂之合金層與聚碳酸酯樹脂層之積層體。此積層體在160℃溫度下進行熱成形時，不會產生不良的狀態。但是此積層體之苯乙烯-馬來酸酐共聚物與甲基丙烯酸樹脂之合金層的表面具有硬塗層的樹脂積層體，在160℃溫度下進行熱成形時，樹脂積層體之彎曲部分有產生龜裂的問題。 [先前技術文獻] [專利文獻] Patent Document 2 discloses a laminate of an alloy layer of a styrene-maleic anhydride copolymer and a methacrylic resin and a polycarbonate resin layer for thermoforming at a temperature of 160°C. When this laminate was thermoformed at a temperature of 160°C, no defective state occurred. However, in the resin laminate having a hard coat layer on the surface of the alloy layer of the styrene-maleic anhydride copolymer and the methacrylic resin, when thermoforming was performed at 160°C, the resin laminate had a curved portion. Crack problem. [Prior Art Literature] [Patent Literature]

[專利文獻1] 國際公開第2016/060100號公報 [專利文獻2] 國際公開第2015/133530號公報 [Patent Document 1] International Publication No. 2016/060100 [Patent Document 2] International Publication No. 2015/133530

[發明所欲解決之課題][The problem to be solved by the invention]

本發明之課題係提供低溫之熱成形性優異，且抑制干涉條紋發生之外觀良好的樹脂積層體。 [用以解決課題之手段] An object of the present invention is to provide a resin laminate having excellent thermal formability at low temperature and suppressing the occurrence of interference fringes and having a good appearance. [means to solve the problem]

本發明人等為了解決上述課題而精心檢討的結果，而完成本發明。具體而言，本發明如下述。The inventors of the present invention have completed the present invention as a result of careful examination in order to solve the above-mentioned problems. Specifically, the present invention is as follows.

[1] 一種樹脂積層體，其係在包含聚碳酸酯系樹脂(A)之層的至少一面，具有包含熱塑性樹脂(B)之層，在包含該熱塑性樹脂(B)之層的至少單側表面，具有硬塗層的樹脂積層體，前述聚碳酸酯系樹脂(A)之玻璃轉移溫度為115℃~140℃，前述熱塑性樹脂(B)含有甲基丙烯酸樹脂(C)與苯乙烯共聚物(D)，以前述甲基丙烯酸樹脂(C)及苯乙烯共聚物(D)之含量之合計100質量份為基準，前述甲基丙烯酸樹脂(C)之含量為15~70質量份，前述苯乙烯共聚物(D)之含量為85~30質量份，前述苯乙烯共聚物(D)為乙烯基芳香族單體單元(d1)含有68~84質量%與環狀酸酐單體單元(d2)含有16~32質量%的共聚物，重量平均分子量為50,000~130,000，以模具溫度為120℃的熱壓機，進行50mmR之熱成形後，彎曲部分不會發生龜裂及回彈。 [2] 如上述[1]之樹脂積層體，其中前述聚碳酸酯系樹脂(A)之玻璃轉移溫度與前述熱塑性樹脂(B)之玻璃轉移溫度之差為0~15℃之範圍。 [3] 如上述[1]或[2]之樹脂積層體，其中前述熱塑性樹脂(B)為前述甲基丙烯酸樹脂(C)與前述苯乙烯共聚物(D)之聚合物合金。 [4] 如上述[1]~[3]中任一項之樹脂積層體，其中前述苯乙烯共聚物(D)所含有之乙烯基芳香族單體單元(d1)為苯乙烯。 [5] 如上述[1]~[4]中任一項之樹脂積層體，其中前述苯乙烯共聚物(D)所含有之環狀酸酐單體單元(d2)為馬來酸酐。 [6] 如上述[1]~[5]中任一項之樹脂積層體，其中前述聚碳酸酯系樹脂(A)具有自下述通式(1)表示之一元酚所衍生的末端結構與自二元酚所衍生的構成單元。

(式中，R ₁表示碳數8~36之烷基，或碳數8~36之烯基，R ₂~R ₅各自表示氫、鹵素、或可具有取代基之碳數1~20之烷基或碳數6~12之芳基，前述取代基為鹵素、碳數1~20之烷基、或碳數6~12之芳基)。 [7] 如上述[1]~[6]中任一項之樹脂積層體，其中前述包含熱塑性樹脂(B)之層的厚度為10~250μm，前述樹脂積層體之全體厚度為0.4~4.0mm之範圍。 [8] 如上述[1]~[7]中任一項之樹脂積層體，其中前述包含聚碳酸酯系樹脂(A)之層、前述包含熱塑性樹脂(B)之層、及前述硬塗層之至少一層含有紫外線吸收劑。 [9] 如上述[1]~[8]中任一項之樹脂積層體，其中前述硬塗層為丙烯酸系硬塗膜。 [10] 如上述[1]~[9]中任一項之樹脂積層體，其中在前述樹脂積層體之單面或兩面，施予耐指紋處理、抗反射處理、防眩處理、耐候性處理、抗靜電處理及防污處理中之至少1種而成。 [11] 一種熱成形體，其係將如上述[1]~[10]中任一項之樹脂積層體進行熱彎曲加工。 [12] 一種透明基板材料，其係包含如上述[1]~[10]中任一項之樹脂積層體或如上述[11]之熱成形體。 [13] 一種透明保護材料，其係包含如上述[1]~[10]中任一項之樹脂積層體或如上述[11]之熱成形體。 [14] 一種觸控面板前面保護板，其係包含如上述[1]~[10]中任一項之樹脂積層體、或如上述[11]之熱成形體。 [15] 一種汽車導航(Car navigation)用、OA機器用或攜帶電子機器用的前面板，其係包含如上述[1]~[12]中任一項之樹脂積層體或如上述[11]之熱成形體。 [16] 一種熱成形體之製造方法，其係包含將樹脂積層體以100℃~135℃之模具溫度進行熱彎曲加工的步驟，前述樹脂積層體在包含聚碳酸酯系樹脂(A)之層之至少一面，具有包含熱塑性樹脂(B)之層，且在包含該熱塑性樹脂(B)之層之至少單側表面，具有硬塗層，前述聚碳酸酯系樹脂(A)之玻璃轉移溫度為115℃~140℃，前述熱塑性樹脂(B)含有甲基丙烯酸樹脂(C)與苯乙烯共聚物(D)，以前述甲基丙烯酸樹脂(C)及苯乙烯共聚物(D)之含量之合計100質量份為基準，前述甲基丙烯酸樹脂(C)之含量為15~70質量份，前述苯乙烯共聚物(D)之含量為85~30質量份，前述苯乙烯共聚物(D)為乙烯基芳香族單體單元(d1)含有68~84質量%與環狀酸酐單體單元(d2)含有16~32質量%的共聚物，且重量平均分子量為50,000~130,000。 [發明效果] [1] A resin laminate having a layer containing a thermoplastic resin (B) on at least one side of a layer containing a polycarbonate-based resin (A), and having a layer containing the thermoplastic resin (B) on at least one side of the layer containing the thermoplastic resin (B) A resin laminate having a hard coat layer on the surface, the glass transition temperature of the polycarbonate resin (A) is 115°C to 140°C, and the thermoplastic resin (B) contains a methacrylic resin (C) and a styrene copolymer (D), the content of the methacrylic resin (C) is 15 to 70 parts by mass based on the total of 100 parts by mass of the content of the methacrylic resin (C) and the styrene copolymer (D), the benzene The content of the ethylene copolymer (D) is 85 to 30 parts by mass, and the aforementioned styrene copolymer (D) is a vinyl aromatic monomer unit (d1) containing 68 to 84 mass % and a cyclic acid anhydride monomer unit (d2) It contains 16 to 32 mass % of the copolymer, the weight average molecular weight is 50,000 to 130,000, and after thermoforming at 50 mmR in a hot press with a die temperature of 120°C, cracks and springback will not occur in the curved portion. [2] The resin laminate according to the above [1], wherein the difference between the glass transition temperature of the polycarbonate resin (A) and the glass transition temperature of the thermoplastic resin (B) is in the range of 0 to 15°C. [3] The resin laminate according to the above [1] or [2], wherein the thermoplastic resin (B) is a polymer alloy of the methacrylic resin (C) and the styrene copolymer (D). [4] The resin laminate according to any one of the above [1] to [3], wherein the vinyl aromatic monomer unit (d1) contained in the styrene copolymer (D) is styrene. [5] The resin laminate according to any one of the above [1] to [4], wherein the cyclic acid anhydride monomer unit (d2) contained in the styrene copolymer (D) is maleic anhydride. [6] The resin laminate according to any one of the above [1] to [5], wherein the polycarbonate-based resin (A) has a terminal structure derived from a monohydric phenol represented by the following general formula (1) and A unit derived from a dihydric phenol.

(In the formula, R ₁ represents an alkyl group with 8 to 36 carbon atoms, or an alkenyl group with 8 to 36 carbon atoms, and R ₂ to R ₅ each represent hydrogen, halogen, or an alkane with 1 to 20 carbon atoms that may have a substituent. group or an aryl group having 6 to 12 carbon atoms, the aforementioned substituents are halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms). [7] The resin laminate according to any one of the above [1] to [6], wherein the thickness of the layer containing the thermoplastic resin (B) is 10 to 250 μm, and the overall thickness of the resin laminate is 0.4 to 4.0 mm range. [8] The resin laminate according to any one of the above [1] to [7], wherein the layer comprising the polycarbonate-based resin (A), the layer comprising the thermoplastic resin (B), and the hard coat layer At least one of the layers contains an ultraviolet absorber. [9] The resin laminate according to any one of the above [1] to [8], wherein the hard coat layer is an acrylic hard coat film. [10] The resin laminate according to any one of the above [1] to [9], wherein anti-fingerprint treatment, anti-reflection treatment, anti-glare treatment, and weather resistance treatment are applied to one side or both sides of the aforementioned resin laminate. , at least one of antistatic treatment and antifouling treatment. [11] A thermoformed body obtained by subjecting the resin laminate according to any one of the above [1] to [10] to a heat bending process. [12] A transparent substrate material comprising the resin laminate according to any one of the above [1] to [10] or the thermoformed body according to the above [11]. [13] A transparent protective material comprising the resin laminate according to any one of the above [1] to [10] or the thermoformed body according to the above [11]. [14] A touch panel front protection plate comprising the resin laminate according to any one of the above [1] to [10], or the thermoformed body according to the above [11]. [15] A front panel for car navigation, OA equipment, or portable electronic equipment, comprising the resin laminate according to any one of the above [1] to [12] or the above [11] The thermoformed body. [16] A method for producing a thermoformed body, comprising the step of thermally bending a resin laminate at a mold temperature of 100°C to 135°C, wherein the resin laminate is formed in a layer comprising a polycarbonate-based resin (A). At least one side has a layer containing a thermoplastic resin (B), and at least one side surface of the layer containing the thermoplastic resin (B) has a hard coat layer, and the glass transition temperature of the polycarbonate resin (A) is 115°C ~ 140°C, the thermoplastic resin (B) contains methacrylic resin (C) and styrene copolymer (D), the total content of the methacrylic resin (C) and styrene copolymer (D) Based on 100 parts by mass, the content of the aforementioned methacrylic resin (C) is 15 to 70 parts by mass, the content of the aforementioned styrene copolymer (D) is 85 to 30 parts by mass, and the aforementioned styrene copolymer (D) is ethylene The aromatic monomer unit (d1) contains 68 to 84 mass % and the cyclic acid anhydride monomer unit (d2) contains a copolymer of 16 to 32 mass %, and the weight average molecular weight is 50,000 to 130,000. [Inventive effect]

依據本發明時，可提供低溫下之熱成形優異，且可成形抑制了干涉條紋之發生之熱成形品的樹脂積層體。亦即，本發明之樹脂積層體，可得到熱成形時之白化･龜裂之發生被抑制，具有良好外觀的成形品。該樹脂積層體，可作為透明基板材料或透明保護材料使用。具體而言，適合作為行動電話終端、携帶型電子遊具、行動資訊終端、攜帶PC等之携帶型的顯示器裝置或、筆記型PC、桌上型PC液晶監視器、汽車導航液晶監視器、液晶電視等之設置型的顯示器裝置等中，例如作為保護此等機器之前面板使用。 [實施發明之形態] According to the present invention, it is possible to provide a resin laminate which is excellent in thermoforming at low temperature and can form a thermoformed product in which the occurrence of interference fringes is suppressed. That is, according to the resin laminate of the present invention, the occurrence of whitening and cracking during thermoforming can be suppressed, and a molded article having a good appearance can be obtained. This resin laminate can be used as a transparent substrate material or a transparent protective material. Specifically, it is suitable for portable display devices such as mobile phone terminals, portable electronic games, mobile information terminals, and portable PCs, notebook PCs, desktop PC LCD monitors, car navigation LCD monitors, and LCD TVs. For example, it is used as a front panel for protecting the front panel of such equipment in installation-type display devices and the like. [Form of implementing the invention]

以下舉製造例或實施例等，詳細地說明本發明，但是本發明不限於例示之製造例或實施例等，在不遠超出本發明之內容的範圍時，可變更為任意的方法來進行。Hereinafter, the present invention will be described in detail with reference to production examples and examples, but the present invention is not limited to the illustrated production examples or examples, and can be carried out by any method without departing from the scope of the content of the present invention.

＜聚碳酸酯系樹脂(A)＞本發明所使用之聚碳酸酯系樹脂(A)係以聚碳酸酯樹脂為主成分的聚碳酸酯系樹脂(A)。在此，「以聚碳酸酯樹脂為主成分」係指聚碳酸酯樹脂之含量超過50質量%。聚碳酸酯系樹脂(A)含有75質量%以上之聚碳酸酯樹脂較佳，含有90質量%以上之聚碳酸酯樹脂更佳，又更佳為實質上由聚碳酸酯樹脂所構成者。聚碳酸酯系樹脂(A)係分子主鏈中包含碳酸酯鍵。亦即，包含-[O-R-OCO]-單位(式中，R包含脂肪族基、芳香族基、或脂肪族基與芳香族基之兩者，且表示具有直鏈結構或支鏈結構者)時，無特別限定，特別是使用包含下述式(2)之結構單元的聚碳酸酯為佳。藉由使用這種聚碳酸酯，可得到耐衝撃性優異的樹脂積層體。

<Polycarbonate-based resin (A)> The polycarbonate-based resin (A) used in the present invention is a polycarbonate-based resin (A) containing a polycarbonate resin as a main component. Here, "contains a polycarbonate resin as a main component" means that the content of the polycarbonate resin exceeds 50 mass %. The polycarbonate resin (A) preferably contains 75% by mass or more of the polycarbonate resin, more preferably contains 90% by mass or more of the polycarbonate resin, and more preferably consists of the polycarbonate resin substantially. The polycarbonate-based resin (A) contains a carbonate bond in the molecular main chain. That is, a -[OR-OCO]-unit is included (in the formula, R includes an aliphatic group, an aromatic group, or both of an aliphatic group and an aromatic group, and represents those having a straight-chain structure or a branched-chain structure) In this case, it is not particularly limited, but it is particularly preferable to use a polycarbonate containing a structural unit of the following formula (2). By using such a polycarbonate, a resin laminate excellent in impact resistance can be obtained.

聚碳酸酯系樹脂(A)係將下述通式(1)表示之一元酚作為封端劑使用，進行合成較佳。

(式中，R ₁表示碳數8~36之烷基、或碳數8~36之烯基， R ₂~R ₅各自表示氫、鹵素、或可具有取代基之碳數1~20之烷基或碳數6~12之芳基，前述取代基為鹵素、碳數1~20之烷基、或碳數6~12之芳基。) The polycarbonate-based resin (A) is preferably synthesized by using a monohydric phenol represented by the following general formula (1) as an end-capping agent.

(In the formula, R ₁ represents an alkyl group having 8 to 36 carbon atoms, or an alkenyl group having 8 to 36 carbon atoms, and R ₂ to R ₅ each represent hydrogen, halogen, or an alkane having 1 to 20 carbon atoms that may have a substituent. group or an aryl group having 6 to 12 carbon atoms, the aforementioned substituents are halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms.)

通式(1)之一元酚係以下述通式(3)表示之一元酚更佳。

(式中，R ₁表示碳數8~36之烷基、或碳數8~36之烯基。) More preferably, the monohydric phenol of the general formula (1) is represented by the following general formula (3).

(In the formula, R ₁ represents an alkyl group having 8 to 36 carbon atoms, or an alkenyl group having 8 to 36 carbon atoms.)

通式(1)或通式(3)中之R ₁之碳數為特定數值範圍內更佳。具體而言，R ₁之碳數之上限值，較佳為36，更佳為22，特佳為18。又，R ₁之碳數的下限值，較佳為8，更佳為12。 The carbon number of R ₁ in the general formula (1) or the general formula (3) is more preferably within a specific numerical range. Specifically, the upper limit of the carbon number of R ₁ is preferably 36, more preferably 22, and particularly preferably 18. Moreover, as for the lower limit of carbon number of R< ₁ >, 8 is preferable, and 12 is more preferable.

通式(1)或通式(3)表示之一元酚(封端劑)之中，特佳為對羥基苯甲酸十六烷基酯、對羥基苯甲酸2-己基癸基酯之任一或兩者作為封端劑使用。Among the monohydric phenols (end-capping agents) represented by the general formula (1) or the general formula (3), any one of cetyl p-hydroxybenzoate and 2-hexyldecyl p-hydroxybenzoate or Both are used as capping agents.

通式(1)或通式(3)中之R ₁，例如使用具有碳數16之烷基之一元酚(封端劑)時，玻璃轉移溫度、熔融流動性、成形性、耐垂流(draw down)性、聚碳酸酯樹脂製造時之一元酚的溶劑溶解性優異，特佳為作為本發明用之聚碳酸酯樹脂所使用的封端劑。 R ₁ in general formula (1) or general formula (3), for example, when a monohydric phenol having an alkyl group having 16 carbon atoms (terminal capping agent) is used, the glass transition temperature, melt fluidity, formability, sag resistance ( It is excellent in the solvent solubility of monohydric phenol at the time of production of polycarbonate resin and is excellent in draw down property, and it is especially preferable as a terminal blocking agent used for the polycarbonate resin used in the present invention.

此外，通式(1)或通式(3)中之R ₁之碳數過度增加時，一元酚(封端劑)之有機溶劑溶解性有降低的傾向，聚碳酸酯樹脂製造時有生產性降低的情形。舉一例，R ₁之碳數為36以下時，製造聚碳酸酯樹脂時，生產性高，經濟性也佳。R ₁之碳數為22以下時，一元酚特別是有機溶劑溶解性優異，製造聚碳酸酯樹脂時，可使生產性非常高，也可提高經濟性。通式(1)或通式(3)中之R ₁之碳數過小時，聚碳酸酯樹脂之玻璃轉移溫度不會成為非常低的值，熱成形性有降低的情形。 In addition, when the carbon number of R ₁ in the general formula (1) or the general formula (3) is excessively increased, the organic solvent solubility of the monohydric phenol (end-capping agent) tends to decrease, and the productivity at the time of polycarbonate resin production increases. reduced situation. For example, when the carbon number of R ₁ is 36 or less, the productivity is high and the economical efficiency is also good when manufacturing a polycarbonate resin. When the carbon number of R ₁ is 22 or less, the monohydric phenol, especially the organic solvent, is excellent in solubility, and when manufacturing a polycarbonate resin, the productivity can be very high, and the economical efficiency can also be improved. When the carbon number of R ₁ in the general formula (1) or the general formula (3) is too small, the glass transition temperature of the polycarbonate resin does not become a very low value, and the thermoformability may decrease.

聚碳酸酯系樹脂(A)所含有之其他的樹脂，有聚酯系樹脂。聚酯系樹脂係含有作為二羧酸成分之對苯二甲酸作為主成分即可，也可含有對苯二甲酸以外之二羧酸成分。例如，相對於主成分之乙二醇80~60(莫耳比率)，含有20~40(莫耳比率，合計100)之1,4-環己烷二甲醇的乙二醇成分與二羧酸成分進行聚縮合而成的聚酯系樹脂，所謂的「PETG」較佳。又，聚碳酸酯系樹脂(A)，也可包含在聚合物骨架中具有酯鍵與碳酸酯鍵的聚酯碳酸酯系樹脂。Other resins contained in the polycarbonate-based resin (A) include polyester-based resins. The polyester-based resin may contain terephthalic acid as a dicarboxylic acid component as a main component, and may contain dicarboxylic acid components other than terephthalic acid. For example, an ethylene glycol component and a dicarboxylic acid containing 20 to 40 (molar ratio, 100 in total) of 1,4-cyclohexanedimethanol relative to 80 to 60 (molar ratio) of ethylene glycol as the main component The polyester-based resin obtained by polycondensation of the components is preferably so-called "PETG". Moreover, the polycarbonate-type resin (A) may contain the polyester carbonate-type resin which has an ester bond and a carbonate bond in a polymer skeleton.

本發明中，聚碳酸酯系樹脂(A)的重量平均分子量影響樹脂積層體之耐衝撃性及成形條件。換言之，重量平均分子量過小時，樹脂積層體之耐衝撃性降低，故不佳。重量平均分子量過高時，積層包含聚碳酸酯系樹脂(A)之層時，有需要過剩之熱源的情形，故不佳。又，藉由成形法，需要高的溫度，故聚碳酸酯系樹脂(A)處於高溫，對該熱安定性有不良影響。聚碳酸酯系樹脂(A)之重量平均分子量，較佳為10,000~75,000，更佳為15,000~ 60,000。又更佳為20,000~50,000。In the present invention, the weight average molecular weight of the polycarbonate resin (A) affects the impact resistance and molding conditions of the resin laminate. In other words, when the weight average molecular weight is too small, the impact resistance of the resin laminate decreases, which is not preferable. When the weight average molecular weight is too high, when a layer containing the polycarbonate-based resin (A) is laminated, an excess heat source may be required, which is not preferable. In addition, since a high temperature is required by the molding method, the polycarbonate-based resin (A) is at a high temperature, which adversely affects the thermal stability. The weight average molecular weight of the polycarbonate resin (A) is preferably 10,000 to 75,000, more preferably 15,000 to 60,000. More preferably, it is 20,000 to 50,000.

＜聚碳酸酯系樹脂(A)之重量平均分子量之測定法＞聚碳酸酯系樹脂(A)之重量平均分子量，可依據日本特開2007-179018號公報段落0061~0064之記載來測定。測定法之詳細如下述。

<Measuring method of weight average molecular weight of polycarbonate resin (A)> The weight average molecular weight of polycarbonate resin (A) can be measured according to the description of Unexamined-Japanese-Patent No. 2007-179018 paragraphs 0061-0064. The details of the measurement method are as follows.

使用作為標準聚合物之聚苯乙烯(PS)進行測定後，藉由通用校正法(Universal Calibration)，求溶出時間與聚碳酸酯(PC)之分子量的關係作為檢量線。然後，以與檢量線的情形相同的條件測定PC的溶出曲線(色譜)，由溶出時間(分子量)與其溶出時間之波峰面積(分子數)，求各平均分子量。分子量Mi之分子數作為Ni時，重量平均分子量係如以下表示。又，換算式係使用以下的式子。 (重量平均分子量) Mw=Σ(NiMi ²)/Σ(NiMi) (換算式) MPC=0.47822MPS ^1.01470又，MPC表示PC的分子量，MPS表示PS的分子量。 After the measurement was performed using polystyrene (PS) as a standard polymer, the relationship between the elution time and the molecular weight of polycarbonate (PC) was obtained as a calibration curve by a universal calibration method. Then, the dissolution curve (chromatogram) of PC was measured under the same conditions as in the case of the calibration curve, and each average molecular weight was obtained from the peak area (number of molecules) between the dissolution time (molecular weight) and the dissolution time. When the number of molecules of the molecular weight Mi is defined as Ni, the weight average molecular weight is represented as follows. In addition, the following formula is used as a conversion formula. (weight average molecular weight) Mw=Σ(NiMi ² )/Σ(NiMi) (conversion formula) MPC=0.47822MPS ^{1.01470 In} addition, MPC represents the molecular weight of PC, and MPS represents the molecular weight of PS.

本發明所使用之聚碳酸酯系樹脂(A)的玻璃轉移溫度，較佳為115~140℃，更佳為115~135℃，又更佳為115℃~130℃，特佳為115℃以上未達130℃。又，本說明書中之聚碳酸酯系樹脂(A)之玻璃轉移溫度係指使用示差掃描熱量計，以昇溫速度10℃/分鐘測定，在基線與反曲點之切線的交點算出時的溫度。The glass transition temperature of the polycarbonate resin (A) used in the present invention is preferably 115 to 140°C, more preferably 115 to 135°C, still more preferably 115 to 130°C, and particularly preferably 115°C or higher less than 130°C. In addition, the glass transition temperature of the polycarbonate resin (A) in this specification refers to the temperature at the time of measuring at the intersection of the base line and the tangent of the inflection point measured at a heating rate of 10° C./min using a differential scanning calorimeter.

前述聚碳酸酯系樹脂(A)之熔體流動速率(Melt Flow Rate)，較佳為1~30g/10分鐘之範圍，更佳為8~20g/10分鐘的範圍，又更佳為11~15g/10分鐘的範圍。熔體流動速率為1~30g/10分鐘的範圍時，加熱熔融成形之安定性良好。又，本說明書中之聚碳酸酯系樹脂(A)的熔體流動速率係指使用熱流動性評價裝置，在溫度300℃、1.2kg荷重下的條件進行測定者。The melt flow rate (Melt Flow Rate) of the aforementioned polycarbonate resin (A) is preferably in the range of 1 to 30 g/10 minutes, more preferably in the range of 8 to 20 g/10 minutes, and more preferably in the range of 11 to 11 g/10 minutes. 15g/10min range. When the melt flow rate is in the range of 1 to 30 g/10 minutes, the stability of heat-melt molding is good. In addition, the melt flow rate of the polycarbonate-type resin (A) in this specification refers to what was measured under the conditions of temperature 300 degreeC and 1.2 kg load using the thermal fluidity evaluation apparatus.

本發明所使用之聚碳酸酯系樹脂(A)的製造方法係藉由公知之光氣法(界面聚合法)、酯交換法(熔融法)等使用的單體來適宜選擇。The manufacturing method of the polycarbonate-type resin (A) used by this invention is suitably selected by the monomer used, such as a well-known phosgene method (interfacial polymerization method), a transesterification method (melt method).

＜熱塑性樹脂(B)＞本發明所使用之熱塑性樹脂(B)包含甲基丙烯酸樹脂(C)與苯乙烯共聚物(D)。關於各自之構成要素如以下說明。 <Thermoplastic resin (B)> The thermoplastic resin (B) used in the present invention includes a methacrylic resin (C) and a styrene copolymer (D). The respective constituent elements are described below.

＜甲基丙烯酸樹脂(C)＞本發明之熱塑性樹脂(B)所含有之甲基丙烯酸樹脂(C)，可列舉包含來自甲基丙烯酸酯單體之結構單元的樹脂。 <Methacrylic resin (C)> The methacrylic resin (C) contained in the thermoplastic resin (B) of the present invention includes a resin containing a structural unit derived from a methacrylate monomer.

前述甲基丙烯酸樹脂(C)的甲基丙烯酸酯單體，可列舉甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸n-丙酯、甲基丙烯酸異丙酯、甲基丙烯酸n-丁酯、甲基丙烯酸異丁酯、甲基丙烯酸tert-丁酯、甲基丙烯酸戊酯、甲基丙烯酸己酯、甲基丙烯酸庚酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸壬酯、甲基丙烯酸癸酯、甲基丙烯酸十二烷酯等的甲基丙烯酸烷基酯；甲基丙烯酸1-甲基環戊酯、甲基丙烯酸環己酯、甲基丙烯酸環庚酯、甲基丙烯酸環辛酯、甲基丙烯酸三環[5.2.1.02,6]癸-8-酯等之甲基丙烯酸環烷基酯；甲基丙烯酸苯酯等之甲基丙烯酸芳基酯；甲基丙烯酸苄酯等之甲基丙烯酸芳烷基酯等，從取得性的觀點，甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸n-丙酯、甲基丙烯酸異丙酯、甲基丙烯酸n-丁酯、甲基丙烯酸異丁酯，及甲基丙烯酸tert-丁酯為佳，最佳為甲基丙烯酸甲酯。The methacrylate monomer of the methacrylic resin (C) includes methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, and n- methacrylate Butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate methyl methacrylate, decyl methacrylate, dodecyl methacrylate and other alkyl methacrylates; 1-methylcyclopentyl methacrylate, cyclohexyl methacrylate, cycloheptyl methacrylate, methyl methacrylate Cyclooctyl methacrylate, cyclooctyl methacrylate, tricyclo[5.2.1.02,6]dec-8-ester methacrylate, etc.; aryl methacrylate, such as phenyl methacrylate; methacrylic acid Aralkyl methacrylates such as benzyl esters, etc., from the viewpoint of availability, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-methacrylate -Butyl, isobutyl methacrylate, and tert-butyl methacrylate are preferred, and methyl methacrylate is the most preferred.

又，由耐熱性的觀點，上述甲基丙烯酸樹脂(C)含有80質量%以上之來自甲基丙烯酸酯單體之結構單元為佳，含有90質量%以上更佳，又更佳為含有95質量%以上。甲基丙烯酸樹脂(C)含有80質量%以上之來自甲基丙烯酸酯單體之結構單元時，與苯乙烯共聚物(D)之相溶性變得良好，故較佳。而來自甲基丙烯酸酯單體之結構單元為未達80質量%時，不會與苯乙烯共聚物(D)相溶，而有白濁的情形。Furthermore, from the viewpoint of heat resistance, the methacrylic resin (C) preferably contains 80% by mass or more of structural units derived from methacrylate monomers, more preferably 90% by mass or more, and more preferably 95% by mass or more. %above. When the methacrylic resin (C) contains a structural unit derived from a methacrylate monomer in an amount of 80% by mass or more, the compatibility with the styrene copolymer (D) becomes good, which is preferable. On the other hand, when the structural unit derived from the methacrylate monomer is less than 80% by mass, it is not compatible with the styrene copolymer (D) and may become cloudy.

又，前述甲基丙烯酸樹脂(C)，也可含有來自甲基丙烯酸酯以外之其他單體的結構單元。此其他的單體，可列舉丙烯酸甲酯、丙烯酸乙酯、丙烯酸n-丙酯、丙烯酸異丙酯、丙烯酸n-丁酯、丙烯酸異丁酯、丙烯酸tert-丁酯、丙烯酸己酯、丙烯酸2-乙基己酯、丙烯酸壬酯、丙烯酸癸酯、丙烯酸十二烷酯、丙烯酸十八烷酯、丙烯酸2-羥基乙酯、丙烯酸2-羥基丙酯、丙烯酸4-羥基丁酯、丙烯酸環己酯、丙烯酸2-甲氧基乙酯、丙烯酸3-甲氧基丁酯、丙烯酸三氟甲酯、丙烯酸三氟乙酯、丙烯酸五氟乙酯、縮水甘油丙烯酸酯、丙烯酸烯丙酯、丙烯酸苯酯、丙烯酸甲醯酯、丙烯酸二苯基乙二酮、丙烯酸異莰酯、丙烯酸3-二甲基胺基乙酯等之丙烯酸酯，就取得性的觀點，較佳為丙烯酸甲酯、丙烯酸乙酯、丙烯酸n-丙酯、丙烯酸異丙酯、丙烯酸n-丁酯、丙烯酸異丁酯、丙烯酸tert-丁酯等之丙烯酸酯，更佳為丙烯酸甲酯及丙烯酸乙酯，最佳為丙烯酸甲酯。甲基丙烯酸樹脂(C)中之來自此等其他單體之結構單元的含量，合計較佳為20質量%以下，更佳為10質量%以下，又更佳為5質量%以下。Moreover, the said methacrylic resin (C) may contain the structural unit derived from the other monomer other than methacrylate. The other monomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hexyl acrylate, 2 acrylate -Ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, octadecyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, cyclohexyl acrylate ester, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, trifluoromethyl acrylate, trifluoroethyl acrylate, pentafluoroethyl acrylate, glycidyl acrylate, allyl acrylate, benzene acrylate Acrylates such as methyl acrylate, diphenyl ethylene glycol acrylate, isobornyl acrylate, 3-dimethylaminoethyl acrylate, and the like, are preferably methyl acrylate and ethyl acrylate from the viewpoint of availability. Acrylates such as ester, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, etc., more preferably methyl acrylate and ethyl acrylate, most preferably methyl acrylate ester. The total content of the structural units derived from these other monomers in the methacrylic resin (C) is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less.

甲基丙烯酸樹脂(C)係三分體(triad)顯示之對排度(syndiotacticity：rr)的下限，較佳為50莫耳%以上，更佳為51%莫耳以上，又更佳為52%莫耳以上。此結構之含量的下限值為50莫耳%以上，成為耐熱性優異者。The lower limit of the syndiotacticity (syndiotacticity: rr) displayed by the methacrylic resin (C) is a triad, preferably 50 mol% or more, more preferably 51% mol or more, and more preferably 52 mol% or more % molar or more. The lower limit of the content of this structure is 50 mol % or more, which is excellent in heat resistance.

在此，三分體顯示之對排度(rr)(以下有時僅稱為「對排度(rr)」)係連續之3個結構單元之連鏈(3分體、triad)所具有之2個連鏈(2分體、diad)皆為二分體(稱為rr)的比例。又，聚合物分子中之結構單元的連鏈(2分體、diad)中，立體配置為相同者稱為內消旋(meso)，相反者稱為二分體(racemo)，各自以m、r表示。甲基丙烯酸樹脂(C)之對排度(rr)(%)係在氘化氯仿中，30℃下測定 ¹H-NMR光譜，由其光譜，將四甲基矽烷(TMS)設為0ppm時計測0.6~0.95ppm之區域的面積(X)與0.6~1.35ppm之區域的面積(Y)，可以式：(X/Y)×100計算得到。 Here, the opposite degree (rr) shown by the triad (hereinafter sometimes referred to as "the opposite degree (rr)") is the property of the chain (triad, triad) of three consecutive structural units. The ratio of the two linked chains (diad, diad) is the diad (referred to as rr). In addition, in the chain (diad, diad) of the structural units in the polymer molecule, those with the same three-dimensional configuration are called meso (meso), and those on the contrary are called dyads (racemo), each with m, r express. The relative displacement (rr) (%) of the methacrylic resin (C) is measured in deuterated chloroform at 30°C by measuring the ¹ H-NMR spectrum, and from the spectrum, when tetramethylsilane (TMS) is set to 0 ppm Measure the area (X) of the region of 0.6 to 0.95 ppm and the area (Y) of the region of 0.6 to 1.35 ppm, which can be calculated by the formula: (X/Y)×100.

前述甲基丙烯酸樹脂(C)之重量平均分子量係以與苯乙烯共聚物(D)之混合(分散)之容易度及此等熱塑性樹脂(B)之製造容易度來決定。換言之，甲基丙烯酸樹脂(C)之重量平均分子量過大時，與苯乙烯共聚物(D)之熔融黏度差變得太大，故兩者混合(分散)變差，產生前述熱塑性樹脂(B)之透明性惡化、或安定的熔融混練無法繼續等的不良現象。相反地，甲基丙烯酸樹脂(C)之重量平均分子量過小時，因熱塑性樹脂(B)之強度降低，故可能發生樹脂積層體之耐衝撃性降低的問題。甲基丙烯酸樹脂(C)之重量平均分子量，較佳為50,000~700,000之範圍，更佳為60,000~500,000之範圍。又更佳為70,000~200,000之範圍。上述重量平均分子量係藉由凝膠滲透層析(GPC)所測定之標準聚苯乙烯換算的重量平均分子量。The weight average molecular weight of the aforementioned methacrylic resin (C) is determined by the ease of mixing (dispersion) with the styrene copolymer (D) and the ease of manufacture of these thermoplastic resins (B). In other words, when the weight average molecular weight of the methacrylic resin (C) is too large, the difference in melt viscosity with the styrene copolymer (D) becomes too large, so the mixing (dispersion) of the two becomes poor, resulting in the aforementioned thermoplastic resin (B) Deterioration of transparency, or failure to continue stable melt-kneading. Conversely, when the weight-average molecular weight of the methacrylic resin (C) is too small, the strength of the thermoplastic resin (B) is lowered, which may cause a problem that the impact resistance of the resin laminate is lowered. The weight average molecular weight of the methacrylic resin (C) is preferably in the range of 50,000 to 700,000, more preferably in the range of 60,000 to 500,000. More preferably, it is the range of 70,000-200,000. The above-mentioned weight average molecular weight is the weight average molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC).

前述甲基丙烯酸樹脂(C)之玻璃轉移溫度，較佳為100℃以上，更佳為、105℃以上，又更佳為108℃以上。此玻璃轉移溫度為100℃以上，本發明提供的樹脂積層體，在熱環境中，產生變形或龜裂的情形少。又，本說明書中之甲基丙烯酸樹脂(C)的玻璃轉移溫度係指使用示差掃描熱量計，以昇溫速度10℃/分鐘測定，在基線與反曲點之切線之交點算出時的溫度。The glass transition temperature of the methacrylic resin (C) is preferably 100°C or higher, more preferably 105°C or higher, and still more preferably 108°C or higher. The glass transition temperature is 100° C. or higher, and the resin laminate provided by the present invention is less likely to be deformed or cracked in a thermal environment. In addition, the glass transition temperature of the methacrylic resin (C) in this specification means the temperature when measured at the intersection of the base line and the tangent of the inflection point at a temperature increase rate of 10° C./min using a differential scanning calorimeter.

前述甲基丙烯酸樹脂(C)的熔體流動速率，較佳為1~10 g/10分鐘的範圍。此熔體流動速率的下限值，更佳為1.2g/10分鐘以上，又更佳為1.5g/10分鐘。又，此熔體流動速率的上限值，更佳為7.0g/10分鐘以下，又更佳為4.0g/10分鐘以下。熔體流動速率在1~10g/10分鐘之範圍時，加熱熔融成形之安定性良好。又，本說明書中之甲基丙烯酸樹脂(C)之熔體流動速率係指使用熱流動性評價裝置，在溫度230℃、3.8kg荷重下測定之值。The melt flow rate of the aforementioned methacrylic resin (C) is preferably in the range of 1 to 10 g/10 minutes. The lower limit of the melt flow rate is more preferably 1.2 g/10 minutes or more, and still more preferably 1.5 g/10 minutes. In addition, the upper limit of the melt flow rate is more preferably 7.0 g/10 minutes or less, and still more preferably 4.0 g/10 minutes or less. When the melt flow rate is in the range of 1~10g/10min, the stability of heating and melting molding is good. In addition, the melt flow rate of the methacrylic resin (C) in this specification means the value measured under the temperature of 230 degreeC and the load of 3.8 kg using the thermal fluidity evaluation apparatus.

＜苯乙烯共聚物(D)＞本發明之熱塑性樹脂(B)所含有的苯乙烯共聚物(D)，包含乙烯基芳香族單體單元(d1)與環狀酸酐單體單元(d2)，相對於前述苯乙烯共聚物(D)中之全單體單元之合計，乙烯基芳香族單體單元(d1)與環狀酸酐單體單元(d2)之合計比例為92~100質量%為特徵者。 <Styrene copolymer (D)> The styrene copolymer (D) contained in the thermoplastic resin (B) of the present invention contains the vinyl aromatic monomer unit (d1) and the cyclic acid anhydride monomer unit (d2). ), the total ratio of the total monomer units in the vinyl aromatic monomer unit (d1) and the cyclic acid anhydride monomer unit (d2) is characterized by being 92 to 100% by mass.

前述苯乙烯共聚物(D)之前述乙烯基芳香族單體單元(d1)，無特別限定，可使用任意公知的芳香族乙烯單體，但是就取得容易性的觀點，可列舉苯乙烯、α-甲基苯乙烯、o-甲基苯乙烯、m-甲基苯乙烯、p-甲基苯乙烯、t-丁基苯乙烯等。此等之中，就相溶性的觀點，特佳為苯乙烯。此等芳香族乙烯單體也可混合2種以上。The vinyl aromatic monomer unit (d1) of the styrene copolymer (D) is not particularly limited, and any known aromatic vinyl monomer can be used, but from the viewpoint of easiness of acquisition, styrene, α - methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, etc. Among these, from the viewpoint of compatibility, styrene is particularly preferred. Two or more of these aromatic vinyl monomers may be mixed.

前述苯乙烯共聚物(D)之前述環狀酸酐單體單元(d2)，可列舉馬來酸、依康酸、檸康酸、烏頭酸等的酸酐，就與丙烯酸樹脂之相溶性的觀點，較佳為馬來酸酐。此等之不飽和二羧酸酐單體，可混合2種以上。The aforementioned cyclic acid anhydride monomer units (d2) of the aforementioned styrene copolymer (D) include acid anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid. From the viewpoint of compatibility with acrylic resins, Maleic anhydride is preferred. These unsaturated dicarboxylic acid anhydride monomers can be mixed with 2 or more types.

本發明使用之前述苯乙烯共聚物(D)中，相對於前述苯乙烯共聚物(D)中之全單體單元之合計，前述乙烯基芳香族單體單元(d1)與前述環狀酸酐單體單元(d2)之合計比例為92~100質量%，較佳為95~100質量%，更佳為98~100質量%。亦即，前述苯乙烯共聚物(D)相對於全單體單元之合計，可在8質量%以下之範圍含有前述乙烯基芳香族單體單元(d1)與前述環狀酸酐單體單元(d2)以外的單體單元。前述乙烯基芳香族單體單元(d1)與前述環狀酸酐單體單元(d2)以外的單體單元，可列舉例如甲基丙烯酸酯單體單元、N-取代型馬來醯亞胺單體等。苯乙烯共聚物(D)中之甲基丙烯酸酯單體單元，可列舉甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸n-丙酯、甲基丙烯酸異丙酯、甲基丙烯酸n-丁酯、甲基丙烯酸異丁酯、甲基丙烯酸tert-丁酯、甲基丙烯酸戊酯、甲基丙烯酸己酯、甲基丙烯酸庚酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸壬酯、甲基丙烯酸癸酯、甲基丙烯酸十二烷酯等之甲基丙烯酸烷基酯；甲基丙烯酸1-甲基環戊酯、甲基丙烯酸環己酯、甲基丙烯酸環庚酯、甲基丙烯酸環辛酯、甲基丙烯酸三環[5.2.1.02,6]癸-8-酯等之甲基丙烯酸環烷基酯；甲基丙烯酸苯酯等之甲基丙烯酸芳酯；甲基丙烯酸苄酯等之甲基丙烯酸芳烷酯等，就與甲基丙烯酸樹脂之相溶性的觀點，較佳為甲基丙烯酸甲酯。此等之甲基丙烯酸酯單體，可混合2種以上。苯乙烯共聚物(D)中之N-取代型馬來醯亞胺單體，可列舉N-苯基馬來醯亞胺、N-氯苯基馬來醯亞胺、N-甲基苯基馬來醯亞胺、N-萘基馬來醯亞胺、N-羥基苯基馬來醯亞胺、N-甲氧基苯基馬來醯亞胺、N-羧基苯基馬來醯亞胺、N-硝基苯基馬來醯亞胺、N-三溴苯基馬來醯亞胺等之N-芳基馬來醯亞胺等，就與甲基丙烯酸樹脂之相溶性的觀點，較佳為N-苯基馬來醯亞胺。此等之N-取代型馬來醯亞胺單體，可混合2種以上。 In the aforementioned styrene copolymer (D) used in the present invention, the aforementioned vinyl aromatic monomer unit (d1) and the aforementioned cyclic acid anhydride monomer are composed of the total amount of all monomer units in the aforementioned styrene copolymer (D). The total ratio of the body units (d2) is 92 to 100 mass %, preferably 95 to 100 mass %, more preferably 98 to 100 mass %. That is, the styrene copolymer (D) may contain the vinyl aromatic monomer unit (d1) and the cyclic acid anhydride monomer unit (d2) in a range of 8 mass % or less based on the total of all monomer units. ) other than monomer units. Monomer units other than the aforementioned vinyl aromatic monomer unit (d1) and the aforementioned cyclic acid anhydride monomer unit (d2) include, for example, methacrylate monomer units and N-substituted maleimide monomers. Wait. The methacrylate monomer units in the styrene copolymer (D) include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-methacrylate -Butyl, isobutyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid Nonyl methacrylate, decyl methacrylate, dodecyl methacrylate and other alkyl methacrylates; 1-methylcyclopentyl methacrylate, cyclohexyl methacrylate, cycloheptyl methacrylate, Cyclooctyl methacrylate, tricyclo[5.2.1.02,6]dec-8-ester methacrylate, etc. cycloalkyl methacrylate; phenyl methacrylate, etc. aryl methacrylate; methacrylic acid Aralkyl methacrylate such as benzyl ester or the like is preferably methyl methacrylate from the viewpoint of compatibility with the methacrylic resin. Two or more of these methacrylate monomers can be mixed. N-substituted maleimide monomers in the styrene copolymer (D) include N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenyl Maleimide, N-naphthylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide , N-arylmaleimide such as N-nitrophenylmaleimide, N-tribromophenylmaleimide, etc., from the point of view of compatibility with methacrylic resin, compared with Preferred is N-phenylmaleimide. Two or more of these N-substituted maleimide monomers may be mixed.

相對於前述苯乙烯共聚物(D)中之全單體單元之合計，前述乙烯基芳香族單體單元(d1)之比例為68~84質量%，較佳為70~82質量%，更佳為74~80質量%，又更佳為76~79質量%。相對於前述苯乙烯共聚物(D)中之全單體單元之合計，前述環狀酸酐單體單元(d2)之比例為16~32質量%，較佳為18~30質量%，更佳為20~26質量%，又更佳為21~24質量%。相對於前述苯乙烯共聚物(D)中之全單體單元之合計，前述乙烯基芳香族單體單元(d1)之比例為68~84質量%以外時，與甲基丙烯酸樹脂(C)之相溶性變差。又，相對於苯乙烯共聚物(D)中之全單體單元之合計，前述環狀酸酐單體單元(d2)之比例為16~32質量%以外時，與甲基丙烯酸樹脂(C)之相溶性變差。 The ratio of the vinyl aromatic monomer unit (d1) is 68 to 84 mass %, preferably 70 to 82 mass %, more preferably relative to the total of all monomer units in the styrene copolymer (D). It is 74-80 mass %, More preferably, it is 76-79 mass %. The ratio of the aforementioned cyclic acid anhydride monomer unit (d2) is 16 to 32 mass %, preferably 18 to 30 mass %, and more preferably 20-26 mass %, More preferably, it is 21-24 mass %. When the ratio of the vinyl aromatic monomer unit (d1) is other than 68 to 84 mass % with respect to the total of all monomer units in the styrene copolymer (D), the ratio with the methacrylic resin (C) Compatibility becomes poor. Moreover, when the ratio of the aforementioned cyclic acid anhydride monomer unit (d2) is other than 16 to 32 mass % with respect to the total of all monomer units in the styrene copolymer (D), the ratio with the methacrylic resin (C) Compatibility becomes poor.

前述苯乙烯共聚物(D)之重量平均分子量，就低溫下之熱成形性的觀點，較佳為50,000~130,000，更佳為55,000~100,000，特佳為60,000~90,000。上述重量平均分子量係藉由凝膠滲透層析(GPC)測定之標準聚苯乙烯換算的重量平均分子量。The weight average molecular weight of the styrene copolymer (D) is preferably 50,000 to 130,000, more preferably 55,000 to 100,000, particularly preferably 60,000 to 90,000, from the viewpoint of thermoformability at low temperatures. The above-mentioned weight average molecular weight is the weight average molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC).

前述苯乙烯共聚物(D)之玻璃轉移溫度，較佳為120~190℃之範圍，又更佳為130~170℃之範圍。藉由玻璃轉移溫度為120℃以上，本發明所提供之樹脂積層體在熱環境中，產生變形或龜裂的情形少。又，由於在190℃以下，藉由鏡面輥或賦形輥之連續式熱賦形、或藉由鏡面模具或賦形模具之分批式熱賦形等的加工性優異。又，本說明書中之苯乙烯共聚物(D)的玻璃轉移溫度係指使用示差掃描熱量計，以昇溫速度10℃/分鐘測定，在基線與反曲點之切線的交點算出時的溫度。The glass transition temperature of the aforementioned styrene copolymer (D) is preferably in the range of 120 to 190°C, and more preferably in the range of 130 to 170°C. Since the glass transition temperature is 120° C. or higher, the resin laminate provided by the present invention is less likely to be deformed or cracked in a thermal environment. Moreover, since it is 190 degrees C or less, it is excellent in workability, such as continuous heat shaping by a mirror surface roll or a shaping roll, or batch type heat shaping by a mirror surface die or a shaping die. In addition, the glass transition temperature of the styrene copolymer (D) in this specification refers to the temperature when measured at a temperature increase rate of 10° C./min using a differential scanning calorimeter and calculated at the intersection of the tangent of the base line and the inflection point.

前述苯乙烯共聚物(D)之熔體流動速率，較佳為1~10g/10分鐘之範圍，更佳為3~8g/10分鐘之範圍，又更佳為4~7g/10分鐘。熔體流動速率為1~10g/10分鐘之範圍時，加熱熔融成形之安定性良好。又，本說明書中之苯乙烯共聚物(D)的熔體流動速率係指使用熱流動性評價裝置，在溫度230℃、3.8kg荷重下測定之值。The melt flow rate of the aforementioned styrene copolymer (D) is preferably in the range of 1 to 10 g/10 minutes, more preferably in the range of 3 to 8 g/10 minutes, and still more preferably in the range of 4 to 7 g/10 minutes. When the melt flow rate is in the range of 1~10g/10min, the stability of heat-melt forming is good. In addition, the melt flow rate of the styrene copolymer (D) in this specification means the value measured under the temperature of 230 degreeC and the load of 3.8 kg using the thermal fluidity evaluation apparatus.

前述苯乙烯共聚物(D)之製造方法，無特別限定，可適宜選擇公知的溶液聚合法、塊狀聚合法、懸浮聚合法等。The manufacturing method of the said styrene copolymer (D) is not specifically limited, A well-known solution polymerization method, a block polymerization method, a suspension polymerization method, etc. can be suitably selected.

前述苯乙烯共聚物(D)為包含乙烯基芳香族單體單元(d1)與環狀酸酐單體單元(d2)的二元共聚物或多元共聚物，藉由組合使用甲基丙烯酸樹脂(C)，相較於僅使用苯乙烯共聚物(D)的情形，硬度較高，相較於僅使用甲基丙烯酸樹脂(C)的情形，可得到熱成形性優異的樹脂積層體。The aforementioned styrene copolymer (D) is a binary copolymer or a multicomponent copolymer comprising a vinyl aromatic monomer unit (d1) and a cyclic acid anhydride monomer unit (d2), by using a methacrylic resin (C) in combination ), the hardness is higher than the case where only the styrene copolymer (D) is used, and the resin laminate having excellent thermoformability can be obtained as compared with the case where only the methacrylic resin (C) is used.

本發明中，前述甲基丙烯酸樹脂(C)與前述苯乙烯共聚物(D)之質量比係以甲基丙烯酸樹脂(C)與苯乙烯共聚物(D)之含量的合計100質量份為基準，相對於前述甲基丙烯酸樹脂(C)15~70質量份，較佳為前述苯乙烯共聚物(D)為85~30質量份。更佳為相對於前述甲基丙烯酸樹脂(C)20~65質量份，前述苯乙烯共聚物(D)為80~35質量份，又更佳為相對於前述甲基丙烯酸樹脂(C)20~55質量份，前述苯乙烯共聚物(D)為80~45質量份。藉由設為此質量比內，可維持透明性，耐熱性優異，折射率高，低溫下之熱成形性優異，且外觀良好優異的熱塑性樹脂(B)。In the present invention, the mass ratio of the methacrylic resin (C) and the styrene copolymer (D) is based on 100 parts by mass of the total content of the methacrylic resin (C) and the styrene copolymer (D). , it is preferable that the said styrene copolymer (D) is 85-30 mass parts with respect to the said methacrylic resin (C) 15-70 mass parts. More preferably, the styrene copolymer (D) is 80 to 35 parts by mass relative to the aforementioned methacrylic resin (C), and more preferably 20 to 65 parts by mass relative to the aforementioned methacrylic resin (C). 55 parts by mass, the aforementioned styrene copolymer (D) is 80 to 45 parts by mass. By setting it within this mass ratio, the thermoplastic resin (B) which maintains transparency, is excellent in heat resistance, has a high refractive index, is excellent in thermoformability at low temperature, and is excellent in appearance is excellent.

前述熱塑性樹脂(B)之玻璃轉移溫度，較佳為120~165℃之範圍，又更佳為120~155℃之範圍。由於玻璃轉移溫度為120℃以上，本發明所提供之樹脂積層體在熱環境下，產生變形或龜裂的情形少。又，因165℃以下，藉由鏡面輥或賦形輥之連續式熱賦形、或藉由鏡面模具或賦形模具之分批式熱賦形等的加工性優異。又，本說明書中之熱塑性樹脂(B)的玻璃轉移溫度係指使用示差掃描熱量計，以昇溫速度10℃/分鐘測定，在基線與反曲點之切線的交點算出時的溫度。The glass transition temperature of the thermoplastic resin (B) is preferably in the range of 120 to 165°C, and more preferably in the range of 120 to 155°C. Since the glass transition temperature is 120° C. or higher, the resin laminate provided by the present invention is less likely to be deformed or cracked in a thermal environment. Moreover, since it is 165 degrees C or less, it is excellent in workability, such as continuous heat forming by a mirror roll or a forming roll, or batch heat forming by a mirror die or a forming die. In addition, the glass transition temperature of thermoplastic resin (B) in this specification means the temperature at the time of calculating at the intersection of the tangent of the base line and the inflection point measured at a temperature increase rate of 10° C./min using a differential scanning calorimeter.

前述熱塑性樹脂(B)之熔體流動速率，較佳為1~10g/10分鐘之範圍，更佳為1.5~7g/10分鐘之範圍，又更佳為2~5g/10分鐘。熔體流動速率為1~10g/10分鐘之範圍時，加熱熔融成形之安定性良好。又，本說明書中之熱塑性樹脂(B)之熔體流動速率係指使用熱流動性評價裝置，在溫度230℃、3.8kg荷重下測定之值。The melt flow rate of the thermoplastic resin (B) is preferably in the range of 1 to 10 g/10 minutes, more preferably in the range of 1.5 to 7 g/10 minutes, and still more preferably in the range of 2 to 5 g/10 minutes. When the melt flow rate is in the range of 1~10g/10min, the stability of heat-melt forming is good. In addition, the melt flow rate of thermoplastic resin (B) in this specification means the value measured under the temperature of 230 degreeC and the load of 3.8 kg using the thermal fluidity evaluation apparatus.

本發明中，熱塑性樹脂(B)之製造方法，無特別限制，將必要的成分例如使用轉筒或V型混合機、高速混合機等的混合機預先混合，然後，可使用以班伯里混合機、輥、單螺桿擠壓機(Brabender)、單軸擠壓機、二軸擠壓機、加壓捏合機等的機械進行熔融混練的習知的方法。In the present invention, the method for producing the thermoplastic resin (B) is not particularly limited, and the necessary components are mixed in advance using a mixer such as a tumbler, a V-type mixer, a high-speed mixer, etc. A known method of melt-kneading using machines such as a machine, a roll, a single-screw extruder (Brabender), a single-screw extruder, a double-screw extruder, and a pressure kneader.

本發明所使用之熱塑性樹脂(B)的玻璃轉移溫度比較高，且與前述聚碳酸酯系樹脂(A)之玻璃轉移溫度之差較少，故熱壓成形或熱彎曲加工時，即使接近聚碳酸酯系樹脂(A)之玻璃轉移溫度，有在包含熱塑性樹脂(B)之層產生外觀不良的問題少的優點。聚碳酸酯系樹脂(A)之玻璃轉移溫度與熱塑性樹脂(B)之玻璃轉移溫度之差，較佳為0~15℃之範圍，更佳為0~10℃之範圍。The glass transition temperature of the thermoplastic resin (B) used in the present invention is relatively high, and the difference between the glass transition temperature of the polycarbonate resin (A) and the polycarbonate resin (A) described above is relatively small. The glass transition temperature of the carbonate-based resin (A) has the advantage that there is less problem of poor appearance in the layer containing the thermoplastic resin (B). The difference between the glass transition temperature of the polycarbonate resin (A) and the glass transition temperature of the thermoplastic resin (B) is preferably in the range of 0 to 15°C, more preferably in the range of 0 to 10°C.

＜硬塗層＞在本發明之硬塗層與包含熱塑性樹脂(B)之層間也可再存在層，較佳為硬塗層積層於包含熱塑性樹脂(B)之層之表面或兩面。硬塗層較佳為丙烯酸系硬化塗層。本說明書中，「丙烯酸系硬化塗層」係指將含有作為聚合基之(甲基)丙烯醯基的單體或寡聚物或預聚物進行聚合形成交聯結構的塗膜。丙烯酸系硬化塗層之組成為包含(甲基)丙烯酸系單體2~98質量%，(甲基)丙烯酸系寡聚物2~98質量%及表面改質劑0~15質量%者為佳，此外，相對於(甲基)丙烯酸系單體與(甲基)丙烯酸系寡聚物與表面改質劑之總和100質量份，包含0.001~7質量份之光聚合起始劑為佳。＜Hard Coating＞ A layer may further exist between the hard coat layer of the present invention and the layer containing the thermoplastic resin (B). Preferably, the hard coat layer is laminated on the surface or both sides of the layer containing the thermoplastic resin (B). The hard coat layer is preferably an acrylic hard coat layer. In the present specification, the "acrylic hard coat layer" refers to a coating film obtained by polymerizing a monomer, oligomer or prepolymer containing a (meth)acryloyl group as a polymer group to form a cross-linked structure. The composition of the acrylic hard coat layer is preferably one containing 2 to 98 mass % of (meth)acrylic monomers, 2 to 98 mass % of (meth)acrylic oligomers, and 0 to 15 mass % of surface modifiers. In addition, it is preferable to include 0.001 to 7 parts by mass of the photopolymerization initiator relative to 100 parts by mass of the total of (meth)acrylic monomers, (meth)acrylic oligomers and surface modifiers.

硬塗層更佳為包含(甲基)丙烯酸系單體5~50質量%，(甲基)丙烯酸系寡聚物50~95質量%及表面改質劑1~10質量%，特佳為包含(甲基)丙烯酸系單體20~40質量%，(甲基)丙烯酸系寡聚物60~80質量%及表面改質劑2~5質量%。光聚合起始劑的量係相對於(甲基)丙烯酸系單體與(甲基)丙烯酸系寡聚物與表面改質劑之總和100質量份，更佳為0.01~5質量份，特佳為0.1~3質量份。 The hard coat layer preferably contains 5 to 50 mass % of the (meth)acrylic monomer, 50 to 95 mass % of the (meth)acrylic oligomer, and 1 to 10 mass % of the surface modifier, and particularly preferably contains (meth)acrylic monomer 20-40 mass %, (meth)acrylic oligomer 60-80 mass % and surface modifier 2-5 mass %. The amount of the photopolymerization initiator is based on 100 parts by mass of the total of (meth)acrylic monomers, (meth)acrylic oligomers and surface modifiers, more preferably 0.01 to 5 parts by mass, especially preferred 0.1 to 3 parts by mass.

(甲基)丙烯酸系單體，只要是分子內存在(甲基)丙烯醯基為官能基者時，即可使用，可為1官能單體、2官能單體、或3官能以上的單體。 1官能單體，例如有(甲基)丙烯酸、(甲基)丙烯酸酯，2官能及/或3官能以上之(甲基)丙烯酸系單體之具體例，可列舉二乙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、雙酚A二縮水甘油醚二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、羥基新戊酸新戊二醇二丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,4-丁二醇二丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、二環戊基二(甲基)丙烯酸酯、聚乙二醇二丙烯酸酯、1,4-丁二醇寡丙烯酸酯、新戊二醇寡丙烯酸酯、1,6-己二醇寡丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、三羥甲基丙烷乙氧基三(甲基)丙烯酸酯、三羥甲基丙烷丙氧基三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、甘油基丙氧基三(甲基)丙烯酸酯、三羥甲基丙烷三甲基丙烯酸酯、三羥甲基丙烷環氧乙烷加成物三丙烯酸酯、丙三醇環氧丙烷加成物三丙烯酸酯、季戊四醇四丙烯酸酯等。硬塗層也可包含1種類或2種類以上之(甲基)丙烯酸系單體。 (Meth)acrylic monomers can be used as long as there is a (meth)acryloyl group in the molecule as a functional group, and may be monofunctional, bifunctional, or trifunctional or higher. . Monofunctional monomers, such as (meth)acrylic acid, (meth)acrylates, and bifunctional and/or trifunctional or more (meth)acrylic monomers Specific examples include diethylene glycol di(methyl) base) acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate base) acrylate, tetraethylene glycol di(meth)acrylate, hydroxypivalate, neopentyl glycol diacrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol diacrylate ester, 1,3-butanediol di(meth)acrylate, dicyclopentyl di(meth)acrylate, polyethylene glycol diacrylate, 1,4-butanediol oligoacrylate, neopentyl Diol oligoacrylate, 1,6-hexanediol oligoacrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxy tri(meth)acrylate, trimethylol Propane propoxy tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glyceryl propoxy tri(meth)acrylate, trimethylolpropane trimethacrylate, trimethylolpropane Ethylene oxide adduct triacrylate, glycerol propylene oxide adduct triacrylate, pentaerythritol tetraacrylate, etc. The hard coat layer may contain one kind or two or more kinds of (meth)acrylic monomers.

(甲基)丙烯酸系寡聚物，可列舉2官能以上之多官能胺基甲酸酯(甲基)丙烯酸酯寡聚物[以下也稱為多官能胺基甲酸酯(甲基)丙烯酸酯寡聚物]、2官能以上之多官能聚酯(甲基)丙烯酸酯寡聚物[以下也稱為多官能聚酯(甲基)丙烯酸酯寡聚物]、2官能以上之多官能環氧(甲基)丙烯酸酯寡聚物[以下也稱為多官能環氧(甲基)丙烯酸酯寡聚物]等。硬塗層也可包含1種類或2種類以上之(甲基)丙烯酸系寡聚物。多官能胺基甲酸酯(甲基)丙烯酸酯寡聚物，可列舉1分子中具有至少1個之(甲基)丙烯醯氧基及羥基的(甲基)丙烯酸酯單體與聚異氰酸酯的胺基甲酸酯化反應產物；使多元醇類與聚異氰酸酯反應所得之異氰酸酯化合物與1分子中具有至少1個以上之(甲基)丙烯醯氧基及羥基的(甲基)丙烯酸酯單體的胺基甲酸酯化反應產物等。 (Meth)acrylic-based oligomers, polyfunctional urethane (meth)acrylate oligomers with two or more functionalities can be mentioned [hereinafter also referred to as polyfunctional urethane (meth)acrylates oligomer], polyfunctional polyester (meth)acrylate oligomer with more than two functions [hereinafter also referred to as polyfunctional polyester (meth)acrylate oligomer], polyfunctional epoxy resin with more than two functions (Meth)acrylate oligomer [hereinafter also referred to as polyfunctional epoxy (meth)acrylate oligomer] and the like. The hard coat layer may contain one kind or two or more kinds of (meth)acrylic oligomers. Polyfunctional urethane (meth)acrylate oligomers include (meth)acrylate monomers having at least one (meth)acryloyloxy group and a hydroxyl group in one molecule and polyisocyanates. Urethane reaction product; isocyanate compound obtained by reacting polyols with polyisocyanate and (meth)acrylate monomer having at least one (meth)acryloyloxy group and hydroxyl group in one molecule The urethane reaction product, etc.

胺基甲酸酯化反應所使用之1分子中具有至少1個之(甲基)丙烯醯氧基及羥基的(甲基)丙烯酸酯單體，可列舉2-羥基乙基(甲基)丙烯酸酯、2-羥基丙基(甲基)丙烯酸酯、2-羥基丁基(甲基)丙烯酸酯、2-羥基-3-苯氧基丙基(甲基)丙烯酸酯、丙三醇二(甲基)丙烯酸酯、三羥甲基丙烷二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯。The (meth)acrylate monomer having at least one (meth)acryloyloxy group and a hydroxyl group in one molecule used for the urethane reaction includes 2-hydroxyethyl (meth)acrylic acid. ester, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, glycerol di(meth)acrylate base) acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate.

胺基甲酸酯化反應所使用之聚異氰酸酯，可列舉六亞甲基二異氰酸酯、離胺酸二異氰酸酯、異佛爾酮二異氰酸酯、二環己基甲烷二異氰酸酯、甲伸苯基二異氰酸酯、亞二甲苯基二異氰酸酯、將此等二異氰酸酯之中芳香族之異氰酸酯類進行氫化所得之二異氰酸酯(例如氫化甲伸苯基二異氰酸酯、氫化亞二甲苯基二異氰酸酯等之二異氰酸酯)、三苯基甲烷三異氰酸酯、二亞甲基三苯基三異氰酸酯等之二或三之聚異氰酸酯、或二異氰酸酯進行多聚化所得的聚異氰酸酯。The polyisocyanate used for the urethane reaction includes hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tolyl diisocyanate, Xylylene diisocyanate, diisocyanates obtained by hydrogenating aromatic isocyanates among these diisocyanates (for example, diisocyanates such as hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, etc.), triphenylene Methane triisocyanate, dimethylene triphenyl triisocyanate, etc., two or three polyisocyanates, or polyisocyanates obtained by polymerizing diisocyanates.

胺基甲酸酯化反應所使用之多元醇類，一般除了芳香族、脂肪族及脂環式之多元醇外，可使用聚酯多元醇、聚醚多元醇等。通常，脂肪族及脂環式之多元醇，可列舉1,4-丁二醇、1,6-己二醇、新戊二醇、乙二醇、丙二醇、三羥甲基乙烷、三羥甲基丙烷、二羥甲基庚烷、二羥甲基丙酸、二羥甲基丁酸、丙三醇、氫化雙酚A等。The polyols used in the urethane reaction generally include polyester polyols, polyether polyols, etc. in addition to aromatic, aliphatic and alicyclic polyols. Generally, aliphatic and alicyclic polyols include 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, ethylene glycol, propylene glycol, trimethylolethane, trihydroxy Methyl propane, dimethylol heptane, dimethylol propionic acid, dimethylol butyric acid, glycerol, hydrogenated bisphenol A, etc.

聚酯多元醇，可列舉上述多元醇類與聚羧酸之脫水縮合反應所得者。聚羧酸之具體的化合物，可列舉琥珀酸、己二酸、馬來酸、偏苯三甲酸、六氫鄰苯二甲酸、苯二甲酸、間苯二甲酸、對苯二甲酸等。此等之聚羧酸也可為酸酐。又，聚醚多元醇除了聚伸烷二醇外，可列舉上述多元醇類或酚類與環氧烷之反應所得的聚氧化烯改質多元醇。As the polyester polyol, those obtained by the dehydration condensation reaction of the above-mentioned polyols and polycarboxylic acid are exemplified. Specific compounds of the polycarboxylic acid include succinic acid, adipic acid, maleic acid, trimellitic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, and the like. These polycarboxylic acids may also be acid anhydrides. In addition to polyalkylene glycol, polyether polyols include polyoxyalkylene-modified polyols obtained by the reaction of the above-mentioned polyols or phenols with alkylene oxides.

又，多官能聚酯(甲基)丙烯酸酯寡聚物係使用(甲基)丙烯酸、聚羧酸及多元醇藉由脫水縮合反應所得。脫水縮合反應所使用之聚羧酸，可列舉琥珀酸、己二酸、馬來酸、依康酸、偏苯三甲酸、均苯四甲酸、六氫鄰苯二甲酸、苯二甲酸、間苯二甲酸、對苯二甲酸等。此等之聚羧酸也可為酸酐。又，脫水縮合反應所使用之多元醇，可列舉1,4-丁二醇、1,6-己二醇、二乙二醇、三乙二醇、丙二醇、新戊二醇、二羥甲基庚烷、二羥甲基丙酸、二羥甲基丁酸、三羥甲基丙烷、二(三羥甲基)丙烷、季戊四醇、二季戊四醇等。Moreover, a polyfunctional polyester (meth)acrylate oligomer is obtained by dehydration condensation reaction using (meth)acrylic acid, a polycarboxylic acid, and a polyhydric alcohol. Examples of polycarboxylic acids used in the dehydration condensation reaction include succinic acid, adipic acid, maleic acid, itaconic acid, trimellitic acid, pyromellitic acid, hexahydrophthalic acid, phthalic acid, and isophthalic acid. Dicarboxylic acid, terephthalic acid, etc. These polycarboxylic acids may also be acid anhydrides. In addition, the polyhydric alcohol used in the dehydration condensation reaction includes 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, and dimethylol. Heptane, dimethylol propionic acid, dimethylol butyric acid, trimethylol propane, bis(trimethylol) propane, pentaerythritol, dipentaerythritol, etc.

多官能環氧(甲基)丙烯酸酯寡聚物係藉由聚縮水甘油醚與(甲基)丙烯酸之加成反應所得。聚縮水甘油醚，可列舉乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、三丙二醇二縮水甘油醚、1,6-己二醇二縮水甘油醚、雙酚A二縮水甘油醚等。The polyfunctional epoxy (meth)acrylate oligomer is obtained by the addition reaction of polyglycidyl ether and (meth)acrylic acid. Polyglycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A diglycidyl ether, and the like.

本發明所使用的表面改質劑係指平坦劑、抗靜電劑、界面活性劑、撥水撥油劑、無機粒子、有機粒子等之改變硬塗層的表面性能者。平坦劑可列舉例如聚醚改質聚烷基矽氧烷、聚醚改質矽氧烷、含有聚酯改質羥基之聚烷基矽氧烷、具有烷基之聚醚改質聚二甲基矽氧烷、改質聚醚、矽改質丙烯酸等。 The surface modifier used in the present invention refers to a leveling agent, an antistatic agent, a surfactant, a water-repellent and oil-repellent agent, inorganic particles, organic particles, etc., which change the surface properties of the hard coat layer. Examples of the leveling agent include polyether-modified polyalkylsiloxanes, polyether-modified siloxanes, polyalkylsiloxanes containing polyester-modified hydroxyl groups, and polyether-modified polydimethylsiloxanes having an alkyl group. Siloxane, modified polyether, silicon modified acrylic, etc.

抗靜電劑，可列舉例如丙三醇脂肪酸酯單甘油酯、丙三醇脂肪酸酯有機酸單甘油酯、聚丙三醇脂肪酸酯、山梨糖醇酐脂肪酸酯、陽離子性界面活性劑、陰離子性界面活性劑等。無機粒子，可列舉例如二氧化矽粒子、氧化鋁粒子、二氧化鋯粒子、矽粒子銀粒子、玻璃粒子等。有機粒子，可列舉例如丙烯酸粒子、矽粒子等。界面活性劑及撥水撥油劑，可列舉例如含氟基･含有親油性基之寡聚物、含氟基･含有親水性基･親油性基･UV反應性基之寡聚物等之含有氟的界面活性劑及撥水撥油劑。 Examples of antistatic agents include glycerol fatty acid ester monoglycerides, glycerol fatty acid ester organic acid monoglycerides, polyglycerol fatty acid esters, sorbitan fatty acid esters, cationic surfactants, Anionic surfactants, etc. Examples of inorganic particles include silica particles, alumina particles, zirconia particles, silicon particles, silver particles, glass particles, and the like. The organic particles include, for example, acrylic particles, silicon particles, and the like. Surfactants and water and oil repellents include, for example, oligomers containing fluorine groups, lipophilic groups, and oligomers containing fluorine groups, hydrophilic groups, lipophilic groups, and UV reactive groups. Fluorine surfactant and water and oil repellent.

硬塗層也可含有光聚合起始劑。本說明書中，光聚合起始劑係指光自由基產生劑。The hard coat layer may also contain a photopolymerization initiator. In this specification, the photopolymerization initiator refers to a photoradical generator.

本發明可使用之單官能光聚合起始劑，可列舉例如4-(2-羥基乙氧基)苯基(2-羥基-2-丙基)酮[DAROCUR-2959：Merck公司製]；α-羥基-α,α’-二甲基苯乙酮[DAROCUR-1173：Merck公司製]；甲氧基苯乙酮、2,2’-二甲氧基-2-苯基苯乙酮[IRGACURE-651]、1-羥基-環己基苯基酮等之苯乙酮系起始劑；苯偶因***、苯偶因異丙醚等之苯偶因醚系起始劑；其他，鹵化酮、醯基氧化膦、醯基膦酸酯(Phosphonate)等。As the monofunctional photopolymerization initiator that can be used in the present invention, for example, 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone [DAROCUR-2959: manufactured by Merck Corporation]; α -Hydroxy-α,α'-dimethylacetophenone [DAROCUR-1173: manufactured by Merck]; methoxyacetophenone, 2,2'-dimethoxy-2-phenylacetophenone [IRGACURE -651], acetophenone-based initiators such as 1-hydroxy-cyclohexyl phenyl ketone; benzene-in-ether-based initiators such as phenyl-i-diethyl ether, benzene-i-isopropyl ether, etc.; other, halogenated ketones, Acyl phosphine oxide, acyl phosphonate (Phosphonate) and the like.

硬塗層之形成方法無特別限定，例如可在位於硬塗層之下的層上塗佈硬塗液後，藉由光聚合而形成。The formation method of a hard coat layer is not specifically limited, For example, after apply|coating a hard coat liquid to the layer located under the hard coat layer, it can be formed by photopolymerization.

塗佈硬塗液(聚合性組成物)的方法無特別限定，可使用習知的方法。可列舉例如旋轉塗佈法、浸漬法、噴霧法、斜板式塗佈法、棒塗法、輥塗法、凹版塗佈法、凹面塗佈法、凸版印刷法、網版印刷法、玻璃球塗佈法、刷毛塗佈法等。The method of applying the hard coating liquid (polymerizable composition) is not particularly limited, and a known method can be used. For example, a spin coating method, a dipping method, a spray method, an inclined plate coating method, a bar coating method, a roll coating method, a gravure coating method, a gravure coating method, a letterpress printing method, a screen printing method, a glass ball coating method can be mentioned. Cloth method, brush coating method, etc.

光聚合中之光照射所使用的燈，可使用光波長420nm以下之具有發光分布者，可列舉例如低壓水銀燈、中壓水銀燈、高壓水銀燈、超高壓水銀燈、化學燈、黑光燈、微波激發水銀燈、金屬鹵素燈等。其中，高壓水銀燈或金屬鹵素燈，可有效地使起始劑之活性波長範圍的光發光，因交聯使所得之高分子之黏彈性的性質降低之短波長的光，或使反應組成物加熱蒸發之長波長的光避免大量發光，故較佳。Lamps used for light irradiation in photopolymerization can be those with a light wavelength of 420 nm or less and have a luminescence distribution, such as low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, ultra-high pressure mercury lamps, chemical lamps, black light lamps, microwave excited mercury lamps, Metal halide lamps, etc. Among them, high-pressure mercury lamps or metal halide lamps can effectively emit light in the active wavelength range of the initiator, short-wavelength light in which the viscoelastic properties of the obtained polymer are reduced due to cross-linking, or heat the reaction composition. Evaporated long-wavelength light is preferred to avoid a large amount of light emission.

上述燈的照射強度係左右所得之聚合物之聚合度的重要因素，適宜地控制各目的製品的性能。調配通常具有苯乙酮基之開裂型之起始劑時，照度較佳為0.1~300mW/cm ²的範圍。特別是使用金屬鹵素燈，照度設為10~40mW/cm ²較佳。 The irradiation intensity of the above-mentioned lamp is an important factor affecting the degree of polymerization of the obtained polymer, and the properties of each intended product are appropriately controlled. When preparing a cracking initiator with an acetophenone group, the illuminance is preferably in the range of 0.1 to 300 mW/cm ² . In particular, a metal halide lamp is used, and the illuminance is preferably set to 10 to 40 mW/cm ² .

光聚合反應係受因空氣中的氧或溶解於反應性組成物中的氧阻礙。因此，光照射係使用可消除氧所致之反應阻礙的手法來實施較佳。這種手法之一，例如將反應性組成物以聚對苯二甲酸乙二酯或鐵氟龍製薄膜覆蓋，遮斷與氧接觸，透過薄膜使光照射反應性組成物的方法。又，可藉由如氮氣或二氧化碳之惰性氣體，取代氧之惰性氣體氣氛下，通過光線穿透性的窗，對組成物照射光。The photopolymerization reaction is hindered by oxygen in the air or oxygen dissolved in the reactive composition. Therefore, it is preferable to carry out the light irradiation using the method which can eliminate the reaction inhibition by oxygen. One of such methods is, for example, a method of covering the reactive composition with a polyethylene terephthalate or Teflon film, blocking contact with oxygen, and irradiating the reactive composition with light through the film. In addition, the composition may be irradiated with light through a light-transmitting window in an atmosphere of an inert gas such as nitrogen or carbon dioxide instead of oxygen.

在惰性氣體氣氛下進行光照射時，為了使該環境氧濃度保持低水平，經常導入一定量的惰性氣體。藉由此惰性氣體之導入，在反應性組成物表面產生氣流，產生單體蒸發。為了抑制單體蒸發的水平時，惰性氣體的氣流速度係相對於惰性氣體氣氛下塗佈有移動之硬化塗層液之積層體的相對速度，較佳為1m/sec以下，更佳為0.1m/sec以下。藉由將氣流速度設為上述範圍，因氣流所致之單體蒸發實質上被抑制。When light irradiation is performed in an inert gas atmosphere, in order to keep the ambient oxygen concentration low, a certain amount of inert gas is often introduced. By the introduction of this inert gas, a gas flow is generated on the surface of the reactive composition, resulting in the evaporation of the monomers. In order to suppress the evaporation of the monomer, the gas flow velocity of the inert gas is the relative velocity of the layered body to which the moving hard coating liquid is applied under the inert gas atmosphere, preferably 1 m/sec or less, more preferably 0.1 m /sec or less. By setting the airflow velocity to the above-mentioned range, the evaporation of the monomer due to the airflow is substantially suppressed.

為了提高硬塗層之密著性之目的，有在塗佈面進行前處理的情形。處理例，可列舉噴砂法、溶劑處理法、電暈放電處理法、鉻酸處理法、火焰處理法、熱風處理法、臭氧處理法、紫外線處理法、藉由樹脂組成物之底塗處理法等的習知方法。For the purpose of improving the adhesiveness of the hard coat layer, pretreatment may be performed on the coated surface. Examples of the treatment include sandblasting, solvent treatment, corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone treatment, ultraviolet treatment, primer treatment with a resin composition, etc. habitual method.

硬塗層使用UV光(254nm)之照射輸出為20mW/cm ²之金屬鹵素燈進行紫外線照射時，鉛筆硬度為2H以上較佳。 When the hard coat layer is irradiated with UV light using a metal halide lamp with an irradiation output of UV light (254 nm) of 20 mW/cm ² , the pencil hardness is preferably 2H or higher.

硬塗層之膜厚，較佳為1μm以上40μm以下，更佳為2μm以上10μm以下。由於膜厚為1μm以上，可得到充分的硬度。又，由於膜厚為40μm以下，可抑制因彎曲加工時之龜裂發生。又，硬塗層之膜厚係以顯微鏡等觀察斷面，藉由實測由塗膜界面至表面而可測定。The film thickness of the hard coat layer is preferably 1 μm or more and 40 μm or less, more preferably 2 μm or more and 10 μm or less. Since the film thickness is 1 μm or more, sufficient hardness can be obtained. In addition, since the film thickness is 40 μm or less, the occurrence of cracks during bending can be suppressed. In addition, the film thickness of a hard-coat layer can be measured from the coating-film interface to the surface by observing a cross section with a microscope or the like.

＜Haze(霧度)＞具有本發明之樹脂積層體，無特別限制，較佳為Haze≦1.0%，更佳為Haze≦0.8%，特佳為Haze≦0.7%。Haze超過1.0%時，以目視可看見稍微白色樹脂積層體的情形。＜Haze (Haze)＞ The resin laminate having the present invention is not particularly limited, but preferably Haze≦1.0%, more preferably Haze≦0.8%, and particularly preferably Haze≦0.7%. When Haze exceeds 1.0%, a slightly white resin laminate is visually recognized.

＜樹脂積層體＞本發明中，包含熱塑性樹脂(B)之層的厚度，會影響樹脂積層體之表面硬度或耐衝撃性。換言之，包含熱塑性樹脂(B)之層的厚度過薄時，表面硬度變低，故不佳。包含熱塑性樹脂(B)之層的厚度過大時，耐衝撃性變差，故不佳。包含熱塑性樹脂(B)之層的厚度，較佳為10~250 μm，更佳為20~200μm。又更佳為30~150μm。 <Resin laminate> In the present invention, the thickness of the layer containing the thermoplastic resin (B) affects the surface hardness or impact resistance of the resin laminate. In other words, when the thickness of the layer containing the thermoplastic resin (B) is too thin, the surface hardness becomes low, which is not preferable. When the thickness of the layer containing the thermoplastic resin (B) is too large, the impact resistance is deteriorated, which is not preferable. The thickness of the layer containing the thermoplastic resin (B) is preferably 10 to 250 μm, more preferably 20 to 200 μm. More preferably, it is 30-150 micrometers.

本發明中，包含聚碳酸酯系樹脂(A)之層與包含熱塑性樹脂(B)之層與硬塗層之合計厚度，過薄或過厚也難成形。樹脂積層體的全體厚度，較佳為0.4~4.0 mm，更佳為0.5~3.5mm，又更佳為0.5~3.0mm。In the present invention, the total thickness of the layer containing the polycarbonate resin (A), the layer containing the thermoplastic resin (B), and the hard coat layer is too thin or too thick to be formed. The overall thickness of the resin laminate is preferably 0.4 to 4.0 mm, more preferably 0.5 to 3.5 mm, and still more preferably 0.5 to 3.0 mm.

本發明中，聚碳酸酯系樹脂(A)與熱塑性樹脂(B)之折射率差，較佳為0~0.07之範圍，更佳為0~0.06之範圍，又更佳為0~0.05之範圍。聚碳酸酯系樹脂(A)與熱塑性樹脂(B)之折射率差大於0.07時，包含聚碳酸酯系樹脂(A)之層/包含熱塑性樹脂(B)之層之界面的反射光強度大，有時會發生干涉條紋等之不佳的情形。In the present invention, the difference in refractive index between the polycarbonate resin (A) and the thermoplastic resin (B) is preferably in the range of 0 to 0.07, more preferably in the range of 0 to 0.06, and still more preferably in the range of 0 to 0.05 . When the difference in refractive index between the polycarbonate-based resin (A) and the thermoplastic resin (B) is greater than 0.07, the reflected light intensity at the interface of the layer containing the polycarbonate-based resin (A)/the layer containing the thermoplastic resin (B) is large, Disadvantages such as interference fringes may occur.

本發明之樹脂積層體，其單面或兩面可施予耐指紋處理、抗反射處理、防污處理、抗靜電處理、耐候性處理及防眩處理中任一個以上。抗反射處理、防污處理、抗靜電處理、耐候性處理及防眩處理的方法，無特別限定，可使用習知的方法。可列舉例如塗佈反射低減塗料的方法、蒸鍍介電體薄膜的方法、塗佈抗靜電塗料的方法等。The resin laminate of the present invention may be given any one or more of anti-fingerprint treatment, anti-reflection treatment, anti-fouling treatment, anti-static treatment, weather resistance treatment and anti-glare treatment on one side or both sides. The methods of antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment, and antiglare treatment are not particularly limited, and conventional methods can be used. For example, a method of applying a reflection-reducing paint, a method of evaporating a dielectric thin film, and a method of applying an antistatic paint can be mentioned.

＜任意的添加劑＞本發明中，包含形成基材層之聚碳酸酯系樹脂(A)的層及/或包含形成表層之熱塑性樹脂(B)的層，也可包含上述主成分以外的成分。 <Optional additives> In the present invention, the layer containing the polycarbonate resin (A) forming the base layer and/or the layer containing the thermoplastic resin (B) forming the surface layer may contain components other than the above-mentioned main components.

例如，包含形成基材層之聚碳酸酯系樹脂(A)的層及/或包含形成表層之熱塑性樹脂(B)的層，可混合紫外線吸收劑使用。又，本發明中，硬塗層也可含有紫外線吸收劑。紫外線吸收劑之含量過多時，因成形法，過剩紫外線吸收劑因施加高的溫度，而產生飛散，污染成形環境，故有產生不理想的情形。因此，紫外線吸收劑之含有比例，較佳為0~5質量%，更佳為0~3質量%，又更佳為0~1質量%。紫外線吸收劑，可列舉例如2,4-二羥基二苯甲酮、2-羥基-4-甲氧基二苯甲酮、2-羥基-4-n-辛氧基二苯甲酮、2-羥基-4-十二烷氧基二苯甲酮、2-羥基-4-十八烷氧基二苯甲酮、2,2’-二羥基-4-甲氧基二苯甲酮、2,2’-二羥基-4,4’-二甲氧基二苯甲酮、2,2’,4,4’-四羥基二苯甲酮等之二苯甲酮系紫外線吸收劑、2-(2-羥基-5-甲基苯基)苯并***、2-(2-羥基-3,5-二-t-丁基苯基)苯并***、2-(2-羥基-3-t-丁基-5-甲基苯基)苯并***、(2H-苯并***-2-基)-4,6-雙(1-甲基-1-苯基乙基)苯酚等之苯并***系紫外線吸收劑、水楊酸苯酯、2,4-二-t-丁基苯基-3,5-二-t-丁基-4-羥基苯甲酸酯等之苯甲酸酯系紫外線吸收劑、雙(2,2,6,6-四甲基哌啶-4-基)癸二酸酯等之受阻胺系紫外線吸收劑、2,4-二苯基-6-(2-羥基-4-甲氧基苯基)-1,3,5-三嗪、2,4-二苯基-6-(2-羥基-4-乙氧基苯基)-1,3,5-三嗪、2,4-基-(2-羥基-4-丙氧基苯基)-1,3,5-三嗪、2,4-二苯基-(2-羥基-4-丁氧基苯基)1,3,5-三嗪、2,4-二苯基-6-(2-羥基-4-丁氧基苯基)-1,3,5-三嗪、2,4-二苯基-6-(2-羥基-4-己氧基苯基)-1,3,5-三嗪、2,4-二苯基-6-(2-羥基-4-辛氧基苯基)-1,3,5-三嗪、2,4-二苯基-6-(2-羥基-4-十二烷氧基苯基)-1,3,5-三嗪、2,4-二苯基-6-(2-羥基-4-苄氧基苯基)-1,3,5-三嗪等之三嗪系紫外線吸收劑、2-[2-(6-羥基苯並[1,3]二氧雜環戊烯-5-基)-2H-苯并***-5-基]乙基甲基丙烯酸酯、2-[2-(6-羥基苯並[1,3]二氧雜環戊烯-5-基)-2H-苯并***-5-基]乙基丙烯酸酯、3-[2-(6-羥基苯並[1,3]二氧雜環戊烯-5-基)-2H-苯并***-5-基]丙基甲基丙烯酸酯、3-[2-(6-羥基苯並[1,3]二氧雜環戊烯-5-基)-2H-苯并***-5-基]丙基丙烯酸酯、4-[2-(6-羥基苯並[1,3]二氧雜環戊烯-5-基)-2H-苯并***-5-基]丁基甲基丙烯酸酯、4-[2-(6-羥基苯並[1,3]二氧雜環戊烯-5-基)-2H-苯并***-5-基]丁基丙烯酸酯、2-[2-(6-羥基苯並[1,3]二氧雜環戊烯-5-基)-2H-苯并***-5-氧基]乙基甲基丙烯酸酯、2-[2-(6-羥基苯並[1,3]二氧雜環戊烯-5-基)-2H-苯并***-5-氧基]乙基丙烯酸酯、2-[3-{2-(6-羥基苯並[1,3]二氧雜環戊烯-5-基)-2H-苯并***-5-基}丙醯氧基]乙基甲基丙烯酸酯、2-[3-{2-(6-羥基苯並[1,3]二氧雜環戊烯-5-基)-2H-苯并***-5-基}丙醯氧基]乙基丙烯酸酯、4-[3-{2-(6-羥基苯並[1,3]二氧雜環戊烯-5-基)-2H-苯并***-5-基}丙醯氧基]丁基甲基丙烯酸酯、4-[3-{2-(6-羥基苯並[1,3]二氧雜環戊烯-5-基)-2H-苯并***-5-基}丙醯氧基]丁基丙烯酸酯、2-[3-{2-(6-羥基苯並[1,3]二氧雜環戊烯-5-基)-2H-苯并***-5-基}丙醯氧基]乙基甲基丙烯酸酯、2-[3-{2-(6-羥基苯並[1,3]二氧雜環戊烯-5-基)-2H-苯并***-5-基}丙醯氧基]乙基丙烯酸酯、2-(甲基丙烯醯氧基)乙基2-(6-羥基苯並[1,3]二氧雜環戊烯-5-基)-2H-苯并***-5羧酸鹽、2-(丙烯醯氧基)乙基2-(6-羥基苯並[1,3]二氧雜環戊烯-5-基)-2H-苯并***-5-羧酸鹽、4-(甲基丙烯醯氧基)丁基2-(6-羥基苯並[1,3]二氧雜環戊烯-5-基)-2H-苯并***-5-羧酸鹽、4-(丙烯醯氧基)丁基2-(6-羥基苯並[1,3]二氧雜環戊烯-5-基)-2H-苯并***-5-羧酸鹽等等之芝麻酚型苯并***系紫外線吸收劑等。混合的方法無特別限定，可使用全量混合的方法、將母料乾燥混合的方法、全量乾燥混合的方法等。For example, the layer containing the polycarbonate resin (A) forming the base layer and/or the layer containing the thermoplastic resin (B) forming the surface layer may be mixed with an ultraviolet absorber and used. Moreover, in this invention, a hard-coat layer may contain an ultraviolet absorber. If the content of the ultraviolet absorber is too large, the excess ultraviolet absorber may scatter due to the application of high temperature in the molding method, and the molding environment may be polluted, which may be undesirable. Therefore, the content ratio of the ultraviolet absorber is preferably 0 to 5 mass %, more preferably 0 to 3 mass %, and still more preferably 0 to 1 mass %. Examples of ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2- Hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2, 2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone and other benzophenone-based ultraviolet absorbers, 2-( 2-Hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-t-butylphenyl)benzotriazole, 2-(2-hydroxy-3- t-Butyl-5-methylphenyl)benzotriazole, (2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, etc. Benzotriazole UV absorbers, phenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, etc. Formate-based UV absorbers, hindered amine-based UV absorbers such as bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate, 2,4-diphenyl-6 -(2-Hydroxy-4-methoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-ethoxyphenyl)-1, 3,5-triazine, 2,4-yl-(2-hydroxy-4-propoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-(2-hydroxy-4 -Butoxyphenyl)1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, 2 ,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-octane) oxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-dodecyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-benzyloxyphenyl)-1,3,5-triazine and other triazine-based ultraviolet absorbers, 2-[2-(6-hydroxyl Benzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yl]ethyl methacrylate, 2-[2-(6-hydroxybenzo[1] ,3]dioxol-5-yl)-2H-benzotriazol-5-yl]ethyl acrylate, 3-[2-(6-hydroxybenzo[1,3]dioxa Cyclopenten-5-yl)-2H-benzotriazol-5-yl]propyl methacrylate, 3-[2-(6-hydroxybenzo[1,3]dioxol- 5-yl)-2H-benzotriazol-5-yl]propyl acrylate, 4-[2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H -Benzotriazol-5-yl]butyl methacrylate, 4-[2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazole- 5-yl]butylacrylate, 2-[2-(6-hydroxybenzo[1,3]dioxane Penten-5-yl)-2H-benzotriazole-5-oxy]ethyl methacrylate, 2-[2-(6-hydroxybenzo[1,3]dioxol- 5-yl)-2H-benzotriazole-5-oxy]ethyl acrylate, 2-[3-{2-(6-hydroxybenzo[1,3]dioxol-5- yl)-2H-benzotriazol-5-yl}propionyloxy]ethyl methacrylate, 2-[3-{2-(6-hydroxybenzo[1,3]dioxolane) Alken-5-yl)-2H-benzotriazol-5-yl}propionyloxy]ethyl acrylate, 4-[3-{2-(6-hydroxybenzo[1,3]dioxa) Cyclopenten-5-yl)-2H-benzotriazol-5-yl}propionyloxy]butyl methacrylate, 4-[3-{2-(6-hydroxybenzo[1,3]di) Oxol-5-yl)-2H-benzotriazol-5-yl}propionyloxy]butylacrylate, 2-[3-{2-(6-hydroxybenzo[1,3 ]dioxol-5-yl)-2H-benzotriazol-5-yl}propionyloxy]ethyl methacrylate, 2-[3-{2-(6-hydroxybenzoate [1,3]Dioxol-5-yl)-2H-benzotriazol-5-yl}propionyloxy]ethyl acrylate, 2-(methacryloyloxy)ethyl 2-(6-Hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazole-5 carboxylate, 2-(propenyloxy)ethyl 2-( 6-Hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazole-5-carboxylate, 4-(methacryloyloxy)butyl 2-( 6-Hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazole-5-carboxylate, 4-(propenyloxy)butyl 2-(6- Sesamol-type benzotriazole-based ultraviolet absorbers, etc., such as hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazole-5-carboxylate and the like. The method of mixing is not particularly limited, and the method of mixing the entire amount, the method of dry mixing the master batch, the method of dry mixing the entire amount, and the like can be used.

本發明中，包含形成基材層之聚碳酸酯系樹脂(A)的層及/或包含形成表層之熱塑性樹脂(B)的層，除上述紫外線吸收劑外，也可混合各種添加劑使用。這種添加劑，可列舉例如抗氧化劑或抗著色劑、抗靜電劑、脫模劑、滑劑、染料、顏料、可塑劑、難燃劑、樹脂改質劑、相溶化劑、有機填料或無機填料等的強化材等。混合方法無特別限定，可使用全量混合的方法、將母料乾燥混合的方法、全量乾燥混合的方法等。In the present invention, the layer containing the polycarbonate resin (A) forming the base layer and/or the layer containing the thermoplastic resin (B) forming the surface layer may be mixed with various additives in addition to the above-mentioned ultraviolet absorber. Examples of such additives include antioxidants, anti-colorants, antistatic agents, mold release agents, slip agents, dyes, pigments, plasticizers, flame retardants, resin modifiers, compatibilizers, organic fillers or inorganic fillers Reinforcing materials, etc. The mixing method is not particularly limited, and a method of mixing the entire amount, a method of dry mixing a master batch, a method of dry mixing the entire amount, and the like can be used.

本發明中包含聚碳酸酯系樹脂(A)之層、包含熱塑性樹脂(B)之層及硬塗層的各材料，例如聚碳酸酯系樹脂(A)及熱塑性樹脂(B)等，藉由過濾器處理經過濾純化為佳。通過過濾器，藉由純化或積層，可得到異物或缺點等外觀不良少的樹脂積層體。過濾方法無特別限制，可使用熔融過濾、溶液過濾、或其組合等。In the present invention, each material including the layer of the polycarbonate resin (A), the layer including the thermoplastic resin (B), and the hard coat layer, such as the polycarbonate resin (A) and the thermoplastic resin (B), etc. Filter treatment is preferably purified by filtration. A resin laminate with few appearance defects such as foreign matter and defects can be obtained by purification or lamination through a filter. The filtration method is not particularly limited, and melt filtration, solution filtration, or a combination thereof, or the like can be used.

使用的過濾器無特別限制，可使用公知物，依各材料之使用溫度、黏度、過濾精度適宜地選擇。過濾器的濾材，無特別限定，可使用聚丙烯、綿、聚酯、黏液嫘縈或玻璃織維之不織布或彩棉線卷狀物、含浸酚樹脂之纖維素、金屬纖維不織布燒結體、金屬粉末燒結體、多孔板、或此等之組合等皆可使用。特別是考慮耐熱性或耐久性、耐壓力性時，較佳為將金屬纖維不織布進行燒結的型態。The filter used is not particularly limited, and a well-known filter can be used, and is appropriately selected according to the use temperature, viscosity, and filtration precision of each material. The filter material of the filter is not particularly limited, and can use polypropylene, cotton, polyester, mucus rayon or glass woven non-woven fabric or colored cotton thread roll, cellulose impregnated with phenol resin, metal fiber non-woven fabric sintered body, metal A powder sintered body, a porous plate, or a combination of these can be used. In particular, when heat resistance, durability, and pressure resistance are considered, a form in which a metal fiber nonwoven fabric is sintered is preferable.

針對聚碳酸酯系樹脂(A)及熱塑性樹脂(B)，過濾精度為50μm以下，較佳為30μm以下，又更佳為10μm以下。又，由於塗佈於樹脂積層體之最表層，故硬化處理劑的過濾精度為20μm以下，較佳為10μm以下，又更佳為2μm以下。For the polycarbonate resin (A) and the thermoplastic resin (B), the filtration accuracy is 50 μm or less, preferably 30 μm or less, and more preferably 10 μm or less. Moreover, since it is apply|coated to the outermost surface layer of a resin laminated body, the filtration precision of a hardening treatment agent is 20 micrometers or less, Preferably it is 10 micrometers or less, More preferably, it is 2 micrometers or less.

聚碳酸酯系樹脂(A)與熱塑性樹脂(B)之過濾，例如使用熱塑性樹脂熔融過濾所使用之聚合物過濾器較佳。聚合物過濾器，依其構造可分為薄盤狀過濾器(leaf disk filter)、燭形過濾器、過濾碟過濾器、圓筒型過濾器等，特別是以有效過濾面積大的薄盤狀過濾器為佳。For the filtration of the polycarbonate resin (A) and the thermoplastic resin (B), for example, a polymer filter used for melt filtration of thermoplastic resin is preferably used. Polymer filters can be divided into leaf disk filters, candle filters, filter disc filters, cylindrical filters, etc., according to their structures, especially those with a large effective filtration area. Filters are better.

＜熱彎曲加工＞本發明之樹脂積層體之熱彎曲加工，無特別限定。例如在壓製機裝設凸模(公模)與凹模(母模)的模具，以該2個模具挾住使加熱軟化的積層薄片之「熱壓成形」，藉由使加熱軟化之積層薄片與凸模(公模)的模具成為真空狀態，使積層薄片密著於模具，製成所希望的形狀的「真空成形」，藉由對加熱軟化之積層薄片與凸模(公模)的模具，施加大於大氣壓的壓力，使積層薄片密著於模具，製成所希望的形狀的「加壓成形」。本發明之樹脂積層體係以低溫(例如100~135℃)進行熱彎曲加工時，可得到不會產生回彈的熱成形體。＜Hot bending process＞ The thermal bending process of the resin laminate of the present invention is not particularly limited. For example, "hot press molding" in which a punch (male) and a female (female) are installed in a press, and the laminated sheet softened by heating is sandwiched between the two dies. The mold with the punch (male) is in a vacuum state, and the laminated sheet is adhered to the mold to form a desired shape "vacuum forming", by heating the softened laminated sheet and the punch (male) mold , "Pressure molding" in which a pressure greater than atmospheric pressure is applied to make the laminated sheet adhere to the mold to obtain the desired shape. When the resin lamination system of the present invention is subjected to thermal bending at a low temperature (for example, 100 to 135° C.), a thermoformed body that does not spring back can be obtained.

＜熱成形體＞將使用了以往之聚碳酸酯樹脂(例如，由Mitsubishi Engineering-Plastics股份公司市售之Iupilon S-2000、Iupilon S-1000、Iupilon E-2000)的積層薄片進行熱壓成形時，在135~145℃下，必須將薄片加熱直到聚碳酸酯樹脂充分地拉伸為止，結果對於熱塑性樹脂，施加過多的熱，故在熱塑性樹脂層與聚碳酸酯樹脂層之界面產生剝離，而有產生表面白化，或產生龜裂的情形。又，將薄片加熱至160℃時，表面突然燒起來，或轉印模具之傷痕的情形。此外，為了抑制熱成形不良，在100℃~135℃之低溫下進行熱壓成形時，無法再現模具的形狀，而有由模具的形狀返回至平坦的「回彈」的情形。 <Thermoforming body> When a laminated sheet using a conventional polycarbonate resin (for example, Iupilon S-2000, Iupilon S-1000, and Iupilon E-2000 commercially available from Mitsubishi Engineering-Plastics Co., Ltd.) is subjected to thermocompression molding, the temperature is 135 to 145 At ℃, the sheet must be heated until the polycarbonate resin is sufficiently stretched. As a result, too much heat is applied to the thermoplastic resin, so peeling occurs at the interface between the thermoplastic resin layer and the polycarbonate resin layer, resulting in surface whitening. or cracks. In addition, when the sheet is heated to 160°C, the surface is suddenly burned, or the scratches of the mold are transferred. In addition, in order to suppress defects in thermoforming, when thermoforming is performed at a low temperature of 100°C to 135°C, the shape of the mold cannot be reproduced, and the shape of the mold may return to a flat "springback".

相對於此，本發明之實施形態之樹脂積層體係使用特定的聚碳酸酯系樹脂(A)，故以100℃~135℃之低溫進行熱壓成形時，也不會發生回彈，可得到在低溫下之創意性優異的熱成形體。On the other hand, since the resin lamination system of the embodiment of the present invention uses a specific polycarbonate resin (A), it does not spring back even when hot-press molding is performed at a low temperature of 100° C. to 135° C. A thermoformed body with excellent creativity at low temperature.

又，在包含聚碳酸酯樹脂之層上具有包含熱塑性樹脂之層，在包含該熱塑性樹脂之層的表面具有硬塗層的樹脂積層體在100℃~135℃之低溫下進行熱壓成形時，樹脂積層體之彎曲部分，而有產生龜裂的情形。In addition, when a layer containing a thermoplastic resin is provided on a layer containing a polycarbonate resin, and a resin laminate having a hard coat layer on the surface of the layer containing the thermoplastic resin is subjected to thermocompression molding at a low temperature of 100°C to 135°C, Cracks may occur in the curved portion of the resin laminate.

相對於此，本發明之實施形態之樹脂積層體係使用特定熱塑性樹脂(B)，故在包含熱塑性樹脂(B)之層之表面具有硬塗層的樹脂積層體，在100℃~135℃之低溫進行熱壓成形的情形，樹脂積層體之彎曲部分也未發生龜裂，可得到低溫下之創意性優異的熱成形體。On the other hand, the resin laminate system of the embodiment of the present invention uses a specific thermoplastic resin (B), so the resin laminate having a hard coat layer on the surface of the layer containing the thermoplastic resin (B) can be stored at a low temperature of 100° C. to 135° C. In the case of thermoforming, cracks did not occur in the curved portion of the resin laminate, and a thermoformed body excellent in creativity at a low temperature was obtained.

＜用途＞實施形態之成形品(例如熱成形體)係包含含有上述各種較佳形態、構成之本發明之樹脂積層體的成形品。成形品的形狀、模樣、色彩、尺寸等無限制，可配合其用途任意設定即可。實施形態之樹脂積層體、熱成形體，在低溫(例如100~135℃)下之熱成形性優異，且可抑制干涉條紋之發生。因此，可適合作為透明基板材料或透明保護材料等使用。具體而言，可適合作為行動電話終端、携帶型電子遊戲游樂設施、行動資訊終端、攜帶PC等之携帶型的顯示器裝置或、筆記型PC、桌上型PC液晶監視器、汽車導航液晶監視器、液晶電視等之設置型顯示器裝置等之透明基板材料及透明保護材料(例如，前面板)使用，其中適合作為要求高創意性之觸控面板前面保護板或、汽車導航用、OA機器用或攜帶電子機器用的前面板使用。＜Use＞ The molded article (for example, a thermoformed article) of the embodiment includes a molded article including the resin laminate of the present invention having the above-mentioned various preferred forms and configurations. The shape, pattern, color, size, etc. of the molded product are not limited, and can be arbitrarily set according to the application. The resin laminate and thermoformed body of the embodiment are excellent in thermoformability at low temperature (eg, 100 to 135° C.), and can suppress the occurrence of interference fringes. Therefore, it can be suitably used as a transparent substrate material, a transparent protective material, or the like. Specifically, it can be suitably used as a portable display device such as a mobile phone terminal, a portable electronic game amusement facility, a mobile information terminal, a portable PC, a notebook PC, a desktop PC LCD monitor, and a car navigation LCD monitor. It is used as a transparent substrate material and a transparent protective material (for example, a front panel) for setting-type display devices such as LCD TVs, etc., and is suitable for use as a front protective plate for touch panels requiring high creativity, car navigation, OA equipment, or It is used as a front panel for portable electronic equipment.

[實施例][Example]

以下藉由實施例更詳細地說明本實施形態，但是本實施形態不限於此等實施例者。Hereinafter, the present embodiment will be described in more detail by way of examples, but the present embodiment is not limited to these examples.

＜苯乙烯共聚物中之單體單元的組成比＞使用日本電子(股)製JNM-AL400，由 ¹H-NMR及 ¹³C-NMR(400MHz：溶劑為CDCl ₃)之測定值計算。 <Composition ratio of monomer units in styrene copolymer> Using JNM-AL400 manufactured by JEOL Ltd., it was calculated from the measured values of ¹ H-NMR and ¹³ C-NMR (400 MHz: CDCl ₃ as the solvent).

＜玻璃轉移溫度＞使用Seiko Instruments(股)製示差掃描熱量測定裝置DSC6200。在氮30ml/min.流通下，以10℃/min.由30℃昇溫至200℃，接著，以50℃/min.由200℃降溫至30℃，再度以10℃/min.由30℃昇溫至200℃。以第2次昇溫中之基線與反曲點之切線的交點作為玻璃轉移溫度使用。 <Glass transition temperature> A differential scanning calorimeter DSC6200 manufactured by Seiko Instruments was used. Under the flow of nitrogen 30ml/min., the temperature was raised from 30°C to 200°C at 10°C/min. Then, the temperature was lowered from 200°C to 30°C at 50°C/min, and the temperature was raised again from 30°C at 10°C/min. to 200°C. The intersection of the baseline and the tangent of the inflection point in the second temperature rise was used as the glass transition temperature.

＜顆粒外觀＞顆粒製作時，以目視評價顆粒外觀。以下述基準判定顆粒外觀合格與否，○為合格。 ○：透明 ×：半透明或白濁＜Particle appearance＞ When the pellets were produced, the appearance of the pellets was visually evaluated. The appearance of the particles was judged to be acceptable or not based on the following criteria, and ○ was deemed acceptable. ○: Transparent ×: Translucent or cloudy

＜折射率＞以射出成型機製作試驗片，切成長40mm、寬10mm、厚度3mm。以(股)ATAGO製多波長阿貝折射計DR-M2測定此試料的折射率。測定溫度為20℃、測定波長為589nm，中間液使用單溴萘。 <Refractive index> A test piece was produced by an injection molding machine, and cut into a length of 40 mm, a width of 10 mm, and a thickness of 3 mm. The refractive index of this sample was measured with a multi-wavelength Abbe refractometer DR-M2 manufactured by ATAGO. The measurement temperature was 20° C., the measurement wavelength was 589 nm, and monobromonaphthalene was used as the intermediate solution.

＜全光穿透率＞使用反射･透過率計HR-100型(股份公司村上色彩技術研究所製)，依據JIS K7361-1測量樹脂積層體的全光穿透率。＜Total light transmittance＞ The total light transmittance of the resin laminate was measured according to JIS K7361-1 using a reflectance-transmittance meter HR-100 (manufactured by Murakami Color Technology Laboratory Co., Ltd.).

＜Haze(霧度)＞使用反射･透過率計HR-100型(股份公司村上色彩技術研究所製)，依據JIS K7136測定樹脂積層體的Haze。＜Haze (Haze)＞ The Haze of the resin laminate was measured according to JIS K7136 using a reflection and transmittance meter HR-100 (manufactured by Murakami Color Technology Laboratory Co., Ltd.).

＜鉛筆硬度＞依據JIS K 5600-5-4，對樹脂積層體之中央附近之包含熱塑性樹脂(B)之層上之硬塗層的表面，以角度45度、荷重750g，對表面逐漸增加硬度，緊壓鉛筆，未產生傷痕之最硬之鉛筆硬度作為鉛筆硬度進行評價。＜Pencil Hardness＞ According to JIS K 5600-5-4, on the surface of the hard coat layer on the layer containing the thermoplastic resin (B) near the center of the resin laminate, at an angle of 45 degrees and a load of 750 g, the hardness is gradually increased on the surface, and the pencil is pressed tightly. , the hardest pencil hardness without scratches was evaluated as pencil hardness.

＜干涉條紋＞樹脂積層體之包含聚碳酸酯系樹脂(A)之層側或包含熱塑性樹脂(B)之層側，黏貼黑膠帶(3M Japan(股)製黑色絕緣膠帶(Vinyl tape)型號117BLA)，由包含熱塑性樹脂(B)之層的表面，照射三波長型螢光燈((有) (technical inverter light 60 AL-60231)，評價干涉條紋。依據下述的基準，判定干涉條紋之合格與否，○為合格。 ○：未見干涉條紋，或干涉條紋微弱 ×：干涉條紋強 <Interference fringes> On the side of the layer containing the polycarbonate resin (A) or the side of the layer containing the thermoplastic resin (B) of the resin laminate, a black tape (Vinyl tape type 117BLA made by 3M Japan Co., Ltd.) The surface of the layer of thermoplastic resin (B) was irradiated with a three-wavelength fluorescent lamp (with) (technical inverter light 60 AL-60231) to evaluate the interference fringes. According to the following criteria, the acceptance of the interference fringes was judged, ○ is qualified. ○: No interference fringes are seen, or the interference fringes are weak ×: Strong interference fringes

＜熱壓成形加工性＞製作1mmt之樹脂積層體為50mmR彎曲之凸模(公模)與凹模(母模)的模具。樹脂積層體在成形前，於90℃下進行1分鐘預備加熱，硬塗層表面成為凸的方式，置於模具內，模具溫度80℃或120℃或160℃進行3分鐘壓製，藉由自然冷卻製作熱壓成形體。 <Hot press forming processability> To make a 1mmt resin laminate, a 50mmR curved punch (male) and a female (female) were used as molds. Before molding, the resin laminate was preheated at 90°C for 1 minute, and the surface of the hard coat layer became convex, placed in a mold, and the mold temperature was 80°C, 120°C, or 160°C for 3 minutes and pressed by natural cooling. A hot-pressed body is produced.

＜熱壓成形體之外觀＞以目視評價上述熱壓成形體的外觀。以下述的基準判定熱壓成形體之外觀合格與否，○為合格。 ○：熱壓成形體，突然焚燒，模具未見傷痕 ×：熱壓成形體，突然焚燒，模具可看見傷痕 <Appearance of hot-pressed body> The appearance of the above-mentioned hot press-formed body was visually evaluated. The appearance of the hot-press-formed body was judged to be acceptable or not based on the following criteria, and ○ was deemed acceptable. ○: Hot-pressed body, suddenly burnt, no scratches on the mold ×: Hot-pressed molded body was suddenly burned, and scratches were visible on the mold

＜彎曲部分之龜裂＞以目視評價上述熱壓成形體之彎曲部分之龜裂。依據下述基準判定彎曲部分龜裂之合格與否，○為合格。 ○：熱壓成形體之彎曲部分未見龜裂 ×：熱壓成形體之彎曲部分看見龜裂 <Cracks in the bent part> The cracks in the curved portion of the above-mentioned hot press-formed body were visually evaluated. According to the following criteria, it was judged whether the cracks in the bent portion were acceptable or not, and ○ was deemed acceptable. ○: No cracks were seen in the curved portion of the hot-pressed body ×: Cracks are seen in the bent portion of the hot-pressed body

＜回彈＞將上述熱壓成形體沿著50mmR的圓筒，依據下述基準判定回彈之合格與否，○為合格。 ○：沿著圓筒。(無回彈) ×：未沿著圓筒。(有回彈) 且，「○」為50±2mmR以內，「×」為此以外。＜Rebound＞ The above-mentioned hot-pressed body was placed along a cylinder of 50 mmR, and the following criteria were used to determine whether the springback was acceptable or not, and ○ was deemed acceptable. ○: Along the cylinder. (no rebound) ×: Not along the cylinder. (with rebound) In addition, "○" is within 50±2 mmR, and "x" is outside of this.

為了實施例，聚碳酸酯系樹脂(A-1)，熱塑性樹脂(B-1)~(B-2)，甲基丙烯酸樹脂(C-1)，苯乙烯共聚物(D-1)及硬塗膜(H-1)，使用下述所示的材料，但是不限定於此等。此外，為了比較例，各自使用下述所示之聚碳酸酯系樹脂(F-1)，熱塑性樹脂(G-1)~(G-11)，苯乙烯共聚物(E-1)~(E-3)。For example, polycarbonate resin (A-1), thermoplastic resin (B-1)~(B-2), methacrylic resin (C-1), styrene copolymer (D-1) and hard For the coating film (H-1), the materials shown below are used, but are not limited to these. In addition, for comparative examples, the following polycarbonate resins (F-1), thermoplastic resins (G-1) to (G-11), and styrene copolymers (E-1) to (E) were used, respectively. -3).

＜甲基丙烯酸樹脂(C-1)、苯乙烯共聚物(D-1)、苯乙烯共聚物(E-1)~(E-2)及聚碳酸酯系樹脂(F-1)＞甲基丙烯酸樹脂(C-1)：arkema股份公司製ALTUGLAS (註冊商標)V020(重量平均分子量：127,000，玻璃轉移溫度：109℃，溫度230℃･3.8kg荷重下之熔體流動速率：1.8g/10分鐘，甲基丙烯酸甲酯/丙烯酸甲酯=96.1質量%/3.9質量%，折射率1.49，mm/mr/rr=7.4莫耳%/37.4莫耳%/55.2莫耳%) 苯乙烯共聚物(D-1)：Polyscope公司製XIRANSO23110 ((d1)/(d2)=苯乙烯/馬來酸酐=78質量%/22質量%，重量平均分子量：74,300，玻璃轉移溫度：145℃，溫度230℃･3.8kg荷重下之熔體流動速率：5.9g/10分鐘，折射率1.58) 苯乙烯共聚物(E-1)：Polyscope公司製XIRANSO26080 ((d1)/(d2)=苯乙烯/馬來酸酐=75質量%/25質量%，重量平均分子量：47,600，玻璃轉移溫度：150℃，溫度230℃･3.8kg荷重下之熔體流動速率：8.3g/10分鐘、折射率1.58) 苯乙烯共聚物(E-2)：Polyscope公司製XIBOND140 ((d1)/(d2)=苯乙烯/馬來酸酐=85質量%/15質量%，重量平均分子量：134,000，玻璃轉移溫度：129℃，溫度230℃･3.8kg荷重下之熔體流動速率：6.9g/10分鐘、折射率1.59) 苯乙烯共聚物(E-3)：Polyscope公司製XIBOND180 ((d1)/(d2)=苯乙烯/馬來酸酐=67質量%/33質量%，重量平均分子量：50,100，玻璃轉移溫度：157℃，溫度230℃･3.8kg荷重下之熔體流動速率：1.0g/10分鐘、折射率1.59) 聚碳酸酯系樹脂(F-1)：Mitsubishi Engineering-Plastics股份公司製IupilonS-1000(重量平均分子量：33,000，玻璃轉移溫度：147℃，溫度300℃･1.2kg荷重下之熔體流動速率：7.5g/10分鐘，折射率1.59) <Methacrylic resin (C-1), styrene copolymer (D-1), styrene copolymers (E-1) to (E-2), and polycarbonate resin (F-1)> Methacrylic resin (C-1): ALTUGLAS (registered trademark) V020 manufactured by Arkema Co., Ltd. (weight average molecular weight: 127,000, glass transition temperature: 109°C, temperature 230°C ･ Melt flow rate under a load of 3.8 kg: 1.8 g /10 minutes, methyl methacrylate/methyl acrylate=96.1 mass%/3.9 mass%, refractive index 1.49, mm/mr/rr=7.4 mol%/37.4 mol%/55.2 mol%) Styrene copolymer (D-1): XIRANSO23110 manufactured by Polyscope Corporation ((d1)/(d2)=styrene/maleic anhydride=78% by mass/22% by mass, weight average molecular weight: 74,300, glass transition temperature: 145°C , Melt flow rate under 230℃･3.8kg load: 5.9g/10min, refractive index 1.58) Styrene copolymer (E-1): XIRANSO26080 manufactured by Polyscope Corporation ((d1)/(d2)=styrene/maleic anhydride=75% by mass/25% by mass, weight average molecular weight: 47,600, glass transition temperature: 150°C , Melt flow rate at 230℃･3.8kg load: 8.3g/10min, refractive index 1.58) Styrene copolymer (E-2): XIBOND140 manufactured by Polyscope Corporation ((d1)/(d2)=styrene/maleic anhydride=85% by mass/15% by mass, weight average molecular weight: 134,000, glass transition temperature: 129°C , Melt flow rate under 230℃･3.8kg load: 6.9g/10min, refractive index 1.59) Styrene copolymer (E-3): XIBOND180 manufactured by Polyscope Corporation ((d1)/(d2)=styrene/maleic anhydride=67% by mass/33% by mass, weight average molecular weight: 50,100, glass transition temperature: 157°C , Melt flow rate at 230℃･3.8kg load: 1.0g/10min, refractive index 1.59) Polycarbonate resin (F-1): Iupilon S-1000 manufactured by Mitsubishi Engineering-Plastics Co., Ltd. (weight average molecular weight: 33,000, glass transition temperature: 147°C, temperature 300°C ･ Melt flow rate under 1.2 kg load: 7.5 g/10min, refractive index 1.59)

＜聚碳酸酯系樹脂(A-1)之合成＞合成例1 [聚碳酸酯樹脂鏈終止劑(chain terminator)之合成] 依據有機化學手冊P143~150，使用東京化成工業(股)製4-羥基苯甲酸與東京化成工業(股)製1-十六烷醇，進行脫水反應之酯化，得到對羥基苯甲酸十六烷基酯(CEPB)。 <Synthesis of polycarbonate resin (A-1)> Synthesis Example 1 [Synthesis of Polycarbonate Resin Chain Terminator] According to the organic chemistry manual P143~150, use 4-hydroxybenzoic acid manufactured by Tokyo Chemical Industry Co., Ltd. and 1-hexadecanol manufactured by Tokyo Chemical Industry Co., Ltd. for esterification of dehydration reaction to obtain hexadecyl p-hydroxybenzoic acid. Alkyl Esters (CEPB).

合成例2 [聚碳酸酯系樹脂(A-1)顆粒之製造] 在9w/w%之氫氧化鈉水溶液57.2kg中，加入新日鐵住友化學(股)製之雙酚A(以下稱為BPA)7.1kg(31.14mol)與亞硫酸氫鹽30g予以溶解。此中加入二氯甲烷40kg，邊攪拌邊將溶液溫度保持在15℃~25℃的範圍，以30分鐘吹入光氣4.33kg。光氣吹入結束後，加入將9w/w%之氫氧化鈉水溶液6kg、二氯甲烷11kg及作為鏈終止劑之對羥基苯甲酸十六烷基酯(CEPB)443g(1.22mol)溶解於二氯甲烷10kg的溶液，劇烈攪拌使乳化。然後，將作為聚合觸媒之10ml的三乙基胺加入溶液中，使聚合約40分鐘。將聚合液分離成水相與有機相，以磷酸中和有機相，使用純水重複水洗直到洗液之pH成為中性。自此純化後之聚碳酸酯樹脂溶液中，藉由蒸發餾除有機溶劑得到聚碳酸酯樹脂粉末。將所得之聚碳酸酯樹脂粉末，使用螺桿直徑35mm的2軸擠壓機，以圓柱溫度260℃下進行熔融混練，擠壓成股線狀，使用造粒機進行顆粒化。聚碳酸酯系樹脂(A-1)之重量平均分子量：29,000、玻璃轉移溫度：127℃、溫度300℃･1.2kg荷重下的熔體流動速率：12.1g/10分鐘，折射率1.59。 Synthesis Example 2 [Production of Polycarbonate-Based Resin (A-1) Particles] In 57.2 kg of 9w/w% sodium hydroxide aqueous solution, 7.1 kg (31.14 mol) of bisphenol A (hereinafter referred to as BPA) and 30 g of bisulfite by Nippon Steel Sumitomo Chemical Co., Ltd. were added to dissolve. To this, 40 kg of dichloromethane was added, and while stirring, the solution temperature was maintained in the range of 15° C. to 25° C., and 4.33 kg of phosgene was blown in over 30 minutes. After the phosgene blowing in, add 6kg of 9w/w% sodium hydroxide aqueous solution, 11kg of dichloromethane and 443g (1.22mol) of cetylparaben (CEPB) as chain terminator to dissolve in dichloromethane. A solution of 10 kg of methyl chloride was vigorously stirred to emulsify. Then, 10 ml of triethylamine as a polymerization catalyst was added to the solution, and polymerization was performed for about 40 minutes. The polymerization solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washed repeatedly with pure water until the pH of the washing solution became neutral. From the polycarbonate resin solution after this purification, the organic solvent was distilled off by evaporation to obtain polycarbonate resin powder. The obtained polycarbonate resin powder was melt-kneaded at a cylinder temperature of 260° C. using a 2-axis extruder with a screw diameter of 35 mm, extruded into strands, and pelletized using a pelletizer. Weight-average molecular weight of polycarbonate resin (A-1): 29,000, glass transition temperature: 127°C, temperature 300°C ･ Melt flow rate under load of 1.2 kg: 12.1 g/10 minutes, refractive index 1.59.

製造例1[熱塑性樹脂(B-1)之顆粒製造] 相對於甲基丙烯酸樹脂(C-1)25質量份與、苯乙烯共聚物(D-1)75質量份之合計100質量份，加入磷系添加劑PEP-36(股份公司ADEKA製)500ppm，及硬脂酸單甘油酯(製品名：H-100、理研vitamin股份公司製)0.2質量%，以摻混機混合20分鐘後，使用裝設有篩孔10μm之聚合物過濾器之螺桿直徑26mm的2軸擠壓機(東芝機械股份公司製、TEM-26SS、L/D≒40)，以圓柱溫度240℃下進行熔融混練，擠壓成股線狀，使用造粒機進行顆粒化。可安定製造熱塑性樹脂(B-1)的顆粒。熱塑性樹脂(B-1)之顆粒，外觀：○(透明)，玻璃轉移溫度：134℃，折射率1.56。 Production Example 1 [Pellet Production of Thermoplastic Resin (B-1)] With respect to 100 parts by mass in total of 25 parts by mass of methacrylic resin (C-1) and 75 parts by mass of styrene copolymer (D-1), 500 ppm of phosphorus-based additive PEP-36 (manufactured by ADEKA Co., Ltd.) was added, and 0.2% by mass of monoglyceryl stearate (product name: H-100, manufactured by Riken Vitamin Co., Ltd.), mixed with a blender for 20 minutes, and then a 26mm screw with a polymer filter with a mesh size of 10 μm was used. A 2-axis extruder (manufactured by Toshiba Machinery Co., Ltd., TEM-26SS, L/D≒40) was melt-kneaded at a cylinder temperature of 240°C, extruded into strands, and pelletized using a pelletizer. Pellets of thermoplastic resin (B-1) can be stably produced. Particles of thermoplastic resin (B-1), appearance: ○ (transparent), glass transition temperature: 134°C, refractive index 1.56.

製造例2[熱塑性樹脂(B-2)之顆粒製造] 相對於甲基丙烯酸樹脂(C-1)50質量份，與苯乙烯共聚物(D-1)50質量份之合計100質量份，加入磷系添加劑PEP-36 500ppm及硬脂酸單甘油酯0.2質量%，與製造例1同樣進行混合、顆粒化。可安定製造熱塑性樹脂(B-2)的顆粒。熱塑性樹脂(B-2)的顆粒，外觀：○(透明)，玻璃轉移溫度：122℃，折射率1.54。 Production Example 2 [Pellet Production of Thermoplastic Resin (B-2)] With respect to 50 parts by mass of methacrylic resin (C-1), 100 parts by mass in total of 50 parts by mass of styrene copolymer (D-1), 500 ppm of phosphorus-based additive PEP-36 and 0.2 stearic acid monoglyceride were added mass %, mixed and pelletized in the same manner as in Production Example 1. Pellets of thermoplastic resin (B-2) can be stably produced. Particles of thermoplastic resin (B-2), appearance: ○ (transparent), glass transition temperature: 122°C, refractive index 1.54.

製造比較例1[熱塑性樹脂(G-1)之顆粒製造] 相對於甲基丙烯酸樹脂(C-1)75質量份，與苯乙烯共聚物(D-1)25質量份之合計100質量份，加入磷系添加劑PEP-36 500ppm，及硬脂酸單甘油酯0.2質量%，與製造例1同樣進行混合、顆粒化。可安定製造熱塑性樹脂(G-1)的顆粒。熱塑性樹脂(G-1)的顆粒，外觀：○(透明)，玻璃轉移溫度：114℃，折射率1.52。 Production Comparative Example 1 [Pellet Production of Thermoplastic Resin (G-1)] With respect to 75 parts by mass of methacrylic resin (C-1), 100 parts by mass in total of 25 parts by mass of styrene copolymer (D-1), 500 ppm of phosphorus-based additive PEP-36, and stearic acid monoglyceride were added 0.2 mass %, mixed and pelletized in the same manner as in Production Example 1. Pellets of thermoplastic resin (G-1) can be stably produced. Particles of thermoplastic resin (G-1), appearance: ○ (transparent), glass transition temperature: 114°C, refractive index 1.52.

製造比較例2[熱塑性樹脂(G-2)之顆粒製造] 相對於甲基丙烯酸樹脂(C-1)25質量份，與苯乙烯共聚物(E-1)75質量份之合計100質量份，加入磷系添加劑PEP-36 500ppm，及硬脂酸單甘油酯0.2質量%，與製造例1同樣進行混合、顆粒化。可安定製造熱塑性樹脂(G-2)的顆粒。熱塑性樹脂(G-2)的顆粒，外觀：○(透明)，玻璃轉移溫度：136℃，折射率1.56。 Production Comparative Example 2 [Pellet Production of Thermoplastic Resin (G-2)] With respect to 25 parts by mass of methacrylic resin (C-1), 100 parts by mass in total of 75 parts by mass of styrene copolymer (E-1), 500 ppm of phosphorus-based additive PEP-36, and stearic acid monoglyceride were added 0.2 mass %, mixed and pelletized in the same manner as in Production Example 1. Pellets of thermoplastic resin (G-2) can be stably produced. Particles of thermoplastic resin (G-2), appearance: ○ (transparent), glass transition temperature: 136°C, refractive index 1.56.

製造比較例3[熱塑性樹脂(G-3)之顆粒製造] 相對於甲基丙烯酸樹脂(C-1)50質量份，與苯乙烯共聚物(E-1)50質量份之合計100質量份，加入磷系添加劑PEP-36 500ppm，及硬脂酸單甘油酯0.2質量%，與製造例1同樣進行混合、顆粒化。可安定製造熱塑性樹脂(G-3)的顆粒。熱塑性樹脂(G-3)的顆粒，外觀：○(透明)，玻璃轉移溫度：124℃，折射率1.54。 Production Comparative Example 3 [Pellet Production of Thermoplastic Resin (G-3)] With respect to 50 parts by mass of methacrylic resin (C-1), 100 parts by mass in total of 50 parts by mass of styrene copolymer (E-1), 500 ppm of phosphorus-based additive PEP-36, and stearic acid monoglyceride were added 0.2 mass %, mixed and pelletized in the same manner as in Production Example 1. Pellets of thermoplastic resin (G-3) can be stably produced. Particles of thermoplastic resin (G-3), appearance: ○ (transparent), glass transition temperature: 124°C, refractive index 1.54.

製造比較例4[熱塑性樹脂(G-4)之顆粒製造] 相對於甲基丙烯酸樹脂(C-1)75質量份，與苯乙烯共聚物(E-1)25質量份之合計100質量份，加入磷系添加劑PEP-36 500ppm，及硬脂酸單甘油酯0.2質量%，與製造例1同樣進行混合、顆粒化。可安定製造熱塑性樹脂(G-4)的顆粒。熱塑性樹脂(G-4)的顆粒，外觀：○(透明)，玻璃轉移溫度：115℃，折射率1.51。 Production Comparative Example 4 [Pellet Production of Thermoplastic Resin (G-4)] With respect to 75 parts by mass of methacrylic resin (C-1), 100 parts by mass in total of 25 parts by mass of styrene copolymer (E-1), 500 ppm of phosphorus-based additive PEP-36, and stearic acid monoglyceride were added 0.2 mass %, mixed and pelletized in the same manner as in Production Example 1. Pellets of thermoplastic resin (G-4) can be stably produced. Particles of thermoplastic resin (G-4), appearance: ○ (transparent), glass transition temperature: 115°C, refractive index 1.51.

製造比較例5[熱塑性樹脂(G-5)之顆粒製造] 相對於甲基丙烯酸樹脂(C-1)100質量份，加入磷系添加劑PEP-36 500ppm，及硬脂酸單甘油酯0.2質量%，與製造例1同樣進行混合、顆粒化。可安定製造熱塑性樹脂(G-5)的顆粒。熱塑性樹脂(G-5)的顆粒，外觀：○(透明)，玻璃轉移溫度：109℃，折射率1.49。 Production Comparative Example 5 [Pellet Production of Thermoplastic Resin (G-5)] With respect to 100 parts by mass of methacrylic resin (C-1), 500 ppm of phosphorus-based additive PEP-36 and 0.2 mass % of stearic acid monoglyceride were added, and the mixture was mixed and granulated in the same manner as in Production Example 1. Pellets of thermoplastic resin (G-5) can be stably produced. Particles of thermoplastic resin (G-5), appearance: ○ (transparent), glass transition temperature: 109°C, refractive index 1.49.

製造比較例6[熱塑性樹脂(G-6)之顆粒製造] 相對於苯乙烯共聚物(D-1)100質量份，加入磷系添加劑PEP-36 500ppm，及硬脂酸單甘油酯0.2質量%，與製造例1同樣進行混合、顆粒化。可安定製造熱塑性樹脂(G-6)的顆粒。熱塑性樹脂(G-6)的顆粒，外觀：○(透明)，玻璃轉移溫度：145℃，折射率1.58。 Production Comparative Example 6 [Pellet Production of Thermoplastic Resin (G-6)] With respect to 100 parts by mass of the styrene copolymer (D-1), 500 ppm of phosphorus-based additive PEP-36 and 0.2 mass % of stearic acid monoglyceride were added, and the mixture was mixed and granulated in the same manner as in Production Example 1. Pellets of thermoplastic resin (G-6) can be stably produced. Particles of thermoplastic resin (G-6), appearance: ○ (transparent), glass transition temperature: 145°C, refractive index 1.58.

製造比較例7[熱塑性樹脂(G-7)之顆粒製造] 相對於苯乙烯共聚物(E-1)100質量份，加入磷系添加劑PEP-36 500ppm，及硬脂酸單甘油酯0.2質量%，與製造例1同樣進行混合、顆粒化。可安定製造熱塑性樹脂(G-7)的顆粒。熱塑性樹脂(G-7)的顆粒，外觀：○(透明)，玻璃轉移溫度：150℃，折射率1.58。 Production Comparative Example 7 [Pellet Production of Thermoplastic Resin (G-7)] With respect to 100 parts by mass of the styrene copolymer (E-1), 500 ppm of the phosphorus-based additive PEP-36 and 0.2 mass % of stearic acid monoglyceride were added, and the mixture was mixed and granulated in the same manner as in Production Example 1. Pellets of thermoplastic resin (G-7) can be stably produced. Particles of thermoplastic resin (G-7), appearance: ○ (transparent), glass transition temperature: 150°C, refractive index 1.58.

製造比較例8[熱塑性樹脂(G-8)之顆粒製造] 相對於甲基丙烯酸樹脂(C-1)25質量份，與苯乙烯共聚物(E-2)75質量份之合計100質量份，加入磷系添加劑PEP-36 500ppm，及硬脂酸單甘油酯0.2質量%，與製造例1同樣進行混合、顆粒化。可安定製造熱塑性樹脂(G-8)的顆粒。熱塑性樹脂(G-8)的顆粒，外觀：×(半透明)。 Production Comparative Example 8 [Pellet Production of Thermoplastic Resin (G-8)] With respect to 25 parts by mass of methacrylic resin (C-1), 100 parts by mass in total of 75 parts by mass of styrene copolymer (E-2), 500 ppm of phosphorus-based additive PEP-36, and stearic acid monoglyceride were added 0.2 mass %, mixed and pelletized in the same manner as in Production Example 1. Pellets of thermoplastic resin (G-8) can be stably produced. Pellets of thermoplastic resin (G-8), appearance: × (translucent).

製造比較例9[熱塑性樹脂(G-9)之顆粒製造] 相對於甲基丙烯酸樹脂(C-1)50質量份，與苯乙烯共聚物(E-2)50質量份之合計100質量份，加入磷系添加劑PEP-36 500ppm，及硬脂酸單甘油酯0.2質量%，與製造例1同樣進行混合、顆粒化。可安定製造熱塑性樹脂(G-9)的顆粒。熱塑性樹脂(G-9)的顆粒，外觀：×(半透明)。 Production Comparative Example 9 [Pellet Production of Thermoplastic Resin (G-9)] With respect to 50 parts by mass of methacrylic resin (C-1), 100 parts by mass in total of 50 parts by mass of styrene copolymer (E-2), 500 ppm of phosphorus-based additive PEP-36, and stearic acid monoglyceride were added 0.2 mass %, mixed and pelletized in the same manner as in Production Example 1. Pellets of thermoplastic resin (G-9) can be stably produced. Pellets of thermoplastic resin (G-9), appearance: × (translucent).

製造比較例10[熱塑性樹脂(G-10)之顆粒製造] 相對於甲基丙烯酸樹脂(C-1)25質量份，與苯乙烯共聚物(E-2)75質量份之合計100質量份，加入磷系添加劑PEP-36 500ppm，及硬脂酸單甘油酯0.2質量%，與製造例1同樣進行混合、顆粒化。可安定製造熱塑性樹脂(G-10)的顆粒。熱塑性樹脂(G-10)的顆粒，外觀：×(白濁)。 Production Comparative Example 10 [Pellet Production of Thermoplastic Resin (G-10)] With respect to 25 parts by mass of methacrylic resin (C-1), 100 parts by mass in total of 75 parts by mass of styrene copolymer (E-2), 500 ppm of phosphorus-based additive PEP-36, and stearic acid monoglyceride were added 0.2 mass %, mixed and pelletized in the same manner as in Production Example 1. Pellets of thermoplastic resin (G-10) can be stably produced. Pellets of thermoplastic resin (G-10), appearance: × (cloudy).

製造比較例11[熱塑性樹脂(G-11)之顆粒製造] 相對於甲基丙烯酸樹脂(C-1)50質量份，與苯乙烯共聚物(E-2)50質量份之合計100質量份，加入磷系添加劑PEP-36 500ppm，及硬脂酸單甘油酯0.2質量%，與製造例1同樣進行混合、顆粒化。可安定製造熱塑性樹脂(G-11)的顆粒。熱塑性樹脂(G-11)的顆粒，外觀：×(白濁)。 Production Comparative Example 11 [Pellet Production of Thermoplastic Resin (G-11)] With respect to 50 parts by mass of methacrylic resin (C-1), 100 parts by mass in total of 50 parts by mass of styrene copolymer (E-2), 500 ppm of phosphorus-based additive PEP-36, and stearic acid monoglyceride were added 0.2 mass %, mixed and pelletized in the same manner as in Production Example 1. Pellets of thermoplastic resin (G-11) can be stably produced. Pellets of thermoplastic resin (G-11), appearance: × (cloudy).

實施例1[樹脂積層體(I-1)之製造] 使用具有軸徑32mm之單軸擠壓機、軸徑65mm之單軸擠壓機、全擠壓機所連結之進料塊( Feed Block)及進料塊所連結之650mm寬之T模之多層擠壓機，且具有與各擠壓機連結之多重分歧管模的多層擠壓裝置，將樹脂積層體進行成形。以製造例1製得之熱塑性樹脂(B-1)連續地導入軸徑32mm之單軸擠壓機中，在料筒溫度240℃、吐出量2.0kg/h的條件下進行擠壓。又，將合成例2所得之聚碳酸酯系樹脂(A-1)連續地導入軸徑65mm之單軸擠壓機中，在料筒溫度280℃、吐出量31.8kg/h下進行擠壓。又，全擠壓機所連結之進料塊具備2種2層的分配孔，形成溫度270℃，導入熱塑性樹脂(B-1)與聚碳酸酯系樹脂(A-1)進行積層。以前面所連結之溫度270℃的T模，擠壓成薄片狀，自上游側以溫度110℃、105℃、165℃等的3支鏡面加工輥，邊轉印鏡面邊冷卻，得到熱塑性樹脂(B-1)與聚碳酸酯系樹脂(A-1)之樹脂積層體。所得之樹脂積層體之中央部之全體厚度為1000μm，表層(包含熱塑性樹脂(B)之層)的厚度為60μm。此外，在上述所得之樹脂積層體之熱塑性樹脂(B-1)之表面，以塗佈棒塗佈，相對於6官能胺基甲酸酯丙烯酸酯寡聚物(製品名：U6HA、新中村化學工業股份公司製) 60質量份，PEG200#二丙烯酸酯(製品名：4EG-A、共榮社化學股份公司製)35質量份，及含氟基･親水性基･親油性基･含有UV反應性基之寡聚物(製品名：RS-90、DIC股份公司製)5質量份之合計100質量份，加入光聚合起始劑(製品名：I-184[化合物名：1-羥基-環己基苯基酮]BASF股份公司製)1質量%的塗料，然後，以金屬鹵素燈(20mW/cm2)照射5秒，使硬塗膜硬化，製作樹脂積層體(I-1)。硬塗層(H-1)厚度為6μm。此樹脂積層體(I-1)係全光線穿透率：90.8%，Haze：0.2%，鉛筆硬度：3H，干涉條紋：○，以模具溫度80℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形體之彎曲部分之龜裂：○，熱壓成形體之回彈：×，以模具溫度120℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形體之彎曲部分之龜裂：○，熱壓成形體之回彈：○，以模具溫度160℃進行熱壓成形時，熱壓成形體之外觀：×，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：○。 Example 1 [Manufacture of resin laminate (I-1)] Multilayer using a uniaxial extruder with a shaft diameter of 32mm, a uniaxial extruder with a shaft diameter of 65mm, a feed block connected to the full extruder, and a 650mm wide T die connected to the feed block An extruder and a multi-layer extrusion device having a multi-branch pipe die connected to each extruder molds the resin laminate. The thermoplastic resin (B-1) obtained in Production Example 1 was continuously introduced into a uniaxial extruder with a shaft diameter of 32 mm, and extruded under the conditions of a barrel temperature of 240° C. and a discharge rate of 2.0 kg/h. Moreover, the polycarbonate resin (A-1) obtained in Synthesis Example 2 was continuously introduced into a uniaxial extruder with a shaft diameter of 65 mm, and extruded at a barrel temperature of 280° C. and a discharge rate of 31.8 kg/h. In addition, the feed block connected to the full extruder was provided with two kinds of two-layer distribution holes, and the forming temperature was 270°C, and the thermoplastic resin (B-1) and the polycarbonate resin (A-1) were introduced and laminated. Using the T-die with a temperature of 270°C connected above, it was extruded into a sheet shape, and cooled from the upstream side with three mirror-finished rollers with temperatures of 110°C, 105°C, and 165°C while transferring the mirror surface to obtain a thermoplastic resin ( B-1) Resin laminate with polycarbonate resin (A-1). The overall thickness of the central portion of the obtained resin laminate was 1000 μm, and the thickness of the surface layer (layer including the thermoplastic resin (B)) was 60 μm. In addition, on the surface of the thermoplastic resin (B-1) of the resin laminate obtained above, it was coated with a coating bar, and a hexafunctional urethane acrylate oligomer (product name: U6HA, Shin Nakamura Chemical) was applied. Industrial Co., Ltd.) 60 parts by mass, PEG200# diacrylate (product name: 4EG-A, manufactured by Kyōeisha Chemical Co., Ltd.) 35 parts by mass, and fluorine-containing, hydrophilic, lipophilic, and UV reactive 100 parts by mass in total of 5 parts by mass of an oligomer of a property group (product name: RS-90, manufactured by DIC Co., Ltd.), and a photopolymerization initiator (product name: I-184 [compound name: 1-hydroxy-ring] was added. Hexyl phenyl ketone] BASF Co., Ltd.) 1 mass % paint, and then irradiated with a metal halide lamp (20 mW/cm 2 ) for 5 seconds to harden the hard coat film to prepare a resin laminate (I-1). The thickness of the hard coat layer (H-1) was 6 μm. This resin laminate (I-1) has total light transmittance: 90.8%, Haze: 0.2%, pencil hardness: 3H, interference fringes: ○, When hot-pressing was performed at a mold temperature of 80°C, the appearance of the hot-pressed body: ○, the crack of the curved part of the hot-pressed body: ○, the springback of the hot-pressed body: ×, When hot-pressed at a mold temperature of 120°C, the appearance of the hot-pressed body: ○, the crack of the curved part of the hot-pressed body: ○, the springback of the hot-pressed body: ○, When hot-press molding was performed at a die temperature of 160°C, the appearance of the hot-press-molded body: ×, the crack of the curved portion of the hot-press-formed body: ×, and the springback of the hot-press-formed body: ○.

實施例2[樹脂積層體(I-2)之製造] 除了取代熱塑性樹脂(B-1)，使用熱塑性樹脂(B-2)外，與實施例1之樹脂積層體(I-1)同樣，得到硬塗層(H-1)與熱塑性樹脂(B-2)與聚碳酸酯系樹脂(A-1)之樹脂積層體(I-2)。所得之樹脂積層體(I-2)之中央部的全體厚度為1006μm，表層(B-2)厚度為60μm，硬塗層(H-1)厚度為6μm。此樹脂積層體(I-2)為全光線穿透率：90.8%，Haze：0.2%，鉛筆硬度：3H，干涉條紋：○，以模具溫度80℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形體之彎曲部分之龜裂：○，熱壓成形體之回彈：×，以模具溫度120℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形體之彎曲部分之龜裂：○，熱壓成形體之回彈：○，以模具溫度160℃進行熱壓成形時，熱壓成形體之外觀：×，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：○。 Example 2 [Manufacture of resin laminate (I-2)] A hard coat layer (H-1) and a thermoplastic resin (B- 2) Resin laminate (I-2) with polycarbonate resin (A-1). The overall thickness of the central portion of the obtained resin laminate (I-2) was 1006 μm, the thickness of the surface layer (B-2) was 60 μm, and the thickness of the hard coat layer (H-1) was 6 μm. This resin laminate (I-2) has total light transmittance: 90.8%, Haze: 0.2%, pencil hardness: 3H, interference fringes: ○, When hot-pressing was performed at a die temperature of 80°C, the appearance of the hot-pressed body: ○, the crack of the curved part of the hot-pressed body: ○, the springback of the hot-pressed body: ×, When hot-pressed at a mold temperature of 120°C, the appearance of the hot-pressed body: ○, the crack of the curved part of the hot-pressed body: ○, the springback of the hot-pressed body: ○, When hot press molding was performed at a die temperature of 160°C, the appearance of the hot press molded body: ×, the crack of the curved portion of the hot press molded body: ×, and the springback of the hot press molded body: ○.

比較例1[樹脂積層體(J-1)之製造] 除了取代熱塑性樹脂(B-1)，使用熱塑性樹脂(G-1)外，與實施例1之樹脂積層體(I-1)同樣，得到硬塗層(H-1)與熱塑性樹脂(G-1)與聚碳酸酯系樹脂(A-1)之樹脂積層體(J-1)。所得之樹脂積層體(J-1)之中央部的全體厚度為1006μm，表層(G-1)厚度為60μm，硬塗層(H-1)厚度為6μm。此樹脂積層體(J-1)為全光線穿透率：91.0%，Haze：0.2%，鉛筆硬度：3H，干涉條紋：○，以模具溫度80℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形體之彎曲部分之龜裂：○，熱壓成形體之回彈：×，以模具溫度120℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：○，以模具溫度160℃進行熱壓成形時，熱壓成形體之外觀：×，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：○。 Comparative Example 1 [Manufacture of resin laminate (J-1)] A hard coat layer (H-1) and a thermoplastic resin (G- 1) Resin laminate (J-1) with polycarbonate resin (A-1). The overall thickness of the central portion of the obtained resin laminate (J-1) was 1006 μm, the thickness of the surface layer (G-1) was 60 μm, and the thickness of the hard coat layer (H-1) was 6 μm. This resin laminate (J-1) has total light transmittance: 91.0%, Haze: 0.2%, pencil hardness: 3H, interference fringes: ○, When hot-pressing was performed at a die temperature of 80°C, the appearance of the hot-pressed body: ○, the crack of the curved part of the hot-pressed body: ○, the springback of the hot-pressed body: ×, When hot-pressed at a mold temperature of 120°C, the appearance of the hot-pressed body: ○, the crack of the curved part of the hot-pressed body: ×, the springback of the hot-pressed body: ○, When hot press molding was performed at a die temperature of 160°C, the appearance of the hot press molded body: ×, the crack of the curved portion of the hot press molded body: ×, and the springback of the hot press molded body: ○.

比較例2[樹脂積層體(J-2)之製造] 除了取代熱塑性樹脂(B-1)，使用熱塑性樹脂(G-2)外，與實施例1之樹脂積層體(I-1)同樣，得到硬塗層(H-1)與熱塑性樹脂(G-2)與聚碳酸酯系樹脂(A-1)之樹脂積層體(J-2)。所得之樹脂積層體(J-2)之中央部的全體厚度為1006μm，表層(G-2)厚度為60μm，硬塗層(H-1)厚度為6μm。此樹脂積層體(J-2)為全光線穿透率：90.9%，Haze：0.2%，鉛筆硬度：3H，干涉條紋：○，以模具溫度80℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：×，以模具溫度120℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：○，以模具溫度160℃進行熱壓成形時，熱壓成形體之外觀：×，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：○。 Comparative Example 2 [Manufacture of resin laminate (J-2)] A hard coat layer (H-1) and a thermoplastic resin (G- 2) Resin laminate (J-2) with polycarbonate resin (A-1). The overall thickness of the central portion of the obtained resin laminate (J-2) was 1006 μm, the thickness of the surface layer (G-2) was 60 μm, and the thickness of the hard coat layer (H-1) was 6 μm. This resin laminate (J-2) has total light transmittance: 90.9%, Haze: 0.2%, pencil hardness: 3H, interference fringes: ○, When hot-pressed at a mold temperature of 80°C, the appearance of the hot-pressed body: ○, the crack of the curved part of the hot-pressed body: ×, the springback of the hot-pressed body: ×, When hot-pressed at a mold temperature of 120°C, the appearance of the hot-pressed body: ○, the crack of the curved part of the hot-pressed body: ×, the springback of the hot-pressed body: ○, When hot press molding was performed at a die temperature of 160°C, the appearance of the hot press molded body: ×, the crack of the curved portion of the hot press molded body: ×, and the springback of the hot press molded body: ○.

比較例3[樹脂積層體(J-3)之製造] 除了取代熱塑性樹脂(B-1)，使用熱塑性樹脂(G-3)外，與實施例1之樹脂積層體(I-1)同樣，得到硬塗層(H-1)與熱塑性樹脂(G-3)與聚碳酸酯系樹脂(A-1)之樹脂積層體(J-3)。所得之樹脂積層體(J-3)之中央部的全體厚度為1006μm，表層(G-3)厚度為60μm，硬塗層(H-1)厚度為6μm。此樹脂積層體(J-3)為全光線穿透率：91.2%，Haze：0.2%，鉛筆硬度：3H，干涉條紋：○，以模具溫度80℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形體之彎曲部分之龜裂：○，熱壓成形體之回彈：×，以模具溫度120℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：○，以模具溫度160℃進行熱壓成形時，熱壓成形體之外觀：×，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：○。 Comparative Example 3 [Manufacture of resin laminate (J-3)] A hard coat layer (H-1) and a thermoplastic resin (G- 3) Resin laminate (J-3) with polycarbonate resin (A-1). The overall thickness of the central portion of the obtained resin laminate (J-3) was 1006 μm, the thickness of the surface layer (G-3) was 60 μm, and the thickness of the hard coat layer (H-1) was 6 μm. This resin laminate (J-3) has total light transmittance: 91.2%, Haze: 0.2%, pencil hardness: 3H, interference fringes: ○, When hot-pressing was performed at a die temperature of 80°C, the appearance of the hot-pressed body: ○, the crack of the curved part of the hot-pressed body: ○, the springback of the hot-pressed body: ×, When hot-pressed at a mold temperature of 120°C, the appearance of the hot-pressed body: ○, the crack of the curved part of the hot-pressed body: ×, the springback of the hot-pressed body: ○, When hot press molding was performed at a die temperature of 160°C, the appearance of the hot press molded body: ×, the crack of the curved portion of the hot press molded body: ×, and the springback of the hot press molded body: ○.

比較例4[樹脂積層體(J-4)之製造] 除了取代熱塑性樹脂(B-1)，使用熱塑性樹脂(G-4)外，與實施例1之樹脂積層體(I-1)同樣，得到硬塗層(H-1)與熱塑性樹脂(G-4)與聚碳酸酯系樹脂(A-1)之樹脂積層體(J-4)。所得之樹脂積層體(J-4)之中央部的全體厚度為1006μm，表層(G-4)厚度為60μm，硬塗層(H-1)厚度為6μm。此樹脂積層體(J-4)為全光線穿透率：91.2%，Haze：0.2%，鉛筆硬度：3H，干涉條紋：○，以模具溫度80℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形體之彎曲部分之龜裂：○，熱壓成形體之回彈：×，以模具溫度120℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：○，以模具溫度160℃進行熱壓成形時，熱壓成形體之外觀：×，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：○。 Comparative Example 4 [Manufacture of resin laminate (J-4)] A hard coat layer (H-1) and a thermoplastic resin (G- 4) Resin laminate (J-4) with polycarbonate resin (A-1). The overall thickness of the central portion of the obtained resin laminate (J-4) was 1006 μm, the thickness of the surface layer (G-4) was 60 μm, and the thickness of the hard coat layer (H-1) was 6 μm. This resin laminate (J-4) has total light transmittance: 91.2%, Haze: 0.2%, pencil hardness: 3H, interference fringes: ○, When hot-pressing was performed at a die temperature of 80°C, the appearance of the hot-pressed body: ○, the crack of the curved part of the hot-pressed body: ○, the springback of the hot-pressed body: ×, When hot-pressed at a mold temperature of 120°C, the appearance of the hot-pressed body: ○, the crack of the curved part of the hot-pressed body: ×, the springback of the hot-pressed body: ○, When hot press molding was performed at a die temperature of 160°C, the appearance of the hot press molded body: ×, the crack of the curved portion of the hot press molded body: ×, and the springback of the hot press molded body: ○.

比較例5[樹脂積層體(J-5)之製造] 除了取代熱塑性樹脂(B-1)，使用熱塑性樹脂(G-5)外，與實施例1之樹脂積層體(I-1)同樣，得到硬塗層(H-1)熱與可塑性樹脂(G-5)與聚碳酸酯系樹脂(A-1)之樹脂積層體(J-5)。所得之樹脂積層體(J-5)之中央部的全體厚度為1006μm，表層(G-5)厚度為60μm，硬塗層(H-1)厚度為6μm。此樹脂積層體(J-5)為全光線穿透率：91.4%，Haze：0.3%，鉛筆硬度：3H，干涉條紋：○，以模具溫度80℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形體之彎曲部分之龜裂：○，熱壓成形體之回彈：×，以模具溫度120℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：○，以模具溫度160℃進行熱壓成形時，熱壓成形體之外觀：×，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：○。 Comparative Example 5 [Manufacture of resin laminate (J-5)] In the same manner as the resin laminate (I-1) of Example 1, except that the thermoplastic resin (B-1) was used instead of the thermoplastic resin (G-5), the hard coat layer (H-1) was obtained as a thermal and plastic resin (G-5). -5) Resin laminate (J-5) with polycarbonate resin (A-1). The overall thickness of the central portion of the obtained resin laminate (J-5) was 1006 μm, the thickness of the surface layer (G-5) was 60 μm, and the thickness of the hard coat layer (H-1) was 6 μm. This resin laminate (J-5) has total light transmittance: 91.4%, Haze: 0.3%, pencil hardness: 3H, interference fringes: ○, When hot-pressing was performed at a die temperature of 80°C, the appearance of the hot-pressed body: ○, the crack of the curved part of the hot-pressed body: ○, the springback of the hot-pressed body: ×, When hot-pressed at a mold temperature of 120°C, the appearance of the hot-pressed body: ○, the crack of the curved part of the hot-pressed body: ×, the springback of the hot-pressed body: ○, When hot press molding was performed at a die temperature of 160°C, the appearance of the hot press molded body: ×, the crack of the curved portion of the hot press molded body: ×, and the springback of the hot press molded body: ○.

比較例6[樹脂積層體(J-6)之製造] 除了取代熱塑性樹脂(B-1)，使用熱塑性樹脂(G-6)外，與實施例1之樹脂積層體(I-1)同樣，得到硬塗層(H-1)與熱塑性樹脂(G-6)與聚碳酸酯系樹脂(A-1)之樹脂積層體(J-6)。所得之樹脂積層體(J-6)之中央部的全體厚度為1006 μm，表層(G-6)厚度為60μm，硬塗層(H-1)厚度為6μm。此樹脂積層體(J-6)為全光線穿透率：90.5%，Haze：0.2%，鉛筆硬度：H，干涉條紋：○，以模具溫度80℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：×，以模具溫度120℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形加工性之彎曲部分之龜裂：×，熱壓成形體之回彈：○，以模具溫度160℃進行熱壓成形時，熱壓成形體之外觀：×，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：○。 Comparative Example 6 [Manufacture of resin laminate (J-6)] A hard coat layer (H-1) and a thermoplastic resin (G- 6) Resin laminate (J-6) with polycarbonate resin (A-1). The overall thickness of the central portion of the obtained resin laminate (J-6) was 1006 μm, the thickness of the surface layer (G-6) was 60 μm, and the thickness of the hard coat layer (H-1) was 6 μm. This resin laminate (J-6) has total light transmittance: 90.5%, Haze: 0.2%, pencil hardness: H, interference fringes: ○, When hot-pressed at a mold temperature of 80°C, the appearance of the hot-pressed body: ○, the crack of the curved part of the hot-pressed body: ×, the springback of the hot-pressed body: ×, When hot-pressing was performed at a die temperature of 120°C, the appearance of the hot-press-formed body: ○, the crack of the bent portion of the hot-press-forming processability: ×, the springback of the hot-press-formed body: ○, When hot press molding was performed at a die temperature of 160°C, the appearance of the hot press molded body: ×, the crack of the curved portion of the hot press molded body: ×, and the springback of the hot press molded body: ○.

比較例7[樹脂積層體(J-7)之製造] 除了取代熱塑性樹脂(B-1)，使用熱塑性樹脂(G-7)外，與實施例1之樹脂積層體(I-1)同樣，硬塗層(H-1)與熱塑性樹脂(G-7)與聚碳酸酯系樹脂(A-1)之樹脂積層體(J-7)。所得之樹脂積層體(J-7)之中央部的全體厚度為1006μm，表層(G-7)厚度為60μm，硬塗層(H-1)厚度為6μm。此樹脂積層體(J-7)為全光線穿透率：90.6%，Haze：0.2%，鉛筆硬度：H，干涉條紋：○，以模具溫度80℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：×，以模具溫度120℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：○，以模具溫度160℃進行熱壓成形時，熱壓成形體之外觀：×，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：○。 Comparative Example 7 [Manufacture of resin laminate (J-7)] In the same manner as the resin laminate (I-1) of Example 1, except that the thermoplastic resin (G-7) was used instead of the thermoplastic resin (B-1), the hard coat layer (H-1) and the thermoplastic resin (G-7 ) and the resin laminate (J-7) of the polycarbonate resin (A-1). The overall thickness of the central portion of the obtained resin laminate (J-7) was 1006 μm, the thickness of the surface layer (G-7) was 60 μm, and the thickness of the hard coat layer (H-1) was 6 μm. This resin laminate (J-7) has total light transmittance: 90.6%, Haze: 0.2%, pencil hardness: H, interference fringes: ○, When hot-pressed at a mold temperature of 80°C, the appearance of the hot-pressed body: ○, the crack of the curved part of the hot-pressed body: ×, the springback of the hot-pressed body: ×, When hot-pressed at a mold temperature of 120°C, the appearance of the hot-pressed body: ○, the crack of the curved part of the hot-pressed body: ×, the springback of the hot-pressed body: ○, When hot press molding was performed at a die temperature of 160°C, the appearance of the hot press molded body: ×, the crack of the curved portion of the hot press molded body: ×, and the springback of the hot press molded body: ○.

比較例8[樹脂積層體(J-8)之製造] 除了取代聚碳酸酯系樹脂(A-1)，使用聚碳酸酯系樹脂(F-1)，自上游側，以溫度設為130℃、140℃、185℃之3支鏡面加工輥，邊轉印鏡面邊冷卻進行變更外，與實施例1之樹脂積層體(I-1)同樣，得到硬塗層(H-1)與熱塑性樹脂(B-1)與聚碳酸酯系樹脂(F-1)之樹脂積層體(J-8)。所得之樹脂積層體(J-8)之中央部的全體厚度為1006μm，表層(B-1)厚度為60μm，硬塗層(H-1)厚度為6μm。此樹脂積層體(J-8)為全光線穿透率：90.8%，Haze：0.2%，鉛筆硬度：3H，干涉條紋：○，以模具溫度80℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形體之彎曲部分之龜裂：○，熱壓成形體之回彈：×，以模具溫度120℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形體之彎曲部分之龜裂：○，熱壓成形體之回彈：×，以模具溫度160℃進行熱壓成形時，熱壓成形體之外觀：×，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：○。 Comparative Example 8 [Manufacture of resin laminate (J-8)] In addition to replacing the polycarbonate resin (A-1), using the polycarbonate resin (F-1), from the upstream side, three mirror-finished rollers with a temperature of 130°C, 140°C, and 185°C were used to rotate while rotating. In the same manner as the resin laminate (I-1) of Example 1, except that the cooling of the mirror surface was changed, a hard coat layer (H-1), a thermoplastic resin (B-1) and a polycarbonate resin (F-1) were obtained ) of the resin laminate (J-8). The overall thickness of the central portion of the obtained resin laminate (J-8) was 1006 μm, the thickness of the surface layer (B-1) was 60 μm, and the thickness of the hard coat layer (H-1) was 6 μm. This resin laminate (J-8) has total light transmittance: 90.8%, Haze: 0.2%, pencil hardness: 3H, interference fringes: ○, When hot-pressing was performed at a die temperature of 80°C, the appearance of the hot-pressed body: ○, the crack of the curved part of the hot-pressed body: ○, the springback of the hot-pressed body: ×, When hot-pressing was performed at a mold temperature of 120°C, the appearance of the hot-pressed body: ○, the crack of the curved part of the hot-pressed body: ○, the springback of the hot-pressed body: ×, When hot press molding was performed at a die temperature of 160°C, the appearance of the hot press molded body: ×, the crack of the curved portion of the hot press molded body: ×, and the springback of the hot press molded body: ○.

比較例9[樹脂積層體(J-9)之製造] 除了取代熱塑性樹脂(B-1)，使用熱塑性樹脂(B-2)外，與比較例8之樹脂積層體(J-8)同樣，得到硬塗層(H-1)與熱塑性樹脂(B-2)與聚碳酸酯系樹脂(F-1)之樹脂積層體(J-9)。所得之樹脂積層體(J-9)之中央部的全體厚度為1006μm，表層(B-2)厚度為60μm，硬塗層(H-1)厚度為6μm。此樹脂積層體(J-9)為全光線穿透率：90.8%，Haze：0.2%，鉛筆硬度：3H，干涉條紋：○，以模具溫度80℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形體之彎曲部分之龜裂：○，熱壓成形體之回彈：×，以模具溫度120℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形體之彎曲部分之龜裂：○，熱壓成形體之回彈：×，以模具溫度160℃進行熱壓成形時，熱壓成形體之外觀：×，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：○。 Comparative Example 9 [Manufacture of resin laminate (J-9)] A hard coat layer (H-1) and a thermoplastic resin (B- 2) Resin laminate (J-9) with polycarbonate resin (F-1). The overall thickness of the central portion of the obtained resin laminate (J-9) was 1006 μm, the thickness of the surface layer (B-2) was 60 μm, and the thickness of the hard coat layer (H-1) was 6 μm. This resin laminate (J-9) has total light transmittance: 90.8%, Haze: 0.2%, pencil hardness: 3H, interference fringes: ○, When hot-pressing was performed at a die temperature of 80°C, the appearance of the hot-pressed body: ○, the crack of the curved part of the hot-pressed body: ○, the springback of the hot-pressed body: ×, When hot-pressing was performed at a mold temperature of 120°C, the appearance of the hot-pressed body: ○, the crack of the curved part of the hot-pressed body: ○, the springback of the hot-pressed body: ×, When hot press molding was performed at a die temperature of 160°C, the appearance of the hot press molded body: ×, the crack of the curved portion of the hot press molded body: ×, and the springback of the hot press molded body: ○.

比較例10[樹脂積層體(J-10)之製造] 除了取代熱塑性樹脂(B-1)，使用熱塑性樹脂(G-1)外，與比較例8之樹脂積層體(J-8)同樣，得到硬塗層(H-1)與熱塑性樹脂(G-1)與聚碳酸酯系樹脂(F-1)之樹脂積層體(J-10)。所得之樹脂積層體(J-10)之中央部的全體厚度為1006μm，表層(G-1)厚度為60μm，硬塗層(H-1)厚度為6μm。此樹脂積層體(J-10)為全光線穿透率：91.0%，Haze：0.2%，鉛筆硬度：3H，干涉條紋：○，以模具溫度80℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形體之彎曲部分之龜裂：○，熱壓成形體之回彈：×，以模具溫度120℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：×，以模具溫度160℃進行熱壓成形時，熱壓成形體之外觀：×，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：○。 Comparative Example 10 [Manufacture of resin laminate (J-10)] A hard coat layer (H-1) and a thermoplastic resin (G- 1) Resin laminate (J-10) with polycarbonate resin (F-1). The overall thickness of the central portion of the obtained resin laminate (J-10) was 1006 μm, the thickness of the surface layer (G-1) was 60 μm, and the thickness of the hard coat layer (H-1) was 6 μm. This resin laminate (J-10) has total light transmittance: 91.0%, Haze: 0.2%, pencil hardness: 3H, interference fringes: ○, When hot-pressing was performed at a die temperature of 80°C, the appearance of the hot-pressed body: ○, the crack of the curved part of the hot-pressed body: ○, the springback of the hot-pressed body: ×, When hot-pressed at a mold temperature of 120°C, the appearance of the hot-pressed body: ○, the crack of the curved part of the hot-pressed body: ×, the springback of the hot-pressed body: ×, When hot press molding was performed at a die temperature of 160°C, the appearance of the hot press molded body: ×, the crack of the curved portion of the hot press molded body: ×, and the springback of the hot press molded body: ○.

比較例11[樹脂積層體(J-11)之製造] 除了取代熱塑性樹脂(B-1)，使用熱塑性樹脂(G-2)外，與比較例8之樹脂積層體(J-8)同樣，得到硬塗層(H-1)與熱塑性樹脂(G-2)與聚碳酸酯系樹脂(F-1)之樹脂積層體(J-11)。所得之樹脂積層體(J-11)之中央部的全體厚度為1006μm，表層(G-2)厚度為60μm，硬塗層(H-1)厚度為6μm。此樹脂積層體(J-11)為全光線穿透率：90.9%，Haze：0.2%，鉛筆硬度：3H，干涉條紋：○，以模具溫度80℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：×，以模具溫度120℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：×，以模具溫度160℃進行熱壓成形時，熱壓成形體之外觀：×，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：○。 Comparative Example 11 [Manufacture of resin laminate (J-11)] A hard coat layer (H-1) and a thermoplastic resin (G- 2) Resin laminate (J-11) with polycarbonate resin (F-1). The overall thickness of the central portion of the obtained resin laminate (J-11) was 1006 μm, the thickness of the surface layer (G-2) was 60 μm, and the thickness of the hard coat layer (H-1) was 6 μm. This resin laminate (J-11) has total light transmittance: 90.9%, Haze: 0.2%, pencil hardness: 3H, interference fringes: ○, When hot-pressed at a mold temperature of 80°C, the appearance of the hot-pressed body: ○, the crack of the curved part of the hot-pressed body: ×, the springback of the hot-pressed body: ×, When hot-pressed at a mold temperature of 120°C, the appearance of the hot-pressed body: ○, the crack of the curved part of the hot-pressed body: ×, the springback of the hot-pressed body: ×, When hot press molding was performed at a die temperature of 160°C, the appearance of the hot press molded body: ×, the crack of the curved portion of the hot press molded body: ×, and the springback of the hot press molded body: ○.

比較例12[樹脂積層體(J-12)之製造] 除了取代熱塑性樹脂(B-1)，使用熱塑性樹脂(G-3)外，與比較例8之樹脂積層體(J-8)同樣，得到硬塗層(H-1)與熱塑性樹脂(G-3)與聚碳酸酯系樹脂(F-1)之樹脂積層體(J-12)。所得之樹脂積層體(J-12)之中央部的全體厚度為1006μm，表層(G-3)厚度為60μm，硬塗層(H-1)厚度為6μm。此樹脂積層體(J-12)為全光線穿透率：91.2%，Haze：0.2%，鉛筆硬度：3H，干涉條紋：○，以模具溫度80℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形體之彎曲部分之龜裂：○，熱壓成形體之回彈：×，以模具溫度120℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：×，以模具溫度160℃進行熱壓成形時，熱壓成形體之外觀：×，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：○。 Comparative Example 12 [Manufacture of resin laminate (J-12)] The hard coat layer (H-1) and the thermoplastic resin (G-1) were obtained in the same manner as the resin laminate (J-8) of Comparative Example 8 except that the thermoplastic resin (G-3) was used instead of the thermoplastic resin (B-1). 3) Resin laminate (J-12) with polycarbonate resin (F-1). The overall thickness of the central portion of the obtained resin laminate (J-12) was 1006 μm, the thickness of the surface layer (G-3) was 60 μm, and the thickness of the hard coat layer (H-1) was 6 μm. This resin laminate (J-12) has total light transmittance: 91.2%, Haze: 0.2%, pencil hardness: 3H, interference fringes: ○, When hot-pressing was performed at a die temperature of 80°C, the appearance of the hot-pressed body: ○, the crack of the curved part of the hot-pressed body: ○, the springback of the hot-pressed body: ×, When hot-pressed at a mold temperature of 120°C, the appearance of the hot-pressed body: ○, the crack of the curved part of the hot-pressed body: ×, the springback of the hot-pressed body: ×, When hot press molding was performed at a die temperature of 160°C, the appearance of the hot press molded body: ×, the crack of the curved portion of the hot press molded body: ×, and the springback of the hot press molded body: ○.

比較例13[樹脂積層體(J-13)之製造] 除了取代熱塑性樹脂(B-1)，使用熱塑性樹脂(G-4)外，與比較例8之樹脂積層體(J-8)同樣，得到硬塗層(H-1)與熱塑性樹脂(G-4)與聚碳酸酯系樹脂(F-1)之樹脂積層體(J-13)。所得之樹脂積層體(J-13)之中央部的全體厚度為1006μm，表層(G-4)厚度為60μm，硬塗層(H-1)厚度為6μm。此樹脂積層體(J-13)為全光線穿透率：91.2%，Haze：0.2%，鉛筆硬度：3H，干涉條紋：○，以模具溫度80℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形體之彎曲部分之龜裂：○，熱壓成形體之回彈：×，以模具溫度120℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：×，以模具溫度160℃進行熱壓成形時，熱壓成形體之外觀：×，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：○。 Comparative Example 13 [Manufacture of resin laminate (J-13)] The hard coat layer (H-1) and the thermoplastic resin (G-1) were obtained in the same manner as the resin laminate (J-8) of Comparative Example 8 except that the thermoplastic resin (G-4) was used instead of the thermoplastic resin (B-1). 4) Resin laminate (J-13) with polycarbonate resin (F-1). The overall thickness of the central portion of the obtained resin laminate (J-13) was 1006 μm, the thickness of the surface layer (G-4) was 60 μm, and the thickness of the hard coat layer (H-1) was 6 μm. This resin laminate (J-13) has total light transmittance: 91.2%, Haze: 0.2%, pencil hardness: 3H, interference fringes: ○, When hot-pressing was performed at a die temperature of 80°C, the appearance of the hot-pressed body: ○, the crack of the curved part of the hot-pressed body: ○, the springback of the hot-pressed body: ×, When hot-pressed at a mold temperature of 120°C, the appearance of the hot-pressed body: ○, the crack of the curved part of the hot-pressed body: ×, the springback of the hot-pressed body: ×, When hot press molding was performed at a die temperature of 160°C, the appearance of the hot press molded body: ×, the crack of the curved portion of the hot press molded body: ×, and the springback of the hot press molded body: ○.

比較例14[樹脂積層體(J-14)之製造] 除了取代熱塑性樹脂(B-1)，使用熱塑性樹脂(G-5)外，與比較例8之樹脂積層體(J-8)同樣，得到硬塗層(H-1)與熱塑性樹脂(G-5)與聚碳酸酯系樹脂(F-1)之樹脂積層體(J-14)。所得之樹脂積層體(J-14)之中央部的全體厚度為1006μm，表層(G-5)厚度為60μm，硬塗層(H-1)厚度為6μm。此樹脂積層體(J-14)為全光線穿透率：91.4%，Haze：0.3%，鉛筆硬度：3H，干涉條紋：○，以模具溫度80℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形體之彎曲部分之龜裂：○，熱壓成形體之回彈：×，以模具溫度120℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：×，以模具溫度160℃進行熱壓成形時，熱壓成形體之外觀：×，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：○。 Comparative Example 14 [Manufacture of resin laminate (J-14)] In the same manner as the resin laminate (J-8) of Comparative Example 8, except that the thermoplastic resin (B-1) was replaced with the thermoplastic resin (G-5), the hard coat layer (H-1) and the thermoplastic resin (G-1) were obtained. 5) Resin laminate (J-14) with polycarbonate resin (F-1). The overall thickness of the central portion of the obtained resin laminate (J-14) was 1006 μm, the thickness of the surface layer (G-5) was 60 μm, and the thickness of the hard coat layer (H-1) was 6 μm. This resin laminate (J-14) has total light transmittance: 91.4%, Haze: 0.3%, pencil hardness: 3H, interference fringes: ○, When hot-pressing was performed at a die temperature of 80°C, the appearance of the hot-pressed body: ○, the crack of the curved part of the hot-pressed body: ○, the springback of the hot-pressed body: ×, When hot-pressed at a mold temperature of 120°C, the appearance of the hot-pressed body: ○, the crack of the curved part of the hot-pressed body: ×, the springback of the hot-pressed body: ×, When hot press molding was performed at a die temperature of 160°C, the appearance of the hot press molded body: ×, the crack of the curved portion of the hot press molded body: ×, and the springback of the hot press molded body: ○.

比較例15[樹脂積層體(J-15)之製造] 除了取代熱塑性樹脂(B-1)，使用熱塑性樹脂(G-6)外，與比較例8之樹脂積層體(J-8)同樣，得到硬塗層(H-1)與熱塑性樹脂(G-6)與聚碳酸酯系樹脂(F-1)之樹脂積層體(J-15)。所得之樹脂積層體(J-15)之中央部的全體厚度為1006μm，表層(G-6)厚度為60μm，硬塗層(H-1)厚度為6μm。此樹脂積層體(J-15)為全光線穿透率：90.5%，Haze：0.2%，鉛筆硬度：H，干涉條紋：○，以模具溫度80℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：×，以模具溫度120℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：×，以模具溫度160℃進行熱壓成形時，熱壓成形體之外觀：×，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：○。 Comparative Example 15 [Manufacture of resin laminate (J-15)] A hard coat layer (H-1) and a thermoplastic resin (G-6) were obtained in the same manner as the resin laminate (J-8) of Comparative Example 8, except that the thermoplastic resin (B-1) was used instead of the thermoplastic resin (G-6). 6) Resin laminate (J-15) with polycarbonate resin (F-1). The overall thickness of the central portion of the obtained resin laminate (J-15) was 1006 μm, the thickness of the surface layer (G-6) was 60 μm, and the thickness of the hard coat layer (H-1) was 6 μm. This resin laminate (J-15) has total light transmittance: 90.5%, Haze: 0.2%, pencil hardness: H, interference fringes: ○, When hot-pressed at a mold temperature of 80°C, the appearance of the hot-pressed body: ○, the crack of the curved part of the hot-pressed body: ×, the springback of the hot-pressed body: ×, When hot-pressed at a mold temperature of 120°C, the appearance of the hot-pressed body: ○, the crack of the curved part of the hot-pressed body: ×, the springback of the hot-pressed body: ×, When hot press molding was performed at a die temperature of 160°C, the appearance of the hot press molded body: ×, the crack of the curved portion of the hot press molded body: ×, and the springback of the hot press molded body: ○.

比較例16[樹脂積層體(J-16)之製造] 除了取代熱塑性樹脂(B-1)，使用熱塑性樹脂(G-7)外，與比較例8之樹脂積層體(J-8)同樣，得到硬塗層(H-1)與熱塑性樹脂(G-7)與聚碳酸酯系樹脂(F-1)之樹脂積層體(J-16)。所得之樹脂積層體(J-16)之中央部的全體厚度為1006μm，表層(G-7)厚度為60μm，硬塗層(H-1)厚度為6μm。此樹脂積層體(J-7)為全光線穿透率：90.6%，Haze：0.2%，鉛筆硬度：H，干涉條紋：○，以模具溫度80℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：×，以模具溫度120℃進行熱壓成形時，熱壓成形體之外觀：○，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：×，以模具溫度160℃進行熱壓成形時，熱壓成形體之外觀：×，熱壓成形體之彎曲部分之龜裂：×，熱壓成形體之回彈：○。 Comparative Example 16 [Manufacture of resin laminate (J-16)] A hard coat layer (H-1) and a thermoplastic resin (G- 7) Resin laminate (J-16) with polycarbonate resin (F-1). The overall thickness of the central portion of the obtained resin laminate (J-16) was 1006 μm, the thickness of the surface layer (G-7) was 60 μm, and the thickness of the hard coat layer (H-1) was 6 μm. This resin laminate (J-7) has total light transmittance: 90.6%, Haze: 0.2%, pencil hardness: H, interference fringes: ○, When hot-pressed at a mold temperature of 80°C, the appearance of the hot-pressed body: ○, the crack of the curved part of the hot-pressed body: ×, the springback of the hot-pressed body: ×, When hot-pressed at a mold temperature of 120°C, the appearance of the hot-pressed body: ○, the crack of the curved part of the hot-pressed body: ×, the springback of the hot-pressed body: ×, When hot press molding was performed at a die temperature of 160°C, the appearance of the hot press molded body: ×, the crack of the curved portion of the hot press molded body: ×, and the springback of the hot press molded body: ○.

如以上，藉由滿足本發明之條件，可發揮得到在低溫下之熱成形性優異，且抑制干涉條紋之發生之外觀良好之樹脂積層體的有利的效果。As described above, by satisfying the conditions of the present invention, the advantageous effect of obtaining a resin laminate having excellent thermoformability at low temperatures and suppressing the occurrence of interference fringes and having a good appearance can be exhibited.

亦即，如表2所示，對於顆粒化後之熱塑性樹脂(B)，摻合有特定之甲基丙烯酸樹脂(C)與特定之苯乙烯共聚物(D)的製造例1~2與特定之甲基丙烯酸樹脂(C)單體之製造比較例5進行比較時，製造例1~2的折射率較高。又，製造例1~2與以特定質量比摻合有特定之甲基丙烯酸樹脂(C)與特定之苯乙烯共聚物(D)以外之苯乙烯共聚物(E-2、E-3)的製造比較例8~11進行比較時，製造例1~2為透明且外觀良好。 That is, as shown in Table 2, for the thermoplastic resin (B) after pelletization, the production examples 1 to 2 and the specific methacrylic resin (C) and the specific styrene copolymer (D) were blended. The refractive index of manufacture examples 1-2 is high when comparing the manufacture comparative example 5 of the methacrylic resin (C) monomer. Moreover, the production examples 1 to 2 and the styrene copolymers (E-2, E-3) other than the specific methacrylic resin (C) and the specific styrene copolymer (D) were blended in a specific mass ratio. When the production comparative examples 8 to 11 were compared, the production examples 1 to 2 were transparent and had good appearance.

如表3所示，對於硬塗膜塗裝後之樹脂積層體，以特定比率摻合特定之甲基丙烯酸樹脂(C)與特定之苯乙烯共聚物(D)，積層顆粒化後之折射率高的熱塑性樹脂(B)與聚碳酸酯系樹脂(A)，在熱塑性樹脂(B)之單側表面具有硬塗膜之實施例1~2與，以特定比率以外摻合特定之甲基丙烯酸樹脂(C)與特定之苯乙烯共聚物(D)，積層顆粒化後之熱塑性樹脂(G)與聚碳酸酯系樹脂(A)，在熱塑性樹脂(G)之單側表面具有硬塗膜之比較例1進行比較時，實施例1~2之樹脂積層體，可抑制模具溫度120℃下之熱壓成形體之彎曲部分之龜裂。又，實施例1~2與，以特定比率摻合特定之甲基丙烯酸樹脂(C)與特定之重量平均分子量以外之苯乙烯共聚物(E-1)，積層顆粒化後之熱塑性樹脂(G)與聚碳酸酯系樹脂(A)，在熱塑性樹脂(G)之單側表面具有硬塗膜之比較例2~3進行比較時，實施例1~2之樹脂積層體，可抑制在模具溫度120℃下之熱壓成形體之彎曲部分之龜裂。此外，積層將特定之甲基丙烯酸樹脂(C)單體進行顆粒化後之熱塑性樹脂(G)與特定之聚碳酸酯系樹脂(A)，在熱塑性樹脂(G)之單側表面具有硬塗膜之比較例5進行比較時，實施例1~2之樹脂積層體，可抑制在模具溫度120℃下之熱壓成形體之彎曲部分之龜裂。 As shown in Table 3, for the resin laminate after hard coat coating, a specific methacrylic resin (C) and a specific styrene copolymer (D) were blended in a specific ratio, and the refractive index after the layer was granulated High thermoplastic resin (B) and polycarbonate resin (A), and Examples 1 to 2 with a hard coat film on one surface of thermoplastic resin (B), and blended with specific methacrylic acid in a specific ratio The resin (C) and the specific styrene copolymer (D), the thermoplastic resin (G) and the polycarbonate resin (A) after lamination and granulation, have a hard coating film on one surface of the thermoplastic resin (G). In comparison with Comparative Example 1, the resin laminates of Examples 1 to 2 were able to suppress cracks in the curved portion of the thermoformed body at a mold temperature of 120°C. In addition, Examples 1 to 2 were mixed with a specific methacrylic resin (C) and a styrene copolymer (E-1) other than a specific weight-average molecular weight at a specific ratio, and the thermoplastic resin (G) after lamination and granulation ) When compared with Comparative Examples 2 to 3 in which the thermoplastic resin (G) has a hard coat film on one surface of the polycarbonate resin (A), the resin laminates of Examples 1 to 2 can suppress the mold temperature Cracks in the bent portion of the hot press-formed body at 120°C. In addition, a thermoplastic resin (G) obtained by granulating a specific methacrylic resin (C) monomer and a specific polycarbonate resin (A) are laminated, and a hard coating is provided on one surface of the thermoplastic resin (G) When comparing the film of Comparative Example 5, the resin laminates of Examples 1 to 2 were able to suppress cracks in the curved portion of the hot-pressed molded body at a mold temperature of 120°C.

又，實施例1~2與，積層將特定之苯乙烯共聚物(D)單體進行顆粒化之熱塑性樹脂(G)與特定之聚碳酸酯系樹脂(A)，在熱塑性樹脂(G)之單側表面具有硬塗膜之比較例6~7進行比較時，實施例1~2之樹脂積層體，鉛筆硬度較高，可抑制熱壓成形體之彎曲部分之龜裂。此外，實施例1~2與，以特定比率摻合特定之甲基丙烯酸樹脂(C)與特定之苯乙烯共聚物(D)，積層進行顆粒化之熱塑性樹脂(B)與聚碳酸酯系樹脂(F)，在熱塑性樹脂(B)之單側表面具有硬塗膜之比較例8~9進行比較時，實施例1~2之樹脂積層體，可抑制在模具溫度120℃下之熱壓成形體之回彈。 In addition, in Examples 1 to 2, a thermoplastic resin (G) obtained by pelletizing a specific styrene copolymer (D) monomer and a specific polycarbonate resin (A) are laminated, and the thermoplastic resin (G) is formed between the thermoplastic resin (G). When comparing Comparative Examples 6 to 7 having a hard coat film on one surface, the resin laminates of Examples 1 to 2 have high pencil hardness and can suppress cracks in the curved portion of the thermoformed body. In addition, in Examples 1 to 2, a specific methacrylic resin (C) and a specific styrene copolymer (D) were blended in a specific ratio, and the thermoplastic resin (B) and the polycarbonate resin were laminated and pelletized. (F), when comparing Comparative Examples 8 to 9 with a hard coat film on one surface of the thermoplastic resin (B), the resin laminates of Examples 1 to 2 can suppress the hot press molding at a mold temperature of 120° C. Body rebound.

又，實施例1~2中，模具溫度為80℃時，發生熱壓成形體之回彈，模具溫度為160℃時，發生熱壓成形體之外觀惡化及彎曲部分之龜裂。而模具溫度為120℃時，熱壓成形體之外觀、彎曲部分之龜裂及回彈良好。Further, in Examples 1 and 2, when the mold temperature was 80°C, springback of the hot-pressed molded body occurred, and when the mold temperature was 160°C, the appearance of the hot-pressed molded body deteriorated and cracks in the bent portion occurred. On the other hand, when the mold temperature was 120° C., the appearance of the hot-pressed body, the cracking of the bent portion, and the springback were good.

Claims

一種樹脂積層體，其係在包含聚碳酸酯系樹脂(A)之層的至少一面，具有包含熱塑性樹脂(B)之層，在包含該熱塑性樹脂(B)之層的至少單側表面，具有硬塗層的樹脂積層體，前述聚碳酸酯系樹脂(A)之玻璃轉移溫度為115℃~140℃，前述熱塑性樹脂(B)含有甲基丙烯酸樹脂(methacrylic resin)(C)與苯乙烯共聚物(D)，以前述甲基丙烯酸樹脂(C)及苯乙烯共聚物(D)之含量之合計100質量份為基準，前述甲基丙烯酸樹脂(C)之含量為15~70質量份，前述苯乙烯共聚物(D)之含量為85~30質量份，前述苯乙烯共聚物(D)為乙烯基芳香族單體單元(d1)含有68~84質量%與環狀酸酐單體單元(d2)含有16~32質量%的共聚物，重量平均分子量為50,000~130,000，以模具溫度為120℃的熱壓機，進行50mmR之熱成形後，彎曲部分不會發生龜裂及回彈(spring back)。 A resin laminate having a layer containing a thermoplastic resin (B) on at least one side of a layer containing a polycarbonate resin (A), and having a layer containing the thermoplastic resin (B) on at least one side surface of the layer containing the thermoplastic resin (B) Hard coat resin laminate, The glass transition temperature of the aforementioned polycarbonate resin (A) is 115°C to 140°C, The thermoplastic resin (B) contains a methacrylic resin (C) and a styrene copolymer (D), and the total content of the methacrylic resin (C) and the styrene copolymer (D) is 100 mass The content of the aforementioned methacrylic resin (C) is 15 to 70 parts by mass, and the content of the aforementioned styrene copolymer (D) is 85 to 30 parts by mass, The aforementioned styrene copolymer (D) is a copolymer containing 68 to 84 mass % of vinyl aromatic monomer units (d1) and 16 to 32 mass % of cyclic acid anhydride monomer units (d2), and has a weight average molecular weight of 50,000 ~130,000, With a hot press with a mold temperature of 120°C, after hot forming at 50 mmR, no cracks and spring back occurred in the curved part.

如請求項1之樹脂積層體，其中前述聚碳酸酯系樹脂(A)之玻璃轉移溫度與前述熱塑性樹脂(B)之玻璃轉移溫度之差為0~15℃之範圍。The resin laminate according to claim 1, wherein the difference between the glass transition temperature of the polycarbonate resin (A) and the glass transition temperature of the thermoplastic resin (B) is in the range of 0 to 15°C.

如請求項1或2之樹脂積層體，其中前述熱塑性樹脂(B)為前述甲基丙烯酸樹脂(C)與前述苯乙烯共聚物(D)之聚合物合金。The resin laminate according to claim 1 or 2, wherein the thermoplastic resin (B) is a polymer alloy of the methacrylic resin (C) and the styrene copolymer (D).

如請求項1~3中任一項之樹脂積層體，其中前述苯乙烯共聚物(D)所含有之乙烯基芳香族單體單元(d1)為苯乙烯。The resin laminate according to any one of claims 1 to 3, wherein the vinyl aromatic monomer unit (d1) contained in the styrene copolymer (D) is styrene.

如請求項1~4中任一項之樹脂積層體，其中前述苯乙烯共聚物(D)所含有之環狀酸酐單體單元(d2)為馬來酸酐。The resin laminate according to any one of claims 1 to 4, wherein the cyclic acid anhydride monomer unit (d2) contained in the styrene copolymer (D) is maleic anhydride.

如請求項1~5中任一項之樹脂積層體，其中前述聚碳酸酯系樹脂(A)具有自下述通式(1)表示之一元酚所衍生的末端結構與自二元酚所衍生的構成單元，

(式中，R ₁表示碳數8~36之烷基，或碳數8~36之烯基，R ₂~R ₅各自表示氫、鹵素、或可具有取代基之碳數1~20之烷基或碳數6~12之芳基，前述取代基為鹵素、碳數1~20之烷基、或碳數6~12之芳基)。 The resin laminate according to any one of claims 1 to 5, wherein the polycarbonate-based resin (A) has a terminal structure derived from a monohydric phenol represented by the following general formula (1) and a terminal structure derived from a dihydric phenol the constituent unit,

(In the formula, R ₁ represents an alkyl group with 8 to 36 carbon atoms, or an alkenyl group with 8 to 36 carbon atoms, and R ₂ to R ₅ each represent hydrogen, halogen, or an alkane with 1 to 20 carbon atoms that may have a substituent. group or an aryl group having 6 to 12 carbon atoms, the aforementioned substituents are halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms).

如請求項1~6中任一項之樹脂積層體，其中前述包含熱塑性樹脂(B)之層的厚度為10~250μm，前述樹脂積層體之全體厚度為0.4~4.0mm之範圍。The resin laminate according to any one of claims 1 to 6, wherein the thickness of the layer containing the thermoplastic resin (B) is 10 to 250 μm, and the overall thickness of the resin laminate is in the range of 0.4 to 4.0 mm.

如請求項1~7中任一項之樹脂積層體，其中前述包含聚碳酸酯系樹脂(A)之層、前述包含熱塑性樹脂(B)之層、及前述硬塗層之至少一層含有紫外線吸收劑。The resin laminate according to any one of claims 1 to 7, wherein at least one layer comprising the polycarbonate-based resin (A), the layer comprising the thermoplastic resin (B), and the hard coat layer comprises ultraviolet absorbing agent.

如請求項1~8中任一項之樹脂積層體，其中前述硬塗層為丙烯酸系硬塗膜。The resin laminate according to any one of claims 1 to 8, wherein the hard coat layer is an acrylic hard coat film.

如請求項1~9中任一項之樹脂積層體，其中在前述樹脂積層體之單面或兩面，施予耐指紋處理、抗反射處理、防眩處理、耐候性處理、抗靜電處理及防污處理中之至少1種處理而成。The resin laminate according to any one of claims 1 to 9, wherein anti-fingerprint treatment, anti-reflection treatment, anti-glare treatment, weather resistance treatment, anti-static treatment and anti-glare treatment are applied to one side or both sides of the aforementioned resin laminate. It is formed by at least one of the pollution treatments.

一種熱成形體，其係將如請求項1~10中任一項之樹脂積層體進行熱彎曲加工。A thermoformed body obtained by subjecting the resin laminate according to any one of claims 1 to 10 to thermal bending.

一種透明基板材料，其係包含如請求項1~10中任一項之樹脂積層體或如請求項11之熱成形體。A transparent substrate material comprising the resin laminate according to any one of claims 1 to 10 or the thermoformed body according to claim 11.

一種透明保護材料，其係包含如請求項1~10中任一項之樹脂積層體或如請求項11之熱成形體。A transparent protective material comprising the resin laminate as claimed in any one of claims 1 to 10 or the thermoformed body as claimed in claim 11.

一種觸控面板前面保護板，其係包含如請求項1~10中任一項之樹脂積層體、或如請求項11之熱成形體。A touch panel front protection plate comprising the resin laminate as claimed in any one of claims 1 to 10, or the thermoformed body as claimed in claim 11.

一種汽車導航(Car navigation)用、OA機器用或攜帶電子機器用的前面板，其係包含如請求項1~10中任一項之樹脂積層體或如請求項11之熱成形體。A front panel for car navigation, OA equipment, or portable electronic equipment, comprising the resin laminate according to any one of claims 1 to 10 or the thermoformed body according to claim 11.

一種熱成形體之製造方法，其係包含將樹脂積層體以100℃~135℃之模具溫度進行熱彎曲加工的步驟，前述樹脂積層體在包含聚碳酸酯系樹脂(A)之層之至少一面，具有包含熱塑性樹脂(B)之層，且在包含該熱塑性樹脂(B)之層之至少單側表面，具有硬塗層，前述聚碳酸酯系樹脂(A)之玻璃轉移溫度為115℃~140℃，前述熱塑性樹脂(B)含有甲基丙烯酸樹脂(C)與苯乙烯共聚物(D)，以前述甲基丙烯酸樹脂(C)及苯乙烯共聚物(D)之含量之合計100質量份為基準，前述甲基丙烯酸樹脂(C)之含量為15~70質量份，前述苯乙烯共聚物(D)之含量為85~30質量份，前述苯乙烯共聚物(D)為乙烯基芳香族單體單元(d1)含有68~84質量%與環狀酸酐單體單元(d2)含有16~32質量%的共聚物，且重量平均分子量為50,000~130,000。 A method for producing a thermoformed body, comprising the step of subjecting a resin laminate to a hot bending process at a mold temperature of 100°C to 135°C, The resin laminate has a layer containing a thermoplastic resin (B) on at least one side of a layer containing a polycarbonate resin (A), and has a hard coat on at least one surface of the layer containing the thermoplastic resin (B). layer, The glass transition temperature of the aforementioned polycarbonate resin (A) is 115°C to 140°C, The thermoplastic resin (B) contains a methacrylic resin (C) and a styrene copolymer (D), based on 100 parts by mass of the total content of the methacrylic resin (C) and the styrene copolymer (D), The content of the aforementioned methacrylic resin (C) is 15 to 70 parts by mass, and the content of the aforementioned styrene copolymer (D) is 85 to 30 parts by mass, The aforementioned styrene copolymer (D) is a copolymer in which the vinyl aromatic monomer unit (d1) contains 68 to 84 mass % and the cyclic acid anhydride monomer unit (d2) contains 16 to 32 mass %, and the weight average molecular weight is 50,000~130,000.