TW202208173A

TW202208173A - Resin multilayer body

Info

Publication number: TW202208173A
Application number: TW110118411A
Authority: TW
Inventors: 平林正樹; 小澤帰心
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: 2020-05-27
Filing date: 2021-05-21
Publication date: 2022-03-01
Also published as: JPWO2021241426A1; WO2021241426A1

Abstract

The present invention is able to provide a resin multilayer body which comprises a layer containing a polycarbonate-based resin (A) that is mainly composed of a polycarbonate resin and a layer containing a thermoplastic resin (B), said layer being superposed on at least one surface of the layer containing a polycarbonate-based resin (A). The curl shape of the resin multilayer body after being left to stand in an environment at 23 DEG C at 50% RH has a recess in the layer containing a thermoplastic resin (B), while satisfying 11 m ≤ curvature radius R ≤ 1,225 m.

Description

樹脂積層體resin laminate

本發明有關適宜使用於透明基板材料及保護材料之包含聚碳酸酯系樹脂層與熱塑性樹脂層之樹脂積層體，較佳有關抗反射層積層後之耐捲曲性優異之樹脂積層體。The present invention relates to a resin laminate comprising a polycarbonate resin layer and a thermoplastic resin layer suitable for use in transparent substrate materials and protective materials, and preferably relates to a resin laminate having excellent curl resistance after lamination of the antireflection layer.

聚碳酸酯樹脂板之透明性及耐衝擊性與耐熱性優異，已利用於隔音牆及車庫、看板、玻璃質材料、照明用器具、OA，電子設備之顯示器及觸控面板前面板等，但有表面硬度低因此易損壞之缺點，用途受到限制。專利文獻1中為了改良該缺點，提案以紫外線硬化樹脂等塗覆表面之方法，及對於將聚碳酸酯樹脂與丙烯酸系樹脂共擠出之基板上實施塗層之方法。然而，於聚碳酸酯樹脂表面實施塗層，無法滿足所要求之鉛筆硬度，有無法使用於要求高表面硬度之用途。因此，丙烯酸系樹脂與聚碳酸酯樹脂之積層體，某程度提高表面硬度，而廣泛使用於電子設備之顯示器及觸控面板之前面板等。又，專利文獻2中，為了抑制於高溫高濕環境下放置後捲曲之大小，揭示一種積層板，其特徵係於將(甲基)丙烯酸酯與以脂肪乙烯基作為構成單位之樹脂積層於聚碳酸酯樹脂上。Polycarbonate resin sheet has excellent transparency, impact resistance and heat resistance, and has been used in soundproof walls and garages, signboards, glass materials, lighting equipment, OA, electronic equipment monitors and touch panel front panels, etc. It has the disadvantage of low surface hardness and therefore easy to damage, and its use is limited. Patent Document 1 proposes a method of coating the surface with an ultraviolet curable resin or the like, and a method of coating a substrate in which a polycarbonate resin and an acrylic resin are co-extruded, in order to improve this disadvantage. However, the coating on the surface of polycarbonate resin cannot meet the required pencil hardness and cannot be used for applications requiring high surface hardness. Therefore, the laminated body of an acrylic resin and a polycarbonate resin improves the surface hardness to some extent, and is widely used for the display of an electronic device, the front panel of a touch panel, etc. In addition, in order to suppress the size of the curl after being left in a high temperature and high humidity environment, Patent Document 2 discloses a laminate characterized by laminating (meth)acrylate and a resin having an aliphatic vinyl as a constituent unit on a polymer. on carbonate resin.

近年來，為了減少陽光朝車載導航系統及智慧型手機畫面之映入，而於塑膠表面進行反射防止膜的抗反射塗層。抗反射塗層由於係邊加熱邊進行金屬蒸鍍，形成SiOx或TiOx等之複數金屬膜，故因樹脂積層體與金屬膜的線膨脹係數不同，而有在室溫下於塑膠表面成為凸面而較大捲曲的形狀之問題，在液晶顯示器保護膜或觸控面板前面板等之電子設備相關用途中，成為嚴重缺陷。 [先前技術文獻] [專利文獻]In recent years, in order to reduce the reflection of sunlight on the screen of the car navigation system and smart phone, the anti-reflection coating of the anti-reflection film is applied to the plastic surface. The anti-reflection coating is subjected to metal vapor deposition while heating to form multiple metal films such as SiOx or TiOx. Therefore, due to the difference in the linear expansion coefficients of the resin laminate and the metal film, the plastic surface may become convex at room temperature. The problem of the large curled shape is a serious defect in electronic equipment-related applications such as liquid crystal display protective films and touch panel front panels. [Prior Art Literature] [Patent Literature]

[專利文獻1]日本特開2006-103169號公報 [專利文獻2]WO2011/145630號公報[Patent Document 1] Japanese Patent Laid-Open No. 2006-103169 [Patent Document 2] WO2011/145630

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

本發明之目的在於提供於透明基板材料或保護材料中使用之於23℃50%RH環境下之捲曲可被抑制，表面硬度優異之樹脂積層體。進而本發明之目的在於提供於抗反射塗布後之於23℃50%RH環境下之捲曲可被抑制，表面硬度優異之樹脂積層體。 [用以解決課題之手段]An object of the present invention is to provide a resin laminate having excellent surface hardness while suppressing curling in an environment of 23°C and 50% RH for use in transparent substrate materials or protective materials. Further, an object of the present invention is to provide a resin laminate having excellent surface hardness while suppressing curling in an environment of 23° C. and 50% RH after antireflection coating. [means to solve the problem]

本發明人等為了解決上述課題而重複積極研究之結果，發現藉由以下態樣之本發明可解決上述課題。具體而言，本發明係如下。The inventors of the present invention, as a result of repeated active studies in order to solve the above-mentioned problems, found that the above-mentioned problems can be solved by the present invention of the following aspects. Specifically, the present invention is as follows.

[1] 一種樹脂積層體，其係包含：包含將聚碳酸酯樹脂作為主成分之聚碳酸酯系樹脂(A)之層，與包含積層於該層之至少一者之面之熱可塑性樹脂(B)之層之樹脂積層體，於23℃50%RH環境下放置後之樹脂積層體之捲曲形狀為將包含前述熱可塑性樹脂(B)之層側作為凹部且11m≦曲率半徑R≦1225m。 [2] 如上述[1]之樹脂積層體，其中，對包含前述熱可塑性樹脂(B)之層側之表面施予硬塗布處理、反射防止處理、防汙處理、耐指紋處理、抗靜電處理、耐候性處理及防眩處理中任一種以上。 [3] 如上述[1]或[2]之樹脂積層體，其中，於包含前述熱可塑性樹脂(B)之層側之表面進而有積層抗反射層，於23℃50%RH環境下放置後之樹脂積層體之捲曲形狀為將包含前述熱可塑性樹脂(B)之層側作為凹部或凸部且曲率半徑R≧21m。 [4] 一種樹脂積層體，其係包含：包含將聚碳酸酯樹脂作為主成分之聚碳酸酯系樹脂(A)之層，與包含積層於包含該樹脂(A)之層之至少一者之面之熱可塑性樹脂(B)之層，與積層於包含該樹脂(B)之層之表面之抗反射層之樹脂積層體，於23℃50%RH環境下放置後之樹脂積層體之捲曲形狀為將前述抗反射層側作為凹部或凸部且曲率半徑R≧21m。 [5] 如上述[4]之樹脂積層體，其中，於包含前述熱可塑性樹脂(B)之層與前述抗反射層之間施予硬塗布處理、反射防止處理、防汙處理、耐指紋處理、抗靜電處理、耐候性處理及防眩處理中任一種以上。 [6] 如上述[1]~[5]中任一項之樹脂積層體，其中，包含前述熱可塑性樹脂(B)之層側之表面之鉛筆硬度為HB以上。 [7] 如上述[1]~[6]中任一項之樹脂積層體，其中，前述聚碳酸酯系樹脂(A)之重量平均分子量為15,000~75,000。 [8] 如上述[1]~[7]中任一項之樹脂積層體，其中，包含前述聚碳酸酯系樹脂(A)之層及/或包含前述熱可塑性樹脂(B)之層含有紫外線吸收劑。 [9] 一種透明基板材料，其係包含如上述[1]~[8]中任一項之樹脂積層體。 [10] 一種透明保護材料，其係包含如上述[1]~[8]中任一項之樹脂積層體。 [11] 一種觸控面板前面保護板，其係包含如上述[1]~[8]中任一項之樹脂積層體。 [發明效果][1] A resin laminate comprising: a layer comprising a polycarbonate resin (A) containing a polycarbonate resin as a main component, and A resin laminate comprising a layer of thermoplastic resin (B) laminated on the surface of at least one of the layers, The curl shape of the resin laminate after being left to stand in a 23° C. 50% RH environment was such that the layer side containing the thermoplastic resin (B) was a recess and 11 m≦curvature radius R≦1225 m. [2] The resin laminate according to the above [1], wherein a hard coat treatment, antireflection treatment, antifouling treatment, anti-fingerprint treatment, and antistatic treatment are applied to the surface of the layer side including the thermoplastic resin (B) , any one or more of weather resistance treatment and anti-glare treatment. [3] The resin laminate according to the above [1] or [2], wherein a laminated anti-reflection layer is further formed on the surface of the layer side containing the thermoplastic resin (B), after being left to stand at 23°C and 50% RH. The curl shape of the resin laminated body is such that the side of the layer containing the thermoplastic resin (B) is a concave portion or a convex portion, and the curvature radius R≧21m. [4] A resin laminate comprising: a layer comprising a polycarbonate resin (A) containing a polycarbonate resin as a main component, and a layer comprising a thermoplastic resin (B) laminated on the face of at least one of the layers comprising the resin (A), and A resin laminate having an antireflection layer laminated on the surface of the layer comprising the resin (B), The curl shape of the resin laminate after being left at 23° C. 50% RH is such that the antireflection layer side is defined as a concave portion or a convex portion, and the curvature radius R≧21m. [5] The resin laminate according to the above [4], wherein a hard coat treatment, antireflection treatment, antifouling treatment, and anti-fingerprint treatment are applied between the layer comprising the thermoplastic resin (B) and the antireflection layer , any one or more of antistatic treatment, weather resistance treatment and anti-glare treatment. [6] The resin laminate according to any one of the above [1] to [5], wherein the pencil hardness of the surface on the side of the layer containing the thermoplastic resin (B) is HB or more. [7] The resin laminate according to any one of the above [1] to [6], wherein the polycarbonate-based resin (A) has a weight average molecular weight of 15,000 to 75,000. [8] The resin laminate according to any one of the above [1] to [7], wherein the layer containing the polycarbonate-based resin (A) and/or the layer containing the thermoplastic resin (B) contains ultraviolet rays absorbent. [9] A transparent substrate material comprising the resin laminate according to any one of the above [1] to [8]. [10] A transparent protective material comprising the resin laminate according to any one of the above [1] to [8]. [11] A touch panel front protection plate comprising the resin laminate according to any one of the above [1] to [8]. [Inventive effect]

依據本發明，提供於23℃50%RH環境下之捲曲(較佳係抗反射塗布後之於23℃50%RH環境下之捲曲)可被抑制，表面硬度優異之樹脂積層體，該樹脂積層體可使用作為透明基板材料或透明保護材料。具體而言該樹脂積層體可適當地使用於攜帶電話終端、攜帶型電子遊具、攜帶資訊終端、行動PC之攜帶型顯示器裝置、或筆記型PC、桌上型PC液晶監視器、液晶電視、車載用汽車導航等之設置型的顯示器裝置等。According to the present invention, the curling (preferably, the curling at 23 °C 50% RH environment after anti-reflection coating) can be suppressed in an environment of 23°C and 50% RH, and a resin laminate having excellent surface hardness is provided. The body can be used as a transparent substrate material or a transparent protective material. Specifically, the resin laminate can be suitably used for portable telephone terminals, portable electronic games, portable information terminals, portable display devices for mobile PCs, notebook PCs, desktop PC liquid crystal monitors, liquid crystal televisions, and vehicle-mounted PCs. Installation-type display devices, etc. for car navigation, etc.

下文將針對本發明例示製造例及實施例等詳細說明，但本發明不限於例示之製造例及實施例，只要於不大幅偏離本發明內容之範圍內，亦可以任意方法進行變更。Hereinafter, the present invention will be described in detail by exemplifying manufacturing examples and embodiments, but the present invention is not limited to the exemplified manufacturing examples and embodiments, and can be modified in any method as long as it does not significantly deviate from the content of the present invention.

＜聚碳酸酯系樹脂(A)＞本發明使用之聚碳酸酯系樹脂(A)係以聚碳酸酯樹脂為主成分之聚碳酸酯系樹脂(A)。此處，「以聚碳酸酯樹脂為主成分」意指聚碳酸酯樹脂之含量超過50質量%。聚碳酸酯系樹脂(A)較佳含有75質量%以上之聚碳酸酯樹脂，更佳含有90質量%以上之聚碳酸酯樹脂，又更佳實質上由聚碳酸酯樹脂所成。聚碳酸酯系樹脂(A)於分子主鏈中包含碳酸酯鍵。亦即，若為包含-[O-R-OCO]-單位(式中，R為脂肪族基、芳香族基或包含脂肪族基與芳香族基兩者，進而顯示具有直鏈構造或分支構造者)者，則未特別限制，但特佳使用包含下述式(3)之構造單位之聚碳酸酯。藉由使用此等聚碳酸酯，可獲得耐衝擊性優異之樹脂積層體。

具體而言，作為聚碳酸酯系樹脂(A)，可使用芳香族聚碳酸酯樹脂(例如，由三菱工程塑膠股份有限公司市售之LUPILON S-2000、LUPILON S-1000、LUPILON E-2000)等。本發明中使用的聚碳酸酯系樹脂(A)之玻璃轉移溫度較佳為120~160℃，更佳為125~155℃，特佳為130℃~150℃。近年來，由於對前面板進行彎曲加工的期望增加，故聚碳酸酯樹脂(A)較佳使用由下述通式(4)表示之1價酚作為末端停止劑而合成。

(式中，R₁ 表示具有碳數8~36之烷基、或具有碳數8~36之烯基，R₂ ~R₅ 分別表示氫、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，前去取代基為鹵素、碳數1~20之烷基或碳數6~12之芳基)。<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, "containing the polycarbonate resin as the 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 is more preferably substantially composed of the polycarbonate resin. The polycarbonate resin (A) contains a carbonate bond in the molecular main chain. That is, if it contains -[OR-OCO]- units (in the formula, R is an aliphatic group, an aromatic group, or a group containing both aliphatic groups and aromatic groups, and it is shown that it has a straight-chain structure or a branched structure) If it is not particularly limited, it is particularly preferable to use a polycarbonate containing the structural unit of the following formula (3). By using these polycarbonates, a resin laminate having excellent impact resistance can be obtained.

Specifically, as the polycarbonate-based resin (A), an aromatic polycarbonate resin (for example, LUPILON S-2000, LUPILON S-1000, and LUPILON E-2000 commercially available from Mitsubishi Engineering Plastics Co., Ltd.) can be used. Wait. The glass transition temperature of the polycarbonate resin (A) used in the present invention is preferably 120 to 160°C, more preferably 125 to 155°C, and particularly preferably 130 to 150°C. In recent years, since the desire for bending a front panel has increased, it is preferable to synthesize the polycarbonate resin (A) using a monovalent phenol represented by the following general formula (4) as a terminal stopper.

(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 represent hydrogen, halogen, or a substituent with 1 to 20 carbon atoms, respectively. An alkyl group or an aryl group with a carbon number of 6-12, the preceding substituent is a halogen, an alkyl group with a carbon number of 1-20 or an aryl group with a carbon number of 6-12).

通式(4)之1價酚更較佳為由以下述式(5)表示之1價酚。

(式中，R₁ 表示碳數8~36之烷基或碳數8~36之烯基)。The monovalent phenol of the general formula (4) is more preferably a monovalent phenol represented by the following formula (5).

(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(4)或通式(5)之R¹ 的碳數更佳於特定數值範圍內。具體而言，作為R₁ 之碳數的上限較佳為36，更佳為22，特佳為18。作為R₁ 之碳數的下限，較佳為8，更佳為12。The carbon number of R ¹ in the general formula (4) or the general formula (5) is more preferably within a specific numerical range. Specifically, the upper limit of the carbon number as R ₁ is preferably 36, more preferably 22, and particularly preferably 18. As a lower limit of the carbon number of R< ₁ >, 8 is preferable, and 12 is more preferable.

通式(4)或通式(5)所示之1價酚(末端停止劑)中，特佳使用對羥基苯甲酸十六烷酯、對羥基苯甲酸2-十六烷酯之任一者或兩者作為末端停止劑。Among the monovalent phenols (terminal stoppers) represented by the general formula (4) or the general formula (5), it is particularly preferable to use any one of cetyl p-hydroxybenzoate and 2-hexadecyl p-hydroxybenzoate or both as end stoppers.

使用具有例如碳數16之烷基作為通式(4)或通式(5)之R₁ 的1價酚(末端停止劑)時，玻璃轉移溫度、熔融流動性、成形性、耐掉落性、製造聚碳酸酯樹脂時之1價酚的溶劑溶解性優異，作為本發明中使用的聚碳酸酯樹脂中使用之末端停止劑特佳。When using, for example, a monovalent phenol (terminal stopper) having an alkyl group having 16 carbon atoms as R ₁ of the general formula (4) or general formula (5), glass transition temperature, melt fluidity, formability, and drop resistance . The monovalent phenol has excellent solvent solubility in the production of polycarbonate resin, and is particularly preferred as a terminal stopper used in the polycarbonate resin used in the present invention.

另一方面，若通式(4)或通式(5)之R₁ 的碳數增加，則有1價酚(末端停止劑)之有機溶劑溶解性降低之傾向，有聚碳酸酯樹脂製造時之生產性降低之情況。作為一例，若R₁ 之碳數為36以下，則製造聚碳酸酯樹脂時之生產性高，經濟性亦良好。若R₁ 之碳數為22以下，則1價酚於特別是有機溶劑溶解性優異，在製造聚碳酸酯樹脂時生產性可非常高，經濟性亦提高。若通式(4)或通式(5)之R₁ 的碳數過小，則聚碳酸酯樹脂之玻璃轉移溫度無法成為充分低之值，而有熱成形性降低之情況。On the other hand, when the carbon number of R ₁ in the general formula (4) or the general formula (5) increases, the solubility in the organic solvent of the monovalent phenol (terminal stopper) tends to decrease, and there is a tendency for a polycarbonate resin to be produced. of reduced productivity. As an example, when the carbon number of R ₁ is 36 or less, the productivity at the time of manufacturing a polycarbonate resin is high, and the economical efficiency is also favorable. When the carbon number of R ₁ is 22 or less, the monovalent phenol is excellent in solubility in an organic solvent in particular, the productivity can be very high when manufacturing a polycarbonate resin, and the economical efficiency is also improved. When the carbon number of R ₁ in the general formula (4) or the general formula (5) is too small, the glass transition temperature of the polycarbonate resin cannot be a sufficiently low value, and the thermoformability may decrease.

作為聚碳酸酯樹脂(A)所含之其他樹脂，有聚酯系樹脂。聚酯系樹脂只要含有對苯二甲酸作為主成分作為二羧酸成分即可，亦可含有對苯二甲酸以外之二羧酸成分。較佳為例如相對於主成分的乙二醇80~60(莫耳比率)含有1,4-環己烷二甲醇20~40(莫耳比率，合計100)之二醇成分與二羧酸成分聚縮合之聚酯系樹脂，即所謂「PETG」。且，聚碳酸酯系樹脂(A)中亦可包含於聚合物骨架中具有酯鍵與碳酸酯鍵之聚酯碳酸酯系樹脂。As other resins contained in the polycarbonate resin (A), there are polyester-based resins. The polyester resin may contain dicarboxylic acid components other than terephthalic acid as long as it contains terephthalic acid as a main component as a dicarboxylic acid component. Preferably, for example, a diol component and a dicarboxylic acid component containing 1,4-cyclohexanedimethanol 20 to 40 (molar ratio, 100 in total) with respect to 80 to 60 (molar ratio) of ethylene glycol as the main component Polycondensed polyester resin is called "PETG". Moreover, the polyester carbonate-type resin which has an ester bond and a carbonate bond in a polymer frame|skeleton may also be contained in polycarbonate-type resin (A).

本發明中，聚碳酸酯系樹脂(A)之重量平均分子量會影響樹脂積層體之耐衝擊性及成形條件。亦即，重量平均分子量過小時，由於樹脂積層體之耐衝擊性降低故而欠佳。重量平均分子量過高時，積層包含聚碳酸酯系樹脂(A)之層時有需要過量熱源之情況而欠佳。又，由於根據成形法而需要高溫，故聚碳酸酯系樹脂(A)將暴露於高溫，有對其熱安定性造成不利影響之情況。聚碳酸酯系樹脂(A)之重量平均分子量較佳為15,000~75,000，更佳為20,000~70,000。又更佳為25,000 ~65,000。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. That is, when the weight-average molecular weight is too small, the impact resistance of the resin layered product is lowered, which is unfavorable. When the weight average molecular weight is too high, an excessive heat source may be required when laminating a layer containing the polycarbonate-based resin (A), which is unfavorable. Moreover, since high temperature is required by a molding method, polycarbonate-type resin (A) may be exposed to high temperature, and the thermal stability may be adversely affected. The weight average molecular weight of the polycarbonate resin (A) is preferably 15,000 to 75,000, more preferably 20,000 to 70,000. More preferably, it is 25,000 to 65,000.

＜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基於日本特開2007-179018號公報之段落0061~0064之記載測定。測定法之細節如下所示。

表1：重量平均分子量之測定條件

裝置 Waters公司製「Aliance」管柱昭和電工製Shodex K-805L(2根) 檢測器 UV檢測器：254nm 溶離液氯仿

<Method for Measuring Weight Average Molecular Weight of Polycarbonate-based Resin (A)> The weight-average molecular weight of polycarbonate-based resin (A) can be measured based on the descriptions in paragraphs 0061 to 0064 of JP-A-2007-179018. Details of the assay are shown below.

Table 1: Measurement Conditions for Weight Average Molecular Weight

device "Aliance" made by Waters Corporation pipe string Showa Denko Shodex K-805L (2 pieces) Detector UV detector: 254nm chaotropic solution Chloroform

使用聚苯乙烯(PS)作為標準聚合物進行測定後，藉由通用校準法，求出溶離時間與聚碳酸酯(PC)之分子量的關係作成校正線。然後，在與校正線之情況相同條件下測定PC之溶離曲線(色譜圖)，自溶離時間(分子量)與其溶離時間之峰面積(分子數)求出各平均分子量。將分子量Mi之分子數設為Ni時，重量平均分子量表示如下。且換算式使用以下之式。 (重量平均分子量) Mw=Σ(NiMi² )/Σ(NiMi) (換算式) MPC=0.47822MPS^1.01470 又，MPC表示PC之分子量，MPS表示PS之分子量。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 by a general calibration method, and a calibration line was prepared. Then, the elution curve (chromatogram) of PC was measured under the same conditions as in the case of the calibration line, and each average molecular weight was obtained from the peak area (number of molecules) between elution time (molecular weight) and elution time. The weight average molecular weight is expressed as follows when the number of molecules of the molecular weight Mi is Ni. In addition, the following formula is used for the conversion formula. (weight average molecular weight) Mw=Σ(NiMi ² )/Σ(NiMi) (conversion formula) MPC=0.47822MPS ^1.01470 Also, MPC represents the molecular weight of PC, and MPS represents the molecular weight of PS.

本發明中使用的聚碳酸酯系樹脂(A)之製造方法，可根據使用之單體適當選擇習知之光氣法(界面聚合法)、酯交換法(熔融法)等。For the production method of the polycarbonate resin (A) used in the present invention, the known phosgene method (interfacial polymerization method), transesterification method (melt method), etc. can be appropriately selected according to the monomer to be used.

＜熱塑性樹脂(B)＞本發明中使用的熱塑性樹脂(B)主要包含高硬度樹脂。本說明書中，所謂高硬度樹脂意指硬度比聚碳酸酯系樹脂(A)高的樹脂，係鉛筆硬度為HB以上之樹脂。高硬度樹脂之鉛筆硬度較佳為HB~5H，更佳為H~4H，特佳為2H~4H。本發明中使用之高硬度樹脂可為1種亦可為2種以上。高硬度樹脂較佳係選自以下所示樹脂(B1)~(B6)之至少一種，更佳為選自樹脂(B1)~(B3)之至少一種，特佳為樹脂(B1)。<Thermoplastic resin (B)> The thermoplastic resin (B) used in the present invention mainly contains a high hardness resin. In this specification, the high-hardness resin means a resin whose hardness is higher than that of the polycarbonate resin (A), and is a resin whose pencil hardness is HB or higher. The pencil hardness of the high-hardness resin is preferably HB~5H, more preferably H~4H, and particularly preferably 2H~4H. The high-hardness resin used in the present invention may be one type or two or more types. The high-hardness resin is preferably at least one selected from the resins (B1) to (B6) shown below, more preferably at least one selected from the resins (B1) to (B3), and particularly preferably the resin (B1).

＜樹脂(B1)＞樹脂(B1)包含後述之乙烯基共聚物(C)與苯乙烯共聚物(D)。以下說明各構成要素。<Resin (B1)> The resin (B1) contains the vinyl copolymer (C) and the styrene copolymer (D) described later. Each of the constituent elements will be described below.

＜乙烯基共聚物(C)＞樹脂(B1)中所含之乙烯基共聚物(C)之特徵係包含以下述通式(6)表示之(甲基)丙烯酸酯單體單位(c1)與以下述通式(7)表示之脂肪族乙烯基單體單位(c2)，前述(甲基)丙烯酸酯單體單位(c1)與前述脂肪族乙烯基單體單位(c2)之合計比例相對於乙烯基共聚物(C)中總單體單位的合計為90~100莫耳%，前述(甲基)丙烯酸酯單體單位(c1)之比例相對於前述乙烯基共聚物(C)中總單體單位的合計為60~80莫耳%，前述脂肪族乙烯基單體單位(c2)之比例相對於乙烯基共聚物(C)中總單體單位之合計為40~20莫耳%。<Vinyl copolymer (C)> The vinyl copolymer (C) contained in the resin (B1) is characterized in that it contains a (meth)acrylate monomer unit (c1) represented by the following general formula (6) and a (meth)acrylate monomer unit (c1) represented by the following general formula (7) The aliphatic vinyl monomer unit (c2), the total ratio of the aforementioned (meth)acrylate monomer unit (c1) and the aforementioned aliphatic vinyl monomer unit (c2) relative to the total in the vinyl copolymer (C) The total of the monomer units is 90 to 100 mol %, and the ratio of the aforementioned (meth)acrylate monomer units (c1) to the total of the total monomer units in the aforementioned vinyl copolymer (C) is 60 to 80 mol % %, the proportion of the aforementioned aliphatic vinyl monomer units (c2) is 40 to 20 mol % relative to the total of the total monomer units in the vinyl copolymer (C).

(式中，R1表示氫原子或甲基，R2表示碳數1~18之烷基)。

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

(式中，R3表示氫原子或甲基，R4表示具有碳數1~4之烴取代基之環己基)。

(in the formula, R3 represents a hydrogen atom or a methyl group, and R4 represents a cyclohexyl group having a hydrocarbon substituent having 1 to 4 carbon atoms).

以前述通(6)表示之(甲基)丙烯酸酯單體單位(c1)中，R2為碳數1~18之烷基，較佳為碳數1~12之烷基，具體而言舉例為甲基、乙基、丁基、月桂基、硬脂基、環己基、異冰片基等。前述(甲基)丙烯酸酯單體單位(c1)中，較佳係R2為甲基及/或乙基的(甲基)丙烯酸酯單體單位，更佳係R1為甲基，R2為甲基的甲基丙烯酸甲酯單體單位。In the (meth)acrylate monomer unit (c1) represented by the aforementioned general (6), R2 is an alkyl group having 1 to 18 carbon atoms, preferably an alkyl group having 1 to 12 carbon atoms. Methyl, ethyl, butyl, lauryl, stearyl, cyclohexyl, isobornyl, etc. Among the aforementioned (meth)acrylate monomer units (c1), preferably R2 is a methyl and/or ethyl (meth)acrylate monomer unit, more preferably R1 is methyl, and R2 is methyl of methyl methacrylate monomer units.

作為以通式(7)表示之脂肪乙烯基單體單位(c2)，舉例為R3係氫原子或甲基，R4為環己基或具有碳數1至4之烴取代基之環己基者。前述脂肪族乙烯基單體單位(c2)中，較佳係R3為氫原子，R4為環己基的脂肪族乙烯基單體單位。Examples of the aliphatic vinyl monomer unit (c2) represented by the general formula (7) include those in which R3 is a hydrogen atom or a methyl group, and R4 is a cyclohexyl group or a cyclohexyl group having a hydrocarbon substituent having 1 to 4 carbon atoms. Among the aforementioned aliphatic vinyl monomer units (c2), it is preferable that R3 is a hydrogen atom, and R4 is a cyclohexyl group of aliphatic vinyl monomer units.

本發明所用之乙烯基共聚物(C)主要由以前述通式(6)表示之(甲基)丙烯酸酯單體單位(c1)與以前述通式(7)表示之脂肪族乙烯基單體單位(c2)所成。乙烯基共聚物(C)可含有1種或2種以上之前述(甲基)丙烯酸酯單體單位(c1)，亦可含有1種或2種以上之前述脂肪族乙烯基單體單位(c2)。前述(甲基)丙烯酸酯單體單位(c1)與前述脂肪族乙烯基單體單位(c2)之合計比例，相對於前述乙烯基共聚物(C)中總單體單位之合計，為90~100莫耳%，較佳為95~100莫耳%，更佳為98~100莫耳%。亦即，前述乙烯基共聚物(C)可於相對於總單體單位為10莫耳%以下之範圍，含有前述(甲基)丙烯酸酯單體單位(c1)及前述脂肪族乙烯基單體單元(c2)以外之單體單位。作為前述(甲基)丙烯酸酯單體單位(c1)及前述脂肪族乙烯基單體單位(c2)以外之單體單位，舉例為例如將(甲基)丙烯酸酯單體與芳香族乙烯基單體聚合後，將源自芳香族乙烯基單體之芳香族雙鍵氫化而得之乙烯基共聚物(C)中源自包含未被氫化之芳香族雙鍵之芳香族乙烯基單體之單體單位。又，以前述通式(6)表示之(甲基)丙烯酸酯單體單位(c1)之比例，相對於前述乙烯基共聚物(C)中之總單體單位之合計為60~80莫耳%，較佳為70~80莫耳%，以前述通式(7)表示之脂肪族乙烯基單體單位(c2)之比例，相對於前述乙烯基共聚物(C)中總單體單位之合計為40~20莫耳%，較佳為30~20莫耳%。相對於乙烯基共聚物(C)中總單體單位之合計的(甲基)丙烯酸酯單體單位(c1)的比例未達60莫耳%時，有與聚碳酸酯系樹脂(A)之密著性或表面硬度降低而不實用之情況。且超過80莫耳%時，有因積層體的吸水而發生翹曲，而不實用之情況。又，相對於乙烯基共聚物(C)中總單體單位之合計的脂肪族乙烯基單體單元(c2)之比例未達20莫耳%時，有玻璃轉移溫度低，耐熱尺寸安定性差而不實用之情況。另一方面，超過40莫耳%時，有耐溶劑性差而不實用之情況。The vinyl copolymer (C) used in the present invention is mainly composed of a (meth)acrylate monomer unit (c1) represented by the aforementioned general formula (6) and an aliphatic vinyl monomer represented by the aforementioned general formula (7) unit (c2). The vinyl copolymer (C) may contain one or more of the aforementioned (meth)acrylate monomer units (c1), or may contain one or more of the aforementioned aliphatic vinyl monomer units (c2) ). The total ratio of the aforementioned (meth)acrylate monomer unit (c1) to the aforementioned aliphatic vinyl monomer unit (c2), relative to the total of the total monomer units in the aforementioned vinyl copolymer (C), is 90~ 100 mol%, preferably 95-100 mol%, more preferably 98-100 mol%. That is, the vinyl copolymer (C) may contain the (meth)acrylate monomer unit (c1) and the aliphatic vinyl monomer in a range of 10 mol % or less with respect to the total monomer units. Monomer units other than unit (c2). As monomer units other than the aforementioned (meth)acrylate monomer unit (c1) and the aforementioned aliphatic vinyl monomer unit (c2), for example, a (meth)acrylate monomer and an aromatic vinyl monomer are exemplified. Monomers derived from aromatic vinyl monomers containing unhydrogenated aromatic double bonds in vinyl copolymer (C) obtained by hydrogenating aromatic double bonds derived from aromatic vinyl monomers after polymerization body unit. In addition, the ratio of the (meth)acrylate monomer unit (c1) represented by the aforementioned general formula (6) is 60 to 80 mol with respect to the total of the total monomer units in the aforementioned vinyl copolymer (C) %, preferably 70-80 mol%, the ratio of the aliphatic vinyl monomer unit (c2) represented by the aforementioned general formula (7) relative to the total monomer unit in the aforementioned vinyl copolymer (C) The total amount is 40 to 20 mol %, preferably 30 to 20 mol %. When the ratio of the (meth)acrylate monomer unit (c1) to the total of the total monomer units in the vinyl copolymer (C) is less than 60 mol%, there is a difference with the polycarbonate resin (A). Adhesion or surface hardness is reduced and is not practical. In addition, when it exceeds 80 mol%, the laminated body may warp due to water absorption, and may not be practical. In addition, when the ratio of the aliphatic vinyl monomer unit (c2) to the total of the total monomer units in the vinyl copolymer (C) is less than 20 mol%, the glass transition temperature is low and the heat-resistant dimensional stability is poor. impractical situation. On the other hand, when it exceeds 40 mol%, solvent resistance may be inferior and it may not be practical.

乙烯基共聚物(C)之製造方法並未特別限制，但適宜使至少1種(甲基)丙烯酸酯單體與至少1種芳香族乙烯基單體聚合後，將源自芳香族乙烯基單體之芳香雙鍵氫化而得者。又，所謂(甲基)丙烯酸表示甲基丙烯酸及/或丙烯酸。作為此時使用之芳香族乙烯基單體，具體舉例為苯乙烯、α-甲基苯乙烯、對-羥基苯乙烯、烷氧基苯乙烯、氯苯乙烯及其衍生物等。該等中較佳為苯乙烯。The production method of the vinyl copolymer (C) is not particularly limited, but it is suitable to polymerize at least one (meth)acrylate monomer and at least one aromatic vinyl monomer, and then polymerize the monomer derived from the aromatic vinyl monomer. It is obtained by hydrogenating the aromatic double bond of the body. In addition, (meth)acrylic acid means methacrylic acid and/or acrylic acid. Specific examples of the aromatic vinyl monomer used at this time include styrene, α-methylstyrene, p-hydroxystyrene, alkoxystyrene, chlorostyrene, and derivatives thereof. Preferred among these is styrene.

(甲基)丙烯酸酯單體與芳香族乙烯基單體之聚合可使用習知方法，例如，可藉由塊狀聚合法或溶液聚合法製造。塊狀聚合法係藉由將包含上述單體、聚合起始劑之單體組成物連續供給至完全混合槽中，於100~180℃連續聚合之方法等進行。上述單體組合物若需要亦可包含鏈轉移劑。The polymerization of the (meth)acrylate monomer and the aromatic vinyl monomer can be produced by a conventional method, for example, by a bulk polymerization method or a solution polymerization method. The block polymerization method is performed by a method of continuously supplying the monomer composition containing the above-mentioned monomers and polymerization initiators to a complete mixing tank, and performing continuous polymerization at 100 to 180° C., for example. The above monomer composition may also contain a chain transfer agent if desired.

聚合起始劑未特別限制，但舉例為第三戊基過氧基-2-乙基己酸酯、第三丁基過氧基-2-乙基己酸酯、過氧化苯甲醯、1,1-二(第三己基過氧基)-3,3,5-三甲基環己烷、1,1-二(第三己基過氧基)環己烷、1,1-二(第三丁基過氧基)環己烷，第三己基丙氧基異丙基單碳酸酯、第三戊基過氧基辛酸酯、第三丁基過氧基異丙基單碳酸酯、二-第三丁基過氧化物之有機過氧化物，2,2'-偶氮雙異丁腈、2,2'-偶氮雙(2-甲基丁腈)、2,2'-偶氮雙(2,4-二甲基戊腈)等之偶氮化合物。該等可單獨使用，亦可組合2種以上使用。The polymerization initiator is not particularly limited, but exemplified by tertiary amyl peroxy-2-ethylhexanoate, tertiary butyl peroxy-2-ethylhexanoate, benzyl peroxide, 1 ,1-bis(3rd hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(3rd hexylperoxy)cyclohexane, 1,1-bis(3rd hexylperoxy)cyclohexane Tributylperoxy) cyclohexane, 3rd hexylpropoxyisopropyl monocarbonate, 3rd amyl peroxyoctanoate, 3rd butylperoxyisopropyl monocarbonate, di- -Organic peroxides of tertiary butyl peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis Azo compounds such as bis(2,4-dimethylvaleronitrile). These may be used alone or in combination of two or more.

鏈轉移劑係根據需要而使用，舉例為例如α-甲基苯乙烯二聚物。A chain transfer agent is used as needed, for example, an α-methylstyrene dimer is exemplified.

作為溶液聚合法所用之溶劑，舉例為例如甲苯、二甲苯、環己烷、甲基環己烷等之烴系溶劑，乙酸乙酯、異丁酸甲酯等之酯系溶劑，丙酮、甲基乙基酮等之酮系溶劑，四氫呋喃、二噁烷等之醚系溶劑，甲醇、異丙醇等之醇系溶劑等。Examples of the solvent used in the solution polymerization method include hydrocarbon-based solvents such as toluene, xylene, cyclohexane, methylcyclohexane, etc., ester-based solvents such as ethyl acetate and methyl isobutyrate, acetone, methyl Ketone-based solvents such as ethyl ketone, ether-based solvents such as tetrahydrofuran and dioxane, and alcohol-based solvents such as methanol and isopropanol.

(甲基)丙烯酸酯單體與芳香族乙烯基單體聚合後用於氫化反應之溶劑可與前述聚合溶劑相同亦可不同。舉例為例如環己烷、甲基環己烷等之烴系溶劑，乙酸乙酯、異丁酸甲酯等之酯系溶劑，丙酮、甲基乙基酮等之酮系溶劑，四氫呋喃、二噁烷等之醚系溶劑，甲醇、異丙醇等之醇系溶劑等。The solvent used for the hydrogenation reaction after the (meth)acrylate monomer and the aromatic vinyl monomer are polymerized may be the same as or different from the aforementioned polymerization solvent. Examples include hydrocarbon-based solvents such as cyclohexane, methylcyclohexane, etc., ester-based solvents such as ethyl acetate, methyl isobutyrate, etc., ketone-based solvents such as acetone, methyl ethyl ketone, etc., tetrahydrofuran, dioxane, etc. Ether-based solvents such as alkane, alcohol-based solvents such as methanol, isopropanol, etc.

如上述之(甲基)丙烯酸酯單體與芳香族乙烯基單體聚合後，藉由使源自芳香族乙烯基單體之芳香族雙鍵氫化，獲得本發明中使用之乙烯基共聚物(C)。氫化方法未特別限制，可使用習知方法。例如於氫壓力3~ 30MPa、反應溫度60~250℃下以批式或連續流通方式進行。藉由使溫度為60℃以上，不會過於耗費反應時間，且藉由為250℃以下，引起分子鏈切斷或酯部位之氫化較少。After the (meth)acrylate monomer and the aromatic vinyl monomer are polymerized as described above, the vinyl copolymer ( C). The hydrogenation method is not particularly limited, and a known method can be used. For example, the hydrogen pressure is 3 to 30 MPa and the reaction temperature is 60 to 250° C. It is carried out in a batch or continuous flow mode. By setting the temperature to be 60°C or higher, the reaction time is not too long, and by setting the temperature to 250°C or lower, molecular chain cleavage and hydrogenation of the ester site are less likely to occur.

作為氫反應所用之觸媒舉例為將例如鎳、鈀、鉑、鈷、釕、銠等之金屬或該等金屬之氧化物或鹽或錯合化合物擔載於碳、氧化鋁、氧化矽、氧化矽・氧化鋁、矽藻土等之多孔質載體之固體觸媒等。Examples of catalysts used in the hydrogen reaction include metals such as nickel, palladium, platinum, cobalt, ruthenium, rhodium, or their oxides, salts, or complex compounds supported on carbon, alumina, silicon oxide, oxide Solid catalysts for porous carriers of silicon, alumina, diatomaceous earth, etc.

乙烯基共聚物(C)較佳係源自芳香族乙烯基單體之芳香族雙鍵的70%以上經氫化者。亦即，芳香族雙鍵之未氫化部位於源自芳香族乙烯基單體之單體單位中之比例較佳為30%以下。超過30%之範圍時，有乙烯基共聚物樹脂(C)之透明性降低之情況。更佳為未達10%之範圍，又更佳為未達5%之範圍。The vinyl copolymer (C) is preferably hydrogenated at least 70% of the aromatic double bonds derived from the aromatic vinyl monomer. That is, the ratio of the unhydrogenated portion of the aromatic double bond in the monomer unit derived from the aromatic vinyl monomer is preferably 30% or less. When it exceeds the range of 30%, the transparency of vinyl copolymer resin (C) may fall. More preferably, it is a range of less than 10%, and still more preferably a range of less than 5%.

乙烯基共聚物(C)之重量平均分子量未特別限制，但基於強度及成形性之觀點，較佳為50,000~ 400,000，更佳為70,000~300,000。上述重量平均分子量係藉由凝膠滲透層析法(GPC)測定之標準聚苯乙烯換算之重量平均分子量。The weight average molecular weight of the vinyl copolymer (C) is not particularly limited, but from the viewpoint of strength and moldability, it is preferably 50,000 to 400,000, more preferably 70,000 to 300,000. The above-mentioned weight average molecular weight is the weight average molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC).

乙烯基共聚物(C)在不損及透明性之範圍內可摻混其他樹脂。舉例為例如甲基丙烯酸甲酯-苯乙烯共聚合樹脂、聚甲基丙烯酸甲酯、聚苯乙烯、聚碳酸酯、環烯烴(共)聚合物樹脂、丙烯腈-苯乙烯共聚合樹脂、丙烯腈-丁二烯-苯乙烯共聚合樹脂、各種彈性體等。The vinyl copolymer (C) may be blended with other resins within the range that does not impair transparency. Examples are, for example, methyl methacrylate-styrene copolymer resin, polymethyl methacrylate, polystyrene, polycarbonate, cycloolefin (co)polymer resin, acrylonitrile-styrene copolymer resin, acrylonitrile -Butadiene-styrene copolymer resins, various elastomers, etc.

前述乙烯基共聚物(C)之玻璃轉移溫度較佳為110~190℃之範圍，更佳為110~160℃之範圍。藉由使玻璃轉移溫度為110℃以上，使本發明提供之積層體在熱環境或濕熱環境中較少產生變形或破裂，且藉由設為190℃以下，使利用鏡面輥或賦形輥之連續熱賦形，或利用鏡面模具或賦形模具之批式熱賦形等之加工性優異。又，本發明之玻璃轉移溫度係使用示差掃描熱量測量裝置，在以10℃/分鐘之升溫速度以中點法算出時之溫度。The glass transition temperature of the said vinyl copolymer (C) becomes like this. Preferably it is the range of 110-190 degreeC, More preferably, it is the range of 110-160 degreeC. By setting the glass transition temperature to be 110°C or higher, the laminated body provided by the present invention is less deformed or broken in a hot environment or a humid heat environment, and by setting the glass transition temperature to 190°C or lower, the mirror surface roller or the shaping roller can be used. Excellent processability for continuous hot forming, or batch hot forming using mirror-surface molds or forming molds. In addition, the glass transition temperature of this invention is the temperature at the time of calculating by the midpoint method at the temperature increase rate of 10 degreeC/min using a differential scanning calorimeter.

＜苯乙烯共聚物(D)＞樹脂(B1)中所含之苯乙烯共聚物(D)之特徵係包含乙烯基芳香族單體單位(d1)、環狀酸酐單體單位(d2)與甲基丙烯酸酯單體單位(d3)，乙烯基芳香族單體單位(d1)、環狀酸酐單體單位(d2)與甲基丙烯酸酯單體單位(d3)之合計比例相對於前述苯乙烯共聚物(D)中的總單體單位之合計為90~100莫耳%，前述乙烯基芳香族單體單位(d1)之比例，相對於前述苯乙烯共聚物(D)中的總單體單位之合計為60~90莫耳%，前述環狀酸酐單體單位(d2)之比例，相對於前述苯乙烯共聚物(D)中總單體單位之合計為10~20莫耳%，前述甲基丙烯酸酯單體單位(d3)之比例，相對於前述苯乙烯共聚物(D)中總單體單位之合計為0~20莫耳%。<Styrene copolymer (D)> The characteristic of the styrene copolymer (D) contained in the resin (B1) is that it contains a vinyl aromatic monomer unit (d1), a cyclic acid anhydride monomer unit (d2) and a methacrylate monomer unit (d3) , the total ratio of vinyl aromatic monomer units (d1), cyclic acid anhydride monomer units (d2) and methacrylate monomer units (d3) relative to the total monomers in the aforementioned styrene copolymer (D) The total of the units is 90 to 100 mol %, and the ratio of the aforementioned vinyl aromatic monomer units (d1) is 60 to 90 mol % relative to the total of the total monomer units in the aforementioned styrene copolymer (D). , the ratio of the aforementioned cyclic acid anhydride monomer units (d2), relative to the total of the total monomer units in the aforementioned styrene copolymer (D), is 10 to 20 mol%, the aforementioned methacrylate monomer units (d3) The ratio is 0 to 20 mol % relative to the total of the total monomer units in the aforementioned styrene copolymer (D).

作為前述苯乙烯共聚物(D)之前述乙烯基芳烴單體單位(d1)並未特別限制，可使用任意已知之芳香族乙烯基單體，但基於取得容易性之觀點，舉例為苯乙烯、α-甲基苯乙烯、鄰-甲基苯乙烯、間-甲基苯乙烯、對-甲基苯乙烯、第三丁基苯乙烯等。該等中，基於相溶性之觀點，特佳為苯乙烯。該等芳香族乙烯基單體亦可混合2種以上。The vinyl aromatic hydrocarbon 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 availability, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, tert-butylstyrene, etc. Among these, from the viewpoint of compatibility, styrene is particularly preferred. Two or more of these aromatic vinyl monomers may be mixed.

作為前述苯乙烯共聚物(D)之前述環狀酸酐單體單位(d2)，舉例為馬來酸、衣康酸、檸康酸、烏頭酸等之酸酐，基於與丙烯酸樹脂之相溶性之觀點，較佳為馬來酸酐。該等不飽和二羧酸酐單體亦可混合2種以上。Examples of the cyclic acid anhydride monomer unit (d2) of the 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 , preferably maleic anhydride. These unsaturated dicarboxylic acid anhydride monomers may mix 2 or more types.

作為前述苯乙烯共聚物(D)之前述甲基丙烯酸酯單體單位(d3)，舉例為丙烯腈、甲基丙烯腈、丙烯酸、甲基丙烯酸、(甲基)丙烯酸酯等。作為(甲基)丙烯酸酯，舉例為例如丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸2-乙基己酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯及甲基丙烯酸2-乙基己酯等。其中，基於與丙烯酸樹脂的相溶性之觀點，較佳為甲基丙烯酸甲酯(MMA)。該等丙烯酸化合物單體亦可混合2種以上。As said methacrylate monomer unit (d3) of the said styrene copolymer (D), acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, (meth)acrylate, etc. are illustrated. Examples of (meth)acrylates include methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, and n-butyl methacrylate. And 2-ethylhexyl methacrylate, etc. Among them, methyl methacrylate (MMA) is preferred from the viewpoint of compatibility with acrylic resins. Two or more of these acrylic compound monomers may be mixed.

本發明所用之前述苯乙烯共聚物(D)中，前述乙烯基芳香族單體單位(d1)、前述環狀酸酐單體單位(d2)與前述甲基丙烯酸酯單體單位(d3)之合計比例，相對於前述苯乙烯共聚物(D)中之總單體單位之合計為90~100莫耳%，較佳為95~100莫耳%，更佳為98~100莫耳%。亦即，前述苯乙烯共聚物(D)於相對於總單體單位之合計為10莫耳%以下之範圍，可包含前述乙烯基芳香族單體單位(d1)、前述環狀酸酐單體單位(d2)與前述甲基丙烯酸酯單體單位(d3)以外之單體單位。作為前述乙烯基芳香族單體單位(d1)、環狀酸酐單體單位(d2)與前述甲基丙烯酸酯單體單位(d3)以外之單體單位，舉例為例如N-取代型馬來醯亞胺單體等。作為N-取代型馬來醯亞胺單體，舉例為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，基於與丙烯酸樹脂之相溶性之觀點，較佳為N-苯基馬來醯亞胺。該等N-取代馬來醯亞胺單體亦可混合2種以上。In the styrene copolymer (D) used in the present invention, the sum of the vinyl aromatic monomer unit (d1), the cyclic acid anhydride monomer unit (d2), and the methacrylate monomer unit (d3) The ratio is 90-100 mol %, preferably 95-100 mol %, more preferably 98-100 mol % relative to the total of the total monomer units in the aforementioned styrene copolymer (D). That is, the above-mentioned styrene copolymer (D) may contain the above-mentioned vinyl aromatic monomer unit (d1) and the above-mentioned cyclic acid anhydride monomer unit in the range of 10 mol % or less with respect to the total of the total monomer units. (d2) A monomer unit other than the aforementioned methacrylate monomer unit (d3). As monomer units other than the aforementioned vinyl aromatic monomer unit (d1), cyclic acid anhydride monomer unit (d2), and the aforementioned methacrylate monomer unit (d3), for example, N-substituted maleic acid is exemplified. imine monomer, etc. Examples of N-substituted maleimide monomers include N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N- Naphthylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide N-arylmaleimide such as lyimide, N-tribromophenylmaleimide, etc. is preferably N-phenylmaleimide from the viewpoint of compatibility with acrylic resins amine. Two or more of these N-substituted maleimide monomers may be mixed.

前述乙烯基芳香族單體單位(d1)之的比例，相對於前述苯乙烯共聚物(D)中總單體單位之合計為60~90莫耳%，較佳為65~90莫耳%，更佳為70~90莫耳%，又更佳為72~88莫耳%，特佳為74~86莫耳%。前述環狀酸酐單體單位(d2)之比例，相對於前述苯乙烯共聚物(D)中總單體單位之合計為10~20莫耳%，較佳為12~18莫耳%，更佳為14~16莫耳%。前述甲基丙烯酸酯單體單位(d3)之比例，相對於前述苯乙烯共聚物(D)中總單體單位之合計為0~20莫耳%，較佳為0~15莫耳%，更佳為0~10莫耳%。前述乙烯基芳香族單體單位(d1)相對於前述苯乙烯共聚物(D)中總單體單位之合計之比例未達60莫耳%時，與乙烯基共聚物(C)之相溶性變差。且超過90莫耳%時，無法賦予充分耐熱性。前述環狀酸酐單體單位(d2)相對於前述苯乙烯共聚物(D)中總單體單位之合計之比例未達10莫耳%時，耐熱性不足。又超過20莫耳%時，與乙烯基共聚物(C)之相溶性變差。The ratio of the aforementioned vinyl aromatic monomer units (d1), relative to the total of the total monomer units in the aforementioned styrene copolymer (D), is 60 to 90 mol %, preferably 65 to 90 mol %, More preferably, it is 70-90 mol %, still more preferably 72-88 mol %, and particularly preferably 74-86 mol %. The ratio of the aforementioned cyclic acid anhydride monomer unit (d2), relative to the total of the total monomer units in the aforementioned styrene copolymer (D), is 10 to 20 mol %, preferably 12 to 18 mol %, more preferably It is 14~16 mol%. The ratio of the aforementioned methacrylate monomer units (d3), relative to the total of the total monomer units in the aforementioned styrene copolymer (D), is 0 to 20 mol %, preferably 0 to 15 mol %, more Preferably, it is 0~10 mol%. When the ratio of the vinyl aromatic monomer unit (d1) to the total of the total monomer units in the styrene copolymer (D) is less than 60 mol%, the compatibility with the vinyl copolymer (C) changes. Difference. And when it exceeds 90 mol%, sufficient heat resistance cannot be provided. When the ratio of the cyclic acid anhydride monomer unit (d2) to the total of the total monomer units in the styrene copolymer (D) is less than 10 mol %, the heat resistance is insufficient. When it exceeds 20 mol% again, the compatibility with the vinyl copolymer (C) will deteriorate.

前述苯乙烯共聚物(D)之製造方法未特別限制，可適當地選擇已知之溶液聚合法、塊狀聚合法等。The manufacturing method of the said styrene copolymer (D) is not specifically limited, A known solution polymerization method, a block polymerization method, etc. can be suitably selected.

前述苯乙烯共聚物(D)之重量平均分子量未特別限制，但基於與乙烯基共聚物(C)之相溶性之觀點，較佳為50,000~400,000，更佳為70,000~300,000。上述重量平均分子量係由凝膠滲透層析法(GPC)測定之標準聚苯乙烯換算之重量平均分子量。The weight average molecular weight of the styrene copolymer (D) is not particularly limited, but from the viewpoint of compatibility with the vinyl copolymer (C), it is preferably 50,000 to 400,000, more preferably 70,000 to 300,000. The above-mentioned weight average molecular weight is the weight average molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC).

前述苯乙烯共聚物(D)之玻璃轉移溫度較佳為100~190℃之範圍，更佳為115~185℃之範圍，特佳為125~185℃之範圍。藉由使玻璃轉移溫度為100℃以上，使本發明提供之積層體在熱環境或濕熱環境中較少產生變形或破裂。且藉由設為190℃以下，使利用鏡面輥或賦形輥之連續熱賦形，或利用鏡面模具或賦形模具之批式熱賦形等之加工性優異。又，本發明之玻璃轉移溫度係使用示差掃描熱量測量裝置，在以10℃/分鐘之升溫速度以中點法算出時之溫度。The glass transition temperature of the aforementioned styrene copolymer (D) is preferably in the range of 100 to 190°C, more preferably in the range of 115 to 185°C, and particularly preferably in the range of 125 to 185°C. By setting the glass transition temperature to 100° C. or higher, the laminate provided by the present invention is less deformed or cracked in a hot environment or a humid heat environment. And by setting it to 190 degrees C or less, it is excellent in workability, such as continuous heat forming by a mirror roll or a forming roll, or batch hot forming by a mirror die or a forming die. In addition, the glass transition temperature of this invention is the temperature at the time of calculating by the midpoint method at the temperature increase rate of 10 degreeC/min using a differential scanning calorimeter.

前述苯乙烯共聚物(D)係包含乙烯基芳香族單體單位(d1)與環狀酸酐單體單位(d2)之二元共聚物，或為包含乙烯基芳香族單體單位(d1)、環狀酸酐單體單位(d2)與甲基丙烯酸酯單體單位(d3)之三元共聚物，但藉由與乙烯基共聚物(C)組合使用，可獲得比僅使用苯乙烯共聚物(D)之情況更高之硬度，比僅使用乙烯基共聚物(C)之情況具有高溫高濕下之形狀安定性的樹脂積層體。The aforementioned styrene copolymer (D) is a binary copolymer comprising a vinyl aromatic monomer unit (d1) and a cyclic acid anhydride monomer unit (d2), or a vinyl aromatic monomer unit (d1), A terpolymer of cyclic acid anhydride monomer unit (d2) and methacrylate monomer unit (d3), but by using in combination with vinyl copolymer (C), it is possible to obtain a In the case of D), the hardness is higher, and the resin laminate has shape stability under high temperature and high humidity than the case of using only the vinyl copolymer (C).

本發明中，前述乙烯基共聚物(C)與前述苯乙烯共聚物(D)之質量比，以乙烯基共聚物(C)與苯乙烯共聚物(D)之含量合計100質量份為基準，相對於前述乙烯基共聚物(C)為5~95質量份，前述苯乙烯共聚物(D)較佳為95~5質量份。更佳相對於前述乙烯基共聚物(C)為85~15質量份，前述苯乙烯共聚物(D)為85~15質量份，又更佳相對於前述乙烯基共聚物(C)為25~75質量份，前述苯乙烯共聚物(D)為75~25質量份，特佳相對於前述乙烯基共聚物(C)為40~60，前述苯乙烯共聚物(D)為60~40質量份。藉由設為此質量比內，可成為維持透明性之同時，即使暴露於高溫高濕下之耐翹曲變形性、耐熱性亦優異、折射率高且外觀良好之優異樹脂(B1)。In the present invention, the mass ratio of the vinyl copolymer (C) to the styrene copolymer (D) is based on the total content of the vinyl copolymer (C) and the styrene copolymer (D) of 100 parts by mass, It is preferable that the said styrene copolymer (D) is 95-5 mass parts with respect to the said vinyl copolymer (C) of 5-95 mass parts. More preferably, it is 85 to 15 parts by mass relative to the aforementioned vinyl copolymer (C), 85 to 15 parts by mass relative to the aforementioned styrene copolymer (D), and still more preferably 25 to 15 parts by mass relative to the aforementioned vinyl copolymer (C). 75 parts by mass, the aforementioned styrene copolymer (D) is 75 to 25 parts by mass, particularly preferably 40 to 60 parts by mass relative to the aforementioned vinyl copolymer (C), and the aforementioned styrene copolymer (D) is 60 to 40 parts by mass . By setting it within this mass ratio, even if it is exposed to high temperature and high humidity, it becomes excellent resin (B1) which is excellent in warpage deformation resistance and heat resistance, high refractive index, and good appearance, while maintaining transparency.

將前述乙烯基共聚物(C)與前述苯乙烯共聚物(D)予以合金化之溫度較佳為230~320℃之範圍，更佳為240~300℃之範圍。合金溫度未達230℃時，相溶性變差，有濁度變高之傾向。且超過320℃時，乙烯基共聚物(C)或/及苯乙烯共聚物(D)會熱分解。The temperature at which the aforementioned vinyl copolymer (C) and the aforementioned styrene copolymer (D) are alloyed is preferably in the range of 230 to 320°C, more preferably in the range of 240 to 300°C. When the alloy temperature is lower than 230°C, the compatibility becomes poor and the turbidity tends to increase. And when it exceeds 320 degreeC, a vinyl copolymer (C) or/and a styrene copolymer (D) will thermally decompose.

本發明中，樹脂(B1)之製造方法並未特別限制，可應用將必要之成分以例如滾筒或亨舍爾混合機、超級混合機等之混合機預先混合，然後，以班伯里混合機、輥、單螺旋擠出機(brabender)、單軸擠出機、雙軸擠出機、加壓捏合機等機器熔融混練之習知方法。樹脂(B1)之玻璃轉移溫度比較高為特徵之一，較佳為110~185℃之範圍，更佳為115~160℃之範圍，特佳為120~ 140℃之範圍。由於樹脂(B1)之玻璃轉移溫度比較高，與前述聚碳酸酯系樹脂(A)之玻璃轉移溫度的差較小，故有熱加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，於包含樹脂(B1)之層發生外觀缺陷之問題亦少之優點。聚碳酸酯系樹脂(A)之玻璃轉移溫度與樹脂(B1)之玻璃轉移溫度之差較佳為0~35℃之範圍，更佳為0~25℃之範圍，特佳為0~20℃之範圍。In the present invention, the method for producing the resin (B1) is not particularly limited, and the necessary components can be pre-mixed with a mixer such as a roller, a Henschel mixer, a super mixer, etc., and then a Banbury mixer can be used. , roll, single screw extruder (brabender), single screw extruder, twin screw extruder, pressure kneader and other machines are known methods of melt mixing. One of the characteristics is that the glass transition temperature of the resin (B1) is relatively high, preferably in the range of 110 to 185°C, more preferably in the range of 115 to 160°C, and particularly preferably in the range of 120 to 140°C. Since the glass transition temperature of the resin (B1) is relatively high and the difference from the glass transition temperature of the polycarbonate resin (A) is relatively small, even if it is close to the polycarbonate resin ( The glass transition temperature of A) has the advantage that there is less problem of appearance defects in the layer containing the resin (B1). The difference between the glass transition temperature of the polycarbonate resin (A) and the glass transition temperature of the resin (B1) is preferably in the range of 0 to 35°C, more preferably in the range of 0 to 25°C, and particularly preferably in the range of 0 to 20°C range.

＜樹脂(B2)＞樹脂(B2)包括前述乙烯基共聚物(C)，在不損及透明性之範圍內可摻合其他樹脂。前述乙烯基共聚物(C)之質量比，以樹脂(B2)之合計100質量份為基準，前述乙烯基共聚物(C)較佳為30~100質量份。更佳前述乙烯基共聚物(C)為40~100質量份，更佳前述乙烯基共聚物(C)為90~100質量份，特佳前述乙烯基共聚物(C)為98~100質量份。藉由設為此質量比內，可成為維持透明性之同時，即使暴露於高溫高濕下之耐翹曲變形性、耐熱性亦優異且外觀良好之優異樹脂(B2)。<Resin (B2)> The resin (B2) includes the aforementioned vinyl copolymer (C), and other resins may be blended within a range that does not impair transparency. The mass ratio of the vinyl copolymer (C) is preferably 30 to 100 parts by mass based on 100 parts by mass of the resin (B2) in total. More preferably, the aforementioned vinyl copolymer (C) is 40 to 100 parts by mass, more preferably, the aforementioned vinyl copolymer (C) is 90 to 100 mass parts, and particularly preferably, the aforementioned vinyl copolymer (C) is 98 to 100 mass parts . By setting it within this mass ratio, even if it is exposed to high temperature and high humidity, it can become an excellent resin (B2) which is excellent in warpage deformation resistance and heat resistance, and has a good appearance while maintaining transparency.

＜樹脂(B3)＞樹脂(B3)包含甲基丙烯酸樹脂(E)與苯乙烯共聚物(F)。以下針對各構成要素加以說明。<Resin (B3)> Resin (B3) contains methacrylic resin (E) and styrene copolymer (F). Each of the constituent elements will be described below.

＜甲基丙烯酸樹脂(E)＞樹脂(B3)所含之甲基丙烯酸樹脂(E)舉例為源自甲基丙烯酸酯單體之構造單位。<Methacrylic resin (E)> The methacrylic resin (E) contained in the resin (B3) is, for example, a structural unit derived from a methacrylate monomer.

作為前述甲基丙烯酸樹脂(E)之甲基丙烯酸酯單體，可舉例為甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丙酯、甲基丙烯酸異丙酯、甲基丙烯酸正丁酯、甲基丙烯酸異丁酯、甲基丙烯酸第三丁酯、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[5.2.1.0^2,6 ]癸-8-基酯等之甲基丙烯酸環烷酯；甲基丙烯酸苯基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，基於取得性之觀點，較佳為甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丙酯、甲基丙烯酸異丙酯、甲基丙烯酸正丁酯、甲基丙烯酸異丁酯及甲基丙烯酸第三丁酯，最佳為甲基丙烯酸甲酯。Examples of the methacrylate monomer of the methacrylic resin (E) include 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 Alkyl methacrylate, decyl methacrylate, dodecyl methacrylate, etc.; 1-methylcyclopentyl methacrylate, cyclohexyl methacrylate, cycloheptyl methacrylate, methyl methacrylate Cycloalkyl methacrylate such as cyclooctyl acrylate, tricyclo[5.2.1.0 ^2,6 ]dec-8-yl methacrylate, etc.; aryl methacrylate such as phenyl methacrylate; benzyl methacrylate Aralkyl methacrylates such as esters, etc., are preferably methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-methacrylate, etc. from the viewpoint of availability. Butyl methacrylate, isobutyl methacrylate and tert-butyl methacrylate, the most preferred being methyl methacrylate.

且基於耐熱性之觀點，上述甲基丙烯酸樹脂(E)較佳含有80莫耳%以上之源自甲基丙烯酸酯單體之構造單位，更佳含有90莫耳%以上，又更佳含有95莫耳%以上。甲基丙烯酸樹脂(E)含有80莫耳%以上之源自甲基丙烯酸酯單體之構造單位時，與苯乙烯共聚物(F)之相溶性變良好而較佳。另一方面，源自甲基丙烯酸酯單體之結構單位若未達80莫耳%，則與苯乙烯共聚物(F)不相溶而變混濁之情況。And from the viewpoint of heat resistance, the above-mentioned methacrylic resin (E) preferably contains 80 mol % or more of structural units derived from methacrylate monomers, more preferably 90 mol % or more, and more preferably 95 mol % or more. More than mol%. When the methacrylic resin (E) contains 80 mol % or more of the structural unit derived from the methacrylate monomer, the compatibility with the styrene copolymer (F) becomes good, which is preferable. On the other hand, if the structural unit derived from the methacrylate monomer is less than 80 mol %, it becomes incompatible with the styrene copolymer (F) and becomes cloudy.

又，甲基丙烯酸樹脂(E)亦可包含源自甲基丙烯酸酯以外之其他單體的結構單位。作為該其他單體，舉例為丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸異丙酯、丙烯酸正丁酯、丙烯酸異丁酯、丙烯酸第三丁酯、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、丙烯酸硬脂酯、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、丙烯酸縮水甘油酯、丙烯酸烯丙酯、丙烯酸苯酯、丙烯酸甲苯酯、丙烯酸苄酯、丙烯酸異冰片酯、丙烯酸3-二甲胺基乙酯等之丙烯酸酯，基於取得性之觀點，較佳為丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸異丙酯、丙烯酸正丁酯、丙烯酸異丁酯、丙烯酸第三丁酯等之丙烯酸酯，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(E)中源自其他單體之結構單位之含量，較佳合計為20莫耳%以下，更佳為10莫耳%以下，又更佳為5莫耳%以下。Moreover, the methacrylic resin (E) may contain the structural unit derived from the other monomer other than methacrylate. Examples of the other monomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hexyl acrylate, and 2-ethyl acrylate. Hexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, cyclohexyl acrylate, acrylic acid 2-Methoxyethyl acrylate, 3-methoxybutyl acrylate, trifluoromethyl acrylate, trifluoroethyl acrylate, pentafluoroethyl acrylate, glycidyl acrylate, allyl acrylate, phenyl acrylate, acrylic acid Acrylates such as cresyl, benzyl acrylate, isobornyl acrylate, 3-dimethylaminoethyl acrylate, etc. are preferably methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, etc. from the viewpoint of availability. Acrylates such as propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, etc. are more preferably methyl acrylate and ethyl acrylate, and the most preferred is methyl acrylate. The content of the structural units derived from other monomers in the methacrylic resin (E) is preferably 20 mol % or less in total, more preferably 10 mol % or less, and still more preferably 5 mol % or less.

甲基丙烯酸樹脂(E)之表示三聯體之對排度(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。該結構含量之下限為50莫耳%以上時成為耐熱性優異。The lower limit of the syndiotacticity (rr) representing the triplet of the methacrylic resin (E) is preferably 50 mol % or more, more preferably 51 mol % or more, and more preferably 52 mol % or more . When the lower limit of the structure content is 50 mol % or more, it is excellent in heat resistance.

此處，表示三聯體之對排度(rr)(以下有時簡稱「對排度(rr)」)係連續之三個結構單位之鏈(3聯體，三元組)所具有之兩個鏈(二聯體，二元組)均為外消旋(racemo)(表示為rr)之比例。又，聚合物分子中結構單位的鏈(2聯體，二元組)之立體配置相同者，稱為內消旋(meso)，反之稱為外消旋(racemo)，分別稱為m、r。甲基丙烯酸樹脂(E)之對排度(rr)(%)於氫化氯仿中，以30℃測定¹ H-NMR光譜，測量自該光譜將四甲基矽烷(TMS)設為0ppm時之0.6～0.95ppm區域之面積(X)與0.6～1.35 ppm區域之面積(Y)，以式：(X/Y)×100算出。Here, it means that the opposite degree (rr) of the triplet (hereinafter sometimes referred to as "the opposite degree (rr)") is two of the chain (triple, triplet) of three consecutive structural units. Chains (doublets, dyads) are all ratios of racemo (denoted rr). In addition, those with the same three-dimensional configuration of the chains (two-links, two-tuple) of structural units in the polymer molecule are called meso, otherwise they are called racemo, and they are called m, r respectively. . The ¹ H-NMR spectrum of the methacrylic resin (E) was measured in hydrogenated chloroform at 30°C, and measured from the spectrum at 0.6 when tetramethylsilane (TMS) was set to 0 ppm The area (X) of the ~0.95 ppm region and the area (Y) of the 0.6 to 1.35 ppm region were calculated by the formula: (X/Y)×100.

前述甲基丙烯酸樹脂(E)之重量平均分子量係由與苯乙烯共聚物(F)之混合(分散)容易性及樹脂(B3)之製造容易性而決定。亦即，由於甲基丙烯酸樹脂(E)之重量平均分子量過大時，與苯乙烯共聚物(F)之熔融黏度差變得過大，故兩者之混合(分散)變差，使樹脂(B3)之透明性惡化，或可能引起無法繼續穩定熔融混練之缺點。相反，甲基丙烯酸樹脂(E)之重量平均分子量過小時，由於樹脂(B3)之強度降低，故可能發生樹脂積層體之耐衝擊性降低之問題。甲基丙烯酸樹脂(E)之重量平均分子量較佳為50,000~700,000，更佳為60,000~500,000。又更佳為70,000~200,000之範圍。上述重量平均分子量係由凝膠滲透層析法(GPC)測定之標準聚苯乙烯換算之重量平均分子量。The weight average molecular weight of the aforementioned methacrylic resin (E) is determined by the ease of mixing (dispersion) with the styrene copolymer (F) and the ease of manufacture of the resin (B3). That is, when the weight average molecular weight of the methacrylic resin (E) is too large, the difference in melt viscosity with the styrene copolymer (F) becomes too large, so the mixing (dispersion) of the two becomes poor, and the resin (B3) The transparency deteriorates, or it may cause the disadvantage that it cannot continue to be melt-kneaded stably. On the contrary, when the weight average molecular weight of the methacrylic resin (E) is too small, the strength of the resin (B3) is lowered, so that the impact resistance of the resin laminate may be lowered. The weight average molecular weight of the methacrylic resin (E) is preferably 50,000 to 700,000, more preferably 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(E)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。藉由使該玻璃轉移溫度為100℃以上，本發明提供之積層體於熱環境下發生變形或破裂較少。又，本說明書中甲基丙烯酸樹脂(E)之玻璃轉移係使用示差掃描熱量測定裝置，以升溫速度10℃/分鐘測定之中點法算出時之溫度。The glass transition temperature of the aforementioned methacrylic resin (E) is preferably 100°C or higher, more preferably 105°C or higher, and still more preferably 108°C or higher. By making the glass transition temperature 100° C. or higher, the laminate provided by the present invention is less deformed or cracked under a thermal environment. In addition, the glass transition system of the methacrylic resin (E) in this specification measures the temperature at the time of calculation using a differential scanning calorimeter at a temperature increase rate of 10° C./min by the midpoint method.

前述甲基丙烯酸樹脂(E)之熔融流速較佳為1~10g/10分鐘之範圍。熔融流速之下限值較佳為1.2g/10分鐘以上，更佳為1.5g/10分鐘以上。且該熔融流速之上限值較佳為7.0g/10分鐘以下，更佳為4.0g/10分鐘以下。熔融流速於1~10g/10分鐘之範圍內時，加熱熔融成形之安定性良好。又本說明書中甲基丙烯酸樹脂(E)之熔融流速係使用熔融分度器，於溫度230℃、3.8 kg荷重下測定之值。The melt flow rate of the aforementioned methacrylic resin (E) is preferably in the range of 1 to 10 g/10 minutes. The lower limit value of the melt flow rate is preferably 1.2 g/10 minutes or more, more preferably 1.5 g/10 minutes or more. And the upper limit of the melt flow rate is preferably 7.0 g/10 minutes or less, more preferably 4.0 g/10 minutes or less. When the melting 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 (E) in this specification is a value measured at a temperature of 230° C. and a load of 3.8 kg using a melt indexer.

＜苯乙烯共聚物(F)＞樹脂(B3)中所含之(F)苯乙烯共聚物之特徵係包含乙烯基芳香族單體單位(f1)與環狀酸酐單體單位(f2)，乙烯基芳香族單體單位(f1)與環狀酸酐單體單位(f2)之合計比例相對於前述苯乙烯共聚物(F)中總單體單位之合計為92~100質量%。<Styrene Copolymer (F)> The characteristics of the (F) styrene copolymer contained in the resin (B3) include vinyl aromatic monomer units (f1) and cyclic acid anhydride monomer units (f2), vinyl aromatic monomer units (f1) The total ratio with the cyclic acid anhydride monomer unit (f2) is 92 to 100 mass % with respect to the total of the total monomer units in the aforementioned styrene copolymer (F).

作為前述苯乙烯共聚物(F)之前述乙烯基芳香族單體單位(f1)並未特別限制，可使用任何習知之芳香族乙烯基單體，但基於取得容易性之觀點，舉例為苯乙烯、α-甲基苯乙烯、鄰-甲基苯乙烯、間-甲基苯乙烯、對-甲基苯乙烯、第三丁基苯乙烯等。該等中，基於相溶性之觀點，特佳為苯乙烯。該等芳香族乙烯基單體亦可混合2種以上。The vinyl aromatic monomer unit (f1) of the styrene copolymer (F) is not particularly limited, and any known aromatic vinyl monomer can be used, but from the viewpoint of availability, styrene is exemplified , α-methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, tertiary butyl styrene, etc. Among these, from the viewpoint of compatibility, styrene is particularly preferred. Two or more of these aromatic vinyl monomers may be mixed.

作為前述苯乙烯共聚物(F)之前述環狀酸酐單體單位(f2)，舉例為馬來酸、衣康酸、檸康酸、烏頭酸等之酸酐，基於與甲基丙烯酸樹脂之相溶性之觀點，較佳為馬來酸酐。該等不飽和二羧酸酐單體亦可混合2種以上。Examples of the cyclic acid anhydride monomer unit (f2) of the styrene copolymer (F) include acid anhydrides such as maleic acid, itaconic acid, citraconic acid, aconitic acid, etc., based on compatibility with methacrylic resins. From the viewpoint of maleic anhydride, maleic anhydride is preferred. These unsaturated dicarboxylic acid anhydride monomers may mix 2 or more types.

本發明所用之前述苯乙烯共聚物(F)中，前述乙烯基芳香族單體單位(f1)與前述環狀酸酐單體單位(f2)之合計比例，相對於前述苯乙烯共聚物(F)中總單體單位之合計為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(F)，於相對於總單體單位之合計為8質量%以下之範圍，可含有前述乙烯基芳香族單體單位(f1)與前述環狀酸酐單體單位(f2)以外之單體單位。作為前述乙烯基芳香族單體單位(f1)與前述環狀酸酐單體單位(f2)以外之單體單位，舉例為例如甲基丙烯酸酯單體單位、N-取代型馬來醯亞胺單體等。作為苯乙烯共聚物(F)中之甲基丙烯酸酯單體單位，舉例為甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丙酯、甲基丙烯酸異丙酯、甲基丙烯酸正丁酯、甲基丙烯酸異丁酯、甲基丙烯酸第三丁酯、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[5.2.1.0^2,6 ]癸-8-基酯等之甲基丙烯酸環烷酯；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；基於與甲基丙烯酸樹脂之相溶性之觀點，較佳為甲基丙烯酸甲酯。該等甲基丙烯酸酯單體亦可混合2種以上。作為苯乙烯共聚物(F)中之N-取代型馬來醯亞胺單體，舉例為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，基於與甲基丙烯酸樹脂之相溶性之觀點，較佳為N-苯基馬來醯亞胺。該等N-取代型馬來醯亞胺單體亦可混合2種以上。In the styrene copolymer (F) used in the present invention, the total ratio of the vinyl aromatic monomer unit (f1) and the cyclic acid anhydride monomer unit (f2) is relative to the styrene copolymer (F) The total of the total monomer units is 92 to 100 mass %, preferably 95 to 100 mass %, more preferably 98 to 100 mass %. That is, the above-mentioned styrene copolymer (F) may contain the above-mentioned vinyl aromatic monomer unit (f1) and the above-mentioned cyclic acid anhydride monomer unit in the range of 8 mass % or less with respect to the total of the total monomer units. Monomer units other than (f2). Examples of monomer units other than the aforementioned vinyl aromatic monomer unit (f1) and the aforementioned cyclic acid anhydride monomer unit (f2) include, for example, methacrylate monomer units, N-substituted maleimide monomer units body etc. As the methacrylate monomer unit in the styrene copolymer (F), there are exemplified methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-methacrylate Butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate Alkyl methacrylate, decyl methacrylate, dodecyl methacrylate, etc.; 1-methylcyclopentyl methacrylate, cyclohexyl methacrylate, cycloheptyl methacrylate, methyl methacrylate Cycloalkyl methacrylate such as cyclooctyl acrylate, tricyclo[5.2.1.0 ^2,6 ]dec-8-yl methacrylate, etc.; aryl methacrylate such as phenyl methacrylate; benzyl methacrylate Aralkyl methacrylate etc. of ester etc. From the viewpoint of compatibility with methacrylic resin, methyl methacrylate is preferable. Two or more of these methacrylate monomers may be mixed. As the N-substituted maleimide monomer in the styrene copolymer (F), for example, N-phenylmaleimide, N-chlorophenylmaleimide, N-methylbenzene ylmaleimide, N-naphthylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide Amines, N-nitrophenylmaleimide, N-arylmaleimide such as N-tribromophenylmaleimide, etc., from the viewpoint of compatibility with methacrylic resins, Preferred is N-phenylmaleimide. Two or more of these N-substituted maleimide monomers may be mixed.

前述乙烯基芳香族單體單位(f1)之比例，相對於前述苯乙烯共聚物(F)中總單體單位之合計為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%。前述環狀酸酐單體單位(f2)之比例，相對於前述苯乙烯共聚物(F)中總單體單位之合計為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%。前述乙烯基芳香族單體單位(f1)相對於前述苯乙烯共聚物(F)中總單體單位之合計的比例為68~84質量%以外時，與甲基丙烯酸樹脂(E)之相溶性變差。且，前述環狀酸酐單體單位(f2)相對於前述苯乙烯共聚物(F)中總單體單位之合計的比例為16~32質量%以外時，與甲基丙烯酸樹脂(E)之相溶性變差。The ratio of the vinyl aromatic monomer unit (f1) to the total of the total monomer units in the styrene copolymer (F) is 68 to 84 mass %, preferably 70 to 82 mass %, more preferably 74-80 mass %, More preferably, it is 76-79 mass %. The ratio of the aforementioned cyclic acid anhydride monomer unit (f2) relative to the total of the total monomer units in the aforementioned styrene copolymer (F) is 16 to 32 mass %, preferably 18 to 30 mass %, more preferably 20 mass % ~26 mass %, more preferably 21 to 24 mass %. Compatibility with methacrylic resin (E) when the ratio of the vinyl aromatic monomer unit (f1) to the total of the total monomer units in the styrene copolymer (F) is other than 68 to 84 mass % worse. Moreover, when the ratio of the aforementioned cyclic acid anhydride monomer unit (f2) to the total of the total monomer units in the aforementioned styrene copolymer (F) is other than 16 to 32 mass %, the phase with the methacrylic resin (E) Solubility becomes poor.

前述苯乙烯共聚物(F)之重量平均分子量未特別限制，但基於與甲基丙烯酸樹脂(E)之相溶性之觀點，較佳為30,000~400,000，更佳為40,000~300,000，特佳為50,000~200,000。重量平均分子量係由凝膠滲透層析法(GPC)測量之標準聚苯乙烯換算之重量平均分子量。The weight average molecular weight of the aforementioned styrene copolymer (F) is not particularly limited, but from the viewpoint of compatibility with the methacrylic resin (E), it is preferably 30,000-400,000, more preferably 40,000-300,000, particularly preferably 50,000 ~200,000. The 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(F)之玻璃轉移溫度較佳為120~190℃之範圍，更佳為130~170℃之範圍。藉由玻璃轉移溫度為120℃以上，本發明提供之積層體在熱環境中發生變形或破裂較少。且，藉由為為190℃以下，利用鏡面輥或賦形輥之連續熱賦形或利用鏡面模具或賦形模具之批式熱賦形等之加工性優異。又，本說明書中苯乙烯共聚物(F)之玻璃轉移溫度係使用示差掃描熱量測定裝置，以升溫速度10℃/分鐘之中點法算出時之溫度。The glass transition temperature of the said styrene copolymer (F) becomes like this. Preferably it is the range of 120-190 degreeC, More preferably, it is the range of 130-170 degreeC. Since the glass transition temperature is 120° C. or higher, the laminate provided by the present invention is less deformed or cracked in a thermal environment. And since it is 190 degrees C or less, it is excellent in workability, such as continuous heat forming by a mirror roll or a forming roll, or batch hot forming by a mirror die or a forming die. In addition, in this specification, the glass transition temperature of a styrene copolymer (F) is the temperature when a differential scanning calorimeter is used, and it calculates by the midpoint method with a temperature increase rate of 10 degreeC/min.

前述苯乙烯共聚物(F)之熔融流速較佳為1~10g/10分鐘之範圍，更佳為4~9g/10分鐘之範圍，又更佳為6~8g/10分鐘。熔融流速為1~10g/10分鐘之範圍時，加熱熔融成形之安定性良好。又本說明書中苯乙烯共聚物(F)之熔融流速係使用熔融分度器，以溫度230℃、3.8kg荷重下測定之值。The melt flow rate of the aforementioned styrene copolymer (F) is preferably in the range of 1 to 10 g/10 minutes, more preferably in the range of 4 to 9 g/10 minutes, and still more preferably in the range of 6 to 8 g/10 minutes. When the melt flow rate is in the range of 1~10g/10min, the stability of heating and melting molding is good. In addition, in this specification, the melt flow rate of the styrene copolymer (F) is a value measured at a temperature of 230° C. and a load of 3.8 kg using a melt indexer.

前述苯乙烯共聚物(F)之製造方法並未特別限制，可適當選擇習知之溶液聚合法、塊狀聚合法、懸浮聚合法等。The manufacturing method of the said styrene copolymer (F) is not specifically limited, A conventional solution polymerization method, a block polymerization method, a suspension polymerization method, etc. can be suitably selected.

前述苯乙烯共聚物(F)為包含乙烯基芳香族單體單位(f1)與環狀酸酐單體單位(f2)之二元共聚物或多元共聚物，但藉由組合使用甲基丙烯酸樹脂(E)，而獲得比僅使用苯乙烯共聚物(F)時更高之硬度，與僅使用甲基丙烯酸樹脂(E)時之熱成形性更優異之樹脂積層體。The aforementioned styrene copolymer (F) is a binary copolymer or a multicomponent copolymer comprising a vinyl aromatic monomer unit (f1) and a cyclic acid anhydride monomer unit (f2), but by combining a methacrylic resin ( E) to obtain a resin laminate having higher hardness than when only the styrene copolymer (F) is used, and more excellent thermoformability when only the methacrylic resin (E) is used.

本發明中，前述甲基丙烯酸樹脂(E)與前述苯乙烯共聚物(F)之質量比，以甲基丙烯酸樹脂(E)與苯乙烯共聚物(F)之含量合計100質量份為基準，較佳前述甲基丙烯酸樹脂(E)為5~70質量份，相對地前述苯乙烯共聚物(F)為95~30質量份。更佳前述甲基丙烯酸樹脂(E)為10~65質量份，相對地所述苯乙烯共聚物(F)為90~35質量份，更佳前述甲基丙烯酸樹脂(E)為15~60質量份，相對地前述苯乙烯共聚物(F)為85~40質量份，特佳前述甲基丙烯酸樹脂(E)為20~55質量份，相對地前述苯乙烯共聚物(F)為80~45質量份。藉由設為該質量比內，成為保持透明性的同時，耐熱性優異、折射率高且外觀良好的樹脂(B3)。In the present invention, the mass ratio of the aforementioned methacrylic resin (E) to the aforementioned styrene copolymer (F) is based on 100 parts by mass of the total content of the methacrylic resin (E) and the styrene copolymer (F), Preferably, the amount of the methacrylic resin (E) is 5 to 70 parts by mass, and the amount of the styrene copolymer (F) is relatively 95 to 30 parts by mass. More preferably, the amount of the methacrylic resin (E) is 10 to 65 parts by mass, and the amount of the styrene copolymer (F) is 90 to 35 parts by mass, and the amount of the methacrylic resin (E) is more preferably 15 to 60 parts by mass. parts, relative to the aforementioned styrene copolymer (F) is 85 to 40 parts by mass, particularly preferably the aforementioned methacrylic resin (E) is 20 to 55 mass parts, relative to the aforementioned styrene copolymer (F) is 80 to 45 parts by mass parts by mass. By setting it within this mass ratio, it becomes a resin (B3) which is excellent in heat resistance, has a high refractive index, and has a good appearance while maintaining transparency.

樹脂(B3)之玻璃轉移溫度較佳為120~165℃之範圍，更佳為120~ 155℃之範圍。藉由玻璃轉移溫度為120℃以上，使本發明提供之積層體在熱環境中發生變形或破裂較少。且，藉由為165℃以下，利用鏡面輥或賦形輥之連續熱賦形或利用鏡面模具或賦形模具之批式熱賦形等之加工性優異。又，本說明書中樹脂(B3)之玻璃轉移溫度係使用示差掃描熱量測定裝置，以升溫速度10℃/分鐘之中點法算出時之溫度。The glass transition temperature of the resin (B3) is preferably in the range of 120 to 165°C, more preferably in the range of 120 to 155°C. Since the glass transition temperature is 120° C. or higher, the laminated body provided by the present invention is less deformed or cracked in a thermal environment. In addition, by being 165° C. or lower, it is excellent in workability such as continuous hot forming by a mirror roll or a forming roll, or batch hot forming by a mirror die or a forming die. In addition, the glass transition temperature of resin (B3) in this specification is the temperature at the time of calculating by the midpoint method of the temperature increase rate of 10 degreeC/min using a differential scanning calorimeter.

樹脂(B3)之熔融流速較佳為1~10g/10分鐘之範圍，更佳為1.5~7g/10分鐘之範圍，又更佳2~5g/10分鐘。熔融流速為1~10g/10分鐘之範圍時，加熱熔融成形之安定性良好。又本說明書中樹脂(B3)之熔融流速係使用熔融分度器，於溫為230℃、3.8kg荷重下測定之值。The melt flow rate of the resin (B3) 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 heating and melting molding is good. In addition, the melt flow rate of resin (B3) in this specification is a value measured at a temperature of 230° C. and a load of 3.8 kg using a melt indexer.

本發明中，樹脂(B3)之製造方法並未特別限制，可應用將必要之成分以例如滾筒或亨舍爾混合機、超級混合機等之混合機預先混合，然後，以班伯里混合機、輥、單螺旋擠出機(brabender)、單軸擠出機、雙軸擠出機、加壓捏合機等機器熔融混練之習知方法。In the present invention, the method for producing the resin (B3) is not particularly limited, and the necessary components can be pre-mixed with a mixer such as a roller, a Henschel mixer, a super mixer, etc., and then a Banbury mixer can be used. , roll, single screw extruder (brabender), single screw extruder, twin screw extruder, pressure kneader and other machines are known methods of melt mixing.

由於樹脂(B3)之玻璃轉移溫度比較高，與前述聚碳酸酯系樹脂(A)之玻璃轉移溫度的差較小，故有熱加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，於包含樹脂(B3)之層發生外觀缺陷之問題亦少之優點。聚碳酸酯系樹脂(A)之玻璃轉移溫度與樹脂(B3)之玻璃轉移溫度之差較佳為0~30℃之範圍，更佳為0~20℃之範圍。Since the glass transition temperature of the resin (B3) is relatively high and the difference from the glass transition temperature of the polycarbonate resin (A) is relatively small, even if it is close to the polycarbonate resin ( The glass transition temperature of A) has the advantage that there is less problem of appearance defects in the layer containing the resin (B3). The difference between the glass transition temperature of the polycarbonate resin (A) and the glass transition temperature of the resin (B3) is preferably in the range of 0 to 30°C, more preferably in the range of 0 to 20°C.

＜樹脂(B4)＞樹脂(B4)係包含以下述通式(8)表示之結構單位(G)與任意之以下述通式(9)表示之結構單位(H)之共聚物。樹脂(B4)亦可包含結構單位(H)亦可不含，但較佳包含。

<Resin (B4)> Resin (B4) is a copolymer containing a structural unit (G) represented by the following general formula (8) and an arbitrary structural unit (H) represented by the following general formula (9). The resin (B4) may contain the structural unit (H) or may not contain it, but it is preferable to contain it.

結構單位(G)於樹脂(B4)之總結構單位中之比例較佳為50~100莫耳%，更佳為60~100莫耳%，特佳為70~100莫耳%。結構單位(H)於樹脂(B4)之總結構單位中之比例較佳為0~50莫耳%，更佳為0~40莫耳%，特佳為0~30莫耳%。The ratio of the structural unit (G) to the total structural unit of the resin (B4) is preferably 50-100 mol %, more preferably 60-100 mol %, and particularly preferably 70-100 mol %. The ratio of the structural unit (H) to the total structural unit of the resin (B4) is preferably 0-50 mol %, more preferably 0-40 mol %, and particularly preferably 0-30 mol %.

結構單位(G)與結構單位(H)之合計含量相對於樹脂(B4)較佳為90~100莫耳%，更佳為95~100莫耳%，特佳為98~100莫耳%。The total content of the structural unit (G) and the structural unit (H) is preferably 90-100 mol % relative to the resin (B4), more preferably 95-100 mol %, and particularly preferably 98-100 mol %.

樹脂(B4)可包含結構單位(G)與結構單位(H)以外之結構單位。包含其他結構單位時，其量相對於樹脂(B4)的總結構單位，較佳為10莫耳%以下，更佳為5莫耳%以下，特佳為2莫耳%以下。作為其他結構單位，舉例為例如以下述通式(10)表示之結構單位。

The resin (B4) may contain structural units other than the structural unit (G) and the structural unit (H). When other structural units are contained, the amount thereof is preferably 10 mol % or less, more preferably 5 mol % or less, and particularly preferably 2 mol % or less with respect to the total structural unit of the resin (B4). As another structural unit, for example, the structural unit represented by the following general formula (10) is exemplified.

樹脂(B4)之製造方法並未特別限制，除使用雙酚C作為單體外，可以與上述聚碳酸酯系樹脂(A)之製造方法相同的方法製造。The manufacturing method of resin (B4) is not specifically limited, It can manufacture by the same method as the manufacturing method of the said polycarbonate resin (A) except using bisphenol C as a monomer.

作為樹脂(B4)，具體舉例為LUPILON KH3410UR、KH3520UR、KS3410UR(由三菱工程塑膠公司製)等。Specific examples of the resin (B4) include LUPILON KH3410UR, KH3520UR, KS3410UR (manufactured by Mitsubishi Engineering Plastics), and the like.

樹脂(B4)之重量平均分子量較佳為15,000~ 75,000，更佳為20,000 ~70,000，特佳為25,000~65,000。樹脂(B4)之重量平均分子量之測定方法可藉與上述聚碳酸酯系樹脂(A)之重量平均分子量的測定方法相同方法測定。The weight average molecular weight of the resin (B4) is preferably 15,000-75,000, more preferably 20,000-70,000, particularly preferably 25,000-65,000. The measurement method of the weight average molecular weight of resin (B4) can be measured by the same method as the measurement method of the weight average molecular weight of the said polycarbonate resin (A).

樹脂(B4)之玻璃轉移溫度較佳為105~150℃，更佳為110~140℃，特佳為110~135℃。藉由玻璃轉移溫度為105℃以上，使本發明提供之積層體在熱環境中發生變形或破裂較少。且，藉由為150℃以下，利用鏡面輥或賦形輥之連續熱賦形或利用鏡面模具或賦形模具之批式熱賦形等之加工性優異。又，本說明書中樹脂(B4)之玻璃轉移溫度係使用示差掃描熱量測定裝置，以升溫速度10℃/分鐘之中點法算出時之溫度。The glass transition temperature of the resin (B4) is preferably 105 to 150°C, more preferably 110 to 140°C, and particularly preferably 110 to 135°C. Since the glass transition temperature is 105° C. or higher, the laminated body provided by the present invention is less deformed or cracked in a thermal environment. In addition, by being 150° C. or lower, it is excellent in workability such as continuous hot forming by a mirror roll or a forming roll, or batch hot forming by a mirror die or a forming die. In addition, in this specification, the glass transition temperature of resin (B4) is the temperature when a differential scanning calorimeter was used, and it calculated by the midpoint method at a temperature increase rate of 10°C/min.

＜樹脂(B5)＞樹脂(B5)係包含(甲基)丙烯酸酯結構單位(i1) 6~77質量%、苯乙烯結構單位(i2) 15~71質量%及不飽和二羧酸結構單位(i3) 8~23質量%之共聚物(I)或共聚物(I)彼此之合金的樹脂，進而為共聚物(I)與共聚物(I)以外之樹脂之合金的樹脂。作為共聚物(I)以外之樹脂，舉例為甲基丙烯酸甲酯-苯乙烯共聚物，丙烯腈-丁二烯-苯乙烯共聚物或聚甲基丙烯酸甲酯、甲基丙烯酸甲酯與丙烯酸甲酯或丙烯酸乙酯之共聚物等。且亦可使用市售品，作為具體例可例示三菱化學(股)之ACRYLPET、住友化學(股)之SUMIPEX、KURARAY(股)之PARAPET、ARKEMA之ALTUGLAS等。作成合金時，為了避免高硬度樹脂之Tg降低，宜為更高Tg之樹脂彼此的合金。<Resin (B5)> Resin (B5) contains (meth)acrylate structural unit (i1) 6-77 mass %, styrene structural unit (i2) 15-71 mass % and unsaturated dicarboxylic acid structural unit (i3) 8-23 mass % % of the copolymer (I) or the resin of the alloy of the copolymers (I), and the resin of the alloy of the copolymer (I) and the resin other than the copolymer (I). Examples of resins other than the copolymer (I) include methyl methacrylate-styrene copolymer, acrylonitrile-butadiene-styrene copolymer or polymethyl methacrylate, methyl methacrylate and methyl acrylate esters or copolymers of ethyl acrylate, etc. Moreover, a commercial item can also be used, and ACRYLPET of Mitsubishi Chemical Co., Ltd., SUMIPEX of Sumitomo Chemical Co., Ltd., PARAPET of KURARAY Co., Ltd., ALTUGLAS of ARKEMA, etc. can be illustrated as a specific example. In order to avoid lowering the Tg of the high-hardness resin when forming the alloy, an alloy of resins with higher Tg is preferable.

作為構成(甲基)丙烯酸酯結構單位(i1)之(甲基)丙烯酸酯單體，舉例為例如丙烯酸、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸2-乙基己酯、甲基丙烯酸、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸2-乙基己酯等，特佳為甲基丙烯酸甲酯。該等(甲基)丙烯酸酯單體亦可混合2種以上使用。 (甲基)丙烯酸酯結構單位(i1)之含量相對於樹脂(B5)總質量為6~77質量%，較佳為20~70質量%。Examples of the (meth)acrylate monomer constituting the (meth)acrylate structural unit (i1) include acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl acrylate, Base acrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, etc., particularly preferably methyl methacrylate. These (meth)acrylate monomers may be used in combination of two or more. Content of the (meth)acrylate structural unit (i1) is 6-77 mass % with respect to the resin (B5) total mass, Preferably it is 20-70 mass %.

作為苯乙烯結構單位(i2)並未特別限制，可以使用任何習知之苯乙烯系單體。基於取得容易性之觀點，較佳為苯乙烯、α-甲基苯乙烯、鄰-甲基苯乙烯、間-甲基苯乙烯、對-甲基苯乙烯、第三丁基苯乙烯等。該等中，基於相溶性之觀點特佳為苯乙烯。該等苯乙烯單體亦可混合2種以上使用。苯乙烯結構單位(i2)之含量相對於樹脂(B5)之總質量為15~71質量%，較佳為20~66質量%。The styrene structural unit (i2) is not particularly limited, and any known styrene-based monomer can be used. From the viewpoint of availability, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, tert-butylstyrene, and the like are preferred. Among these, styrene is particularly preferable from the viewpoint of compatibility. Two or more of these styrene monomers may be mixed and used. Content of a styrene structural unit (i2) is 15-71 mass % with respect to the total mass of resin (B5), Preferably it is 20-66 mass %.

作為構成不飽和二羧酸結構單位(i3)之不飽和二羧酸酐單體，舉例為例如馬來酸、衣康酸、檸康酸、烏頭酸等之酸酐，基於與苯乙烯系單體之相溶性之觀點，較佳為馬來酸。該等不飽和二羧酸酐單體亦可混合2種以上使用。不飽和二羧酸結構單位(i3)之含量相對於樹脂(B5)之總質量為8~23質量%，較佳為10~23質量%。As the unsaturated dicarboxylic acid anhydride monomer constituting the unsaturated dicarboxylic acid structural unit (i3), there are exemplified acid anhydrides such as maleic acid, itaconic acid, citraconic acid, aconitic acid, etc. From the viewpoint of compatibility, maleic acid is preferred. These unsaturated dicarboxylic anhydride monomers may be used in combination of two or more. Content of the unsaturated dicarboxylic acid structural unit (i3) is 8-23 mass % with respect to the total mass of resin (B5), Preferably it is 10-23 mass %.

上述(甲基)丙烯酸酯結構單位(i1)、苯乙烯結構單位(i2)及不飽和二羧酸結構單位(i3)之合計含量，相對於樹脂(B5)之總結構單位，較佳為90~100莫耳%，更佳為95~100莫耳%，特佳為98~100莫耳%。亦即，樹脂(B5)亦可包含上述(甲基)丙烯酸酯結構單位(i1)、苯乙烯結構單位(i2)及不飽和二羧酸結構單位(i3)以外之結構單位。其量相對於樹脂(B5)之總結構單位，較佳為10莫耳%以下，更佳為5莫耳%以下，特佳為2莫耳%以下。The total content of the above-mentioned (meth)acrylate structural unit (i1), styrene structural unit (i2) and unsaturated dicarboxylic acid structural unit (i3) is preferably 90 with respect to the total structural unit of the resin (B5). ~100 mol%, more preferably 95~100 mol%, and particularly preferably 98~100 mol%. That is, the resin (B5) may contain structural units other than the above-mentioned (meth)acrylate structural unit (i1), styrene structural unit (i2), and unsaturated dicarboxylic acid structural unit (i3). The amount thereof is preferably 10 mol % or less, more preferably 5 mol % or less, and particularly preferably 2 mol % or less with respect to the total structural unit of the resin (B5).

作為其他結構單位，舉例為例如N-苯基馬來醯亞胺等。樹脂(B5)之製造方法並未特別限制，舉例為塊狀聚合法及溶液聚合法。As other structural units, for example, N-phenylmaleimide and the like are exemplified. The production method of the resin (B5) is not particularly limited, and examples thereof include a bulk polymerization method and a solution polymerization method.

作為樹脂(B5)，具體舉例為REGISFYI R100、R200、R310 (DENKA公司製)、DELPET 980N(旭化成(股)製)、hw55(DAICEL EVONIK製)等。Specific examples of the resin (B5) include REGISFYI R100, R200, R310 (manufactured by DENKA), DELPET 980N (manufactured by Asahi Kasei Co., Ltd.), hw55 (manufactured by DAICEL EVONIK), and the like.

樹脂(B5)之重量平均分子量未特別限制，較佳為50,000~300,000，更佳為80,000~200,000。上述重量平均分子量係由凝膠滲透層析法(GPC)測定之標準聚苯乙烯換算之重量平均分子量。The weight average molecular weight of the resin (B5) is not particularly limited, but is preferably 50,000 to 300,000, more preferably 80,000 to 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).

樹脂(B5)之玻璃轉移溫度較佳為90~150℃，更佳為100~150℃，特佳為115~150℃。藉由玻璃轉移溫度為90℃以上，使本發明提供之積層體在熱環境中發生變形或破裂較少。且，藉由為150℃以下，利用鏡面輥或賦形輥之連續熱賦形或利用鏡面模具或賦形模具之批式熱賦形等之加工性優異。又，本說明書中樹脂(B5)之玻璃轉移溫度係使用示差掃描熱量測定裝置，以升溫速度10℃/分鐘之中點法算出時之溫度。The glass transition temperature of the resin (B5) is preferably 90 to 150°C, more preferably 100 to 150°C, and particularly preferably 115 to 150°C. Since the glass transition temperature is 90° C. or higher, the laminated body provided by the present invention is less deformed or cracked in a thermal environment. In addition, by being 150° C. or lower, it is excellent in workability such as continuous hot forming by a mirror roll or a forming roll, or batch hot forming by a mirror die or a forming die. In addition, in this specification, the glass transition temperature of resin (B5) is the temperature when a differential scanning calorimeter is used, and it calculates by the midpoint method with a temperature increase rate of 10 degreeC/min.

＜樹脂(B6)＞樹脂(B5)係包含苯乙烯結構單位(j1) 5~20質量%、(甲基)丙烯酸酯結構單位(j2) 60~90質量%及N-取代型馬來醯亞胺結構單位(j3) 5~20質量%之共聚物(J)或共聚物(J)與共聚物(J)以外之樹脂之合金。<Resin (B6)> Resin (B5) contains 5-20 mass % of styrene structural unit (j1), 60-90 mass % of (meth)acrylate structural unit (j2), and N-substituted maleimide structural unit (j3) 5 to 20% by mass of the copolymer (J) or an alloy of the copolymer (J) and a resin other than the copolymer (J).

作為苯乙烯結構單位(j1)並未特別限制，可使用任何習知之苯乙烯系單體，基於取得容易性之觀點，較佳為苯乙烯、α-甲基苯乙烯、鄰-甲基苯乙烯、間-甲基苯乙烯、對-甲基苯乙烯、第三丁基苯乙烯等。該等中，基於相溶性之觀點特佳為苯乙烯。共聚物(J)亦可包含2種以上之該等苯乙烯結構單位。苯乙烯結構單位之含量相對於樹脂(B6)之總質量為5~20質量%，較佳為5~15質量%，更佳為5~10質量%。The styrene structural unit (j1) is not particularly limited, and any known styrene-based monomer can be used, but from the viewpoint of availability, styrene, α-methylstyrene, and o-methylstyrene are preferred , m-methyl styrene, p-methyl styrene, tertiary butyl styrene, etc. Among these, styrene is particularly preferable from the viewpoint of compatibility. The copolymer (J) may contain two or more of these styrene structural units. Content of a styrene structural unit is 5-20 mass % with respect to the total mass of resin (B6), Preferably it is 5-15 mass %, More preferably, it is 5-10 mass %.

作為(甲基)丙烯酸酯結構單位(j2)，可舉例為源自例如丙烯酸、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸2-乙基己酯、甲基丙烯酸、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸2-乙基己酯等之結構單位，特佳為源自甲基丙烯酸甲酯之結構單位。且，共聚物(J)亦可包含2種以上之該等(甲基)丙烯酸酯結構單位。(甲基)丙烯酸酯結構單位之含量相對於樹脂(B6)之總質量為60~90質量%，較佳為70~90質量%，更佳為80~90質量%。As the (meth)acrylate structural unit (j2), for example, those derived from acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate can be exemplified. Structural units such as ester, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, etc., are particularly preferably those derived from methyl methacrylate. In addition, the copolymer (J) may contain two or more of these (meth)acrylate structural units. Content of a (meth)acrylate structural unit is 60-90 mass % with respect to the total mass of resin (B6), Preferably it is 70-90 mass %, More preferably, it is 80-90 mass %.

作為樹脂(B6)中之N-取代型馬來醯亞胺結構單位(j3)，舉例為源自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-芳基馬來醯亞胺等之結構單位，基於與丙烯酸樹脂之相溶性之觀點，較佳為源自N-苯基馬來醯亞胺之結構單位。共聚物(J)可包含2種以上之該等N-取代型馬來醯亞胺結構單位。N-取代型馬來醯亞胺結構單位之含量相對於樹脂(B6)之總質量為5~20質量%，較佳為5~15質量%，更佳為5~10質量%。As the N-substituted maleimide structural unit (j3) in the resin (B6), examples are derived from N-phenylmaleimide, N-chlorophenylmaleimide, N-methyl phenylmaleimide, N-naphthylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide Structural units of N-arylmaleimide such as imide, N-nitrophenylmaleimide, N-tribromophenylmaleimide, etc. are based on compatibility with acrylic resins From a viewpoint, the structural unit derived from N-phenylmaleimide is preferable. The copolymer (J) may contain two or more of these N-substituted maleimide structural units. The content of the N-substituted maleimide structural unit is 5 to 20 mass %, preferably 5 to 15 mass %, more preferably 5 to 10 mass % with respect to the total mass of the resin (B6).

苯乙烯結構單位(j1)、(甲基)丙烯酸酯結構單位(j2)及N-取代型馬來醯亞胺結構單位(j3)之合計含量，相對於樹脂(B6)較佳為90~100莫耳%，更佳為95~100莫耳%，特佳為98~100莫耳%。樹脂(B6)亦可包含上述結構單位以外的織結構單位。包含其他結構單位時，其量相對於樹脂(B6)之總結構單位，較佳為10莫耳%以下，更佳為5莫耳%以下，特佳為2莫耳%以下。The total content of the styrene structural unit (j1), the (meth)acrylate structural unit (j2) and the N-substituted maleimide structural unit (j3) is preferably 90 to 100 relative to the resin (B6) mol%, more preferably 95-100 mol%, and particularly preferably 98-100 mol%. Resin (B6) may contain weave structural units other than the above-mentioned structural units. When other structural units are included, the amount thereof is preferably 10 mol % or less, more preferably 5 mol % or less, particularly preferably 2 mol % or less, based on the total structural unit of the resin (B6).

作為其他結構單位，舉例為例如源自下述通式(11)之結構單位、源自通式(12)之結構單位等。

(式中，R1為氫原子或甲基；R2為碳數1~18之烷基)。

(式中，R3為氫原子或甲基；R4為可經碳數1~4之烴基取代之環己基)。As another structural unit, the structural unit derived from the following general formula (11), the structural unit derived from the general formula (12), etc. are mentioned, for example.

(In the formula, R1 is a hydrogen atom or a methyl group; R2 is an alkyl group with 1 to 18 carbon atoms).

(In the formula, R3 is a hydrogen atom or a methyl group; R4 is a cyclohexyl group which can be substituted by a hydrocarbon group having 1 to 4 carbon atoms).

樹脂(B6)之製造方法未特別限制，可藉由溶液聚合、塊狀聚合等製造。The production method of the resin (B6) is not particularly limited, and it can be produced by solution polymerization, bulk polymerization, or the like.

作為樹脂(B6)，具體舉例為DELPET PM120N (旭化成化學公司製)。Specific examples of the resin (B6) include DELPET PM120N (manufactured by Asahi Kasei Chemicals).

樹脂(B6)之重量平均分子量較佳為50,000~ 250,000，更佳為100,000~200,000。上述重量平均分子量係藉凝膠滲透層析法(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 resin (B6) is preferably 50,000 to 250,000, more preferably 100,000 to 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).

樹脂(B6)之玻璃轉移溫度較佳為110~150℃，更佳為115~140℃，特佳為115~135℃。藉由玻璃轉移溫度為110℃以上，使本發明提供之積層體在熱環境中發生變形或破裂較少。且，藉由為150℃以下，利用鏡面輥或賦形輥之連續熱賦形或利用鏡面模具或賦形模具之批式熱賦形等之加工性優異。又，本說明書中樹脂(B6)之玻璃轉移溫度係使用示差掃描熱量測定裝置，以升溫速度10℃/分鐘之中點法算出時之溫度。The glass transition temperature of the resin (B6) is preferably 110 to 150°C, more preferably 115 to 140°C, and particularly preferably 115 to 135°C. Since the glass transition temperature is 110° C. or higher, the laminated body provided by the present invention is less deformed or cracked in a thermal environment. In addition, by being 150° C. or lower, it is excellent in workability such as continuous hot forming by a mirror roll or a forming roll, or batch hot forming by a mirror die or a forming die. In addition, in this specification, the glass transition temperature of resin (B6) is the temperature when a differential scanning calorimeter is used, and it calculates by the midpoint method with a temperature increase rate of 10 degreeC/min.

＜硬塗布層＞本發明之硬塗布層與包含熱塑性樹脂(B)之層之間亦可存在其他層，較佳硬塗布層積層於包含熱塑性樹脂(B)之層的表面或兩面。硬塗布層較佳為丙烯酸硬塗布層。本說明書中，所謂「丙烯酸系硬塗布層」意指含有(甲基)丙烯醯基作為聚合基之單體或寡聚物或預聚物予以聚合形成交聯結構之塗膜。作為丙烯酸系硬塗布之組成，較佳包含(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%，進而，相對於(甲基)丙烯酸系單體、(甲基)丙烯酸系寡聚物與表面改質劑之總和100質量份，較佳包含0.001~7質量份之光聚合起始劑。<Hard coat layer> There may also be other layers 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 this specification, the "acrylic hard coat layer" means a coating film in which a monomer, oligomer or prepolymer containing a (meth)acryloyl group as a polymerizing group is polymerized to form a cross-linked structure. As the composition of the acrylic hard coating, it preferably contains 2 to 98 mass % of (meth)acrylic monomers, 2 to 98 mass % of (meth)acrylic oligomers, and 0 to 15 mass % of surface modifiers. Furthermore, it is preferable to contain 0.001-7 mass parts of photopolymerization initiators with respect to 100 mass parts of the sum total of (meth)acrylic-type monomer, (meth)acrylic-type oligomer, and surface modifier.

硬塗佈層更佳包含(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%與表面改質劑1~10質量%，特佳包含(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%。光聚合起始劑之量，相對於(甲基)丙烯酸系單體、(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 more preferably contains 5-50 mass % of (meth)acrylic monomers, 50-95 mass % of (meth)acrylic oligomers and 1-10 mass % of surface modifiers, particularly preferably ( 20-40 mass % of meth)acrylic monomers, 60-80 mass % of (meth)acrylic oligomers, and 2-5 mass % of surface modifiers. The amount of the photopolymerization initiator is more preferably 0.01 to 5 parts by mass, and particularly preferably 0.1 to 3 parts by mass.

作為(甲基)丙烯酸系單體，只要分子內存在(甲基)丙烯醯基作為官能基則可使用，可為1官能單體、2官能單體或3官能以上之單體。作為1官能單體，可例示(甲基)丙烯酸、(甲基)丙烯酸酯，作為2官能及/或3官能以上之(甲基)丙烯酸系單體之具體例，可例示二乙二醇二(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、羥基特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-丁二醇寡聚丙烯酸酯、新戊二醇寡聚丙烯酸酯、1,6-己二醇寡聚丙烯酸酯、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、甘油環氧丙烷加成物三丙烯酸酯、季戊四醇四丙烯酸酯等。硬塗布層可包含1種或2種以上之(甲基)丙烯酸系單體。As a (meth)acrylic-type monomer, as long as a (meth)acryloyl group exists as a functional group in a molecule|numerator, it can be used, and it can be a monofunctional monomer, a bifunctional monomer, or a trifunctional or higher monomer. As a monofunctional monomer, (meth)acrylic acid and (meth)acrylate can be exemplified, and as a specific example of a bifunctional and/or trifunctional or higher (meth)acrylic monomer, diethylene glycol diethylene glycol can be exemplified (meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A diglycidyl ether di (meth)acrylate, tetraethylene glycol di(meth)acrylate, hydroxypivalate neopentyl glycol diacrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol Diacrylate, 1,3-Butanediol di(meth)acrylate, Dicyclopentyl di(meth)acrylate, Polyethylene glycol diacrylate, 1,4-Butanediol oligoacrylate , neopentyl glycol oligoacrylate, 1,6-hexanediol oligoacrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxy tri(meth)acrylate , Trimethylolpropane propoxy tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerol propoxytri(meth)acrylate, trimethylolpropane trimethacrylate, trimethylolpropane tri(meth)acrylate Methylol propane ethylene oxide adduct triacrylate, glycerol propylene oxide adduct triacrylate, pentaerythritol tetraacrylate, etc. The hard coat layer may contain one or more (meth)acrylic monomers.

作為(甲基)丙烯酸系寡聚物，舉例為2官能以上之多官能胺基甲酸酯(甲基)丙烯酸酯寡聚物[以下亦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[以下亦稱為多官能聚酯(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[以下亦簡稱為多官能環氧(甲基)丙烯酸酯寡聚物]等。硬塗布層可包含1種或2種以上之(甲基)丙烯酸系寡聚物。作為多官能胺基甲酸酯(甲基)丙烯酸酯寡聚物，舉例為1分子中具有至少1個(甲基)丙烯醯氧基及羥基之(甲基)丙烯酸酯單體與聚異氰酸酯之胺基甲酸酯化反應生成物；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(甲基)丙烯醯氧基及羥基之(甲基)丙烯酸酯單體之胺基甲酸酯化反應生成物等。Examples of the (meth)acrylic oligomer include bifunctional or higher polyfunctional urethane (meth)acrylate oligomers [hereinafter also referred to as polyfunctional urethane (meth)acrylic acid] ester oligomer], polyfunctional polyester (meth)acrylate oligomer with more than 2 functions [hereinafter also referred to as polyfunctional polyester (meth)acrylate oligomer], polyfunctional ring with more than 2 functions Oxygen (meth)acrylate oligomer [hereinafter also simply referred to as polyfunctional epoxy (meth)acrylate oligomer] and the like. The hard coat layer may contain one or more (meth)acrylic oligomers. Examples of the polyfunctional urethane (meth)acrylate oligomer include a (meth)acrylate monomer having at least one (meth)acryloyloxy group and a hydroxyl group in one molecule and a polyisocyanate. Urethane reaction product; isocyanate compound obtained by reacting polyols with polyisocyanate and amine of (meth)acrylate monomer having at least one (meth)acryloyloxy group and hydroxyl group in one molecule Formate esterification reaction products, etc.

作為胺基甲酸酯化反應中使用之1分子中具有至少1個(甲基)丙烯醯氧基及羥基之(甲基)丙烯酸酯單體，可舉例(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥丙基酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯、甘油二(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。As a (meth)acrylate monomer having at least one (meth)acryloyloxy group and a hydroxyl group in one molecule used for the urethanization reaction, 2-hydroxyethyl (meth)acrylate can be exemplified , 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, glycerol di(meth)acrylate, Trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate.

作為胺基甲酸酯化反應中使用之聚異氰酸酯，舉例為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、甲苯二異氰酸酯、二甲苯二異氰酸酯、該等二異氰酸酯中之芳香族異氰酸酯類經氫化而得之二異氰酸酯(例如氫化甲苯二異氰酸酯、氫化二甲苯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的聚異氰酸酯，或使二異氰酸酯多聚化所得之聚異氰酸酯。Examples of the polyisocyanate used in the urethane reaction include hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate, xylene diisocyanate Isocyanates, diisocyanates obtained by hydrogenation of aromatic isocyanates in these diisocyanates (such as hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate, etc.), triphenylmethane triisocyanate, dimethylene triphenyl Two or three polyisocyanates such as base triisocyanates, or polyisocyanates obtained by polymerizing diisocyanates.

作為胺基甲酸酯化反應中使用之多元醇類，除了一般芳香族、脂肪族及脂環式多元醇以外，亦可使用聚酯多元醇、聚醚多元醇等。通常，作為脂肪族及脂環式之多元醇，舉例為1,4-丁二醇、1,6-己二醇、新戊二酚、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、甘油、氫化雙酚A等。As the polyols used in the urethane reaction, in addition to general aromatic, aliphatic, and alicyclic polyols, polyester polyols, polyether polyols, and the like can be used. Generally, as aliphatic and alicyclic polyols, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, ethylene glycol, propylene glycol, trimethylolethane, trimethylol Methylol propane, dimethylol heptane, dimethylol propionic acid, dimethylol butyric acid, glycerin, hydrogenated bisphenol A, etc.

作為聚酯多元醇舉例為上述多元醇類與聚羧酸之脫水縮合反應所得者。作為聚羧酸之具體化合物舉例為琥珀酸、己二酸、馬來酸、苯偏三甲酸、六氫鄰苯二甲酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸等。該等聚羧酸可為酸酐。作為聚醚多元醇，除聚烷二醇以外，亦舉例為藉由上述多元醇類或酚類與環氧烷反應所得之聚氧伸烷基改質多元醇。Examples of polyester polyols include those obtained by the dehydration condensation reaction of the above-mentioned polyols and polycarboxylic acid. Specific examples of the polycarboxylic acid compound include succinic acid, adipic acid, maleic acid, trimellitic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, and the like. These polycarboxylic acids can be acid anhydrides. As the polyether polyol, in addition to the polyalkylene glycol, the polyoxyalkylene modified polyol obtained by reacting the above-mentioned polyols or phenols with an alkylene oxide is also exemplified.

又，多官能聚酯(甲基)丙烯酸酯寡聚物可藉由使用(甲基)丙烯酸、聚羧酸及多元醇之脫水縮合反應而獲得。作為脫水縮合反應中使用之聚羧酸舉例為琥珀酸、己二酸、馬來酸、衣康酸、苯偏三甲酸、均苯四甲酸、六氫鄰苯二甲酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸等。該等聚羧酸可為酸酐。且，作為脫水縮合反應所用之多元醇，舉例為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 can be obtained by the dehydration condensation reaction using (meth)acrylic acid, a polycarboxylic acid, and a polyhydric alcohol. Examples of the polycarboxylic acid used in the dehydration condensation reaction include succinic acid, adipic acid, maleic acid, itaconic acid, trimellitic acid, pyromellitic acid, hexahydrophthalic acid, phthalic acid, m-phthalic acid, and Phthalic acid, terephthalic acid, etc. These polycarboxylic acids can be acid anhydrides. In addition, as the polyhydric alcohol used in the dehydration condensation reaction, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, dimethylol Heptane, dimethylol propionic acid, dimethylol butyric acid, trimethylol propane, di-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)丙烯酸之加成反應而得。作為聚縮水甘油醚舉例為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. Examples of the polyglycidyl ether 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.

本發明中使用之表面改質劑為調平劑、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布層之表面性能者。作為調平劑舉例為例如聚醚改質聚烷基矽氧烷、聚醚改質矽氧烷、聚酯改質含羥基聚烷基矽氧烷、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 modifiers used in the present invention are leveling agents, antistatic agents, surfactants, water and oil repellents, inorganic particles, organic particles, etc., which change the surface properties of the hard coating layer. Examples of leveling agents include polyether-modified polyalkylsiloxanes, polyether-modified siloxanes, polyester-modified hydroxyl-containing polyalkylsiloxanes, and polyether-modified polydimethylsiloxanes with alkyl groups. base siloxane, modified polyether, silicon modified acrylic acid, etc.

作為抗靜電劑舉例為例如甘油脂肪酸酯單甘油酯、甘油脂肪酸酯有機酸單甘油酯、聚甘油脂肪酸酯、山梨醇酐脂肪酸酯、陽離子性界面活性劑、陰離子性界面活性劑等。作為無機粒子舉例為例如氧化矽粒子、氧化鋁粒子、氧化鋯粒子、矽粒子銀顆粒、玻璃顆粒等。作為有機粒子舉例為例如丙烯酸粒子、矽粒子等。作為界面活性劑及撥水撥油劑舉例為例如含氟基・含親油性基之寡聚物、含氟基・親水性基・親油性基・UV反應性基之寡聚物等之含氟之界面活性劑及撥水撥油劑。Examples of the antistatic agent include glycerol fatty acid ester monoglyceride, glycerol fatty acid ester organic acid monoglyceride, polyglycerol fatty acid ester, sorbitan fatty acid ester, cationic surfactant, anionic surfactant, and the like. . Examples of inorganic particles include silicon oxide particles, aluminum oxide particles, zirconium oxide particles, silicon particles, silver particles, glass particles, and the like. Examples of the organic particles include acrylic particles, silicon particles, and the like. Examples of surfactants and water- and oil-repellent agents include fluorine-containing oligomers containing fluorine groups, lipophilic groups, oligomers containing fluorine groups, hydrophilic groups, lipophilic groups, and UV reactive groups. of surfactants and water and oil repellents.

硬塗布層可包含光聚合起始劑。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 contain a photopolymerization initiator. In this specification, the photopolymerization initiator refers to a photoradical generator.

作為本發明中可使用之單官能光聚合起始劑，舉例為例如4-(2-羥基乙氧基)苯基(2-羥基-2-丙基)酮[DAROCURE-2959：MERCK公司製]；α-羥基-α,α'-二甲基苯乙酮[DAROCURE-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；其他為鹵化酮、醯基氧化膦、醯基膦酸酯等。As a monofunctional photopolymerization initiator that can be used in the present invention, for example, 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone [DAROCURE-2959: manufactured by MERCK Corporation] ; α-Hydroxy-α,α'-dimethylacetophenone [DAROCURE-1173: manufactured by MERCK]; Methoxyacetophenone, 2,2'-dimethoxy-2-phenylacetophenone [IRGACURE-651], 1-Hydroxy-cyclohexyl phenyl ketone and other acetophenone-based starters; benzene-in-ether-based starters such as phenyl-diethyl ether, phenyl-in-isopropyl ether, etc.; others are halogenated Ketones, acyl phosphine oxides, acyl phosphonates, etc.

硬塗布層之形成方法未特別限制，例如可藉由將硬塗布液塗布在位於硬塗布層下的層上之後，藉由光聚合而形成。The method of forming the hard coating layer is not particularly limited, and for example, it can be formed by photopolymerization after applying a hard coating liquid on the layer under the hard coating layer.

塗布硬塗布液(聚合性組成物)之方法並未特別限制，可使用習知方法。舉例為例如旋塗法、浸漬法、噴塗法、滑動塗布法、棒塗法、輥塗法、凹版塗布法、半月板塗布法、柔版印刷法、絲網印刷法、拍擊塗布法、刷塗法等。The method of applying the hard coating liquid (polymerizable composition) is not particularly limited, and a known method can be used. Examples are spin coating, dipping, spray coating, slide coating, bar coating, roll coating, gravure coating, meniscus coating, flexographic printing, screen printing, slap coating, brush coating coating etc.

作為光聚合中光照射所用之燈，使用具有於光波長420nm以下的發光分佈者，作為其例舉例為低壓水銀燈、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由於可效率良好地發出起始劑之活性波長區域的光，不會發出太多如使所得高分子之黏彈性性質因交聯而降低般之短波長的光，或如使反應組成物加熱蒸發般之長波長的光，故而較佳。As lamps for light irradiation in photopolymerization, those having a light emission distribution of 420 nm or less in light wavelength are used, and examples thereof include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, chemical lamps, black light lamps, and microwave-excited mercury lamps. , metal halide lamps, etc. Among them, high-pressure mercury lamps or metal halide lamps can efficiently emit light in the active wavelength region of the initiator, and do not emit too much light with short wavelengths such that the viscoelastic properties of the obtained polymer are reduced due to cross-linking. Or light of a long wavelength like heating and evaporating the reaction composition is preferable.

上述燈的照射強度是影響所得聚合物聚合度之因素，且根據目標製品之性能適當控制。調配通常之具有苯乙酮基之開裂型起始劑時，照度較佳為0.1~300 mW/cm² 之範圍。特佳使用金屬鹵素燈，將照度設為10~40 mW/cm² 。The irradiation intensity of the above-mentioned lamps is a factor affecting the degree of polymerization of the resulting polymer, and is appropriately controlled according to the properties of the target product. When preparing a common cracking initiator with an acetophenone group, the illumination intensity is preferably in the range of 0.1-300 mW/cm ² . It is best to use metal halide lamps and set the illuminance to 10~40 mW/cm ² .

光聚合反應受空氣中之氧或溶解於反應組成物中的氧而阻礙。因此，期望使用能夠消除氧所致之阻礙的方法實施光照射。作為此種方法之一，有藉由聚對苯二甲酸乙二酯或鐵氟龍製之膜覆蓋反應性組成物而阻斷與氧之接觸，通過膜對反應性組成物照射光之方法。且，亦可藉由如氮氣或二氧化碳氣體之惰性氣體置換氧之惰性環境下，通過透光視窗對組成物照射光。The photopolymerization reaction is hindered by oxygen in the air or oxygen dissolved in the reaction composition. Therefore, it is desired to perform light irradiation using a method that can eliminate the hindrance by oxygen. As one of such methods, there is a method of covering the reactive composition with a film made of polyethylene terephthalate or Teflon to block 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 under an inert environment in which oxygen is replaced by an inert gas such as nitrogen gas or carbon dioxide gas.

在惰性環境下進行光照射時，為了將其環境氧濃度保持於低程度，經常導入一定量的惰性氣體。藉由導入該惰性氣體，於反應性組成物表面產生氣流，引起單體蒸發。為了抑制單體蒸發之程度，惰性氣體的氣流速度，以相對於在惰性氣體環境下移動之塗布有硬塗布液之積層體之相對速度表示，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，可實質上抑制氣流引起的單體蒸發。When irradiating light in an inert environment, a certain amount of an inert gas is often introduced in order to keep the ambient oxygen concentration low. By introducing the inert gas, a gas flow is generated on the surface of the reactive composition, causing evaporation of the monomers. In order to suppress the degree of evaporation of the monomers, the airflow velocity of the inert gas, expressed in terms of the relative velocity of the layered body coated with the hard coating liquid moving under the inert gas environment, is preferably 1 m/sec or less, more preferably 0.1 m /sec or less. By setting the airflow velocity in the above-mentioned range, the evaporation of the monomer by the airflow can be substantially suppressed.

基於提高硬塗布層之密著性之目的，可對塗布面進行前處理。作為處理例，舉例為噴砂法、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、利用樹脂組成物之底塗處理法等之習知方法。For the purpose of improving the adhesion of the hard coating layer, the coating surface can be pre-treated. 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 using a resin composition, and the like. method of acquaintance.

硬塗佈層使用UV光(254nm)的照射輸出為20 mW/cm² 之金屬鹵素燈進行紫外線照射時，鉛筆硬度較佳為2H以上。When the hard coat layer is irradiated with ultraviolet rays 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 more.

作為硬塗布層之膜厚度期望為1μm以上40μm以下，更期望為2μm以上10μm以下。藉由使膜厚為1μm以上可獲得充分硬度。又藉由使膜厚為40μm以下，可抑制彎曲加工時之龜裂發生。又硬塗布層之膜厚可以顯微鏡等觀察其剖面，測量自塗膜介面到表面而測定。The film thickness of the hard coat layer is desirably 1 μm or more and 40 μm or less, and more desirably 2 μm or more and 10 μm or less. Sufficient hardness can be obtained by making the film thickness 1 μm or more. Furthermore, by setting the film thickness to be 40 μm or less, the occurrence of cracks during bending can be suppressed. Moreover, the film thickness of the hard coat layer can be measured by observing its cross section with a microscope or the like, and measuring from the coating film interface to the surface.

＜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及耐衝擊性。亦即，包含熱塑性樹脂(B)之層的厚度過薄時，表面硬度降低而欠佳。包含熱塑性樹脂(B)之層的厚度過大時，耐衝擊性變差而欠佳。包含熱塑性樹脂(B)之層的厚度較佳為10~250μm，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 and impact resistance of the resin laminate. That is, when the thickness of the layer containing the thermoplastic resin (B) is too thin, the surface hardness decreases and is not preferable. When the thickness of the layer containing the thermoplastic resin (B) is too large, the impact resistance deteriorates and becomes unsatisfactory. 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)之層的合計厚度，太薄或太厚均難以成形。包含聚碳酸酯系樹脂(A)之層與包含熱塑性樹脂(B)之層的合計厚度較佳為0.04～4.0mm，更佳為0.05～3.5mm，又更佳為0.5～3.0mm。In the present invention, if the total thickness of the layer containing the polycarbonate resin (A) and the layer containing the thermoplastic resin (B) is too thin or too thick, it is difficult to mold. The total thickness of the layer containing the polycarbonate resin (A) and the layer containing the thermoplastic resin (B) is preferably 0.04 to 4.0 mm, more preferably 0.05 to 3.5 mm, and still more preferably 0.5 to 3.0 mm.

又，將包含聚碳酸酯系樹脂(A)之層與包含熱塑性樹脂(B)之層的樹脂積層體、或包含聚碳酸酯系樹脂(A)之層與包含熱塑性樹脂(B)之層與於包含熱塑性樹脂(B)之層側的表面實施硬塗布處理、反射防止處理、防汙處理、耐指紋處理、抗靜電處理、耐候性處理及防眩處理之任一種以上的樹脂積層體，在23℃50%RH環境下放置後的捲曲形狀為將包含熱塑性樹脂(B) 之層側為凹部且11m≦曲率半徑R≦1225m，更佳使包含熱塑性樹脂(B)之層側為凹部且12m≦曲率半徑R≦613m，又更佳使包含熱塑性樹脂(B)之層側為凹部且13m≦曲率半徑R≦408m，特佳使包含熱塑性樹脂(B)之層側為凹部且13m≦曲率半徑R≦306m。將包含熱塑性樹脂(B)之層側為凹部且曲率半徑R＜11m時，於樹脂積層體之包含熱塑性樹脂(B)之層側的表面進而積層抗反射層之樹脂積層體於23℃50%RH環境下放置後之凹面翹曲較大，後續步驟的加工變困難。又，包含熱塑性樹脂(B)之層側為凹部且曲率半徑R＞1225m，或包含熱塑性樹脂(B)之層側為凸部時，於樹脂積層體之包含熱塑性樹脂(B)之層側表面進而積層抗反射層之樹脂積層體於23℃50%RH環境下放置後之凸面翹曲較大，後續步驟的加工變困難。Furthermore, a resin laminate comprising a layer comprising a polycarbonate-based resin (A) and a layer comprising a thermoplastic resin (B), or a layer comprising the polycarbonate-based resin (A) and a layer comprising the thermoplastic resin (B) and A resin laminate in which any one or more of hard coating treatment, antireflection treatment, antifouling treatment, anti-fingerprint treatment, antistatic treatment, weather resistance treatment and anti-glare treatment is applied to the surface of the layer side containing the thermoplastic resin (B), The curled shape after being placed in an environment of 23°C 50%RH is such that the layer containing the thermoplastic resin (B) is a concave portion and 11m≦the radius of curvature R≦1225m, more preferably, the layer containing the thermoplastic resin (B) is a concave portion and 12m. ≦curvature radius R≦613m, more preferably, the layer containing thermoplastic resin (B) is a recess and 13m≦curvature radius R≦408m, especially preferably, the layer containing thermoplastic resin (B) is recessed and 13m≦curvature radius R≦306m. When the side of the layer containing the thermoplastic resin (B) is a concave part and the radius of curvature R<11m, the surface of the layer side containing the thermoplastic resin (B) of the resin laminate is further laminated with an anti-reflection layer at 23°C 50% The warpage of the concave surface after being placed in the RH environment is large, and the processing in the subsequent steps becomes difficult. In addition, when the side of the layer containing the thermoplastic resin (B) is a concave portion and the radius of curvature R>1225m, or the side of the layer containing the thermoplastic resin (B) is a convex portion, the surface of the layer side containing the thermoplastic resin (B) in the resin laminate is Furthermore, the convex surface warpage of the resin laminate on which the antireflection layer is laminated is large after being placed in an environment of 23° C. and 50% RH, and the processing in the subsequent steps becomes difficult.

針對對於(i)包含聚碳酸酯系樹脂(A)之層與包含熱塑性樹脂(B)之層的樹脂積層體，或(ii)包含聚碳酸酯系樹脂(A)之層與包含熱塑性樹脂(B)之層與於包含熱塑性樹脂(B)之層側的表面實施硬塗布處理、反射防止處理、防汙處理、耐指紋處理、抗靜電處理、耐候性處理及防眩處理中任一種以上之樹脂積層體，於包含熱塑性樹脂(B)之層側的表面進一步積層抗反射層之樹脂積層體，於23℃50%RH環境下放置後之捲曲形狀較佳為包含熱塑性樹脂(B)之層側為凹部或凸部且曲率半徑R≧21m，更佳包含熱塑性樹脂(B)之層側為凹部或凸部且曲率半徑R≧22m，又更佳包含熱塑性樹脂(B)之層側為凹部或凸部且曲率半徑R≧24m，特佳包含熱塑性樹脂(B)之層側為凹部或凸部且曲率半徑R≧25m。於23℃50%RH環境下放置後之捲曲形狀為包含熱塑性樹脂(B)之層側為凹部或凸部且曲率半徑R＜21m時，樹脂積層體之凹部或凸部的翹曲較大，後續步驟的加工變困難。For (i) a layer comprising a polycarbonate-based resin (A) and a layer comprising a thermoplastic resin (B) for a resin laminate, or (ii) a layer comprising a polycarbonate-based resin (A) and a layer comprising a thermoplastic resin ( The layer of B) and the surface of the layer containing the thermoplastic resin (B) are subjected to any one or more of hard coating treatment, antireflection treatment, antifouling treatment, anti-fingerprint treatment, antistatic treatment, weather resistance treatment and anti-glare treatment The resin laminate is a resin laminate in which an antireflection layer is further laminated on the surface of the layer containing the thermoplastic resin (B), and the curled shape after being placed in an environment of 23°C and 50% RH is preferably a layer containing the thermoplastic resin (B). The side is a concave part or a convex part and the radius of curvature R≧21m, the side of the layer containing the thermoplastic resin (B) is more preferably a concave part or a convex part and the radius of curvature R≧22m, and the side of the layer containing the thermoplastic resin (B) is more preferably a concave part or a convex portion with a radius of curvature R≧24m, and particularly preferably the layer side containing the thermoplastic resin (B) is a concave portion or a convex portion with a radius of curvature R≧25m. When the curled shape after being placed in an environment of 23°C and 50% RH is a concave or convex portion on the side of the layer containing the thermoplastic resin (B) and the radius of curvature R<21m, the concave or convex portion of the resin laminate has a large warpage, Processing in subsequent steps becomes difficult.

將包含聚碳酸酯系樹脂(A)之層與包含熱塑性樹脂(B)之層的樹脂積層體、或包含聚碳酸酯系樹脂(A)之層與包含熱塑性樹脂(B)之層與於包含熱塑性樹脂(B)之層側的表面實施硬塗布處理、反射防止處理、防汙處理、耐指紋處理、抗靜電處理、耐候性處理及防眩處理中任一種以上的樹脂積層體在85℃85%RH環境下放置120hr後的捲曲形狀較佳為包含熱塑性樹脂(B)之層側為凹部且曲率半徑R≧10m，或包含熱塑性樹脂(B)之層側為凸部且曲率半徑R≧31m，更佳包含熱塑性樹脂(B)之層側為凹部且曲率半徑R≧11m，或更佳包含熱塑性樹脂(B)之層側為凸部且曲率半徑R≧41m，又更佳包含熱塑性樹脂(B)之層側為凹部且曲率半徑R≧12m，或包含熱塑性樹脂(B)之層側為凸部且曲率半徑R≧61m，特佳包含熱塑性樹脂(B)之層側為凹部且曲率半徑R≧13m，或包含熱塑性樹脂(B)之層側為凸部且曲率半徑R≧123m。包含熱塑性樹脂(B)之層側為凹部且曲率半徑R＜10m或包含熱塑性樹脂(B)之層側為凸部且曲率半徑R＜31m時，於樹脂積層體之包含熱塑性樹脂(B)之層側表面進而積層抗反射層之樹脂積層體於85℃85%RH環境下放置120h後之凹部或凸部翹曲較大，在高溫高濕環境下發生形狀變化，可能發生品質問題。A resin laminate comprising a layer comprising a polycarbonate resin (A) and a layer comprising a thermoplastic resin (B), or a layer comprising a polycarbonate resin (A) and a layer comprising a thermoplastic resin (B) and a layer comprising The surface of the layer side of the thermoplastic resin (B) is subjected to any one or more of hard coating treatment, antireflection treatment, antifouling treatment, anti-fingerprint treatment, antistatic treatment, weather resistance treatment and anti-glare treatment. The curled shape after 120 hr in the %RH environment is preferably a concave portion on the side of the layer containing the thermoplastic resin (B) and a radius of curvature R≧10m, or a layer containing the thermoplastic resin (B) The side is a convex portion and the radius of curvature R≧31m , more preferably the side of the layer containing the thermoplastic resin (B) is a concave part and the radius of curvature R≧11m, or more preferably the side of the layer containing the thermoplastic resin (B) is a convex part and the radius of curvature R≧41m, and more preferably the thermoplastic resin ( The layer side of B) is a concave part and the curvature radius R≧12m, or the layer side containing the thermoplastic resin (B) is a convex part and the curvature radius R≧61m, especially preferably the layer side containing the thermoplastic resin (B) is a concave part and the curvature radius R≧13m, or the side of the layer containing the thermoplastic resin (B) is a convex portion and the radius of curvature R≧123m. When the side of the layer containing the thermoplastic resin (B) is a concave part and the radius of curvature R<10m, or the side of the layer containing the thermoplastic resin (B) is a convex part and the radius of curvature R<31m, in the resin laminate body containing the thermoplastic resin (B) The concave or convex portion of the resin laminate with the anti-reflection layer on the side surface and the anti-reflection layer is greatly warped after being placed in an environment of 85°C and 85%RH for 120 hours, and the shape changes in a high-temperature and high-humidity environment, which may cause quality problems.

針對對於(i)包含聚碳酸酯系樹脂(A)之層與包含熱塑性樹脂(B)之層的樹脂積層體，或(ii)包含聚碳酸酯系樹脂(A)之層與包含熱塑性樹脂(B)之層與於包含熱塑性樹脂(B)之層側的表面實施硬塗布處理、反射防止處理、防汙處理、耐指紋處理、抗靜電處理、耐候性處理及防眩處理中任一種以上之樹脂積層體，於包含熱塑性樹脂(B)之層側的表面進一步積層抗反射層之樹脂積層體，於85℃85%RH環境下放置120h後之捲曲形狀較佳為包含熱塑性樹脂(B)之層側為凹部或凸部且曲率半徑R≧15m，更佳為包含熱塑性樹脂(B)之層側為凹部或凸部且曲率半徑R≧18m，又更佳包含熱塑性樹脂(B)之層側為凹部或凸部且曲率半徑R≧20m，特佳包含熱塑性樹脂(B)之層側為凹部或凸部且曲率半徑R≧23m。包含熱塑性樹脂(B)之層側為凹部或凸部且曲率半徑R＜15m時，於包含熱塑性樹脂(B)之層側的表面進一步積層抗反射層之樹脂積層體於85℃85%RH環境下放置120h後之凹部或凸部的翹曲較大，在高溫高濕環境下發生形狀變化，可能發生品質問題。For (i) a layer comprising a polycarbonate-based resin (A) and a layer comprising a thermoplastic resin (B) for a resin laminate, or (ii) a layer comprising a polycarbonate-based resin (A) and a layer comprising a thermoplastic resin ( The layer of B) and the surface of the layer containing the thermoplastic resin (B) are subjected to any one or more of hard coating treatment, antireflection treatment, antifouling treatment, anti-fingerprint treatment, antistatic treatment, weather resistance treatment and anti-glare treatment The resin laminate is a resin laminate in which an anti-reflection layer is further laminated on the surface of the layer side containing the thermoplastic resin (B). The layer side is a concave part or a convex part and the curvature radius R≧15m, more preferably the layer side containing the thermoplastic resin (B) is a concave part or a convex part and the curvature radius R≧18m, and more preferably the layer side containing the thermoplastic resin (B) It is a concave part or a convex part, and the curvature radius R≧20m, and it is especially preferable that the layer side containing the thermoplastic resin (B) is a concave part or a convex part and the curvature radius R≧23m. When the side of the layer containing the thermoplastic resin (B) is a concave part or a convex part and the radius of curvature R<15m, the resin laminate with an anti-reflection layer is further laminated on the surface of the layer side containing the thermoplastic resin (B) at 85°C 85%RH environment The warpage of the concave part or the convex part after being left to stand for 120 hours is large, and the shape changes in a high temperature and high humidity environment, which may cause quality problems.

本發明中，包含熱塑性樹脂(A)之層及/或包含熱塑性樹脂(B)之層中可包含上述主要成分以外之成分。例如，包含熱塑性樹脂(A)之層及/或包含熱塑性樹脂(B)之層中可混合紫外線吸收劑而使用。又本發明中，硬塗布層亦可包含紫外線吸收劑。紫外線吸收劑之含量過少時，耐光性不足，含量過多時，根據成形方法而有過量之紫外線吸收劑因經歷高溫度而飛散並汙染成形環境，引起缺陷之情況。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%。作為紫外線吸收劑，舉例為例如2,4-二羥基二苯甲酮、2-羥基-4-甲氧基二苯甲酮、2-羥基-4-正辛氧基二苯甲酮、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-第三丁基苯基)苯并***、2-(2-羥基-3-第三丁基-5-甲基苯基)苯并***、(2H-苯并***-2-基)-4,6-二(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、3,5-二-第三丁基-4-羥基苯甲酸2,4-二-第三丁基苯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、2,4-二苯基-(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等。混合方法並未特別限制，可使用總量化合之方法、乾摻混母批料之方法、全量乾摻混之方法等。In the present invention, components other than the above-mentioned main components may be contained in the layer containing the thermoplastic resin (A) and/or the layer containing the thermoplastic resin (B). For example, an ultraviolet absorber can be mixed and used in the layer containing thermoplastic resin (A) and/or the layer containing thermoplastic resin (B). Moreover, in this invention, a hard-coat layer may contain an ultraviolet absorber. When the content of the ultraviolet absorber is too small, the light resistance is insufficient, and when the content is too large, the excessive ultraviolet absorber may be scattered due to the high temperature due to the molding method, and the molding environment may be polluted, causing defects. The content ratio of the ultraviolet absorber is preferably 0 to 5% by mass, more preferably 0 to 3% by mass, and still more preferably 0 to 1% by mass. As the ultraviolet absorber, for example, 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-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3- tert-butyl-5-methylphenyl)benzotriazole, (2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, etc. Benzotriazole-based UV absorbers, benzoates such as phenyl salicylate, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, etc. UV absorber, hindered amine UV absorber 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-diphenyl-(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, Triazine-based ultraviolet absorbers such as 2,4-diphenyl-6-(2-hydroxy-4-benzyloxyphenyl)-1,3,5-triazine and the like. The mixing method is not particularly limited, and a method of total amount compounding, a method of dry blending a master batch, a method of full amount dry blending, and the like can be used.

本發明之樹脂積層體於其單面獲兩面可實施指紋處理、反射防止處理、防汙處理、抗靜電處理、耐候性處理及防眩處理中任一種以上。反射防止處理、防汙處理、抗靜電處理、耐候性處理及防眩處理之方法並未特別限制，可使用習知方法。舉例為例如塗布反射減低塗料之方法、蒸鍍介電體薄膜之方法、塗布抗靜電塗料之方法。The resin laminate of the present invention can be subjected to any one or more of fingerprint treatment, anti-reflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment and anti-glare treatment on one side or both sides. The methods of anti-reflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment and anti-glare treatment are not particularly limited, and conventional methods can be used. Examples are, for example, a method of applying a reflection-reducing paint, a method of evaporating a dielectric film, and a method of applying an antistatic paint.

＜任意添加劑＞本發明中，於包含聚碳酸酯系樹脂(A)之層及/或包含熱塑性樹脂(B)之層中，除紫外線吸收劑以外，亦可混合各種添加劑而使用。作為此等添加劑，舉例為例如抗氧化劑或抗著色劑、抗靜電劑、脫模劑、潤滑劑、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之強化材。混合方法並未特別限制，可使用總量化合之方法、乾摻混母批料之方法、全量乾摻混之方法等。＜Optional Additives＞ In the present invention, in the layer containing the polycarbonate resin (A) and/or the layer containing the thermoplastic resin (B), various additives other than the ultraviolet absorber may be mixed and used. As such additives, for example, antioxidants or anticolorants, antistatic agents, mold release agents, lubricants, dyes, pigments, plasticizers, flame retardants, resin modifiers, compatibilizers, organic fillers or inorganic Reinforcing materials such as fillers. The mixing method is not particularly limited, and a method of total amount compounding, a method of dry blending a master batch, a method of full amount dry blending, 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)之層及硬塗布之各材料，例如聚碳酸酯系樹脂(A)及熱塑性樹脂(B)等，較佳藉由過濾處理而過濾純化。藉由通過過濾器而生成或積層，可獲得異物或缺陷等之外觀不良少的樹脂積層體。過濾方法並未特別限制，可使用熔融過濾、溶液過濾或其組合等。In the present invention, the layer comprising the polycarbonate resin (A), the layer comprising the thermoplastic resin (B), and the materials of the hard coating, such as the polycarbonate resin (A) and the thermoplastic resin (B), are preferably Filtration purification by filtration treatment. By passing through a filter to generate or laminate, a resin laminate with few appearance defects such as foreign matter and defects can be obtained. The filtration method is not particularly limited, and melt filtration, solution filtration, a combination thereof, or the like can be used.

＜各種材料製造方法＞本發明之一形態有關樹脂積層體之製造方法，其係將包含熱塑性樹脂(B)之層積層於包含聚碳酸酯系樹脂(A)之層的至少一面上。本發明之樹脂積層體之製造方法並未特別限制。可有例如將個別形成之包含熱塑性樹脂(B)之層與包含聚碳酸酯系樹脂(A)之層予以積層並將兩者加熱壓接之方法，將個別形成之包含熱塑性樹脂(B)之層與包含聚碳酸酯系樹脂(A)之層予以積層，利用接著劑將兩者接著之方法，將包含熱塑性樹脂(B)之層與包含聚碳酸酯系樹脂(A)之層共擠出成形之方法，使用預先形成之包含熱塑性樹脂(B)之層，將包含聚碳酸酯系樹脂(A)之層進行模內成形而一體化之方法等之各種方法，但基於製造成本及生產性之觀點，較佳為共擠出成形之方法。作為共擠出成形之方法，可舉例為例如將包含聚碳酸酯系樹脂(A)之層與包含熱塑性樹脂(B)之層分別以擠出機加熱熔融，自T型模嘴之狹縫狀噴出口分別擠出並積層，然後以冷卻輥予以密著固化之製造方法。實施形態之製造方法，係將自模嘴共擠出之熔融狀態之包含聚碳酸酯系樹脂(A)之層與包含熱塑性樹脂(B)之層，夾於第1冷卻輥與第2冷卻輥之間，捲掛於第2冷卻輥之後，捲繞於至少1根後段冷卻輥。隨後，以夾輥進給獲得樹脂積層體。＜Manufacturing methods of various materials＞ One aspect of the present invention relates to a method for producing a resin laminate comprising laminating a thermoplastic resin (B) on at least one surface of a layer containing a polycarbonate resin (A). The manufacturing method of the resin laminated body of this invention is not specifically limited. For example, there may be a method of laminating the separately formed layer containing the thermoplastic resin (B) and the layer containing the polycarbonate-based resin (A) and bonding the two by heat and pressure, and the separately formed layer containing the thermoplastic resin (B) may be used. The layer and the layer containing the polycarbonate resin (A) are laminated, and the two are bonded with an adhesive, and the layer containing the thermoplastic resin (B) and the layer containing the polycarbonate resin (A) are co-extruded The molding method includes various methods such as a method of in-mold molding and integrating a layer containing a polycarbonate resin (A) using a layer containing a thermoplastic resin (B) formed in advance, but based on manufacturing costs and productivity From this viewpoint, the method of co-extrusion molding is preferable. As a method of co-extrusion molding, for example, the layer containing the polycarbonate-based resin (A) and the layer containing the thermoplastic resin (B) are heated and melted by an extruder, respectively, and a slit formed from a T-die is exemplified. A manufacturing method in which the nozzles are extruded and laminated, and then adhered and solidified with a cooling roll. In the production method of the embodiment, the layer containing the polycarbonate-based resin (A) and the layer containing the thermoplastic resin (B) in a molten state coextruded from a die are sandwiched between a first cooling roll and a second cooling roll In between, after being wound on the 2nd cooling roll, it is wound around at least 1 post-stage cooling roll. Subsequently, the resin layered body is obtained by feeding with nip rolls.

以擠出機加熱熔融之溫度較佳比聚碳酸酯系樹脂(A)及熱塑性樹脂(B)之各玻璃轉移溫度(Tg)高80~150℃之溫度。一般擠出聚碳酸酯系樹脂(A)之主擠出機的溫度條件通常為200~290℃，較佳為210~280℃，擠出熱塑性樹脂(B)之副擠出機之溫度條件通常為180~280℃，較佳為190~270℃。The temperature of heating and melting by the extruder is preferably 80 to 150°C higher than the glass transition temperature (Tg) of the polycarbonate resin (A) and the thermoplastic resin (B). Generally, the temperature conditions of the main extruder for extruding the polycarbonate resin (A) are usually 200 to 290°C, preferably 210 to 280°C, and the temperature conditions of the sub-extruder for extruding the thermoplastic resin (B) are usually It is 180-280 degreeC, Preferably it is 190-270 degreeC.

作為共擠出2種熔融樹脂之方法，可採用供料塊方式、多歧管方式等之習知方法。例如，若為供料塊方式之情況，以供料塊將積層之熔融樹脂導入T模嘴等之薄片形成模嘴，成形為薄片狀後，流入至表面經鏡面處理之成形輥(拋光輥)形成堤，於該成形輥通過中進行表面精加工及冷卻即可。於多歧管方式之情況，於多歧管模嘴內將積層之熔融樹脂於模具內成形為薄片狀後，以成形輥進行表面精加工及冷卻即可。As a method of co-extruding two kinds of molten resins, conventional methods such as a feed block method and a multi-manifold method can be used. For example, in the case of the feed block method, the laminated molten resin is introduced into a sheet forming die such as a T-die with a feed block, and after being shaped into a sheet, it flows into a forming roll (polishing roll) whose surface is mirror-finished. The banks may be formed, and surface finishing and cooling may be performed during the passage of the forming roll. In the case of the multi-manifold method, the molten resin layered in the multi-manifold die is formed into a sheet shape in a mold, and then surface finishing and cooling are performed with a forming roll.

任一情況下，模嘴溫度通常設定為230~290℃，其中較佳為250~ 280℃。作為成形輥有剛性輥或彈性輥，任一種均可使用。In either case, the die temperature is usually set to 230 to 290°C, and preferably 250 to 280°C. As the forming roll, either a rigid roll or an elastic roll can be used.

為了對表面進行鏡面處理，夾在第1冷卻輥與第2冷卻輥之間，捲掛於前述第2冷卻輥後，較佳以至少1根後段冷卻輥繞掛聚碳酸酯系樹脂(A)面。第1冷卻輥及第2冷卻輥之溫度通常設定為70~150℃，其中較佳為80~135℃。輥周速度設定為0.5～30.0m/min，其中較佳為0.8～6.0m/min。後段冷卻輥與夾輥之速度比設定為夾輥速度(m/min)/後段冷卻輥速度(m/min)=0.5～2.0，其中較佳為0.7～1.8。In order to mirror-finish the surface, it is sandwiched between the first cooling roll and the second cooling roll, and after being wrapped around the second cooling roll, it is preferable to wrap the polycarbonate-based resin (A) around at least one subsequent cooling roll. noodle. The temperature of the first cooling roll and the second cooling roll is usually set to 70 to 150°C, and preferably 80 to 135°C. The peripheral speed of the roll is set to 0.5 to 30.0 m/min, preferably 0.8 to 6.0 m/min. The speed ratio of the rear cooling roll and the nip roll is set as nip roll speed (m/min)/backward cooling roll speed (m/min)=0.5-2.0, preferably 0.7-1.8.

本發明之製造方法較佳在繞掛於第2冷卻輥後剝離後段冷卻輥後之冷卻過程中以產線內加熱器加熱樹脂積層體之包含熱塑性樹脂(B)之層側。在剝離後段冷卻輥後之冷卻過程中以產線內加熱器加熱樹脂積層體之包含熱塑性樹脂(B)之層側的溫度較佳為200℃~410℃，更佳為250℃~405℃，又更佳為320℃~400℃。以產線內加熱器加熱之溫度未達200℃時，加熱溫度較弱，無法將樹脂積層體之包含熱塑性樹脂(B)之層矯正為凹部。以產線內加熱器加熱之溫度超過410℃時，加熱溫度強，樹脂積層體之包含熱塑性樹脂(B)之層較大變凹，進一步積層抗反射層之樹脂積層體之形狀大為變凹，可能發生品質問題。本發明中之「後段冷卻輥溫度」是指循環的熱介質之後段冷卻輥入口的溫度。In the production method of the present invention, the layer side containing the thermoplastic resin (B) of the resin laminate is preferably heated with an in-line heater during the cooling process after the second cooling roll is peeled off from the second cooling roll. The temperature at which the layer side containing the thermoplastic resin (B) of the resin laminate is heated by an in-line heater during the cooling process after peeling off the cooling roll at the rear stage is preferably 200°C to 410°C, more preferably 250°C to 405°C, More preferably, it is 320 to 400 degreeC. When the temperature heated by the in-line heater is less than 200° C., the heating temperature is weak, and the layer containing the thermoplastic resin (B) of the resin laminate cannot be corrected into a concave portion. When the temperature heated by the heater in the production line exceeds 410°C, the heating temperature is strong, the layer containing the thermoplastic resin (B) in the resin laminate becomes more concave, and the shape of the resin laminate on which the anti-reflection layer is further laminated becomes more concave. , quality problems may occur. The "post-stage cooling roll temperature" in the present invention refers to the temperature at the inlet of the post-stage cooling roll of the circulating heat medium.

所使用之過濾器並未特別限制，可使用習知者，根據各材料之使用溫度、黏度、過濾精度適當選擇。作為過濾器之濾材並未特別限制，聚丙烯、棉、聚酯、人造絲縲縈或玻璃纖維之不織布或編紗捲、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、濾網換網板(breaker plate)或其組合均可使用。尤其若考慮耐熱性及耐久性、耐壓力性，較佳為將金屬纖維不織布予以燒結之類型。The filters used are not particularly limited, and those known in the art can be used, and are appropriately selected according to the use temperature, viscosity, and filtration precision of each material. The filter material of the filter is not particularly limited, such as polypropylene, cotton, polyester, rayon, rayon, or glass fiber non-woven fabric or woven yarn roll, cellulose impregnated with phenol resin, metal fiber non-woven fabric sintered body, metal powder sintered body, Screen breaker plates or combinations thereof may be used. In particular, considering heat resistance, durability, and pressure resistance, a type of sintered metal fiber nonwoven fabric is preferred.

過濾精度，針對聚碳酸酯系樹脂(A)及熱塑性樹脂(B)，為50μm以下，較佳30μm以下，更佳10μm以下。又，硬塗布劑之過濾精度，由於係塗布於樹脂積層體之最表層，故為20μm以下，較佳10μm以下，更佳2μm以下。The filtration accuracy is 50 μm or less, preferably 30 μm or less, and more preferably 10 μm or less, for the polycarbonate resin (A) and the thermoplastic resin (B). In addition, the filtration accuracy of the hard coating agent is 20 μm or less, preferably 10 μm or less, and more preferably 2 μm or less, since it is applied to the outermost layer of the resin laminate.

對於聚碳酸酯系樹脂(A)與熱塑性樹脂(B)之過濾，例如較佳使用用於熱塑性樹脂熔融過濾之聚合物過濾器。聚合物過濾器根據其構造可分類為葉盤過濾器、燭型過濾器、裝盤過濾器、圓筒型過濾器等，但特別適宜為有效過濾面積較大之葉盤過濾器。For filtration of the polycarbonate resin (A) and the thermoplastic resin (B), for example, a polymer filter for melt filtration of thermoplastic resins is preferably used. Polymer filters can be classified into leaf disc filters, candle filters, disc filters, cylindrical filters, etc., according to their structures, but are particularly suitable for leaf disc filters with large effective filtration areas.

＜抗反射層＞抗反射層係積層折射率不同之複數薄膜(較佳2~10層，更佳3~8層)，構成為於各薄膜界面反射之反射光因干涉而被抵消。因此，可減低反射率，可減低因外部光映入所致之眩光。<Anti-reflection layer> The anti-reflection layer is composed of multiple thin films (preferably 2 to 10 layers, more preferably 3 to 8 layers) with different refractive indices, and the reflection light reflected at the interface of each thin film is canceled due to interference. Therefore, the reflectance can be reduced, and the glare caused by the reflection of external light can be reduced.

抗反射層之材料並未特別限制，可使用習知材料，根據樹脂積層體之材料適當選擇即可。例如，可為高折射率層與低折射率層積層之構造。高折射率層與低折射率層可為分別各一層之形態，亦可為各包含2層以上之形態。各包含2層以上之高折射率層與低折射率層時，較佳高折射率層與低折射率層係交替積層。高折射率層與低折射率層之材料並未特別限制，可考慮所需之反射防止性能及生產率等予以選擇。作為構成高折射率層之材料，可較佳地利用包含選自鈮、鈦、鋯、鉭及矽所成之群之1種以上之材料。具體舉例為氧化鈮(Nb₂ O₅ )、氧化鈦(TiO₂ )、氧化鋯(ZrO₂ )、氧化鉭(Ta₂ O₅ )、氮化矽等。作為構成低折射率層之材料，例如可較佳地使用含矽之材料。具體舉例為氧化矽(SiO₂ )、包含Si與Sn之混合氧化物之材料、包含Si與Zr之混合氧化物之材料、包含Si與Al之混合氧化物之材料。The material of the anti-reflection layer is not particularly limited, and conventional materials may be used, and may be appropriately selected according to the material of the resin laminate. For example, the structure of a high-refractive-index layer and a low-refractive-index laminated layer may be used. The high-refractive index layer and the low-refractive index layer may be in the form of one layer, respectively, or may be in the form of two or more layers each. When each includes two or more high-refractive-index layers and low-refractive-index layers, it is preferable that the high-refractive-index layers and the low-refractive-index layers are alternately laminated. The materials of the high-refractive index layer and the low-refractive index layer are not particularly limited, and can be selected in consideration of desired antireflection performance, productivity, and the like. As the material constituting the high refractive index layer, one or more materials selected from the group consisting of niobium, titanium, zirconium, tantalum, and silicon can be preferably used. Specific examples include niobium oxide (Nb ₂ O ₅ ), titanium oxide (TiO ₂ ), zirconium oxide (ZrO ₂ ), tantalum oxide (Ta ₂ O ₅ ), silicon nitride, and the like. As the material constituting the low refractive index layer, for example, a material containing silicon can be preferably used. Specific examples are silicon oxide (SiO ₂ ), a material comprising a mixed oxide of Si and Sn, a material comprising a mixed oxide of Si and Zr, and a material comprising a mixed oxide of Si and Al.

抗反射層之加工方法並未特別限制，可使用習知者，根據各材料適當選擇。舉例為例如真空蒸鍍法及濺鍍法、離子鍍敷法等。對塑膠成膜抗反射層時，較佳使用儘可能不需要加熱之真空蒸鍍法及濺鍍法。抗反射層之合計厚度較佳為100~600nm，更佳為150 ~550nm。合計厚度厚於600nm時，有信賴性、生產性降低，導致成本增加之虞。另一方面，薄於100nm時，有難以設計反射防止性之情況。The processing method of the antireflection layer is not particularly limited, and a conventional one can be used, and it can be appropriately selected according to each material. For example, a vacuum evaporation method, a sputtering method, an ion plating method, etc. are mentioned. When forming an anti-reflection layer on plastic, it is better to use vacuum evaporation method and sputtering method that do not require heating as much as possible. The total thickness of the anti-reflection layer is preferably 100-600 nm, more preferably 150-550 nm. When the total thickness is thicker than 600 nm, the reliability and productivity may be lowered, and the cost may increase. On the other hand, when the thickness is thinner than 100 nm, it may be difficult to design antireflection properties.

＜用途＞實施形態之樹脂積層體之抗反射層之加工性優異，可適當作為透明基板材料或透明保護材料等使用。具體而言，可較佳地使用作為行動電話終端、攜帶型電子遊戲設備、攜帶式資訊終端、移動式PC之攜帶式顯示裝置、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裝置等之透明基板材料及透明保護材料(例如前面板)。 [實施例]＜Use＞ The antireflection layer of the resin laminate of the embodiment is excellent in workability, and can be suitably used as a transparent substrate material, a transparent protective material, and the like. Specifically, it can be preferably used as a mobile phone terminal, a portable electronic game device, a portable information terminal, a portable display device for a mobile PC, a notebook PC, a desktop PC LCD monitor, and a car navigation LCD monitor. Transparent substrate materials and transparent protective materials (such as front panels) for installation-type display devices such as monitors, LCD TVs, etc. [Example]

以下，藉由實施例具體說明本發明。但，本發明不受該等實施例之任何限制。Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited by these embodiments.

製造例所得之共聚物之外觀評價及實施例及比較例所得之樹脂積層體之外觀評價如以下進行。The appearance evaluation of the copolymer obtained in the production example and the appearance evaluation of the resin laminate obtained in the examples and comparative examples were performed as follows.

＜全光線透過率測定＞使用村上色彩技術研究所(股)製之反射・透過率計HR-100型測定全光線透過率。<Total light transmittance measurement> The total light transmittance was measured using a reflectance/transmittance meter HR-100 manufactured by Murakami Color Institute Co., Ltd.

＜濁度測定＞使用日本電色工業(股)製COH-400測定濁度。<turbidity measurement> The turbidity was measured using COH-400 manufactured by Nippon Denshoku Kogyo Co., Ltd.

＜共聚物中單體單位之莫耳比＞使用日本電子(股)製JNM-AL400，自¹ H-NMR及¹³ C-NMR (400MHz：溶劑為CDCl₃ )之測定值計算出。<Molar ratio of monomer unit in 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).

＜共聚物之氫化率＞由氫化反應前後之UV光譜測定中260nm之吸收減少率求出。各種共聚物以任意比例溶解於四氫呋喃中，自氫化反應前之樹脂濃度C1之吸光度A1、氫化反應後之樹脂濃度C2之吸光度A2，由下述式算出。氫化率=100×[1-(A2×C1)/(A1×C2)]<Hydrogenation rate of copolymer> It was calculated|required from the absorption reduction rate at 260 nm in the UV spectrum measurement before and after hydrogenation reaction. Various copolymers were dissolved in tetrahydrofuran at any ratio, and the absorbance A1 of the resin concentration C1 before the hydrogenation reaction and the absorbance A2 of the resin concentration C2 after the hydrogenation reaction were calculated by the following formula. Hydrogenation rate=100×[1-(A2×C1)/(A1×C2)]

＜玻璃轉移溫度＞使用精工儀器(股)製示差掃描熱量測定裝置DSC6200。於氮30ml/min流通下，以10℃/min自30℃升溫至200℃，其次以50℃/min自200℃冷卻至30℃，再次以10℃/min自從30℃升溫至200℃。第2次升溫之中間點玻璃轉移溫度(Tmg)使用作為玻璃轉移溫度。<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, followed by cooling from 200°C to 30°C at 50°C/min, and then heated from 30°C to 200°C at 10°C/min. The glass transition temperature (Tmg) at the midpoint of the second temperature increase was used as the glass transition temperature.

＜折射率測定＞以(股)ATAGO公司製多波長阿貝折射計DR-M2測定。測定溫度為20℃，測定波長為589nm，中間液使用單溴萘。<Refractive index measurement> Measured with a multi-wavelength Abbe refractometer DR-M2 manufactured by ATAGO Corporation. The measurement temperature was 20° C., the measurement wavelength was 589 nm, and monobromonaphthalene was used as the intermediate solution.

＜捲曲形狀之評價(曲率半徑R與凹凸方向)＞由於於23℃50%RH環境下、85℃85%RH環境下放置後之積層體具有捲曲形狀，故捲曲型狀之曲率半徑與凹凸方向係以包含熱塑性樹脂(B)之層側為凸，或包含熱塑性樹脂(B)之層側為凹(包含聚碳酸酯系樹脂(A)之層側為凸)而評價。以曲率半徑(m)={弧長[m](=試驗片長度)}² /(8×箭頭高度[m])而定義。此時，包含熱塑性樹脂(B)之層側為凸時，以「-」符號評價，包含熱塑性樹脂(B)之層側為凹時以「+」符號評價。<Evaluation of curl shape (curvature radius R and concave-convex direction)> Since the laminated body after being left in an environment of 23°C 50% RH and 85°C 85% RH has a curly shape, the radius of curvature of the curl shape and the direction of the concave-convex shape The evaluation was performed on the basis that the side of the layer containing the thermoplastic resin (B) was convex, or the side of the layer containing the thermoplastic resin (B) was concave (the side of the layer containing the polycarbonate resin (A) was convex). It is defined by curvature radius (m)={arc length [m] (=test piece length)} ² /(8×arrow height [m]). At this time, when the layer side containing the thermoplastic resin (B) was convex, it was evaluated with a "-" sign, and when the layer side containing the thermoplastic resin (B) was concave, it was evaluated with a "+" sign.

＜23℃50%環境下放置後之捲曲形狀之評價＞將試驗片切成280mm×140mm四方形。將試驗片設置於2點支撐型支架，於設定於溫度23℃、相對濕度50%之環境試驗機中投入24小時以上進行狀態調整後測定h(=箭頭高度[m])。箭頭高度之測定使用具備電動載臺之三維形狀測定機，將取出之測驗片以凸為上之狀態水平靜置，以2mm的間隔掃描，測定中央部之***作為箭頭高度，以(曲率半徑[m])={0.313(=弧長[m])}² /(8×h[m])評價下述積層體之捲曲形狀：包含聚碳酸酯系樹脂(A)之層與包含熱塑性樹脂(B)之層的樹脂積層體；包含聚碳酸酯系樹脂(A)之層與包含熱塑性樹脂(B)之層與於包含熱塑性樹脂(B)之層側的表面實施硬塗布處理之樹脂積層體；或於上述樹脂積層體之包含熱塑性樹脂(B)之層側表面進而積層抗反射層之樹脂積層體。 (不含抗反射層之樹脂積層體之情況) ○(合格)：包含熱塑性樹脂(B)之層側為凹且11m≦曲率半徑R≦1225m。 ×(不合格)：上述範圍以外。 (包含抗反射層之樹脂積層體之情況) ○(合格)：包含熱塑性樹脂(B)之層側為凹或為凸且曲率半徑R≧21m。 ×(不合格)：上述範圍以外。<Evaluation of curl shape after standing in 23° C. 50% environment> The test piece was cut into a 280 mm×140 mm square. The test piece was placed on a 2-point support type stand, put into an environmental testing machine set at a temperature of 23° C. and a relative humidity of 50% for more than 24 hours to adjust the state, and then measured h (=height of the arrow [m]). The arrow height was measured using a three-dimensional shape measuring machine equipped with a motorized stage. The removed test piece was placed horizontally with the convexity up, and scanned at 2 mm intervals. The bulge at the center was measured as the height of the arrow. m])={0.313(=arc length [m])} ² /(8×h[m]) to evaluate the curl shape of the following laminates: the layer containing the polycarbonate resin (A) and the layer containing the thermoplastic resin ( A resin laminate of the layer of B); a resin laminate of a layer comprising a polycarbonate-based resin (A), a layer comprising a thermoplastic resin (B), and a layer comprising a thermoplastic resin (B) having a hard coat treatment on the surface ; or a resin laminate in which an antireflection layer is further laminated on the side surface of the layer containing the thermoplastic resin (B) of the resin laminate. (In the case of a resin laminate not containing an antireflection layer) ○ (pass): The layer side containing the thermoplastic resin (B) is concave and 11m≦curvature radius R≦1225m. × (unacceptable): outside the above-mentioned range. (In the case of a resin laminate including an antireflection layer) ○ (pass): The layer side including the thermoplastic resin (B) is concave or convex and the radius of curvature R≧21m. × (unacceptable): outside the above-mentioned range.

＜85℃85%環境下放置後之捲曲形狀之評價＞將試驗片切成280mm×140mm四方形。將試驗片設置於2點支撐型支架，於設定於溫度23℃、相對濕度50%之環境試驗機中投入24小時以上進行狀態調整後，將支架投入設定於溫度85℃、相對濕度85%之環境試驗機中，以該狀態保持120小時。進而連同支架移動至設定於溫度23℃、相對濕度50%之環境試驗機中，以該狀態保持4小時後，測定h(=箭頭高度[m])。箭頭高度之測定使用具備電動載臺之三維形狀測定機，將取出之測驗片以凸為上之狀態水平靜置，以2mm的間隔掃描，測定中央部之***作為箭頭高度，以(曲率半徑[m])={0.313(=弧長[m])}² /(8×h[m])評價下述積層體之捲曲形狀：包含聚碳酸酯系樹脂(A)之層與包含熱塑性樹脂(B)之層的樹脂積層體；包含聚碳酸酯系樹脂(A)之層與包含熱塑性樹脂(B)之層與於包含熱塑性樹脂(B)之層側的表面實施硬塗布處理之樹脂積層體；或於上述樹脂積層體之包含熱塑性樹脂(B)之層側表面進而積層抗反射層之樹脂積層體。<Evaluation of curl shape after standing in 85°C 85% environment> The test piece was cut into a 280 mm×140 mm square. Set the test piece on a 2-point support type rack, put it into an environmental testing machine set at a temperature of 23°C and a relative humidity of 50% for more than 24 hours to adjust the state, and then put the rack into a temperature set at a temperature of 85°C and a relative humidity of 85%. In the environmental testing machine, this state was maintained for 120 hours. Furthermore, it moved to the environmental testing machine set at the temperature of 23 degreeC, and the relative humidity of 50% together with the stand, and after maintaining this state for 4 hours, h (=height of arrow [m]) was measured. The arrow height was measured using a three-dimensional shape measuring machine equipped with a motorized stage. The removed test piece was placed horizontally with the convexity up, and scanned at 2 mm intervals. The bulge at the center was measured as the height of the arrow. m])={0.313(=arc length [m])} ² /(8×h[m]) to evaluate the curl shape of the following laminates: the layer containing the polycarbonate resin (A) and the layer containing the thermoplastic resin ( A resin laminate of the layer of B); a resin laminate of a layer comprising a polycarbonate-based resin (A), a layer comprising a thermoplastic resin (B), and a layer comprising a thermoplastic resin (B) having a hard coat treatment on the surface ; or a resin laminate in which an antireflection layer is further laminated on the side surface of the layer containing the thermoplastic resin (B) of the resin laminate.

＜鉛筆畫過硬度試驗＞依據JIS K 5600-5-4，對於表面以角度45度、荷重750g，將鉛筆按壓於包含熱塑性樹脂(B)之層側之表面，逐漸增加硬度，將不產生傷痕之最硬鉛筆的硬度評價為鉛筆硬度。 (不含抗反射層之樹脂積層體之情況) ○(合格)：鉛筆硬度HB以上。 ×(不合格)：上述範圍以外。 (含抗反射層之樹脂積層體之情況) ○(合格)：鉛筆硬度HB以上。 ×(不合格)：上述範圍以外。＜Pencil drawing hardness test＞ According to JIS K 5600-5-4, with an angle of 45 degrees and a load of 750 g, the pencil was pressed against the surface of the layer side containing the thermoplastic resin (B), the hardness was gradually increased, and the hardness of the hardest pencil that did not produce scratches was evaluated. for pencil hardness. (In the case of a resin laminate without an antireflection layer) ○ (pass): pencil hardness HB or more. × (unacceptable): outside the above-mentioned range. (In the case of a resin laminate with an antireflection layer) ○ (pass): pencil hardness HB or more. × (unacceptable): outside the above-mentioned range.

＜抗反射層之積層(加工法)＞藉由真空蒸鍍在樹脂積層體之包含熱塑性樹脂(B)之層側表面進行各層之形成。重複積層SiO₂ (折射率：1.46)與TiO₂ (折射率：2.49)，形成抗反射層。積層順序及膜厚如下。第1層係與樹脂積層體接觸之層，第6層係與空氣層接觸之最外層。第1層：TiO₂ 8nm 第2層：SiO₂ 51nm 第3層：TiO₂ 20nm 第4層：SiO₂ 42nm 第5層：TiO₂ 20nm 第6層：SiO₂ 113nm<Lamination of Antireflection Layer (Processing Method)> Each layer is formed by vacuum deposition on the side surface of the layer containing the thermoplastic resin (B) of the resin laminate. The antireflection layer was formed by repeatedly laminating SiO ₂ (refractive index: 1.46) and TiO ₂ (refractive index: 2.49). The stacking order and film thickness are as follows. The first layer is the layer in contact with the resin laminate, and the sixth layer is the outermost layer in contact with the air layer. 1st layer: _TiO2 8nm 2nd layer: _SiO2 51nm 3rd layer: _TiO2 20nm 4th layer: _SiO2 42nm 5th layer: _TiO2 20nm 6th layer: _SiO2 113nm

用於實施例或比較例，作為聚碳酸酯系樹脂(A-1)、熱塑性樹脂 (B-1)、乙烯基共聚物(C-1)及苯乙烯共聚物(D-1)，係使用如下所示之材料，但不限於該等。Used in Examples or Comparative Examples, used as polycarbonate resin (A-1), thermoplastic resin (B-1), vinyl copolymer (C-1) and styrene copolymer (D-1) Materials shown below, but not limited to these.

＜聚碳酸酯系樹脂(A-1)及苯乙烯共聚物(D-1)＞聚碳酸酯系樹脂(A-1)：三菱工程塑膠股份有限公司製之LUPILONE S-1000(重量平均分子量：33,000，玻璃轉移溫度：147℃，折射率1.586) 苯乙烯共聚物(D-1)：Polyscope公司製XIBOND140(重量平均分子量：114,000，玻璃轉移溫度：134℃，(d1)/(d2)=苯乙烯/馬來酸酐=85莫耳%/15莫耳%，折射率1.590)<Polycarbonate resin (A-1) and styrene copolymer (D-1)> Polycarbonate resin (A-1): LUPILONE S-1000 manufactured by Mitsubishi Engineering Plastics Co., Ltd. (weight average molecular weight: 33,000, glass transition temperature: 147°C, refractive index 1.586) Styrene copolymer (D-1): XIBOND140 manufactured by Polyscope (weight average molecular weight: 114,000, glass transition temperature: 134°C, (d1)/(d2)=styrene/maleic anhydride=85mol%/15mol% ear %, refractive index 1.590)

製造例1[乙烯基共聚物(C-1)之製造] 由作為單體成分之經純化甲基丙烯酸甲酯(三菱氣體化學公司製)75.000莫耳%及經純化之苯乙烯(和光純藥工業公司製)24.998莫耳%以及作為聚合起始劑之過氧基-2-乙基己酸第三戊酯(ARKEMA YOSHITOMI公司製，商品名稱：LUPEROX 575)0.002莫耳%所成之單體組成物，以1kg/h連續供給至附螺旋帶葉片之10L完全混合槽中，平均停留時間為2.5小時，於聚合溫度150℃進行連續聚合。以聚合槽之液面成為一定之方式從底部連續抽出，導入至脫溶劑裝置而獲得顆粒共聚物。所得共聚物之源自甲基丙烯酸甲酯之(甲基)丙烯酸酯單體單位(c1)之比例為73莫耳%。且藉由凝膠滲透層析法測定之重量平均分子量(標準聚苯乙烯換算)為124,000。將該共聚物溶解於異丁酸甲酯(關東化學公司製)中，調製10質量%異丁酸甲酯溶液。於1000mL高壓釜裝置中，饋入該共聚物之10質量%異丁酸甲酯溶液500質量份、作為氫化觸媒之10質量%Pd/C(NE Chemcat公司製)1質量份，於氫壓9MPa、200℃保持15小時，使共聚物之苯乙烯部位的芳香族雙鍵氫化。苯乙烯部位之氫化反應率為99%。且，所得之乙烯基共聚物(C-1)中，源自甲基丙烯酸甲酯之結構單位的比例為73莫耳%，乙烯基共聚物(C-1)係玻璃轉移溫度：121℃，折射率：1.494。Production Example 1 [Production of Vinyl Copolymer (C-1)] Consists of 75.000 mol% of purified methyl methacrylate (manufactured by Mitsubishi Gas Chemical Co., Ltd.) as monomer components, 24.998 mol% of purified styrene (manufactured by Wako Pure Chemical Industries, Ltd.), and a polymerization initiator A monomer composition of 0.002 mol% of tert-amyl oxy-2-ethylhexanoate (manufactured by ARKEMA YOSHITOMI, trade name: LUPEROX 575) was continuously supplied to 10 L with a spiral blade at 1 kg/h In the complete mixing tank, the average residence time was 2.5 hours, and the continuous polymerization was carried out at a polymerization temperature of 150°C. It is continuously drawn from the bottom so that the liquid level of the polymerization tank becomes constant, and is introduced into a desolvation device to obtain a granular copolymer. The ratio of the (meth)acrylate monomer unit (c1) derived from methyl methacrylate of the obtained copolymer was 73 mol%. And the weight average molecular weight (standard polystyrene conversion) measured by gel permeation chromatography was 124,000. This copolymer was dissolved in methyl isobutyrate (manufactured by Kanto Chemical Co., Ltd.) to prepare a 10 mass % methyl isobutyrate solution. Into a 1000 mL autoclave apparatus, 500 parts by mass of a 10 mass % methyl isobutyrate solution of the copolymer and 1 mass part of 10 mass % Pd/C (manufactured by NE Chemcat) as a hydrogenation catalyst were fed under a hydrogen pressure. At 9 MPa and 200°C for 15 hours, the aromatic double bond of the styrene moiety of the copolymer was hydrogenated. The hydrogenation reaction rate of the styrene moiety was 99%. And, in the obtained vinyl copolymer (C-1), the ratio of the structural unit derived from methyl methacrylate was 73 mol %, and the vinyl copolymer (C-1) had a glass transition temperature: 121°C, Refractive index: 1.494.

製造例2[熱塑性樹脂(B-1)之製造] 相對於乙烯基共聚物(C-1)40質量份、苯乙烯共聚物(D-1)60質量份之合計100質量份，添加磷系添加劑PEP-36 (ADEKA公司製)500 ppm及硬脂酸單甘油酯(製品名：H-100，理研維生素股份有限公司製)為0.2質量%，以摻混機混合20分鐘後，使用安裝有網眼開度10μm之聚合物過濾器之螺桿直徑26mm的雙軸擠出機(東芝機械股份有限公司製，TEM-26SS，L/D≒40)，於氣缸溫度240℃熔融混練，以造粒機擠出成線狀。顆粒可安定地製造。所得熱塑性樹脂(B-1)之玻璃過渡溫度：129℃，折射率：1.551。Production Example 2 [Production of Thermoplastic Resin (B-1)] To the total of 100 parts by mass of 40 parts by mass of vinyl copolymer (C-1) and 60 parts by mass of styrene copolymer (D-1), 500 ppm of phosphorus-based additive PEP-36 (manufactured by ADEKA) and stearin were added Acid monoglyceride (product name: H-100, manufactured by Riken Vitamins Co., Ltd.) was 0.2% by mass, and after mixing with a blender for 20 minutes, a screw with a diameter of 26 mm equipped with a polymer filter with a mesh opening of 10 μm was used. The twin-screw extruder (manufactured by Toshiba Machinery Co., Ltd., TEM-26SS, L/D≒40) was melted and kneaded at a cylinder temperature of 240°C, and extruded into a linear shape with a pelletizer. Granules can be produced stably. The glass transition temperature of the obtained thermoplastic resin (B-1): 129°C, and the refractive index: 1.551.

實施例1[樹脂積層體(K-1)之製造] 使用於具有軸徑32mm之單軸擠出機、軸徑65mm之單軸擠出機、連結於全部擠出機之供料塊、連結至供料塊之650mm寬之T模嘴的多層擠出機具有與各擠出機連結之多歧管模嘴之多層擠出裝置，成形樹脂積層體。於軸徑32mm之單軸擠出機連續導入製造例2所得之熱塑性樹脂(B-1)，以氣缸溫度240℃、噴出量2.6kg/h之條件擠出。且，於軸徑65mm之單軸擠出機連續導入聚碳酸酯系樹脂(A-1)(三菱工程塑膠股份有限公司製，產品名：LUPILON S-1000)，以氣缸溫度280℃、噴出量31.8kg/h擠出。連結到全部擠出機之供料塊具備2種2層分配銷，設為270℃之溫度並導入熱塑性樹脂(B-1)與聚碳酸酯系樹脂(A-1)予以積層。以於前端連結之溫度270℃之T模嘴擠出為薄片狀，自上游側邊以設為溫度130℃、140℃、180℃之3根鏡面精加工輥轉印鏡面邊冷卻，剝離第3冷卻輥後以設定為340℃之產線內加熱器加熱樹脂積層體之包含熱塑性樹脂(B-1)之層側，獲得具有包含熱塑性樹脂(B-1)之層與包含聚碳酸酯系樹脂(A-1)之層的樹脂積層體(K-1)。所得樹脂積層體(K-1)之中央部的總厚度為1000μm，表層(包含熱塑性樹脂(B)之層)的厚度為80μm。該樹脂積層體(K-1)之全光線透過率：90.9%，濁度：0.7%，抗反射層積層前於23℃50%RH環境下放置後之捲曲形狀：+116m而為○，抗反射層積層前於85℃85%RH環境下放置後的捲曲形狀：+533m，抗反射層積層前之鉛筆硬度：H而為○，抗反射層積層後於23℃50%RH環境下放置後的捲曲形狀：-55m而為○，抗反射層積層後於85℃85%RH環境下站立後的捲曲形狀：-23m，抗反射層積層後之鉛筆硬度：H而為○，綜合合格否判定為○。Example 1 [Manufacture of resin laminate (K-1)] Used in multi-layer extrusion with a single screw extruder with a shaft diameter of 32mm, a single screw extruder with a shaft diameter of 65mm, a feed block connected to all extruders, and a 650mm wide T die connected to the feed block The machine has a multi-layer extrusion device with a multi-manifold die connected to each extruder, and forms a resin laminate. The thermoplastic resin (B-1) obtained in Production Example 2 was continuously introduced into a uniaxial extruder with a shaft diameter of 32 mm, and extruded under the conditions of a cylinder temperature of 240° C. and a discharge rate of 2.6 kg/h. Furthermore, the polycarbonate resin (A-1) (manufactured by Mitsubishi Engineering Plastics Co., Ltd., product name: LUPILON S-1000) was continuously introduced into a uniaxial extruder with a shaft diameter of 65 mm, and the cylinder temperature was 280°C, and the discharge amount was 31.8kg/h extrusion. The feed block connected to all the extruders was provided with two kinds of two-layer distribution pins, and the temperature was set at 270° C., and the thermoplastic resin (B-1) and the polycarbonate-based resin (A-1) were introduced and laminated. Extruded into a thin sheet with a T-die with a temperature of 270°C connected to the front end, cooled from the upstream side with three mirror finish rollers set at 130°C, 140°C, and 180°C to transfer the mirror surface, peel off the third After cooling the roll, the layer side containing the thermoplastic resin (B-1) of the resin laminate was heated with an in-line heater set at 340° C. to obtain a layer containing the thermoplastic resin (B-1) and a layer containing the polycarbonate resin. The resin laminate (K-1) of the layer of (A-1). The total thickness of the center part of the obtained resin laminated body (K-1) was 1000 micrometers, and the thickness of the surface layer (layer containing thermoplastic resin (B)) was 80 micrometers. The total light transmittance of the resin laminate (K-1): 90.9%, haze: 0.7%, the curled shape after being placed in the environment of 23°C 50%RH before anti-reflection layer lamination: +116m and ○, anti-reflection layer Curly shape after being placed in an environment of 85°C and 85%RH before lamination of the reflective layer: +533m, pencil hardness before lamination of the anti-reflection layer: H but ○, after lamination of the anti-reflection layer and placed in an environment of 23°C and 50% RH The curled shape of the antireflection layer is -55m and ○, the curled shape after standing at 85°C and 85%RH after the antireflection layer is laminated: -23m, the pencil hardness after the antireflection layer is laminated: H and it is ○, the comprehensive qualification is judged is ○.

實施例2[樹脂積層體(K-2)之製造] 除了在剝離第3冷卻輥後以設定360℃之產線內加熱器加熱樹脂積層體之包含熱塑性樹脂(B-1)之層側以外，以與實施例1之樹積層體(K-1)同樣獲得具有包含熱塑性樹脂(B-1)之層與包含聚碳酸酯系樹脂(A-1)之層的樹脂積層體(K-2)。所得樹脂積層體(K-2)之中央部的總厚度為1000μm，表層厚度為80μm。該樹脂積層體(K-2)之全光線透過率：90.9%，濁度：0.7%，抗反射層積層前於23℃50%RH環境下放置後的捲曲形狀：+45m而為○，抗反射層積層前於85℃85%RH環境下放置後的捲曲形狀：+48m，抗反射層積層前之鉛筆硬度：H而為○，抗反射層積層後於23℃50%RH環境下放置後之捲曲形狀為：+208m而為○，抗反射層積層後於85℃85%RH環境下放置後之捲曲形狀：-38m，抗反射層積層後之鉛筆硬度：H而為○，綜合合格否判定為○。Example 2 [Manufacture of resin laminate (K-2)] The same as the tree laminate (K-1) of Example 1, except that the layer side containing the thermoplastic resin (B-1) of the resin laminate was heated with an in-line heater set at 360°C after peeling off the third cooling roll. Similarly, a resin laminate (K-2) having a layer containing the thermoplastic resin (B-1) and a layer containing the polycarbonate resin (A-1) was obtained. The total thickness of the center part of the obtained resin laminated body (K-2) was 1000 micrometers, and the surface layer thickness was 80 micrometers. The total light transmittance of the resin laminate (K-2): 90.9%, the haze: 0.7%, the curled shape after being placed in an environment of 23°C and 50%RH before the anti-reflection layer was laminated: +45m and ○, anti-reflection layer Curly shape after being placed in an environment of 85°C and 85%RH before lamination of the reflective layer: +48m, Pencil hardness before lamination of the anti-reflection layer: H but ○, after lamination of the anti-reflection layer and placed in an environment of 23°C and 50% RH The curled shape is: +208m and ○, the curled shape after the anti-reflection layer is placed in an environment of 85°C and 85%RH: -38m, the pencil hardness after the anti-reflection layer is laminated: H and ○, comprehensively qualified It was judged as ○.

實施例3[樹脂積層體(K-3)之製造] 除了在剝離第3冷卻輥後以設定380℃之產線內加熱器加熱樹脂積層體之包含熱塑性樹脂(B-1)之層側以外，以與實施例1之樹積層體(K-1)同樣獲得具有包含熱塑性樹脂(B-1)之層與包含聚碳酸酯系樹脂(A-1)之層的樹脂積層體(K-3)。所得樹脂積層體(K-3)之中央部的總厚度為1000μm，表層厚度為80μm。該樹脂積層體(K-3)之全光線透過率：90.9%，濁度：0.7%，抗反射層積層前於23℃50%RH環境下放置後的捲曲形狀：+40m而為○，抗反射層積層前於85℃85%RH環境下放置後的捲曲形狀：+36m，抗反射層積層前之鉛筆硬度：H而為○，抗反射層積層後於23℃50%RH環境下放置後之捲曲形狀為：+135m而為○，抗反射層積層後於85℃85%RH環境下放置後之捲曲形狀：-90m，抗反射層積層後之鉛筆硬度：H而為○，綜合合格否判定為○。Example 3 [Manufacture of resin laminate (K-3)] The same as the tree laminate (K-1) of Example 1, except that the layer side containing the thermoplastic resin (B-1) of the resin laminate was heated with an in-line heater set at 380°C after peeling off the third cooling roll. Similarly, a resin laminate (K-3) having a layer containing the thermoplastic resin (B-1) and a layer containing the polycarbonate resin (A-1) was obtained. The total thickness of the center part of the obtained resin laminated body (K-3) was 1000 micrometers, and the surface layer thickness was 80 micrometers. The total light transmittance of the resin laminate (K-3): 90.9%, the haze: 0.7%, the curled shape after being placed in the environment of 23°C 50%RH before the anti-reflection layer was laminated: +40m and ○, the anti-reflection layer Curl shape after being placed in an environment of 85°C and 85%RH before lamination of the reflective layer: +36m, pencil hardness before lamination of the anti-reflection layer: H but ○, after lamination of the anti-reflection layer and placed in an environment of 23°C and 50% RH The curled shape is: +135m and ○, the curled shape after the anti-reflection layer is placed in an environment of 85°C and 85% RH: -90m, the pencil hardness after the anti-reflection layer is laminated: H and ○, whether the overall pass It was judged as ○.

實施例4[樹脂積層體(K-4)之製造] 除了在剝離第3冷卻輥後以設定400℃之產線內加熱器加熱樹脂積層體之包含熱塑性樹脂(B-1)之層側以外，以與實施例1之樹積層體(K-1)同樣獲得具有包含熱塑性樹脂(B-1)之層與包含聚碳酸酯系樹脂(A-1)之層的樹脂積層體(K-4)。所得樹脂積層體(K-4)之中央部的總厚度為1000μm，表層厚度為80μm。該樹脂積層體(K-4)之全光線透過率：91.0%，濁度：0.7%，抗反射層積層前於23℃50%RH環境下放置後的捲曲形狀：+13m而為○，抗反射層積層前於85℃85%RH環境下放置後的捲曲形狀：+13m，抗反射層積層前之鉛筆硬度：H而為○，抗反射層積層後於23℃50%RH環境下放置後之捲曲形狀為：+25m而為○，抗反射層積層後於85℃85%RH環境下放置後之捲曲形狀：+33m，抗反射層積層後之鉛筆硬度：H而為○，綜合合格否判定為○。Example 4 [Manufacture of resin laminate (K-4)] The same as the tree laminate (K-1) of Example 1, except that the layer side containing the thermoplastic resin (B-1) of the resin laminate was heated with an in-line heater set at 400°C after peeling off the third cooling roll. Similarly, a resin laminate (K-4) having a layer containing the thermoplastic resin (B-1) and a layer containing the polycarbonate resin (A-1) was obtained. The total thickness of the center part of the obtained resin laminated body (K-4) was 1000 micrometers, and the surface layer thickness was 80 micrometers. The total light transmittance of the resin laminate (K-4): 91.0%, the haze: 0.7%, the curled shape after being placed in the environment of 23°C 50%RH before the anti-reflection layer was laminated: +13m and ○, the anti-reflection layer Curly shape after being placed in an environment of 85°C and 85%RH before lamination of the reflective layer: +13m, pencil hardness before lamination of the anti-reflection layer: H but ○, after lamination of the anti-reflection layer and placed in an environment of 23°C and 50% RH The curled shape is: +25m and ○, the curled shape after the anti-reflection layer is placed in an environment of 85°C 85%RH: +33m, the pencil hardness after the anti-reflection layer is laminated: H and ○, comprehensively qualified It was judged as ○.

實施例5[樹脂積層體(K-5)之製造] 將對於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有限公司製)60質量份、PEG200#二丙烯酸酯(製品名：4EG-A，共榮社化學股份有限公司製)35質量份及含氟基・親水性基・親油性基・UV反應性基之寡聚物(製品名：RS-90，DIC股份有限公司製)5質量份之合計100質量份，添加1質量%之光聚合起始劑(製品名：I-184[化合物名：1-羥基-環己基苯基酮]BASF股份有限公司製)之塗料，以棒塗布器塗布於實施例1所得之樹脂積層體(K-1)之包含熱塑性樹脂(B-1)之層的表面，以金屬鹵素燈(20 mW/cm² )照射5秒，使硬塗布硬化，製作樹脂積層體(K-5)。硬塗布層之膜厚為6μm。該樹脂積層體(K-5)之全光線透過率：91.0%，濁度：0.6%，抗反射層積層前於23℃50%RH環境下放置後的捲曲形狀：+211m而為○，抗反射層積層前於85℃85%RH環境下放置後的捲曲形狀：+170m，抗反射層積層前之鉛筆硬度：3H而為○，抗反射層積層後於23℃50%RH環境下放置後之捲曲形狀為：-42m而為○，抗反射層積層後於85℃85%RH環境下放置後之捲曲形狀：-26m，抗反射層積層後之鉛筆硬度：3H而為○，綜合合格否判定為○。Example 5 [Manufacture of resin laminate (K-5)] 60 parts by mass of a 6-functional urethane acrylate oligomer (product name: U6HA, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), PEG200# 35 parts by mass of diacrylate (product name: 4EG-A, manufactured by Kyoeisha Chemical Co., Ltd.) and an oligomer containing fluorine group, hydrophilic group, lipophilic group, and UV reactive group (product name: RS- 90, 100 parts by mass in total of 5 parts by mass of DIC Co., Ltd., and 1 mass % of a photopolymerization initiator (product name: I-184 [compound name: 1-hydroxy-cyclohexyl phenyl ketone]] BASF Co., Ltd. was added Co., Ltd.) was applied to the surface of the layer containing the thermoplastic resin (B-1) of the resin laminate (K-1) obtained in Example 1 with a bar coater, and a metal halide lamp (20 mW/cm ² ) was irradiated for 5 seconds to harden the hard coat, and a resin laminate (K-5) was produced. The film thickness of the hard coat layer was 6 μm. The total light transmittance of the resin laminate (K-5): 91.0%, the haze: 0.6%, the curled shape after being placed in an environment of 23°C and 50%RH before the anti-reflection layer was laminated: +211m and ○, anti-reflection layer Curly shape after being placed in an environment of 85°C and 85%RH before lamination of the reflective layer: +170m, pencil hardness before lamination of the anti-reflection layer: 3H but ○, after lamination of the anti-reflection layer and placed in an environment of 23°C and 50% RH The curled shape is: -42m and ○, the curled shape after the anti-reflection layer is placed in the environment of 85°C 85%RH: -26m, the pencil hardness after the anti-reflection layer is laminated: 3H and ○, comprehensive qualification It was judged as ○.

實施例6[樹脂積層體(K-6)之製造] 將與實施例5相同之塗料以棒塗布器塗布於實施例2所得之樹脂積層體(K-2)之包含熱塑性樹脂(B-1)之層的表面，與實施例5同樣使硬塗布硬化，製作樹脂積層體(K-6)。硬塗布層之膜厚為6μm。該樹脂積層體(K-6)之全光線透過率：91.0%，濁度：0.6%，抗反射層積層前於23℃50%RH環境下放置後的捲曲形狀：+52m而為○，抗反射層積層前於85℃85%RH環境下放置後的捲曲形狀：+39m，抗反射層積層前之鉛筆硬度：3H而為○，抗反射層積層後於23℃50%RH環境下放置後之捲曲形狀為：+942m而為○，抗反射層積層後於85℃85%RH環境下放置後之捲曲形狀：-47m，抗反射層積層後之鉛筆硬度：3H而為○，綜合合格否判定為○。Example 6 [Manufacture of resin laminate (K-6)] The same coating material as in Example 5 was applied to the surface of the layer containing the thermoplastic resin (B-1) of the resin laminate (K-2) obtained in Example 2 with a bar coater, and the hard coating was hardened in the same manner as in Example 5. , the resin laminate (K-6) was produced. The film thickness of the hard coat layer was 6 μm. The total light transmittance of the resin laminate (K-6): 91.0%, the haze: 0.6%, the curled shape after being placed in a 23°C 50%RH environment before the anti-reflection layer was laminated: +52m and ○, the anti-reflection layer Curly shape after being placed in an environment of 85°C and 85%RH before lamination of the reflective layer: +39m, pencil hardness before lamination of the anti-reflection layer: 3H but ○, after lamination of the anti-reflection layer and placed in an environment of 23°C and 50% RH The curled shape is: +942m and ○, the curled shape after the anti-reflection layer is placed in an environment of 85°C and 85%RH: -47m, the pencil hardness after the anti-reflection layer is laminated: 3H and it is ○, comprehensive qualification It was judged as ○.

實施例7[樹脂積層體(K-7)之製造] 將與實施例5相同之塗料以棒塗布器塗布於實施例3所得之樹脂積層體(K-3)之包含熱塑性樹脂(B-1)之層的表面，與實施例5同樣使硬塗布硬化，製作樹脂積層體(K-7)。硬塗布層之膜厚為6μm。該樹脂積層體(K-7)之全光線透過率：91.0%，濁度：0.6%，抗反射層積層前於23℃50%RH環境下放置後的捲曲形狀：+47m而為○，抗反射層積層前於85℃85%RH環境下放置後的捲曲形狀：+31m，抗反射層積層前之鉛筆硬度：3H而為○，抗反射層積層後於23℃50%RH環境下放置後之捲曲形狀為：+340m，抗反射層積層後於85℃85%RH環境下放置後之捲曲形狀：-159m，抗反射層積層後之鉛筆硬度：3H而為○，綜合合格否判定為○。Example 7 [Manufacture of resin laminate (K-7)] The same coating material as in Example 5 was applied to the surface of the layer containing the thermoplastic resin (B-1) of the resin laminate (K-3) obtained in Example 3 with a bar coater, and the hard coating was hardened in the same manner as in Example 5. , the resin laminate (K-7) was produced. The film thickness of the hard coat layer was 6 μm. The total light transmittance of the resin laminate (K-7): 91.0%, the haze: 0.6%, the curled shape after being placed in a 23°C 50%RH environment before the anti-reflection layer was laminated: +47m and ○, anti-reflection layer Curly shape after being placed in an environment of 85°C and 85%RH before lamination of the reflective layer: +31m, Pencil hardness before lamination of the anti-reflection layer: 3H but ○, after lamination of the anti-reflection layer and placed in an environment of 23°C and 50% RH The curled shape is: +340m, the curled shape after the anti-reflection layer is placed in an environment of 85°C and 85%RH: -159m, the pencil hardness after the anti-reflection layer is laminated: 3H and is ○, and the comprehensive qualification is judged as ○ .

實施例8[樹脂積層體(K-8)之製造] 將與實施例5相同之塗料以棒塗布器塗布於實施例4所得之樹脂積層體(K-4)之包含熱塑性樹脂(B-1)之層的表面，與實施例5同樣使硬塗布硬化，製作樹脂積層體(K-8)。硬塗布層之膜厚為6μm。該樹脂積層體(K-8)之全光線透過率：91.0%，濁度：0.6%，抗反射層積層前於23℃50%RH環境下放置後的捲曲形狀：+14m而為○，抗反射層積層前於85℃85%RH環境下放置後的捲曲形狀：+12m，抗反射層積層前之鉛筆硬度：3H而為○，抗反射層積層後於23℃50%RH環境下放置後之捲曲形狀為：+26m而為○，抗反射層積層後於85℃85%RH環境下放置後之捲曲形狀：-29m，抗反射層積層後之鉛筆硬度：3H而為○，綜合合格否判定為○。Example 8 [Manufacture of resin laminate (K-8)] The same coating material as in Example 5 was applied on the surface of the layer containing the thermoplastic resin (B-1) of the resin laminate (K-4) obtained in Example 4 with a bar coater, and the hard coating was hardened in the same manner as in Example 5. , the resin laminate (K-8) was produced. The film thickness of the hard coat layer was 6 μm. The total light transmittance of the resin laminate (K-8): 91.0%, the haze: 0.6%, the curled shape after being placed in the environment of 23°C 50%RH before the anti-reflection layer was laminated: +14m and ○, anti-reflection layer Curly shape after being placed in an environment of 85°C and 85%RH before lamination of the reflective layer: +12m, pencil hardness before lamination of the anti-reflection layer: 3H but ○, after lamination of the anti-reflection layer in an environment of 23°C and 50% RH The curled shape is: +26m and ○, the curled shape after the anti-reflection layer is placed in an environment of 85°C and 85%RH: -29m, the pencil hardness after the anti-reflection layer is laminated: 3H and ○, whether it is comprehensively qualified It was judged as ○.

比較例1[樹脂積層體(L-1)之製造] 除了在剝離第3冷卻輥後不使用產線內加熱器以外，以與實施例1之樹積層體(K-1)同樣獲得具有包含熱塑性樹脂(B-1)之層與包含聚碳酸酯系樹脂(A-1)之層的樹脂積層體(L-1)。所得樹脂積層體(L-1)之中央部的總厚度為1000μm，表層厚度為80μm。該樹脂積層體(L-1)之全光線透過率：90.9%，濁度：0.7%，抗反射層積層前於23℃50%RH環境下放置後的捲曲形狀：-47m而為×，抗反射層積層前於85℃85%RH環境下放置後的捲曲形狀：-25m，抗反射層積層前之鉛筆硬度：H而為○，抗反射層積層後於23℃50%RH環境下放置後之捲曲形狀為：-20m而為×，抗反射層積層後於85℃85%RH環境下放置後之捲曲形狀： -7m，抗反射層積層後之鉛筆硬度：H而為○，綜合合格否判定為×。Comparative Example 1 [Manufacture of resin laminate (L-1)] A layer containing a thermoplastic resin (B-1) and a layer containing a polycarbonate system were obtained in the same manner as the tree laminate (K-1) of Example 1, except that the in-line heater was not used after peeling the third cooling roll. The resin laminate (L-1) of the layer of the resin (A-1). The total thickness of the center part of the obtained resin laminated body (L-1) was 1000 micrometers, and the surface layer thickness was 80 micrometers. The total light transmittance of the resin laminate (L-1): 90.9%, the haze: 0.7%, the curled shape after being placed in a 23°C 50%RH environment before the anti-reflection layer was laminated: -47m is ×, anti-reflection layer Curly shape after being placed in an environment of 85°C and 85%RH before lamination of the reflective layer: -25m, pencil hardness before lamination of the anti-reflection layer: H but ○, after lamination of the anti-reflection layer and placed in an environment of 23°C and 50% RH The curled shape is: -20m and ×, the curled shape after the anti-reflection layer is placed in an environment of 85°C and 85%RH: -7m, the pencil hardness after the anti-reflection layer is laminated: H is ○, and the comprehensive pass is judged as ×.

比較例2[樹脂積層體(L-2)之製造] 除了在剝離第3冷卻輥後以設定420℃之產線內加熱器加熱樹脂積層體之包含熱塑性樹脂(B-1)之層側以外，以與實施例1之樹積層體(K-1)同樣獲得具有包含熱塑性樹脂(B-1)之層與包含聚碳酸酯系樹脂(A-1)之層的樹脂積層體(L-2)。所得樹脂積層體(L-2)之中央部的總厚度為1000μm，表層厚度為80μm。該樹脂積層體(L-2)之全光線透過率：90.9%，濁度：0.7%，抗反射層積層前於23℃50%RH環境下放置後的捲曲形狀：+10m而為×，抗反射層積層前於85℃85%RH環境下放置後的捲曲形狀：+9m，抗反射層積層前之鉛筆硬度：H而為○，抗反射層積層後於23℃50%RH環境下放置後之捲曲形狀為：+14m而為×，抗反射層積層後於85℃85%RH環境下放置後之捲曲形狀：+14m，抗反射層積層後之鉛筆硬度：H而為○，綜合合格否判定為×。Comparative Example 2 [Manufacture of resin laminate (L-2)] The same as the tree laminate (K-1) of Example 1, except that the layer side containing the thermoplastic resin (B-1) of the resin laminate was heated with an in-line heater set at 420°C after peeling off the third cooling roll. Similarly, a resin laminate (L-2) having a layer containing the thermoplastic resin (B-1) and a layer containing the polycarbonate resin (A-1) was obtained. The total thickness of the center part of the obtained resin laminated body (L-2) was 1000 micrometers, and the surface layer thickness was 80 micrometers. The total light transmittance of the resin laminate (L-2): 90.9%, the haze: 0.7%, the curled shape after being placed in an environment of 23°C 50%RH before the anti-reflection layer was laminated: +10m is ×, anti-reflection layer Curly shape after being placed in an environment of 85°C and 85%RH before lamination of the reflective layer: +9m, pencil hardness before lamination of the anti-reflection layer: H but ○, after lamination of the anti-reflection layer and placed in an environment of 23°C and 50% RH The curled shape is: +14m and ×, the curled shape after the anti-reflection layer is placed in an environment of 85°C and 85%RH: +14m, the pencil hardness after the anti-reflection layer is laminated: H and ○, comprehensively qualified It was judged as ×.

比較例3[樹脂積層體(L-3)之製造] 將與實施例5相同之塗料以棒塗布器塗布於比較例1所得之樹脂積層體(L-1)之包含熱塑性樹脂(B-1)之層的表面，與實施例5同樣使硬塗布硬化，製作樹脂積層體(L-3)。硬塗布層之膜厚為6μm。該樹脂積層體(L-3)之全光線透過率：91.0%，濁度：0.6%，抗反射層積層前於23℃50%RH環境下放置後的捲曲形狀：-40m而為×，抗反射層積層前於85℃85%RH環境下放置後的捲曲形狀：-28m，抗反射層積層前之鉛筆硬度：3H而為○，抗反射層積層後於23℃50%RH環境下放置後之捲曲形狀為：-18m而為×，抗反射層積層後於85℃85%RH環境下放置後之捲曲形狀：-7m，抗反射層積層後之鉛筆硬度：3H而為○，綜合合格否判定為×。Comparative Example 3 [Manufacture of resin laminate (L-3)] The same coating material as in Example 5 was applied to the surface of the layer containing the thermoplastic resin (B-1) of the resin laminate (L-1) obtained in Comparative Example 1 with a bar coater, and the hard coating was hardened in the same manner as in Example 5. , the resin laminate (L-3) was produced. The film thickness of the hard coat layer was 6 μm. The total light transmittance of the resin laminate (L-3): 91.0%, the haze: 0.6%, the curled shape after being placed in a 23°C 50%RH environment before the anti-reflection layer is laminated: -40m is ×, anti-reflection layer Curly shape after being placed in an environment of 85°C 85%RH before lamination of the reflective layer: -28m, pencil hardness before lamination of the anti-reflection layer: 3H but ○, after lamination of the anti-reflection layer in an environment of 23°C 50%RH The curled shape is: -18m and ×, the curled shape after the anti-reflection layer is placed in an environment of 85°C and 85%RH: -7m, the pencil hardness after the anti-reflection layer is laminated: 3H and it is ○, comprehensively qualified It was judged as ×.

比較例4[樹脂積層體(L-4)之製造] 將與實施例5相同之塗料以棒塗布器塗布於比較例2所得之樹脂積層體(L-2)之包含熱塑性樹脂(B-1)之層的表面，與實施例5同樣使硬塗布硬化，製作樹脂積層體(L-4)。硬塗布層之膜厚為6μm。該樹脂積層體(L-4)之全光線透過率：91.0%，濁度：0.6%，抗反射層積層前於23℃50%RH環境下放置後的捲曲形狀：+10m而為×，抗反射層積層前於85℃85%RH環境下放置後的捲曲形狀：+9m，抗反射層積層前之鉛筆硬度：3H而為○，抗反射層積層後於23℃50%RH環境下放置後之捲曲形狀為：+15m而為×，抗反射層積層後於85℃85%RH環境下放置後之捲曲形狀：+13m，抗反射層積層後之鉛筆硬度：3H而為○，綜合合格否判定為×。Comparative Example 4 [Manufacture of resin laminate (L-4)] The same coating material as in Example 5 was applied to the surface of the layer containing the thermoplastic resin (B-1) of the resin laminate (L-2) obtained in Comparative Example 2 with a bar coater, and the hard coating was hardened in the same manner as in Example 5. , the resin laminate (L-4) was produced. The film thickness of the hard coat layer was 6 μm. The total light transmittance of the resin laminate (L-4): 91.0%, the haze: 0.6%, the curled shape after being placed in a 23°C 50%RH environment before the anti-reflection layer was laminated: +10m is ×, anti-reflection layer Curly shape after being placed in an environment of 85°C and 85% RH before lamination of the reflective layer: +9m, pencil hardness before lamination of the anti-reflection layer: 3H and ○, after lamination of the anti-reflection layer in an environment of 23°C and 50% RH The curled shape is: +15m and ×, the curled shape after the anti-reflection layer is placed in an environment of 85°C and 85%RH: +13m, the pencil hardness after the anti-reflection layer is laminated: 3H and is ○, comprehensively qualified It was judged as ×.

如上所述，藉由滿足本發明之條件，而發揮可獲得抗反射層積層後之耐捲曲性優異之樹脂積層體之有利效果。As described above, by satisfying the conditions of the present invention, the advantageous effect of obtaining a resin laminate excellent in curl resistance after the antireflection layer is obtained is exhibited.

即，如表2所示，抗反射層積層前於23℃50%RH環境下放置後之捲曲形狀為於包含熱塑性樹脂(B)之層側為凹，11m≦曲率半徑R≦1225m之範圍的實施例1~8，與抗反射層積層前之捲曲形狀於包含熱塑性樹脂(B)之層側為凸之比較例1及3相比，實施例1~8於抗反射層積層後在23℃50%RH環境下放置後之捲曲形狀係耐捲曲性更優異。且，實施例1~8與抗反射層積層前於23℃50%RH環境下放置後之捲曲形狀為包含熱塑性樹脂(B)之層側為凹且曲率半徑R＜11m的範圍之比較例2及4比較，實施例1~8之抗反射層積層後於23℃50%RH環境下放置後之捲曲形狀係耐捲曲性更優異。That is, as shown in Table 2, the curl shape after being left in a 23°C 50% RH environment before lamination of the antireflection layer is concave on the side of the layer containing the thermoplastic resin (B), 11m≦curvature radius R≦1225m Examples 1 to 8 are compared with Comparative Examples 1 and 3 in which the curled shape before the anti-reflection layer is convex on the side of the layer comprising the thermoplastic resin (B), and the samples 1 to 8 are heated at 23° C. after the anti-reflection layer is laminated. The curled shape after being left in a 50% RH environment is more excellent in curling resistance. And, the curled shape of Examples 1 to 8 and the anti-reflection layer before being placed under the environment of 23° C. 50% RH is that the side of the layer comprising the thermoplastic resin (B) is concave and the radius of curvature R<11m. Comparative Example 2 Compared with 4, the curled shape of the antireflection layers of Examples 1 to 8 after being left to stand in an environment of 23° C. 50% RH is more excellent in curl resistance.

Claims

一種樹脂積層體，其係包含：包含將聚碳酸酯樹脂作為主成分之聚碳酸酯系樹脂(A)之層，與包含積層於該層之至少一者之面之熱可塑性樹脂(B)之層之樹脂積層體，於23℃50%RH環境下放置後之樹脂積層體之捲曲形狀為將包含前述熱可塑性樹脂(B)之層側作為凹部且11m≦曲率半徑R≦1225m。A resin laminate comprising: a layer comprising a polycarbonate resin (A) containing a polycarbonate resin as a main component, and A resin laminate comprising a layer of thermoplastic resin (B) laminated on the surface of at least one of the layers, The curl shape of the resin laminate after being left to stand in a 23° C. 50% RH environment was such that the layer side containing the thermoplastic resin (B) was a recess and 11 m≦curvature radius R≦1225 m.

如請求項1之樹脂積層體，其中，對包含前述熱可塑性樹脂(B)之層側之表面施予硬塗布處理、反射防止處理、防汙處理、耐指紋處理、抗靜電處理、耐候性處理及防眩處理中任一種以上。The resin laminate according to claim 1, wherein a hard coat treatment, antireflection treatment, antifouling treatment, anti-fingerprint treatment, antistatic treatment, and weathering treatment are applied to the surface of the layer side comprising the thermoplastic resin (B) and any one or more of anti-glare treatments.

如請求項1或2之樹脂積層體，其中，於包含前述熱可塑性樹脂(B)之層側之表面進而有積層抗反射層，於23℃50%RH環境下放置後之樹脂積層體之捲曲形狀為將包含前述熱可塑性樹脂(B)之層側作為凹部或凸部且曲率半徑R≧21m。The resin laminate according to claim 1 or 2, wherein the surface of the layer side containing the thermoplastic resin (B) is further provided with a laminated anti-reflection layer, and the curling of the resin laminate after being placed in an environment of 23°C and 50% RH The shape is such that the side of the layer containing the thermoplastic resin (B) is a concave portion or a convex portion, and the radius of curvature R≧21m.

一種樹脂積層體，其係包含：包含將聚碳酸酯樹脂作為主成分之聚碳酸酯系樹脂(A)之層，與包含積層於包含該樹脂(A)之層之至少一者之面之熱可塑性樹脂(B)之層，與積層於包含該樹脂(B)之層之表面之抗反射層之樹脂積層體，於23℃50%RH環境下放置後之樹脂積層體之捲曲形狀為將前述抗反射層側作為凹部或凸部且曲率半徑R≧21m。A resin laminate comprising: a layer comprising a polycarbonate resin (A) containing a polycarbonate resin as a main component, and a layer comprising a thermoplastic resin (B) laminated on the face of at least one of the layers comprising the resin (A), and A resin laminate having an antireflection layer laminated on the surface of the layer comprising the resin (B), The curl shape of the resin laminate after being left at 23° C. 50% RH is such that the antireflection layer side is defined as a concave portion or a convex portion, and the curvature radius R≧21m.

如請求項4之樹脂積層體，其中，於包含前述熱可塑性樹脂(B)之層與前述抗反射層之間施予硬塗布處理、反射防止處理、防汙處理、耐指紋處理、抗靜電處理、耐候性處理及防眩處理中任一種以上。The resin laminate according to claim 4, wherein a hard coat treatment, antireflection treatment, antifouling treatment, anti-fingerprint treatment, and antistatic treatment are applied between the layer comprising the thermoplastic resin (B) and the antireflection layer , any one or more of weather resistance treatment and anti-glare treatment.

如請求項1~5中任一項之樹脂積層體，其中，包含前述熱可塑性樹脂(B)之層側之表面之鉛筆硬度為HB以上。The resin laminated body of any one of Claims 1-5 whose pencil hardness of the surface of the layer side containing the said thermoplastic resin (B) is HB or more.

如請求項1~6中任一項之樹脂積層體，其中，前述聚碳酸酯系樹脂(A)之重量平均分子量為15,000~ 75,000。The resin laminate according to any one of claims 1 to 6, wherein the polycarbonate-based resin (A) has a weight average molecular weight of 15,000 to 75,000.

如請求項1~7中任一項之樹脂積層體，其中，包含前述聚碳酸酯系樹脂(A)之層及/或包含前述熱可塑性樹脂(B)之層含有紫外線吸收劑。The resin laminate according to any one of claims 1 to 7, wherein the layer containing the polycarbonate-based resin (A) and/or the layer containing the thermoplastic resin (B) contains an ultraviolet absorber.

一種透明基板材料，其係包含如請求項1~8中任一項之樹脂積層體。A transparent substrate material comprising the resin laminate according to any one of claims 1 to 8.

一種透明保護材料，其係包含如請求項1~8中任一項之樹脂積層體。A transparent protective material comprising the resin laminate according to any one of claims 1 to 8.

一種觸控面板前面保護板，其係包含如請求項1~8中任一項之樹脂積層體。A touch panel front protection plate comprising the resin laminate according to any one of claims 1 to 8.