TWI729089B - Manufacturing method of extruded resin board and extruded resin board - Google Patents

Manufacturing method of extruded resin board and extruded resin board Download PDF

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TWI729089B
TWI729089B TW106109081A TW106109081A TWI729089B TW I729089 B TWI729089 B TW I729089B TW 106109081 A TW106109081 A TW 106109081A TW 106109081 A TW106109081 A TW 106109081A TW I729089 B TWI729089 B TW I729089B
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resin
resin sheet
extruded resin
extruded
polycarbonate
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TW201801890A (en
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船崎一男
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日商可樂麗股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/885—External treatment, e.g. by using air rings for cooling tubular films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/91—Heating, e.g. for cross linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911—Cooling
    • B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
    • B29C48/914—Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/06—Copolymers with vinyl aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2069/00—Use of PC, i.e. polycarbonates or derivatives thereof, as moulding material

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Surface Treatment Of Optical Elements (AREA)

Abstract

本發明提供一種擠出樹脂板之製造方法及一種擠出樹脂板，其中該擠出樹脂板係表面性良好且可抑制翹曲發生，即便加熱至高溫，面內遲滯值的下降率也小。 The present invention provides a method for manufacturing an extruded resin board and an extruded resin board, wherein the extruded resin board has good surface properties and can suppress the occurrence of warpage, and even if heated to a high temperature, the decrease rate of the in-plane hysteresis value is small.

本發明為一種擠出樹脂板之製造方法，其包含在熔融狀態下將在含有聚碳酸酯的層的至少一面上積層有玻璃轉移溫度在115℃以上之含有甲基丙烯酸樹脂的層之熱塑性樹脂積層體從T字模擠出之步驟，在前述熱塑性樹脂積層體從最後捲繞的冷卻輥剝離的位置，將樹脂整體的溫度設定成相對於前述含有聚碳酸酯的層的玻璃轉移溫度為-2℃~+15℃的範圍，將前述拉取輥的圓周速度(V4)與前述第2冷卻輥的圓周速度(V2)的圓周速度比(V4/V2)設定為0.98以上1.01以下。 The present invention is a method for manufacturing an extruded resin sheet, which comprises laminating a methacrylic resin-containing layer with a glass transition temperature of 115°C or higher on at least one surface of a polycarbonate-containing layer in a molten state. In the step of extruding the laminated body from the T-die, at the position where the thermoplastic resin laminated body is peeled from the last cooling roll wound, the temperature of the entire resin is set to -2 relative to the glass transition temperature of the polycarbonate-containing layer. In the range of °C to +15 °C, the peripheral speed ratio (V4/V2) of the peripheral speed (V4) of the drawing roll and the peripheral speed (V2) of the second cooling roll is set to 0.98 or more and 1.01 or less.

Description

擠出樹脂板之製造方法及擠出樹脂板 Manufacturing method of extruded resin board and extruded resin board

本發明係關於擠出樹脂板，更詳細地說，本發明係關於一種具備含有甲基丙烯酸樹脂的層與含有聚碳酸酯的層之擠出樹脂板及其製造方法，該擠出樹脂板的表面性良好且可抑制因殘留應力造成的翹曲發生，即便在高溫環境下也能夠控制面內遲滯值，並且適用於觸控面板的保護蓋等。 The present invention relates to an extruded resin sheet. More specifically, the present invention relates to an extruded resin sheet having a layer containing methacrylic resin and a layer containing polycarbonate, and a method of manufacturing the same. The extruded resin sheet It has good surface properties and can suppress warpage caused by residual stress. It can also control the in-plane hysteresis value even in a high-temperature environment. It is also suitable for touch panel protective covers, etc.

觸控面板(或觸控螢幕)為組合顯示裝置與位置輸入裝置的電子元件，能夠透過手指或筆觸摸觸控面板來操作電子設備，觸控面板係使用於銀行等金融機關的ATM、自動販賣機、行動電話、行動資訊終端(PDA)、數位聲訊播放機、行動遊戲機、平板型個人電腦、複印機、傳真、汽車導航等數位資訊設備等。 The touch panel (or touch screen) is an electronic component that combines a display device and a position input device. It can operate electronic equipment by touching the touch panel with a finger or a pen. The touch panel is used in ATMs and vending machines of financial institutions such as banks. Digital information equipment such as computers, mobile phones, mobile information terminals (PDA), digital audio players, mobile game consoles, tablet personal computers, copiers, faxes, car navigation, etc.

在使用觸控面板的輸入操作上有時會刮傷表面或是會壓壞內部，為了防止這種情況，而在觸控面板的表面設置透明保護蓋，主要是使用強化玻璃製的保護蓋，而且從加工性或輕量化的觀點來看，已開發出透明樹脂製的保護蓋。這種保護蓋需要光澤、抗刮性、耐衝擊性等。 In the input operation using the touch panel, the surface may be scratched or the interior may be crushed. In order to prevent this, a transparent protective cover is provided on the surface of the touch panel, mainly using a protective cover made of tempered glass. In addition, from the viewpoint of processability and weight reduction, a protective cover made of transparent resin has been developed. Such a protective cover requires gloss, scratch resistance, impact resistance, and the like.

順便一提，聚碳酸酯為適於得到耐衝擊性優 異的成形品的樹脂之一，甲基丙烯酸樹脂則是適於得到高光澤且具有優異的抗刮性的成形品的樹脂之一。又，藉由同時將聚碳酸酯與甲基丙烯酸樹脂加熱熔融成形(例如共擠出成形)，能夠製造包含含有聚碳酸酯的層與含有甲基丙烯酸樹脂的層的樹脂板。這樣的樹脂板的加熱熔融成形中，因2種樹脂特性的差異而所得到的成形品殘留不少的應變應力。將此成形品中殘留的應變應力稱為殘留應力，具有該殘留應力的成形品會因熱等而產生翹曲或收縮。 By the way, polycarbonate is suitable for obtaining excellent impact resistance One of the resins for different molded products, methacrylic resin is one of the resins suitable for obtaining molded products with high gloss and excellent scratch resistance. In addition, by simultaneously heating and melting polycarbonate and methacrylic resin (for example, co-extrusion molding), a resin plate including a polycarbonate-containing layer and a methacrylic resin-containing layer can be produced. In the heat-melt molding of such a resin plate, a large amount of strain stress remains in the molded product obtained due to the difference in the characteristics of the two types of resins. The strain stress remaining in the molded product is called the residual stress, and the molded product with this residual stress may warp or shrink due to heat or the like.

如上述樹脂板之板狀成形品中，特別是因殘留應力造成的翹曲會成為問題。作為減少板狀成形品中的殘留應力且抑制翹曲產生的方法之一，已知有一種透過調整擠出成形所使用的冷卻輥的旋轉速度之方法(例如參照專利文獻1)。 In the plate-shaped molded product of the above-mentioned resin plate, warpage due to residual stress becomes a problem in particular. As one of the methods for reducing the residual stress in the plate-shaped molded product and suppressing the occurrence of warpage, a method for adjusting the rotation speed of a cooling roll used for extrusion molding is known (for example, refer to Patent Document 1).

又，為解決這樣的問題，已針對甲基丙烯酸樹脂的耐熱性及耐濕性改良進行研究。例如，已報告一種雙層樹脂板，其具有甲基丙烯酸甲酯單元與選自甲基丙烯酸單元、丙烯酸單元、順丁烯二酸酐單元、N-取代或未取代的順丁烯二醯亞胺單元、戊二酸酐結構單元及戊二醯亞胺結構單元的單元，使用玻璃轉移溫度在110℃以上的甲基丙烯酸樹脂形成第1層，並在第1層上具備包含聚碳酸酯的層(例如參照專利文獻2)。然而，這樣的樹脂板的甲基丙烯酸樹脂的耐熱性及耐濕性還是不充分，藉此還是無法達到充分解決上述問題。 In addition, in order to solve such problems, research has been conducted on the improvement of heat resistance and moisture resistance of methacrylic resin. For example, a two-layer resin board has been reported, which has methyl methacrylate units and selected from methacrylic acid units, acrylic acid units, maleic anhydride units, N-substituted or unsubstituted maleimides The unit, the glutaric anhydride structural unit, and the glutaric imine structural unit are used to form the first layer of a methacrylic resin with a glass transition temperature of 110°C or higher, and a layer containing polycarbonate is provided on the first layer ( For example, refer to Patent Document 2). However, the heat resistance and moisture resistance of the methacrylic resin of such a resin plate are still insufficient, and the above-mentioned problems cannot be sufficiently solved by this.

又，為解決這樣的問題，亦已知一種著眼於 縮小2個樹脂片之間的線膨脹係數的差來控制翹曲產生的方法(例如參照專利文獻3)。然而，只達成線膨脹係數的規定並無法解決上述問題。 Also, in order to solve this problem, a known A method of reducing the difference in the coefficient of linear expansion between two resin sheets to control the occurrence of warpage (for example, refer to Patent Document 3). However, only meeting the requirement of linear expansion coefficient cannot solve the above-mentioned problems.

就上述保護蓋而言，已研究使用一種樹脂板，其係為了改善抗刮性、視認性而在至少一面上形成抗刮性(硬塗性)、低反射性的硬化被膜而成之樹脂板。 Regarding the above-mentioned protective cover, it has been studied to use a resin plate, which is a resin plate formed by forming a scratch-resistant (hard coat) and low-reflective hardened film on at least one side in order to improve scratch resistance and visibility. .

例如，專利文獻4已揭示在甲基丙烯酸樹脂板的至少一面上形成硬化被膜，以作為液晶系統的便攜式資訊終端的顯示視窗保護板使用。 For example, Patent Document 4 has disclosed that a hardened film is formed on at least one surface of a methacrylic resin plate for use as a display window protection plate of a portable information terminal of a liquid crystal system.

又，專利文獻5已揭示在聚碳酸酯樹脂層的一面上積層甲基丙烯酸樹脂層而成的積層板的甲基丙烯酸樹脂層上形成硬化被膜，而用於液晶顯示器蓋。 In addition, Patent Document 5 has disclosed that a hardened film is formed on the methacrylic resin layer of a laminated plate in which a methacrylic resin layer is laminated on one surface of a polycarbonate resin layer, and the cured film is used for a liquid crystal display cover.

又，上述保護蓋設置在液晶顯示器的前側(觀看者側)，觀看者通過這樣的保護蓋觀看液晶顯示器的畫面，但在以往的保護蓋中，由於幾乎不改變來自作為偏光的液晶顯示器的射出光的偏振性，因此若配戴偏光太陽眼鏡觀看畫面，則根據射出光的偏光軸與偏光太陽眼鏡的透射軸構成的角度，而有畫面變暗或是難以觀看到影像的情況。因此，已研究一種能夠抑制通過偏光太陽眼鏡等偏振性濾光片觀看液晶顯示器畫面時的影像的視認性下降之液晶顯示器保護蓋。 In addition, the above-mentioned protective cover is provided on the front side (viewer's side) of the liquid crystal display, and the viewer views the screen of the liquid crystal display through such a protective cover. However, the conventional protective cover hardly changes the emission from the liquid crystal display which is polarized light. Because of the polarization of light, if you wear polarized sunglasses to view the screen, depending on the angle formed by the polarization axis of the emitted light and the transmission axis of the polarized sunglasses, the screen may become dark or it may be difficult to view the image. Therefore, a protective cover for a liquid crystal display capable of suppressing a decrease in the visibility of an image when viewing a screen of a liquid crystal display through a polarizing filter such as polarized sunglasses has been studied.

例如，專利文獻6已揭示使面內遲滯值為85~300nm。 For example, Patent Document 6 has disclosed that the in-plane hysteresis value is 85 to 300 nm.

在如上述的樹脂板的表面上形成抗刮性(硬塗性)及低反射性的硬化被膜的步驟中，有時會將樹脂板加熱至 100℃左右的溫度。例如被膜材料若為熱硬化性，則會在被膜的硬化步驟中加熱。又，被膜材料若為光硬化性，則伴隨著光的照射而加熱。又，被膜材料若含有有機溶媒等溶劑，則會為了乾燥而加熱。 In the step of forming a scratch-resistant (hard coat) and low-reflective cured film on the surface of the resin plate as described above, the resin plate may be heated to The temperature is around 100°C. For example, if the coating material is thermosetting, it will be heated in the step of curing the coating. In addition, if the coating material is photocurable, it will be heated with light irradiation. In addition, if the coating material contains a solvent such as an organic solvent, it will be heated for drying.

但是，藉由將樹脂板暴露在高溫下，遲滯值會下降，無法控制在預期的範圍內。 However, by exposing the resin plate to high temperatures, the hysteresis value will decrease and cannot be controlled within the expected range.

此外，在夏季的日照下將使用液晶顯示器的汽車導航系統等車載用顯示裝置或行動電話、智慧型手機放置在汽車內時，還是有液晶顯示器保護板被加熱至高溫的情況，會有樹脂板的遲滯值降低的可能。 In addition, when the car navigation system or other mobile phone or smartphone is placed in the car under the sun in the summer, the LCD protection plate may be heated to a high temperature, and there will be a resin plate. The hysteresis value may be reduced.

[先前技術文獻] [Prior Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本特開2007-185956號公報 [Patent Document 1] JP 2007-185956 A

[專利文獻2]日本特開2009-248416號公報 [Patent Document 2] JP 2009-248416 A

[專利文獻3]日本特開2007-118597號公報 [Patent Document 3] JP 2007-118597 A

[專利文獻4]日本特開2004-299199號公報 [Patent Document 4] JP 2004-299199 A

[專利文獻5]日本特開2006-103169號公報 [Patent Document 5] JP 2006-103169 A

[專利文獻6]日本特開2010-085978號公報 [Patent Document 6] JP 2010-085978 A

在擠出樹脂板中，殘留在各樹脂層的應力的程度是不同的，因此嘗試藉由調整擠出成形所使用的冷卻輥的旋轉速度來減少殘留的應力。然而，當成形品從冷卻輥分離時，在成形品的表面上會有被稱為振動紋 (chatter mark)的條紋狀的缺陷產生，而表面性下降。這一點在將該擠出樹脂板用於觸控面板的保護蓋等上是一個課題。 In the extruded resin sheet, the degree of residual stress in each resin layer is different, so an attempt was made to reduce the residual stress by adjusting the rotation speed of the cooling roll used in extrusion molding. However, when the molded product is separated from the cooling roll, there will be called vibration lines on the surface of the molded product. (chatter mark) streak-shaped defects are generated, and the surface properties are degraded. This point is a problem in the use of the extruded resin sheet for a protective cover of a touch panel, and the like.

本發明之目的為提供一種擠出樹脂板之製造方法及一種擠出樹脂板，其表面性良好且可抑制翹曲發生，即便加熱至高溫，面內遲滯值的下降率也小。 The object of the present invention is to provide a method for manufacturing an extruded resin board and an extruded resin board that has good surface properties and can suppress the occurrence of warpage, and even if heated to a high temperature, the drop rate of the in-plane hysteresis value is small.

本發明人等為達成上述目的而進行研究，結果發現包含下述態樣的本發明，亦即本發明包含下述態樣。 The inventors of the present invention conducted studies to achieve the above object, and as a result, found that the present invention includes the following aspects, that is, the present invention includes the following aspects.

[1]一種擠出樹脂板之製造方法，其係在含有聚碳酸酯的層的至少一面上積層有含有甲基丙烯酸樹脂的層之擠出樹脂板之製造方法，其中，前述含有甲基丙烯酸樹脂的層的玻璃轉移溫度在115℃以上，該製造方法包含下述步驟：在熔融狀態下將在前述含有聚碳酸酯的層的至少一面上積層有前述含有甲基丙烯酸樹脂的層之熱塑性樹脂積層體從T字模擠出，在第1冷卻輥與第2冷卻輥之間夾住前述熱塑性樹脂積層體，藉由將前述熱塑性樹脂積層體捲繞至前述第2冷卻輥之後捲繞至第3冷卻輥來進行冷卻，利用拉取輥拉取前述熱塑性樹脂積層體；在前述熱塑性樹脂積層體從最後捲繞的冷卻輥剝離 的位置，將樹脂整體的溫度設定成相對於前述含有聚碳酸酯的層的玻璃轉移溫度為-2℃~+15℃的範圍，將前述拉取輥的圓周速度(V4)與前述第2冷卻輥的圓周速度(V2)的圓周速度比(V4/V2)設定為0.98以上1.01以下。 [1] A method of manufacturing an extruded resin sheet, which is a method of manufacturing an extruded resin sheet in which a layer containing a methacrylic resin is laminated on at least one surface of a layer containing polycarbonate, wherein the aforementioned methacrylic resin The glass transition temperature of the resin layer is 115°C or higher. The manufacturing method includes the following steps: in a molten state, laminating a thermoplastic resin containing the methacrylic resin layer on at least one surface of the polycarbonate-containing layer The laminate is extruded from a T-die, the thermoplastic resin laminate is sandwiched between the first cooling roll and the second cooling roll, and the thermoplastic resin laminate is wound to the second cooling roll and then to the third The cooling roll is used for cooling, and the thermoplastic resin laminate is pulled by the pull roll; the thermoplastic resin laminate is peeled from the last wound cooling roll on the thermoplastic resin laminate Set the temperature of the entire resin to the range of -2°C to +15°C relative to the glass transition temperature of the polycarbonate-containing layer, and set the peripheral speed (V4) of the pull roll and the second cooling The peripheral speed ratio (V4/V2) of the peripheral speed (V2) of the roller is set to 0.98 or more and 1.01 or less.

[2]如[1]記載之擠出樹脂板之製造方法，其中前述含有聚碳酸酯的層的線膨脹係數(S1)與前述含有甲基丙烯酸樹脂的層的線膨脹係數(S2)的差(S2-S1)、與前述含有聚碳酸酯的層的線膨脹係數(S1)之比((S2-S1)/S1)為-10%~+5%。 [2] The method for producing an extruded resin sheet as described in [1], wherein the difference between the linear expansion coefficient (S1) of the polycarbonate-containing layer and the linear expansion coefficient (S2) of the methacrylic resin-containing layer (S2-S1), the ratio ((S2-S1)/S1) to the linear expansion coefficient (S1) of the aforementioned polycarbonate-containing layer is -10% to +5%.

[3]如[1]或[2]記載之擠出樹脂板之製造方法，其中前述含有甲基丙烯酸樹脂的層含有來自甲基丙烯酸甲酯的結構單元40~80質量%且含有來自以下述通式(I)表示的甲基丙烯酸酯的結構單元20~60質量%。 [3] The method for producing an extruded resin sheet as described in [1] or [2], wherein the methacrylic resin-containing layer contains 40 to 80% by mass of structural units derived from methyl methacrylate and contains The structural unit of the methacrylate represented by general formula (I) is 20-60% by mass.

Figure 106109081-A0202-12-0006-1
Figure 106109081-A0202-12-0006-1

(式中，Cy係表示脂環式烴基)。 (In the formula, Cy represents an alicyclic hydrocarbon group).

[4]如[3]記載之擠出樹脂板之製造方法，其中前述通式(I)中之Cy為多環脂肪族烴基。 [4] The method for producing an extruded resin sheet as described in [3], wherein Cy in the aforementioned general formula (I) is a polycyclic aliphatic hydrocarbon group.

[5]如[1]或[2]中任一項之擠出樹脂板之製造方法，其中前述含有甲基丙烯酸樹脂的層含有：甲基丙烯酸樹脂5質量%以上小於80質量%、與包含來自以下述通式(II)表示的芳香族乙烯化合物的結構單元及來自以下述通式(III)表示的酸酐的結構單元而成的共聚物20質量 %以上。 [5] The method for producing an extruded resin sheet according to any one of [1] or [2], wherein the aforementioned methacrylic resin-containing layer contains: methacrylic resin 5 mass% or more and less than 80 mass%, and A copolymer composed of structural units derived from an aromatic vinyl compound represented by the following general formula (II) and structural units derived from an acid anhydride represented by the following general formula (III) 20 mass %the above.

Figure 106109081-A0202-12-0007-2
Figure 106109081-A0202-12-0007-2

(式中：R1及R2係各自獨立地表示氫原子或烷基)。 (In the formula: R 1 and R 2 each independently represent a hydrogen atom or an alkyl group).

Figure 106109081-A0202-12-0007-3
Figure 106109081-A0202-12-0007-3

(式中：R3及R4係各自獨立地表示氫原子或烷基)。 (In the formula: R 3 and R 4 each independently represent a hydrogen atom or an alkyl group).

[6]如[5]記載之擠出樹脂板之製造方法，其中前述共聚物含有50~84質量%前述來自芳香族乙烯化合物的結構單元、含有15~49質量%的前述來自酸酐的結構單元以及含有1~25質量%的甲基丙烯酸酯單體。 [6] The method for producing an extruded resin sheet as described in [5], wherein the copolymer contains 50 to 84% by mass of the structural unit derived from the aromatic vinyl compound, and 15 to 49% by mass of the structural unit derived from the acid anhydride And it contains 1-25% by mass of methacrylate monomer.

[7]如[6]記載之擠出樹脂板之製造方法，其中前述甲基丙烯酸酯單體為甲基丙烯酸甲酯。 [7] The method for producing an extruded resin sheet as described in [6], wherein the methacrylate monomer is methyl methacrylate.

[8]一種擠出樹脂板，其係藉由如[1]至[7]中任一項之製造方法所得到的擠出樹脂板，其中將前述擠出樹脂板在75℃下加熱5小時時，於加熱前後在寬度方向的至少一部分中，面內遲滯值為50~600nm，於前述加熱前後的前述遲滯值的下降率小於15%。 [8] An extruded resin sheet, which is an extruded resin sheet obtained by the manufacturing method of any one of [1] to [7], wherein the extruded resin sheet is heated at 75°C for 5 hours At this time, in at least a part of the width direction before and after heating, the in-plane hysteresis value is 50 to 600 nm, and the decrease rate of the hysteresis value before and after heating is less than 15%.

[9]一種擠出樹脂板，其係藉由如[1]至[7]中任一項之製造方法所得到的擠出樹脂板，其中將前述擠出樹脂板在100℃下加熱5小時時，於加熱 前後在寬度方向的至少一部分中，面內遲滯值為50~600nm，於前述加熱前後的前述遲滯值的下降率小於15%。 [9] An extruded resin sheet, which is an extruded resin sheet obtained by the manufacturing method of any one of [1] to [7], wherein the extruded resin sheet is heated at 100°C for 5 hours时，于 Heat In at least a part of the width direction before and after, the in-plane hysteresis value is 50 to 600 nm, and the decrease rate of the hysteresis value before and after the heating is less than 15%.

[10]一種擠出樹脂板，其係藉由如[1]至[7]中任一項之製造方法所得到的擠出樹脂板，其中將前述擠出樹脂板在75℃~100℃下加熱5小時時，於加熱前後在寬度方向的至少一部分中，面內遲滯值為50~600nm，於前述加熱前後的前述遲滯值的下降率小於15%。 [10] An extruded resin sheet, which is an extruded resin sheet obtained by the manufacturing method of any one of [1] to [7], wherein the extruded resin sheet is heated at 75°C to 100°C When heating for 5 hours, in at least a part of the width direction before and after heating, the in-plane hysteresis value is 50 to 600 nm, and the reduction rate of the hysteresis value before and after heating is less than 15%.

[11]如[8]~[10]中任一項之擠出樹脂板，其中於前述加熱前後在寬度方向的至少一部分中，面內遲滯值為80~350nm。 [11] The extruded resin sheet according to any one of [8] to [10], wherein the in-plane hysteresis value is 80 to 350 nm in at least a part of the width direction before and after the heating.

[12]如[8]~[11]中任一項之擠出樹脂板，其中於前述加熱前後的前述遲滯值的下降率小於10%。 [12] The extruded resin sheet according to any one of [8] to [11], wherein the reduction rate of the hysteresis value before and after the heating is less than 10%.

[13]如[8]~[12]中任一項之擠出樹脂板，其係進一步在至少一表面上具備抗刮性層。 [13] The extruded resin board as in any one of [8] to [12], which is further provided with a scratch-resistant layer on at least one surface.

[14]一種擠出樹脂板之製造方法，其係藉由如[1]~[7]中任一項之製造方法得到擠出樹脂板，並進一步包含將前述擠出樹脂板在65℃~110℃的溫度下加熱1~30小時之步驟，前述於加熱前後在寬度方向的至少一部分中，面內遲滯值為50~600nm，於前述加熱前後的前述遲滯值的下降率小於15%。 [14] A method for manufacturing an extruded resin board, which is obtained by the manufacturing method as described in any one of [1] to [7], and further comprises heating the extruded resin board at 65°C~ In the step of heating at a temperature of 110°C for 1-30 hours, the in-plane hysteresis value is 50-600nm in at least a part of the width direction before and after heating, and the decrease rate of the hysteresis value before and after heating is less than 15%.

[15]一種擠出樹脂板，其係在含有聚碳酸酯的層的至少一面上積層有含有甲基丙烯酸樹脂的層之擠 出樹脂板，其中前述含有甲基丙烯酸樹脂的層的玻璃轉移溫度在115℃以上，在75℃下加熱5小時時，於加熱前後在寬度方向的至少一部分中，面內遲滯值為50~600nm，於前述加熱前後的前述遲滯值的下降率小於15%，前述含有聚碳酸酯的層的線膨脹係數(S1)與前述含有甲基丙烯酸樹脂的層的線膨脹係數(S2)的差(S2-S1)、與前述含有聚碳酸酯的層的線膨脹係數(S1)之比((S2-S1)/S1)為-10%~+5%。 [15] An extruded resin sheet in which a layer containing methacrylic resin is laminated on at least one surface of a layer containing polycarbonate A resin plate, in which the glass transition temperature of the aforementioned methacrylic resin-containing layer is 115°C or higher, and when heated at 75°C for 5 hours, the in-plane hysteresis value is 50~600nm in at least a part of the width direction before and after heating , The reduction rate of the hysteresis value before and after the heating is less than 15%, the difference between the linear expansion coefficient (S1) of the polycarbonate-containing layer and the linear expansion coefficient (S2) of the methacrylic resin-containing layer (S2) -S1), the ratio ((S2-S1)/S1) to the linear expansion coefficient (S1) of the aforementioned polycarbonate-containing layer is -10% to +5%.

藉由本發明之擠出樹脂板之製造方法所得到的擠出樹脂板，其表面性良好且可抑制翹曲發生，並具有透過偏光太陽眼鏡觀看時之適合作為液晶顯示器保護板的面內遲滯值。 The extruded resin sheet obtained by the manufacturing method of the extruded resin sheet of the present invention has good surface properties and can suppress the occurrence of warpage, and has an in-plane hysteresis value suitable as a protective sheet for liquid crystal displays when viewed through polarized sunglasses .

又，由於其面內遲滯值因加熱而下降的比例小，因此其可承受加熱步驟、高溫環境，其生產性、耐久性優異。 In addition, since the ratio of the in-plane hysteresis value decreased by heating is small, it can withstand heating steps and high-temperature environments, and its productivity and durability are excellent.

又，本發明之擠出樹脂板係例如適合用在尋求光澤、抗刮性及耐衝擊性的觸控面板保護蓋等的用途上。 In addition, the extruded resin sheet of the present invention is suitable for applications such as touch panel protective covers seeking gloss, scratch resistance, and impact resistance, for example.

11‧‧‧T字模 11‧‧‧T font

12‧‧‧第1冷卻輥 12‧‧‧The first cooling roll

13‧‧‧第2冷卻輥 13‧‧‧Second cooling roll

14‧‧‧第3冷卻輥 14‧‧‧The third cooling roll

15‧‧‧拉取輥 15‧‧‧Pull roll

16‧‧‧擠出樹脂板(熱塑性樹脂積層體) 16‧‧‧Extruded resin sheet (thermoplastic resin laminate)

[圖1]為顯示本發明之一實施形態之使用共擠出之擠出樹脂板之製造方法的圖。 Fig. 1 is a diagram showing a method of manufacturing an extruded resin sheet using co-extrusion according to an embodiment of the present invention.

[實施發明之形態] [The form of implementing the invention]

以下，參照圖式來針對本發明的實施形態進行說明。為了明確說明，以下的記載及圖式被適當地省略及簡化。在各圖式中具有相同構成或功能的構成元件及相應的部分中標記相同的符號，並省略其說明。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. In order to clarify the description, the following descriptions and drawings are appropriately omitted and simplified. The constituent elements having the same configuration or function and the corresponding parts in the various drawings are marked with the same symbols, and their descriptions are omitted.

有關本發明之擠出樹脂板係在含有聚碳酸酯的層(之後亦適當地記載為「含聚碳酸酯的層」)的至少一面上積層有含有甲基丙烯酸樹脂的層(之後亦適當地記載為「含甲基丙烯酸樹脂的層」)。 The extruded resin sheet of the present invention is a polycarbonate-containing layer (hereinafter also appropriately referred to as "polycarbonate-containing layer") on at least one side of which a methacrylic resin-containing layer is laminated (hereinafter also appropriately Described as "methacrylic resin-containing layer").

藉由在含聚碳酸酯的層上積層含甲基丙烯酸樹脂的層，而具有優異的透明性、耐衝擊性、抗刮性。 By laminating a methacrylic resin-containing layer on a polycarbonate-containing layer, it has excellent transparency, impact resistance, and scratch resistance.

擠出樹脂板係藉由使用擠出成形法來製造，而具有優異的生產效率。 The extruded resin board is manufactured by using an extrusion molding method, and has excellent production efficiency.

在擠出樹脂板中，含甲基丙烯酸樹脂的層的玻璃轉移溫度(Tg)的下限為115℃，較佳為120℃，更佳為125℃，再更佳為130℃，其玻璃轉移溫度(Tg)的上限較佳為160℃，更佳為155℃，再更佳為150℃。線膨脹比(SR)及含甲基丙烯酸樹脂的層的玻璃轉移溫度(Tg)若在此範圍內，則其表面性良好且因殘留應力造成的翹曲小，故而較佳。 In the extruded resin sheet, the lower limit of the glass transition temperature (Tg) of the methacrylic resin-containing layer is 115°C, preferably 120°C, more preferably 125°C, and still more preferably 130°C. Its glass transition temperature The upper limit of (Tg) is preferably 160°C, more preferably 155°C, and still more preferably 150°C. If the linear expansion ratio (SR) and the glass transition temperature (Tg) of the methacrylic resin-containing layer are within this range, the surface properties are good and the warpage due to residual stress is small, which is preferable.

[甲基丙烯酸樹脂] [Methacrylic resin]

在本發明中，甲基丙烯酸樹脂含有來自甲基丙烯酸酯的結構單元。在甲基丙烯酸樹脂中，係以來自甲基丙烯酸酯的結構單元的含量較佳為50質量%以上、更佳為80質量%以上、再更佳為90質量%以上為佳，亦可為100 質量%。來自甲基丙烯酸酯的結構單元的含量若在上述範圍內，則具有良好的透明性。 In the present invention, the methacrylic resin contains a structural unit derived from methacrylate. In the methacrylic resin, the content of the structural unit derived from methacrylate is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and may also be 100 quality%. If the content of the structural unit derived from methacrylate is within the above range, it has good transparency.

該甲基丙烯酸酯係以通式(IV)表示。 This methacrylate is represented by general formula (IV).

Figure 106109081-A0202-12-0011-4
Figure 106109081-A0202-12-0011-4

通式(IV)中，R係表示烴基。烴基可為飽和烴基，亦可為不飽和烴基。 In the general formula (IV), R represents a hydrocarbon group. The hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.

R表示的烴基可為甲基、乙基、丙基等非環狀脂肪族烴基，亦可為脂環式烴基，亦可為苯基等芳香族烴基。此處在R為脂環式烴基時，甲基丙烯酸酯係以通式(I)表示。之後亦適當地將以通式(I)表示的甲基丙烯酸酯記載為「甲基丙烯酸酯(I)」。 The hydrocarbon group represented by R may be an acyclic aliphatic hydrocarbon group such as a methyl group, an ethyl group, a propyl group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group such as a phenyl group. Here, when R is an alicyclic hydrocarbon group, the methacrylate system is represented by the general formula (I). The methacrylate represented by the general formula (I) will also be appropriately described as "methacrylate (I)" thereafter.

Figure 106109081-A0202-12-0011-5
Figure 106109081-A0202-12-0011-5

(式中，Cy係表示脂環式烴基)。 (In the formula, Cy represents an alicyclic hydrocarbon group).

就甲基丙烯酸酯(I)而言，可列舉：甲基丙烯酸環己酯、甲基丙烯酸環戊酯、甲基丙烯酸環庚酯等甲基丙烯酸單環脂肪族烴酯；甲基丙烯酸-2-降莰酯、甲基丙烯酸-2-甲基-2-降莰酯、甲基丙烯酸-2-乙基-2-降莰酯、甲基丙烯酸-2-異莰酯、甲基丙烯酸-2-甲基-2-異莰酯、甲基丙烯酸-2-乙基-2-異莰酯、甲基丙烯酸-8-三環[5.2.1.02,6]癸酯、甲基丙烯酸-8-甲基-8-三環[5.2.1.02,6]癸酯、甲基丙烯酸-8-乙基-8-三環[5.2.1.02,6]癸酯、甲基 丙烯酸-2-金剛烷酯、甲基丙烯酸-2-甲基-2-金剛烷酯、甲基丙烯酸-2-乙基-2-金剛烷酯、甲基丙烯酸-1-金剛烷酯、甲基丙烯酸-2-葑酯(2-fenchyl methacrylate)、甲基丙烯酸-2-甲基-2-葑酯或甲基丙烯酸-2-乙基-2-葑酯等甲基丙烯酸多環脂肪族烴酯等。其中，較佳為甲基丙烯酸多環脂肪族烴酯，更佳為甲基丙烯酸-8-三環[5.2.1.02,6]癸酯。 Methacrylate (I) includes monocyclic aliphatic hydrocarbon esters of methacrylic acid such as cyclohexyl methacrylate, cyclopentyl methacrylate, and cycloheptyl methacrylate; methacrylic acid-2 -Norbornyl, 2-methyl-2-norbornyl methacrylate, 2-ethyl-2-norbornyl methacrylate, 2-isobornyl methacrylate, methacrylic acid-2 -Methyl-2-isocampanate, methacrylic acid-2-ethyl-2-isocampanate, methacrylic acid-8-tricyclo[5.2.1.0 2,6 ]decyl ester, methacrylic acid-8- Methyl-8-tricyclo[5.2.1.0 2,6 ]decyl ester, methacrylic acid-8-ethyl-8-tricyclo[5.2.1.0 2,6 ]decyl ester, methacrylic acid-2-adamantane Ester, 2-methyl-2-adamantyl methacrylate, 2-ethyl-2-adamantyl methacrylate, 1-adamantyl methacrylate, 2-fenchyl methacrylate (2-fenchyl methacrylate), methacrylic acid polycyclic aliphatic hydrocarbon esters such as 2-methyl-2-fenchyl methacrylate or 2-ethyl-2-fenchyl methacrylate, etc. Among them, polycyclic aliphatic hydrocarbon methacrylate is preferred, and 8-tricyclo[5.2.1.0 2,6 ]decyl methacrylate is more preferred.

本發明所使用的甲基丙烯酸樹脂在一實施形態中，較佳為含有來自甲基丙烯酸甲酯(之後亦適當地記載為「MMA」)的結構單元與來自甲基丙烯酸酯(I)的結構單元，更佳為含有來自MMA的結構單元與來自甲基丙烯酸多環脂肪族烴酯的結構單元，再更佳為含有來自MMA的結構單元與來自甲基丙烯酸-8-三環[5.2.1.02,6]癸酯的結構單元。甲基丙烯酸樹脂亦可含有來自甲基丙烯酸酯(I)與MMA以外的其它單體的結構單元，但其含量較佳為10質量%以下。 In one embodiment, the methacrylic resin used in the present invention preferably contains a structural unit derived from methyl methacrylate (hereinafter also appropriately referred to as "MMA") and a structure derived from methacrylate (I) The unit more preferably contains a structural unit derived from MMA and a structural unit derived from a polycyclic aliphatic hydrocarbon ester of methacrylic acid, and still more preferably contains a structural unit derived from MMA and a structural unit derived from methacrylic acid-8-tricyclic [5.2.1.0 The structural unit of 2,6 ]decyl ester. The methacrylic resin may also contain structural units derived from monomers other than methacrylate (I) and MMA, but the content thereof is preferably 10% by mass or less.

從硬度的觀點來看，本發明所使用的甲基丙烯酸樹脂係以含有40~80質量%的來自MMA的結構單元為佳，更佳為含有50~80質量%，再更佳為含有50~60質量%。 From the viewpoint of hardness, the methacrylic resin used in the present invention preferably contains 40 to 80% by mass of structural units derived from MMA, more preferably 50 to 80% by mass, and even more preferably 50 to 80% by mass. 60% by mass.

從降低後述的線膨脹比(SR)的觀點及使玻璃轉移溫度(Tg)在115℃以上的觀點來看，本發明所使用的甲基丙烯酸樹脂係以含有20~60質量%的來自甲基丙烯酸酯(I)的結構單元為佳，更佳為含有20~50質量%，再更佳為含有40~50質量%。來自甲基丙烯酸酯(I)的結構 單元若超過60質量%，則有甲基丙烯酸樹脂層的耐衝擊性降低的傾向。 From the viewpoint of reducing the linear expansion ratio (SR) described later and the viewpoint of making the glass transition temperature (Tg) 115°C or higher, the methacrylic resin used in the present invention contains 20-60% by mass of methyl The structural unit of the acrylate (I) is preferably, more preferably 20-50% by mass, and still more preferably 40-50% by mass. Structure from methacrylate (I) If the unit exceeds 60% by mass, the impact resistance of the methacrylic resin layer tends to decrease.

本發明所使用的甲基丙烯酸樹脂係藉由將上述的甲基丙烯酸酯及作為任意成分的其它單體聚合而得到。在這樣的聚合中，使用複數種單體時，通常在混合這些複數種單體調製單體混合物後進行聚合。聚合方法並沒有特殊的限制，但從生產性的觀點來看，係以使用塊狀聚合法、懸浮聚合法、溶液聚合法、乳化聚合法等方法進行自由基聚合為佳。 The methacrylic resin used in the present invention is obtained by polymerizing the above-mentioned methacrylate and other monomers as optional components. In such polymerization, when multiple types of monomers are used, the polymerization is usually carried out after mixing these plural types of monomers to prepare a monomer mixture. The polymerization method is not particularly limited, but from the viewpoint of productivity, it is preferable to perform radical polymerization using a method such as a bulk polymerization method, a suspension polymerization method, a solution polymerization method, and an emulsion polymerization method.

本發明所使用的甲基丙烯酸樹脂的重量平均分子量(之後亦適當地記載為「Mw」)較佳為40,000~500,000。藉由使該Mw在40,000以上，本發明之擠出樹脂板會具有優異的抗刮性、耐熱性；藉由在500,000以下，會具有優異的成形加工性，並提高本發明之擠出樹脂板的生產性。 The weight average molecular weight of the methacrylic resin used in the present invention (hereinafter also appropriately described as "Mw") is preferably 40,000 to 500,000. By making the Mw above 40,000, the extruded resin sheet of the present invention will have excellent scratch resistance and heat resistance; by making the Mw below 500,000, it will have excellent molding processability and improve the extruded resin sheet of the present invention The productivity.

還有，在本說明書中，Mw是指使用凝膠滲透層析術(GPC)所測定的標準聚苯乙烯換算值。 In addition, in this specification, Mw means a standard polystyrene conversion value measured using gel permeation chromatography (GPC).

[含有甲基丙烯酸樹脂的樹脂組成物(1)] [Resin composition containing methacrylic resin (1)]

在本發明的一實施形態中，構成含甲基丙烯酸樹脂的層的樹脂為含有5質量%以上小於80質量%的甲基丙烯酸樹脂、及20質量%以上的至少包含來自以下述通式(II)表示的芳香族乙烯化合物(之後亦適當地記載為「芳香族乙烯化合物(II)」)的結構單元與來自以下述通式(III)表示的酸酐(之後亦適當地記載為「酸酐(III)」)的結構單元的共聚物(之後適當地記載為「SMA樹脂」)之樹 脂組成物(之後適當地記載為「樹脂組成物(1)」)。含甲基丙烯酸樹脂的層若是由樹脂組成物(1)構成，則與含聚碳酸酯的層或後述的硬化被膜的密合性會變好。 In one embodiment of the present invention, the resin constituting the methacrylic resin-containing layer contains 5 mass% or more and less than 80 mass% methacrylic resin, and 20 mass% or more containing at least from the following general formula (II ) Represented by the aromatic vinyl compound (hereinafter also appropriately described as "aromatic vinyl compound (II)") and derived from the acid anhydride represented by the following general formula (III) (hereinafter also appropriately described as "acid anhydride (III) )'') of the copolymer of the structural unit (hereinafter appropriately referred to as "SMA resin") tree Grease composition (hereinafter referred to as "resin composition (1)" as appropriate). If the methacrylic resin-containing layer is composed of the resin composition (1), the adhesion with the polycarbonate-containing layer or the cured film described later will be improved.

Figure 106109081-A0202-12-0014-6
Figure 106109081-A0202-12-0014-6

(式中：R1及R2係各自獨立地表示氫原子或烷基)。 (In the formula: R 1 and R 2 each independently represent a hydrogen atom or an alkyl group).

Figure 106109081-A0202-12-0014-7
Figure 106109081-A0202-12-0014-7

(式中：R3及R4係各自獨立地表示氫原子或烷基)。 (In the formula: R 3 and R 4 each independently represent a hydrogen atom or an alkyl group).

樹脂組成物(1)所含的甲基丙烯酸樹脂為包含來自以通式(IV)表示的甲基丙烯酸酯的結構單元的樹脂。 The methacrylic resin contained in the resin composition (1) is a resin containing a structural unit derived from a methacrylate represented by the general formula (IV).

就這樣的甲基丙烯酸酯而言，並沒有特殊的限制，但從取得性的觀點來看，較佳為MMA、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、及甲基丙烯酸三級丁酯，最佳為MMA。該甲基丙烯酸樹脂中之來自甲基丙烯酸酯的結構單元的含量較佳為90質量%以上，更佳為95質量%以上，再更佳為98質量%以上，亦可僅為來自甲基丙烯酸酯的結構單元。 There are no particular restrictions on such methacrylates, but from the viewpoint of availability, MMA, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, N-butyl methacrylate, isobutyl methacrylate, and tertiary butyl methacrylate are most preferably MMA. The content of the structural unit derived from methacrylate in the methacrylic resin is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 98% by mass or more, or only derived from methacrylic acid The structural unit of an ester.

又，從耐熱性的觀點來看，樹脂組成物(1)所含的甲基丙烯酸樹脂係以含有90質量%以上的來自MMA的結構單元為佳，更佳為含有95質量%以上，再更佳為含有98質量%以上，亦可僅為來自MMA的結構單元。 Also, from the viewpoint of heat resistance, the methacrylic resin contained in the resin composition (1) preferably contains 90% by mass or more of structural units derived from MMA, more preferably 95% by mass or more, and still more It is preferable to contain 98% by mass or more, and it may only be a structural unit derived from MMA.

又，樹脂組成物(1)所含的甲基丙烯酸樹脂亦可含有來自甲基丙烯酸酯以外的其它單體的結構單元。就這種其它單體而言，可列舉：丙烯酸甲酯(之後亦適當地記載為「MA」)、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、丙烯酸三級丁酯、丙烯酸己酯、丙烯酸-2-乙基己酯、丙烯酸壬酯、丙烯酸癸酯、丙烯酸十二烷酯、丙烯酸十八烷酯、丙烯酸-2-羥基乙酯、丙烯酸-2-羥基丙酯、丙烯酸-4-羥基丁酯、丙烯酸環己酯、丙烯酸-2-甲氧基乙酯、丙烯酸-3-甲氧基丁酯、丙烯酸三氟甲酯、丙烯酸三氟乙酯、丙烯酸五氟乙酯、丙烯酸環氧丙酯、丙烯酸烯丙酯、丙烯酸苯酯、丙烯酸甲苯酯(toluyl acrylate)、丙烯酸苄酯、丙烯酸異莰酯、丙烯酸-3-二甲基胺基乙酯等丙烯酸酯，從取得性的觀點來看，較佳為MA、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、丙烯酸三級丁酯等丙烯酸酯，更佳為MA及丙烯酸乙酯，最佳為MA。甲基丙烯酸樹脂中之此等來自其它單體的結構單元的含量係以總計為10質量%以下為佳，更佳為5質量%以下，再更佳為2質量%以下。 In addition, the methacrylic resin contained in the resin composition (1) may contain a structural unit derived from other monomers other than methacrylate. Such other monomers include: methyl acrylate (hereinafter also referred to as "MA" as appropriate), ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate , Tertiary butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, octadecyl acrylate, 2-hydroxyethyl acrylate, acrylic acid- 2-hydroxypropyl ester, 4-hydroxybutyl acrylate, cyclohexyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, trifluoromethyl acrylate, trifluoroethyl acrylate , Pentafluoroethyl acrylate, glycidyl acrylate, allyl acrylate, phenyl acrylate, toluyl acrylate, benzyl acrylate, isobornyl acrylate, 3-dimethylaminoethyl acrylate From the viewpoint of availability, acrylates such as MA, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, and tertiary butyl acrylate are preferred. More preferred are MA and ethyl acrylate, and most preferred is MA. The content of these structural units derived from other monomers in the methacrylic resin is preferably 10% by mass or less in total, more preferably 5% by mass or less, and still more preferably 2% by mass or less.

樹脂組成物(1)所含的甲基丙烯酸樹脂係藉由將上述的甲基丙烯酸酯及作為任意成分的其它單體聚 合而得到。在這樣的聚合中，使用複數種單體時，通常在混合這些複數種單體調製單體混合物後進行聚合。聚合方法並沒有特殊的限制，但從生產性的觀點來看，係以使用塊狀聚合法、懸浮聚合法、溶液聚合法、乳化聚合法等方法進行自由基聚合為佳。 The methacrylic resin contained in the resin composition (1) is made by polymerizing the above-mentioned methacrylate and other monomers as optional components. Get together. In such polymerization, when multiple types of monomers are used, the polymerization is usually carried out after mixing these plural types of monomers to prepare a monomer mixture. The polymerization method is not particularly limited, but from the viewpoint of productivity, it is preferable to perform radical polymerization using a method such as a bulk polymerization method, a suspension polymerization method, a solution polymerization method, and an emulsion polymerization method.

樹脂組成物(1)所含的甲基丙烯酸樹脂的重量平均分子量(之後適當地記載為「Mw」)較佳為40,000~500,000。藉由使該Mw在40,000以上，本發明之擠出樹脂板具有優異的抗刮性、耐熱性；藉由在500,000以下，樹脂組成物(1)具有優異的成形加工性，並提高本發明之擠出樹脂板的生產性。 The weight average molecular weight (hereinafter appropriately described as "Mw") of the methacrylic resin contained in the resin composition (1) is preferably 40,000 to 500,000. By making the Mw above 40,000, the extruded resin sheet of the present invention has excellent scratch resistance and heat resistance; by making the Mw below 500,000, the resin composition (1) has excellent moldability, and improves the performance of the present invention. Productivity of extruded resin board.

從降低後述的線膨脹比(SR)的觀點及使玻璃轉移溫度(Tg)在115℃以上的觀點來看，本發明所使用的樹脂組成物(1)中的SMA樹脂的含量較佳為20質量%以上，更佳為45質量%以上小於95質量%的範圍，再更佳為50質量%以上小於90質量%的範圍。 From the viewpoint of reducing the linear expansion ratio (SR) described later and the viewpoint of making the glass transition temperature (Tg) 115°C or higher, the content of the SMA resin in the resin composition (1) used in the present invention is preferably 20 Mass% or more, more preferably 45% by mass or more and less than 95% by mass, and still more preferably 50% by mass or more and less than 90% by mass.

本發明所使用的樹脂組成物(1)中的甲基丙烯酸樹脂的含量較佳為小於80%，更佳為5質量%以上小於55質量%的範圍，再更佳為10質量%以上小於50質量%的範圍。 The content of the methacrylic resin in the resin composition (1) used in the present invention is preferably less than 80%, more preferably 5 mass% or more and less than 55% by mass, still more preferably 10 mass% or more and less than 50%. The range of mass %.

上述SMA樹脂為至少包含來自芳香族乙烯化合物(II)的結構單元與來自酸酐(III)的結構單元而成之共聚物。 The above-mentioned SMA resin is a copolymer containing at least a structural unit derived from an aromatic vinyl compound (II) and a structural unit derived from an acid anhydride (III).

就通式(II)中的R1及R2以及通式(III)中的R3及R4各自獨立地表示的烷基而言，較佳為甲基、乙基、 正丙基、異丙基、正丁基、二級丁基、異丁基、三級丁基、正戊基、異戊基、新戊基、正己基、正庚基、正辛基、2-乙基己基、壬基、癸基、十二基等碳數12以下的烷基，更佳為甲基、乙基、正丙基、異丙基、正丁基、二級丁基、異丁基、三級丁基等碳數4以下的烷基。 For the alkyl groups represented by R 1 and R 2 in the general formula (II) and R 3 and R 4 in the general formula (III) each independently, methyl, ethyl, n-propyl, iso Propyl, n-butyl, secondary butyl, isobutyl, tertiary butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, Nonyl, decyl, dodecyl and other alkyl groups with 12 or less carbon atoms, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary butyl, isobutyl, tertiary An alkyl group with 4 or less carbon atoms such as butyl group.

就R1而言，較佳為氫原子、甲基、乙基及三級丁基。就R2、R3、R4而言，較佳為氫原子、甲基及乙基。 Respect to R 1, preferably a hydrogen atom, methyl, ethyl and tertiary butyl. R 2 , R 3 , and R 4 are preferably a hydrogen atom, a methyl group, and an ethyl group.

上述SMA樹脂中之來自芳香族乙烯化合物(II)的結構單元的含量較佳為50~85質量%的範圍，更佳為55~82質量%，再更佳為60~80質量%的範圍。這樣的含量若為50~85質量%的範圍，則樹脂組成物(1)會具有優異的耐濕性與透明性。 The content of the structural unit derived from the aromatic vinyl compound (II) in the SMA resin is preferably in the range of 50 to 85% by mass, more preferably 55 to 82% by mass, and still more preferably in the range of 60 to 80% by mass. If such a content is in the range of 50 to 85% by mass, the resin composition (1) will have excellent moisture resistance and transparency.

就芳香族乙烯化合物(II)而言，例如可列舉：苯乙烯；2-甲基苯乙烯、3-甲基苯乙烯、4-甲基苯乙烯、4-乙基苯乙烯、4-三級丁基苯乙烯等經核烷基取代的苯乙烯；α-甲基苯乙烯、4-甲基-α-甲基苯乙烯等經α-烷基取代的苯乙烯，從取得性的觀點來看，較佳為苯乙烯。此等芳香族乙烯化合物(II)係可單獨使用1種，亦可併用複數種。 As for the aromatic vinyl compound (II), for example, styrene; 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-tertiary Styrene substituted with nucleoalkyl groups such as butylstyrene; α-alkyl substituted styrenes such as α-methylstyrene and 4-methyl-α-methylstyrene, from the viewpoint of availability , Preferably styrene. These aromatic vinyl compounds (II) may be used singly, or a plurality of them may be used in combination.

上述SMA樹脂中之來自酸酐(III)的結構單元的含量較佳為15~50質量%的範圍，更佳為18~45質量%的範圍，再更佳為20~40質量%的範圍。藉由這樣的含量在15~50質量%的範圍內，樹脂組成物(1)會具有耐熱性與透明性。 The content of the structural unit derived from the acid anhydride (III) in the above-mentioned SMA resin is preferably in the range of 15-50% by mass, more preferably in the range of 18-45% by mass, and still more preferably in the range of 20-40% by mass. With such a content in the range of 15-50% by mass, the resin composition (1) will have heat resistance and transparency.

就酸酐(III)而言，例如可列舉：順丁烯二酸酐、甲基順丁烯二酸酐、二甲基順丁烯二酸酐等，從取得性的觀點來看，較佳為順丁烯二酸酐。此等酸酐(III)係可單獨使用1種，亦可併用複數種。 The acid anhydride (III) includes, for example, maleic anhydride, methyl maleic anhydride, dimethyl maleic anhydride, etc., from the viewpoint of availability, maleic anhydride is preferred Diacid anhydride. These acid anhydrides (III) may be used individually by 1 type, and may use multiple types together.

上述SMA樹脂除了芳香族乙烯化合物(II)及酸酐(III)以外，係以含有來自甲基丙烯酸酯單體的結構單元為佳。上述SMA樹脂中之來自甲基丙烯酸酯單體的結構單元的含量較佳為1~35質量%的範圍，更佳為3~30質量%的範圍，再更佳為5~26質量%的範圍。藉由這樣的含量在1~35質量%的範圍內，會具有優異的彎曲加工性、透明性。 In addition to the aromatic vinyl compound (II) and the acid anhydride (III), the above-mentioned SMA resin preferably contains a structural unit derived from a methacrylate monomer. The content of the structural unit derived from the methacrylate monomer in the SMA resin is preferably in the range of 1 to 35% by mass, more preferably in the range of 3 to 30% by mass, and still more preferably in the range of 5 to 26% by mass . With such a content in the range of 1 to 35% by mass, it has excellent bending workability and transparency.

就此種甲基丙烯酸酯而言，例如可列舉：MMA、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸異丙酯、甲基丙烯酸正丁酯、甲基丙烯酸丙酯、甲基丙烯酸異丙酯、甲基丙烯酸正丁酯、甲基丙烯酸異丁酯、甲基丙烯酸三級丁酯、甲基丙烯酸-2-乙基己酯、甲基丙烯酸環己酯、甲基丙烯酸苯酯、甲基丙烯酸苄酯、甲基丙烯酸-1-苯基乙酯等。在此等的甲基丙烯酸酯之中，較佳為烷基的碳數為1~7的甲基丙烯酸烷酯，從所得到的SMA樹脂的耐熱性或透明性優異來看，特佳為MMA。又，甲基丙烯酸酯係可單獨使用1種，亦可併用複數種。 Such methacrylates include, for example, MMA, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, propyl methacrylate, and methacrylic acid. Isopropyl ester, n-butyl methacrylate, isobutyl methacrylate, tertiary butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, Benzyl methacrylate, 1-phenylethyl methacrylate, etc. Among these methacrylates, alkyl methacrylates having an alkyl group of 1 to 7 carbon atoms are preferred, and MMA is particularly preferred from the viewpoint of excellent heat resistance or transparency of the resulting SMA resin . Moreover, a methacrylate type may be used individually by 1 type, and may use a plurality of types together.

上述SMA樹脂亦可具有來自芳香族乙烯化合物(II)、酸酐(III)及甲基丙烯酸酯以外的其它單體的結構單元。就這樣的其它單體而言，可列舉：MA、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、丙烯酸三級丁酯、丙烯酸己酯、丙烯酸-2-乙酯己酯、丙烯酸壬酯、丙烯酸癸酯、丙烯酸十二烷酯、丙烯酸十八烷酯、丙烯酸-2-羥基乙酯、丙烯酸-2-羥基丙酯、丙烯酸-4-羥基丁酯、丙烯酸環己酯、丙烯酸-2-甲氧基乙酯、丙烯酸-3-甲氧基丁酯、丙烯酸三氟甲酯、丙烯酸三氟乙酯、丙烯酸五氟乙酯、丙烯酸環氧丙酯、丙烯酸烯丙酯、丙烯酸苯酯、丙烯酸甲苯酯(toluyl acrylate)、丙烯酸苄酯、丙烯酸異莰酯、丙烯酸-3-二甲基胺基乙酯等丙烯酸酯。此等其它單體係可單獨使用1種，亦可併用複數種。SMA樹脂中之來自該其它單體的結構單元的含量較佳為10質量%以下，更佳為5質量%以下，再更佳為2質量%以下。 The above-mentioned SMA resin may have a structural unit derived from a monomer other than the aromatic vinyl compound (II), acid anhydride (III), and methacrylate. In terms of such other monomers, examples include MA, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, propylene Isobutyl acrylate, tertiary butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate, 2-hydroxy acrylate Ethyl, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, cyclohexyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, trifluoromethyl acrylate, Trifluoroethyl acrylate, pentafluoroethyl acrylate, glycidyl acrylate, allyl acrylate, phenyl acrylate, toluyl acrylate, benzyl acrylate, isobornyl acrylate, 3-dimethyl acrylate Acrylic esters such as ethyl amino ethyl ester. These other single systems may be used alone or in combination of plural types. The content of the structural unit derived from the other monomer in the SMA resin is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 2% by mass or less.

上述SMA樹脂係藉由將上述的芳香族乙烯化合物(II)、酸酐(III)及甲基丙烯酸酯以及作為任意成分的其它單體聚合而得到。在這樣的聚合中，通常在混合使用的單體調製單體混合物後進行聚合。聚合方法並沒有特殊的限制，但從生產性的觀點來看，係以使用塊狀聚合法、溶液聚合法等方法進行自由基聚合為佳。 The above-mentioned SMA resin is obtained by polymerizing the above-mentioned aromatic vinyl compound (II), acid anhydride (III), methacrylate, and other monomers as optional components. In such polymerization, the monomers to be used are usually mixed to prepare a monomer mixture, and then the polymerization is carried out. The polymerization method is not particularly limited, but from the viewpoint of productivity, it is preferable to perform radical polymerization using a method such as a bulk polymerization method and a solution polymerization method.

上述SMA樹脂的Mw較佳為40,000~300,000的範圍。藉由使該Mw在40,000以上，本發明之擠出樹脂板會具有優異的抗刮性、耐衝擊性；藉由在300,000以下，會具有優異的成形加工性，並提高本發明之擠出樹脂板的生產性。 The Mw of the above-mentioned SMA resin is preferably in the range of 40,000 to 300,000. By making the Mw above 40,000, the extruded resin sheet of the present invention will have excellent scratch resistance and impact resistance; by making the Mw below 300,000, it will have excellent moldability and improve the extruded resin of the present invention The productivity of the board.

上述樹脂組成物(1)係將上述的甲基丙烯酸樹脂與上述的SMA樹脂混合而得到。該混合係可使用例 如熔融混合法、溶液混合法等。在熔融混合法中，例如使用單軸或多軸混煉機、開放式輥(open roll)、班布瑞密閉式混煉機、捏合機等熔融混煉機，並視需要地在氮氣、氬氣、氦氣等惰性氣體環境下進行熔融混煉。在溶液混合法中，使甲基丙烯酸樹脂與SMA樹脂在甲苯、四氫呋喃、甲基乙基酮等有機溶媒中溶解進行混合。 The above-mentioned resin composition (1) is obtained by mixing the above-mentioned methacrylic resin and the above-mentioned SMA resin. Examples of the hybrid system that can be used Such as melt mixing method, solution mixing method and so on. In the melt-mixing method, for example, a single-shaft or multi-shaft mixer, an open roll, a Banbury closed-type mixer, a kneader, and other melt-kneaders are used, and if necessary, nitrogen and argon are used. Melting and kneading in an inert gas environment such as gas and helium. In the solution mixing method, the methacrylic resin and the SMA resin are dissolved and mixed in an organic solvent such as toluene, tetrahydrofuran, and methyl ethyl ketone.

[含甲基丙烯酸樹脂的層] [Layer containing methacrylic resin]

本發明的一實施形態所使用的構成含甲基丙烯酸樹脂的層的樹脂，在不損及本發明的效果的範圍內，亦可含有甲基丙烯酸樹脂與SMA樹脂以外的其它聚合物。就這種其它聚合物而言，可列舉：聚乙烯、聚丙烯等聚烯烴、聚醯胺、聚苯硫醚、聚醚醚酮、聚酯、聚碸、聚苯醚、聚醯亞胺、聚醚醯亞胺、聚縮醛等熱塑性樹脂；酚樹脂、三聚氰胺樹脂、聚矽氧樹脂、環氧樹脂等熱硬化性樹脂等。此等其它聚合物係可單獨使用1種，亦可併用複數種。 The resin constituting the methacrylic resin-containing layer used in one embodiment of the present invention may contain other polymers other than the methacrylic resin and the SMA resin within a range that does not impair the effects of the present invention. Such other polymers include polyolefins such as polyethylene and polypropylene, polyamide, polyphenylene sulfide, polyether ether ketone, polyester, polysulfide, polyphenylene ether, polyimide, Thermoplastic resins such as polyetherimide and polyacetal; thermosetting resins such as phenol resin, melamine resin, silicone resin, epoxy resin, etc. These other polymer systems may be used individually by 1 type, and may use multiple types together.

本發明的一實施形態所使用的構成含甲基丙烯酸樹脂的層的樹脂中之此等其它聚合物的含量較佳為10質量%以下，更佳為5質量%以下，再更佳為2質量%以下。 The content of these other polymers in the resin constituting the methacrylic resin-containing layer used in one embodiment of the present invention is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 2% by mass %the following.

使甲基丙烯酸樹脂含有其它聚合物及/或添加劑時，可在聚合甲基丙烯酸樹脂時添加，亦可在聚合後添加。 When the methacrylic resin contains other polymers and/or additives, it may be added during polymerization of the methacrylic resin, or may be added after the polymerization.

使樹脂組成物(1)含有其它聚合物及/或添加劑時，可在聚合甲基丙烯酸樹脂及/或SMA樹脂時添加，亦可在混合甲基丙烯酸樹脂及SMA樹脂時添加，亦可在混合甲基 丙烯酸樹脂及SMA樹脂後再添加。 When the resin composition (1) contains other polymers and/or additives, it can be added when polymerizing methacrylic resin and/or SMA resin, or when methacrylic resin and SMA resin are mixed, or when mixing methyl Add after acrylic resin and SMA resin.

本發明的一實施形態所使用的構成含甲基丙烯酸樹脂的層的樹脂中可視需要地添加各種添加劑。就該添加劑而言，例如可列舉：抗氧化劑、抗熱劣化劑、紫外線吸收劑、光穩定劑、潤滑劑、脫模劑、高分子加工助劑、抗靜電劑、阻燃劑、染料/顏料、光擴散劑、消光劑、核殼粒子或嵌段共聚物等耐衝擊性改質劑、螢光體等。能夠在不損及本發明之效果的範圍內適當地設定此等添加劑的含量，相對於構成含甲基丙烯酸樹脂的層的樹脂100質量份而言，例如抗氧化劑的含量較佳為0.01~1質量份，紫外線吸收劑的含量較佳為0.01~3質量份，光穩定劑的含量較佳為0.01~3質量份，潤滑劑的含量較佳為0.01~3質量份，染料/顏料的含量較佳為0.01~3質量份。 Various additives may be optionally added to the resin constituting the methacrylic resin-containing layer used in one embodiment of the present invention. The additives include, for example, antioxidants, thermal degradation inhibitors, ultraviolet absorbers, light stabilizers, lubricants, mold release agents, polymer processing aids, antistatic agents, flame retardants, dyes/pigments , Light diffusers, matting agents, impact modifiers such as core-shell particles or block copolymers, phosphors, etc. The content of these additives can be appropriately set within a range that does not impair the effects of the present invention. For example, the content of the antioxidant is preferably 0.01 to 1 relative to 100 parts by mass of the resin constituting the methacrylic resin-containing layer. The content of the ultraviolet absorber is preferably 0.01~3 parts by mass, the content of the light stabilizer is preferably 0.01~3 parts by mass, the content of the lubricant is preferably 0.01~3 parts by mass, and the content of the dye/pigment is more Preferably, it is 0.01 to 3 parts by mass.

本發明的一實施形態所使用的構成含甲基丙烯酸樹脂的層的樹脂的熔融流動速率(之後適當地記載為「MFR」)較佳為1~10g/10分鐘的範圍，更佳為1.5~7g/10分鐘的範圍，再更佳為2~4g/10分鐘。MFR若在1~10g/10分鐘的範圍內，則加熱熔融成形的安定性良好。 The melt flow rate of the resin constituting the methacrylic resin-containing layer used in one embodiment of the present invention (hereinafter appropriately referred to as "MFR") is preferably in the range of 1 to 10 g/10 min, more preferably 1.5 to The range of 7g/10 minutes is more preferably 2~4g/10 minutes. When the MFR is in the range of 1 to 10 g/10 minutes, the stability of the heat-melt molding is good.

還有，本說明書中之構成含甲基丙烯酸樹脂的層的樹脂的MFR是指使用熔融指數儀(melt indexer)在溫度230℃、3.8kg負重下測定的值。 In addition, the MFR of the resin constituting the methacrylic resin-containing layer in this specification refers to a value measured using a melt indexer at a temperature of 230°C and a load of 3.8 kg.

[聚碳酸酯] [Polycarbonate]

適合透過將二元酚與碳酸酯前驅物共聚合來得到用於本發明之擠出樹脂板的聚碳酸酯。 It is suitable to obtain the polycarbonate used in the extruded resin sheet of the present invention by copolymerizing a dihydric phenol and a carbonate precursor.

就上述二元酚而言，可列舉：2,2-雙(4-羥基苯基)丙烷(通稱為雙酚A)、1,1-雙(4-羥基苯基)乙烷、1,1-雙(4-羥基苯基)環己烷、2,2-雙(3-甲基-4-羥基苯基)丙烷、2,2-雙(3,5-二甲基-4-羥基苯基)丙烷、雙(4-羥基苯基)硫醚、雙(4-羥基苯基)碸等，其中較佳為雙酚A，此等的二元酚係可單獨使用1種，亦可併用複數種。 For the above-mentioned dihydric phenols, there can be mentioned: 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A), 1,1-bis(4-hydroxyphenyl)ethane, 1,1 -Bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxybenzene) Yl)propane, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfide, etc., among which bisphenol A is preferred. These dihydric phenols can be used alone or in combination Plural.

就上述碳酸酯前驅物而言，可列舉：光氣等鹵化羰基、碳酸二苯酯等碳酸酯、二元酚的二鹵代甲酸酯(dihaloformate)等鹵代甲酸酯(haloformate)等，此等的碳酸酯前驅物係可單獨使用1種，亦可併用複數種。 The aforementioned carbonate precursors include halogenated carbonyl groups such as phosgene, carbonates such as diphenyl carbonate, and haloformates such as dihaloformates of dihydric phenols. These carbonate precursor systems can be used individually by 1 type, and can also use multiple types together.

上述聚碳酸酯之製造方法並沒有特殊的限制，例如可列舉：使二元酚的水溶液與碳酸酯前驅物的有機溶媒溶液在界面反應之界面聚合法、或使二元酚與碳酸酯前驅物在高溫、減壓、無溶媒條件下反應之酯交換法等。 The production method of the above polycarbonate is not particularly limited. For example, it can be enumerated: an interfacial polymerization method in which an aqueous solution of a dihydric phenol and an organic solvent solution of a carbonate precursor react at the interface, or a dihydric phenol and a carbonate precursor Transesterification method that reacts under high temperature, reduced pressure, and solvent-free conditions, etc.

上述聚碳酸酯的Mw較佳為10,000~100,000的範圍，更佳為20,000~70,000的範圍。該Mw在10,000以上，本發明之擠出樹脂板會具有優異的耐衝擊性、耐熱性，在100,000以下，則聚碳酸酯具有優異的成形加工性，並提高本發明之擠出樹脂板的生產性。 The Mw of the polycarbonate is preferably in the range of 10,000 to 100,000, more preferably in the range of 20,000 to 70,000. If the Mw is above 10,000, the extruded resin sheet of the present invention will have excellent impact resistance and heat resistance. When the Mw is below 100,000, the polycarbonate will have excellent molding processability and improve the production of the extruded resin sheet of the present invention. Sex.

上述聚碳酸酯可在不損及本發明之效果的範圍內含有其它聚合物。就該其它聚合物而言，能夠使用與甲基丙烯酸樹脂、樹脂組成物(1)及上述樹脂組成物(1)可含有的其它聚合物同樣的聚合物。此等其它聚合物係可單獨使用1種，亦可併用複數種。聚碳酸酯中之此等其 它聚合物的含量較佳為15質量%以下，更佳為10質量%以下，再更佳為5質量%以下。 The above-mentioned polycarbonate may contain other polymers within a range that does not impair the effects of the present invention. With regard to this other polymer, the same polymers as other polymers that may be contained in the methacrylic resin, the resin composition (1), and the above-mentioned resin composition (1) can be used. These other polymer systems may be used individually by 1 type, and may use multiple types together. Among other things in polycarbonate The content of the polymer is preferably 15% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less.

上述聚碳酸酯中可視需要地添加各種添加劑，就添加劑而言，能夠使用與上述構成含甲基丙烯酸樹脂的層的樹脂可含有的添加劑同樣的添加劑。此等添加劑的含量能夠在不損及本發明之效果的範圍內適當地設定，相對於聚碳酸酯100質量份而言，抗氧化劑的含量較佳為0.01~1質量份，紫外線吸收劑的含量較佳為0.01~3質量份，光穩定劑的含量較佳為0.01~3質量份，潤滑劑的含量較佳為0.01~3質量份，染料/顏料的含量較佳為0.01~3質量份。 Various additives may be added to the polycarbonate as necessary, and as the additives, the same additives as those that can be contained in the resin constituting the methacrylic resin-containing layer described above can be used. The content of these additives can be appropriately set within a range that does not impair the effects of the present invention. Relative to 100 parts by mass of polycarbonate, the content of antioxidant is preferably 0.01 to 1 part by mass, and the content of ultraviolet absorber It is preferably 0.01 to 3 parts by mass, the content of light stabilizer is preferably 0.01 to 3 parts by mass, the content of lubricant is preferably 0.01 to 3 parts by mass, and the content of dye/pigment is preferably 0.01 to 3 parts by mass.

上述聚碳酸酯中添加其它聚合物及/或添加劑時，可在共聚合二元酚與碳酸酯前驅物時添加，亦可在該共聚合完成後添加而進行熔融混煉。 When other polymers and/or additives are added to the above polycarbonate, they may be added when the dihydric phenol and the carbonate precursor are copolymerized, or they may be added after the copolymerization is completed for melt-kneading.

上述聚碳酸酯的玻璃轉移溫度(Tg)較佳為120~160℃的範圍，更佳為135~155℃的範圍，再更佳為140~150℃的範圍。 The glass transition temperature (Tg) of the polycarbonate is preferably in the range of 120 to 160°C, more preferably in the range of 135 to 155°C, and still more preferably in the range of 140 to 150°C.

上述聚碳酸酯的MFR較佳為1~30g/10分鐘的範圍，更佳為3~20g/10分鐘的範圍，再更佳為5~10g/10分鐘的範圍。MFR若在1~30g/10分鐘的範圍內，則加熱熔融成形的安定性為良好。 The MFR of the polycarbonate is preferably in the range of 1 to 30 g/10 minutes, more preferably in the range of 3 to 20 g/10 minutes, and still more preferably in the range of 5 to 10 g/10 minutes. If the MFR is in the range of 1 to 30 g/10 minutes, the stability of the heat-melt molding is good.

還有，本說明書中之聚碳酸酯的MFR是指使用熔融指數儀在溫度300℃、1.2kg負重下的條件下測定者。 In addition, the MFR of polycarbonate in this specification refers to the one measured with a melt index meter under the conditions of a temperature of 300°C and a load of 1.2 kg.

上述聚碳酸酯係可使用市售品，例如可適當地使用：Sumika Styron Polycarbonate股份有限公司製「 CALIBRE(註冊商標)」及「SD POLYCA(註冊商標)」、Mitsubishi Engineering-Plastics股份有限公司製「Iupilon/NOVAREX(註冊商標)」、出光興產股份有限公司製「TARFLON(註冊商標)」、帝人化成股份有限公司製「Panlite(註冊商標)」等。 Commercial products can be used for the above-mentioned polycarbonate series. For example, it can be suitably used: manufactured by Sumika Styron Polycarbonate Co., Ltd. CALIBRE (registered trademark)" and "SD POLYCA (registered trademark)", "Iupilon/NOVAREX (registered trademark)" manufactured by Mitsubishi Engineering-Plastics Co., Ltd., "TARFLON (registered trademark)" manufactured by Idemitsu Kosan Co., Ltd., Teijin "Panlite (registered trademark)" manufactured by Kasei Co., Ltd., etc.

[擠出樹脂板] [Extruded resin board]

在擠出樹脂板中，以含聚碳酸酯的層的線膨脹係數(S1)與含甲基丙烯酸樹脂的層的線膨脹係數(S2)的關係式表示的線膨脹比(SR)係定義為作為含聚碳酸酯的層的線膨脹係數(S1)和含甲基丙烯酸樹脂的層的線膨脹係數(S2)的差(S2-S1)與線膨脹係數(S1)的比之以計算式((S2-S1)/S1)表示的值。 In the extruded resin sheet, the linear expansion ratio (SR) expressed by the relational expression of the linear expansion coefficient (S1) of the polycarbonate-containing layer and the linear expansion coefficient (S2) of the methacrylic resin-containing layer is defined as As the ratio of the linear expansion coefficient (S1) of the polycarbonate-containing layer and the linear expansion coefficient (S2) of the methacrylic resin-containing layer (S2-S1) to the linear expansion coefficient (S1), the formula ( (S2-S1)/S1) represents the value.

線膨脹比(SR)較佳為-10%~+5%的範圍，從實現良好的翹曲降低之觀點來看，線膨脹比(SR)更佳為-5%~+2%的範圍。線膨脹比(SR)若在此範圍內，則容易得到表面性良好且因殘留應力造成的翹曲小之擠出樹脂板。 The linear expansion ratio (SR) is preferably in the range of -10% to +5%, and from the viewpoint of achieving good warpage reduction, the linear expansion ratio (SR) is more preferably in the range of -5% to +2%. When the linear expansion ratio (SR) is within this range, it is easy to obtain an extruded resin sheet with good surface properties and small warpage due to residual stress.

本發明之擠出樹脂板的厚度較佳為0.1~3.0mm，更佳為0.5~2.0mm。若太薄，則有剛性不充分的傾向；若太厚，則有阻礙液晶顯示裝置等輕量化的傾向。 The thickness of the extruded resin sheet of the present invention is preferably 0.1 to 3.0 mm, more preferably 0.5 to 2.0 mm. If it is too thin, the rigidity tends to be insufficient; if it is too thick, it tends to hinder the weight reduction of liquid crystal display devices and the like.

本發明之擠出樹脂板之含甲基丙烯酸樹脂的層的厚度較佳為20~200μm。若在此範圍內，則抗刮性與耐衝擊性的平衡優良。更佳為25~150μm，再更佳為30~100μm。 The thickness of the methacrylic resin-containing layer of the extruded resin sheet of the present invention is preferably 20 to 200 μm. Within this range, the balance between scratch resistance and impact resistance is excellent. It is more preferably 25 to 150 μm, and still more preferably 30 to 100 μm.

本發明之擠出樹脂板之含聚碳酸酯的層的厚度較佳 為0.1~3.0mm，更佳為0.5~2.0mm。若太薄，則有耐衝擊性不充分的傾向；若太厚，則有阻礙液晶顯示裝置等輕量化的傾向。 The thickness of the polycarbonate-containing layer of the extruded resin sheet of the present invention is better It is 0.1~3.0mm, more preferably 0.5~2.0mm. If it is too thin, the impact resistance tends to be insufficient; if it is too thick, it tends to hinder the weight reduction of liquid crystal display devices and the like.

本發明之擠出樹脂板若在含聚碳酸酯的層的至少一面上積層含甲基丙烯酸樹脂的層的話，則亦可具有其它樹脂層。例如可列舉：含聚碳酸酯的層-含甲基丙烯酸樹脂的層之2層；含甲基丙烯酸樹脂的層-含聚碳酸酯的層-含甲基丙烯酸樹脂的層之3層；含甲基丙烯酸樹脂的層-含聚碳酸酯的層-其它樹脂層之3層；其它樹脂層-含甲基丙烯酸樹脂的層-含聚碳酸酯的層之3層；等的構成。 The extruded resin sheet of the present invention may have another resin layer if a methacrylic resin-containing layer is laminated on at least one surface of the polycarbonate-containing layer. For example, it can include: two layers of polycarbonate-containing layer-methacrylic resin-containing layer; three layers of methacrylic resin-containing layer-polycarbonate-containing layer-methacrylic resin-containing layer; Acrylic resin-based layer-polycarbonate-containing layer-3 layers of other resin layers; other resin layer-methacrylic resin-containing layer-3 layers of polycarbonate-containing layer; etc.

本發明之擠出樹脂板亦可在其至少一面上設置硬化被膜。藉由設置硬化被膜，能夠賦予抗刮性、低反射性等功能。 The extruded resin sheet of the present invention may also be provided with a hardened film on at least one surface. By providing a hardened film, it is possible to provide functions such as scratch resistance and low reflectivity.

例如，抗刮性(硬塗性)硬化被膜的厚度較佳為2~30μm，更佳為5~20μm。若太薄，則表面硬度不夠充分；若太厚，則有因製造步驟中的彎曲而產生裂痕的可能性。 For example, the thickness of the scratch-resistant (hard coating) cured film is preferably 2 to 30 μm, more preferably 5 to 20 μm. If it is too thin, the surface hardness is insufficient; if it is too thick, there is a possibility of cracks due to bending in the manufacturing step.

又，例如，低反射性硬化被膜的厚度較佳為80~200nm，更佳為100~150nm。這是因為不管是太薄或太厚，低反射性能都會變得不足。 Also, for example, the thickness of the low-reflection cured film is preferably 80 to 200 nm, and more preferably 100 to 150 nm. This is because whether it is too thin or too thick, the low reflection performance will become insufficient.

[製造步驟] [Manufacturing steps]

本發明的一實施形態的擠出樹脂板係透過共擠出來製造。將構成含聚碳酸酯的層及含甲基丙烯酸樹脂的層的樹脂加熱熔融，在含聚碳酸酯的層的至少一面上積層 有含甲基丙烯酸樹脂的層的熱塑性樹脂積層體的狀態下，從被稱為T字模的寬幅形狀的吐出口以熔融狀態擠出，使用由第1冷卻輥及第2冷卻輥構成的一對輥夾持而形成為片狀。之後進一步將熱塑性樹脂積層體捲繞至第2冷卻輥之後，至少捲繞至第3冷卻輥，藉以進行冷卻。又，有時將熱塑性樹脂積層體(擠出樹脂板16)在這之後進一步利用更多的冷卻輥進行冷卻。 The extruded resin sheet according to one embodiment of the present invention is produced by coextrusion. The resins constituting the polycarbonate-containing layer and the methacrylic resin-containing layer are heated and melted, and the polycarbonate-containing layer is laminated on at least one surface In the state of a thermoplastic resin laminate with a methacrylic resin-containing layer, it is extruded in a molten state from a wide-shaped discharge port called a T-die, and a first cooling roll and a second cooling roll are used. The rolls are nipped and formed into a sheet shape. After that, the thermoplastic resin laminate is further wound on the second cooling roll, and then is wound on at least the third cooling roll for cooling. In addition, the thermoplastic resin laminate (extruded resin sheet 16) may be further cooled by more cooling rolls after that.

還有，主要將加熱熔融狀態者表示為熱塑性樹脂積層體，將固化者表示為擠出樹脂板，但兩者之間沒有明確的界線。 In addition, the heat-melted state is mainly expressed as a thermoplastic resin laminate, and the cured state is expressed as an extruded resin sheet, but there is no clear boundary between the two.

圖1中顯示使用由T字模11、第1~第3冷卻輥12~14及拉取輥15構成的共擠出裝置的擠出樹脂板之製造方法的概要作為一個實施形態。從T字模11擠出的熱塑性樹脂積層體係使用由第1冷卻輥12及第2冷卻輥13構成的一對輥夾持而形成為片狀的擠出樹脂板16。之後進一步利用第3冷卻輥14將擠出樹脂板16冷卻，透過由一對輥構成的拉取輥15進行拉取。在此情況下，第3冷卻輥14為最後纏繞的冷卻輥。 FIG. 1 shows an outline of a manufacturing method of an extruded resin sheet using a co-extrusion device composed of a T-die 11, first to third cooling rolls 12 to 14 and a drawing roll 15 as an embodiment. The thermoplastic resin laminate system extruded from the T-die 11 is formed into a sheet-like extruded resin sheet 16 sandwiched by a pair of rolls composed of the first cooling roll 12 and the second cooling roll 13. After that, the extruded resin sheet 16 is further cooled by the third cooling roll 14, and it is pulled through the pulling roll 15 composed of a pair of rolls. In this case, the third cooling roll 14 is the cooling roll wound last.

亦可在第3冷卻輥與拉取輥之間設置另外的輥作為圖1以外的形態。在此情況下，最後纏繞的輥在第3冷卻輥或第3冷卻輥與拉取輥之間設置的輥之中，為纏繞熱塑性樹脂積層體的最後的輥。 Another roll may be provided between the third cooling roll and the take-up roll as a form other than FIG. 1. In this case, the roll to be wound last among the third cooling roll or the rolls provided between the third cooling roll and the take-up roll is the last roll to wind the thermoplastic resin laminate.

以下為了簡化，係將最後纏繞的冷卻輥為第3冷卻輥的圖1的形態作為例子進行說明。還有，本發明並不受限於該形態。 In the following, for simplification, the form of FIG. 1 in which the cooling roll wound last is the third cooling roll will be described as an example. In addition, the present invention is not limited to this form.

就此時的T字模的方法而言，能夠採用將加熱熔融狀態的構成含聚碳酸酯的層及含甲基丙烯酸樹脂的層的樹脂在流入T字模前積層之進料塊(feed block)方法、在T字模內部被積層的多重分歧管方法等。從提高構成擠出樹脂板的各層間的界面的平滑性之觀點來看，較佳為多重分歧管方法。 As for the method of the T-shaped mold at this time, it is possible to adopt a feed block method in which the resin constituting the polycarbonate-containing layer and the methacrylic resin-containing layer in a heated and molten state are laminated before flowing into the T-shaped mold, The method of multiple branch pipes layered inside the T-shaped pattern, etc. From the viewpoint of improving the smoothness of the interface between the layers constituting the extruded resin sheet, the multiple branch pipe method is preferred.

又，就此時的拋光輥而言，可列舉：金屬輥或外周部具備金屬製薄膜的彈性輥(以下有時稱為金屬彈性輥)等。就金屬輥而言，只要具高剛性，則沒有特殊的限定，例如可列舉：鑽孔輥、螺旋輥等。金屬輥的表面狀態並沒有特殊的限定，例如可為鏡面，亦可為花紋或凹凸等。金屬彈性輥係例如由略為圓柱狀之設置成可旋轉的軸輥、以覆蓋該軸輥的外周面的方式進行配置並與片狀熱塑性樹脂接觸之圓筒形的金屬製薄膜以及密封在此等軸輥及金屬製薄膜之間的流體構成，金屬彈性輥係透過流體表現出彈性。軸輥並沒有特殊的限定，例如由不鏽鋼等構成。金屬製薄膜係例如由不鏽鋼等構成，其厚度較佳為2~5mm左右。金屬製薄膜係以具有柔性或可撓性等為佳，並以沒有熔接接合部分的無縫結構為佳。具備這樣的金屬製薄膜的金屬彈性輥具有優異的耐久性，並且若使金屬製薄膜鏡面化，則能夠與一般的鏡面輥進行同樣的操作，而且若能夠對金屬製薄膜賦予花紋或凹凸，就會成為能夠轉印其形狀的輥，因此具有良好的實用性。 In addition, as the buffing roller at this time, a metal roller or an elastic roller provided with a metal film on the outer peripheral portion (hereinafter may be referred to as a metal elastic roller), and the like can be mentioned. The metal roll is not particularly limited as long as it has high rigidity, and examples include drill rolls, spiral rolls, and the like. The surface state of the metal roller is not particularly limited. For example, it may be a mirror surface, or may be a pattern or unevenness. The metal elastic roller is composed of, for example, a substantially cylindrical roller that is set to be rotatable, a cylindrical metal film arranged so as to cover the outer peripheral surface of the roller and in contact with a sheet-like thermoplastic resin, and sealed therein. The fluid between the shaft roller and the metal film is formed, and the metal elastic roller system exhibits elasticity through the fluid. The shaft roller is not particularly limited, and is made of stainless steel, for example. The metal thin film is made of, for example, stainless steel, and its thickness is preferably about 2 to 5 mm. The metal film preferably has flexibility or flexibility, etc., and preferably has a seamless structure without welded joints. The metal elastic roller provided with such a metal film has excellent durability, and if the metal film is mirror-finished, it can perform the same operation as a general mirror roller, and if the metal film can be provided with patterns or irregularities, It becomes a roller that can transfer its shape, so it has good practicability.

構成含聚碳酸酯的層及含甲基丙烯酸樹脂的 層的樹脂係以在多層成形前及/或多層成形時使用過濾器進行熔融過濾為佳。藉由使用已熔融過濾的各樹脂進行多層成形，能夠得到因異物或凝膠造成的缺點少的擠出樹脂板。所使用的過濾器的濾材並沒有特殊的限定，可依據使用溫度、黏度、過濾精度進行適當的選擇，例如能夠使用：由聚丙烯、棉、聚酯、嫘縈、玻璃纖維等構成的不織布；酚樹脂含浸纖維素製的片狀物；金屬纖維不織布燒結片狀物；金屬粉末燒結片狀物；金屬絲網；或是此等的組合。其中，從耐熱性及耐久性之觀點來看，係以積層複數片的金屬纖維不織布燒結片狀物來使用為佳。 Constitute a polycarbonate-containing layer and a methacrylic resin-containing layer The resin of the layer is preferably melt-filtered with a filter before and/or during the multilayer molding. Multi-layer molding is performed using each resin that has been melted and filtered, and an extruded resin sheet with few defects due to foreign matter or gel can be obtained. There are no special restrictions on the filter material of the filter used, and it can be appropriately selected according to the temperature, viscosity, and filtration accuracy. For example, it can be used: non-woven fabrics composed of polypropylene, cotton, polyester, rayon, glass fiber, etc.; Phenolic resin impregnated cellulose flakes; metal fiber non-woven fabric sintered flakes; metal powder sintered flakes; metal wire mesh; or a combination of these. Among them, from the standpoint of heat resistance and durability, it is preferable to laminate a plurality of metal fiber nonwoven fabric sintered sheets to use.

前述過濾器的過濾精度並沒有特殊的限制，但較佳為30μm以下，更佳為15μm以下，再更佳為5μm以下。 The filtration accuracy of the aforementioned filter is not particularly limited, but it is preferably 30 μm or less, more preferably 15 μm or less, and still more preferably 5 μm or less.

本發明的一實施形態之擠出樹脂板係以將從第3冷卻輥14剝離的樹脂整體的溫度相對於聚碳酸酯的玻璃轉移溫度(Tg)定為-2℃至+15℃的範圍為佳。這是因為從第3冷卻輥14剝離的樹脂整體的溫度若比聚碳酸酯的玻璃轉移溫度(Tg)還低，則擠出樹脂板會轉印第3冷卻輥的形狀，且翹曲會變大。另一方面，從第3冷卻輥14剝離的樹脂整體的溫度若比與第3冷卻輥接觸的樹脂層的玻璃轉移溫度(Tg)還高，則擠出樹脂板無法得到漂亮的表面性。還有，樹脂整體的溫度不管擠出樹脂板的任何一面，係測定積層有聚碳酸酯樹脂與甲基丙烯酸樹脂的樹脂整體的溫度來使用。溫度測定只要使用紅外線輻 射溫度計即可。 The extruded resin sheet of one embodiment of the present invention is based on the temperature of the entire resin peeled from the third cooling roll 14 relative to the glass transition temperature (Tg) of the polycarbonate in the range of -2°C to +15°C. good. This is because if the temperature of the entire resin peeled off from the third cooling roll 14 is lower than the glass transition temperature (Tg) of polycarbonate, the extruded resin sheet will transfer the shape of the third cooling roll and warp will change Big. On the other hand, if the temperature of the entire resin peeled from the third cooling roll 14 is higher than the glass transition temperature (Tg) of the resin layer in contact with the third cooling roll, the extruded resin sheet cannot obtain beautiful surface properties. In addition, the temperature of the entire resin is used by measuring the temperature of the entire resin in which the polycarbonate resin and the methacrylic resin are laminated regardless of either side of the extruded resin sheet. Only use infrared radiation for temperature measurement Just shoot the thermometer.

本發明的一實施形態之擠出樹脂板係以將線膨脹比(SR)定在-10%~+5%的範圍內為佳，並且以將含甲基丙烯酸樹脂的層的玻璃轉移溫度(Tg)定為115℃以上為佳。以下描述其理由。 The extruded resin sheet of one embodiment of the present invention preferably has a linear expansion ratio (SR) in the range of -10% to +5%, and the glass transition temperature of the layer containing methacrylic resin ( Tg) is preferably set at 115°C or higher. The reason is described below.

從第3冷卻輥14剝離的擠出樹脂板到夾入至拉取輥15之間，其係分別夾入至第3冷卻輥14與拉取輥15，因而成為扁平的形狀。從第3冷卻輥14剝離後的擠出樹脂板的溫度相對於聚碳酸酯的玻璃轉移溫度(Tg)為-2℃至+15℃的範圍，但拉取輥15附近的擠出樹脂板的溫度係冷卻至室溫，因此大約為常溫。 The extruded resin sheet peeled from the third cooling roll 14 is sandwiched between the pull roll 15 and is sandwiched between the third cooling roll 14 and the pull roll 15, and thus has a flat shape. The temperature of the extruded resin sheet after peeling off the third cooling roll 14 is in the range of -2°C to +15°C relative to the glass transition temperature (Tg) of the polycarbonate. However, the temperature of the extruded resin sheet near the pull roll 15 is The temperature is cooled to room temperature, so it is approximately room temperature.

另外，例如假定從第3冷卻輥14剝離的擠出樹脂板的溫度為150℃，拉取輥附近的擠出樹脂板的溫度為25℃。在含聚碳酸酯的層的線膨脹係數(S1)與含甲基丙烯酸樹脂的層的線膨脹係數(S2)之間具有差異的情況下，具體來說，在線膨脹比(SR)之(S1-S2)/S1為零以外的情況下，會在線膨脹係數大的一側收縮而產生翹曲。 In addition, for example, it is assumed that the temperature of the extruded resin sheet peeled from the third cooling roll 14 is 150°C, and the temperature of the extruded resin sheet near the drawing roll is 25°C. In the case where there is a difference between the linear expansion coefficient (S1) of the polycarbonate-containing layer and the linear expansion coefficient (S2) of the methacrylic resin-containing layer, specifically, the linear expansion ratio (SR) of (S1) When -S2)/S1 is other than zero, the side with the larger linear expansion coefficient will shrink and warp will occur.

又，例如假定含甲基丙烯酸樹脂的層的玻璃轉移溫度(Tg)為100℃，含聚碳酸酯的層的玻璃轉移溫度(Tg)為150℃。在此情況下，因為從第3冷卻輥14剝離的擠出樹脂板的溫度為150℃，所以含聚碳酸酯的層會從玻璃轉移溫度(Tg)的150℃冷卻至常溫。因此，在含聚碳酸酯的層中，會有大致上沿著線膨脹係數的收縮。 In addition, for example, it is assumed that the glass transition temperature (Tg) of the methacrylic resin-containing layer is 100°C, and the glass transition temperature (Tg) of the polycarbonate-containing layer is 150°C. In this case, since the temperature of the extruded resin sheet peeled from the third cooling roll 14 is 150°C, the polycarbonate-containing layer is cooled from 150°C of the glass transition temperature (Tg) to room temperature. Therefore, in the polycarbonate-containing layer, there will be a shrinkage approximately along the linear expansion coefficient.

另一方面，含甲基丙烯酸樹脂的層會從比玻璃轉移溫度還要高溫的區域(150℃)冷卻至玻璃轉移溫度(Tg)的 100℃附近，因此即便是在構成含聚碳酸酯的層的線膨脹係數(S1)與含甲基丙烯酸樹脂的層的樹脂的線膨脹係數(S2)之間不具有差異的情況下，在含甲基丙烯酸樹脂的層中還是會有超出線膨脹係數的大收縮產生。 On the other hand, the layer containing methacrylic resin will be cooled from a region higher than the glass transition temperature (150°C) to the glass transition temperature (Tg). Around 100°C, even if there is no difference between the coefficient of linear expansion (S1) of the polycarbonate-containing layer and the coefficient of linear expansion (S2) of the resin of the methacrylic resin-containing layer, the The methacrylic resin layer still has large shrinkage that exceeds the linear expansion coefficient.

此處，一般的樹脂在玻璃轉移溫度以下而為彈性體，但一旦在玻璃轉移溫度以上，則會變成兼具黏性與彈性的功能之黏彈性體。 Here, a general resin is an elastomer below the glass transition temperature, but once it is above the glass transition temperature, it becomes a viscoelastic body that has both viscous and elastic functions.

上述的彈性體若施加應力，則會產生應變，但若卸載，則會消除應變，反之，黏彈性體若在施加應力的狀態下直接冷卻至玻璃轉移溫度，則會殘留應變。從第3冷卻輥14剝離的擠出樹脂板的溫度為例如150℃而含甲基丙烯酸樹脂的層及含聚碳酸酯的層為上述的玻璃轉移溫度時，擠出樹脂板在從第3冷卻輥14剝離之後，含聚碳酸酯的層為彈性體，反之，含甲基丙烯酸樹脂的層為黏彈性體。也就是說，從第3冷卻輥14剝離擠出樹脂板之後，只有作為黏彈性體的含甲基丙烯酸樹脂的層會產生收縮應變。換言之，作為彈性體的聚碳酸酯層相對於應力為可逆的，因此即便有應力的負載/卸載，也不會變形。反之，作為黏彈性體的含甲基丙烯酸樹脂的層會因應力的負載/卸載而產生殘留應變。 If stress is applied to the above-mentioned elastomer, strain will be generated, but if it is unloaded, the strain will be eliminated. Conversely, if the viscoelastic body is directly cooled to the glass transition temperature under stress, strain will remain. When the temperature of the extruded resin sheet peeled off from the third cooling roll 14 is, for example, 150°C and the methacrylic resin-containing layer and the polycarbonate-containing layer are at the above-mentioned glass transition temperature, the extruded resin sheet is cooled from the third After the roller 14 is peeled off, the polycarbonate-containing layer is an elastomer, and on the contrary, the methacrylic resin-containing layer is a viscoelastic body. That is, after peeling off the extruded resin sheet from the third cooling roll 14, only the methacrylic resin-containing layer which is a viscoelastic body undergoes shrinkage strain. In other words, the polycarbonate layer, which is an elastomer, is reversible with respect to stress, and therefore does not deform even if there is a stress load/unload. Conversely, the methacrylic resin-containing layer, which is a viscoelastic body, generates residual strain due to stress loading/unloading.

由上述來看，在含聚碳酸酯的層的線膨脹係數(S1)與含甲基丙烯酸樹脂的層的線膨脹係數(S2)之間具有差異的情況下，換言之即在線膨脹比(SR)的絕對值大的情況下，因彈性體的收縮差造成的翹曲會產生，因此在從拉取輥15釋放擠出樹脂板時翹曲會發生。 From the above point of view, when there is a difference between the linear expansion coefficient (S1) of the polycarbonate-containing layer and the linear expansion coefficient (S2) of the methacrylic resin-containing layer, in other words, the linear expansion ratio (SR) When the absolute value of is large, warpage due to the difference in shrinkage of the elastomer will occur, and therefore warpage will occur when the extruded resin sheet is released from the drawing roll 15.

又，在含甲基丙烯酸樹脂的層的玻璃轉移溫度(Tg)比含聚碳酸酯的層的玻璃轉移溫度(Tg)還低，而且從第3冷卻輥14剝離的擠出樹脂板的溫度在含甲基丙烯酸樹脂的層的玻璃轉移溫度(Tg)與含聚碳酸酯的層的玻璃轉移溫度(Tg)之間的情況下，會因彈性體與黏彈性體的收縮差而在含甲基丙烯酸樹脂的層中殘留應變。此殘留應變會因暴露在高溫及高溫高濕條件中而有釋放應變以及產生翹曲的傾向。此處，由於從第3冷卻輥14剝離之後的擠出樹脂板的溫度相對於聚碳酸酯的玻璃轉移溫度(Tg)為-2℃~+15℃，因此聚碳酸酯亦會存在黏彈性體的狀態。此處，擠出樹脂板的溫度會在到達拉取輥15之前冷卻至常溫，但不管是含甲基丙烯酸樹脂的層或是含聚碳酸酯的層皆會同時冷卻至常溫。因此，從第3冷卻輥14剝離之後到拉取輥15為止的擠出樹脂板的溫度將包含聚碳酸酯的玻璃轉移溫度(Tg)與含甲基丙烯酸樹脂的層的玻璃轉移溫度(Tg)。也就是說，在擠出樹脂板的溫度從聚碳酸酯的玻璃轉移溫度(Tg)冷卻至含甲基丙烯酸樹脂的層的玻璃轉移溫度(Tg)之中，會在含甲基丙烯酸樹脂的層中殘留應變。 In addition, the glass transition temperature (Tg) of the methacrylic resin-containing layer is lower than the glass transition temperature (Tg) of the polycarbonate-containing layer, and the temperature of the extruded resin sheet peeled from the third cooling roll 14 is lower than When the glass transition temperature (Tg) of the methacrylic resin-containing layer is between the glass transition temperature (Tg) of the polycarbonate-containing layer, the difference in shrinkage between the elastomer and the viscoelastic body will cause the Strain remains in the acrylic resin layer. This residual strain tends to release strain and warp due to exposure to high temperature, high temperature and high humidity conditions. Here, since the temperature of the extruded resin sheet after peeling from the third cooling roll 14 relative to the glass transition temperature (Tg) of the polycarbonate is -2°C to +15°C, there is also a viscoelastic body in the polycarbonate status. Here, the temperature of the extruded resin sheet will be cooled to normal temperature before reaching the drawing roll 15, but both the methacrylic resin-containing layer and the polycarbonate-containing layer will be cooled to normal temperature at the same time. Therefore, the temperature of the extruded resin sheet after peeling from the third cooling roll 14 to the drawing roll 15 will include the glass transition temperature (Tg) of the polycarbonate and the glass transition temperature (Tg) of the layer containing the methacrylic resin. . In other words, when the temperature of the extruded resin sheet is cooled from the glass transition temperature (Tg) of the polycarbonate to the glass transition temperature (Tg) of the methacrylic resin-containing layer, the temperature of the methacrylic resin-containing layer In the residual strain.

另一方面，原則上，若使從第3冷卻輥14剝離的擠出樹脂板的溫度低於150℃，則因線膨脹比(SR)造成的翹曲及殘留應力會有減少的傾向，因此翹曲會變小。然而，如上所述，擠出樹脂板藉由轉印第3冷卻輥14的形狀所產生的翹曲會變大，故而不佳。 On the other hand, in principle, if the temperature of the extruded resin sheet peeled from the third cooling roll 14 is lower than 150°C, the warpage and residual stress due to the linear expansion ratio (SR) will tend to decrease, so The warpage will become smaller. However, as described above, the warpage of the extruded resin sheet due to the transfer of the shape of the third cooling roll 14 becomes large, which is not preferable.

由此來看，為了達到本案的目的，將從第3 冷卻輥14剝離的樹脂的溫度相對於聚碳酸酯的玻璃轉移溫度(Tg)定為-2℃至+15℃的範圍，將線膨脹比(SR)定為-10%~+5%的範圍，將含甲基丙烯酸樹脂的層的玻璃轉移溫度(Tg)定在115℃以上，會得到翹曲小之良好的擠出樹脂板，因而較佳。 From this point of view, in order to achieve the purpose of this case, the third The temperature of the resin peeled off by the cooling roller 14 relative to the glass transition temperature (Tg) of the polycarbonate is set in the range of -2°C to +15°C, and the linear expansion ratio (SR) is set in the range of -10% to +5% It is preferable to set the glass transition temperature (Tg) of the layer containing the methacrylic resin to 115° C. or higher to obtain a good extruded resin sheet with less warpage.

遲滯是指分子主鏈方向的光與垂直於其的方向的光之相位差。高分子通常能夠透過加熱成形而得到任意的形狀，但已知在其加熱、冷卻過程中固定的應力會發生，分子會進行配向而產生遲滯。於是，為了控制遲滯，必須要控制分子的配向排列。分子的配向係例如透過在高分子的玻璃轉移溫度附近的成形時的應力而發生。 Hysteresis refers to the phase difference between light in the direction of the molecular main chain and light in the direction perpendicular to it. Polymers can generally be formed into any shape by heating, but it is known that fixed stress occurs during the heating and cooling processes, and the molecules are aligned to cause hysteresis. Therefore, in order to control the hysteresis, it is necessary to control the alignment of the molecules. The alignment of molecules occurs, for example, through stress during molding near the glass transition temperature of the polymer.

本發明人發現一種藉由在擠出成形的過程中進行製造條件的各種調整來控制分子的配向，並防止因擠出樹脂板成形後的加熱造成之寬度方向的至少一部分的面內遲滯值(以下有時僅記載為「面內遲滯值」)的減少之方法。以下分別說明圓周速度比的影響、加熱條件。 The inventors of the present invention found a way to control the alignment of molecules by adjusting various manufacturing conditions during the extrusion molding process, and prevent at least a part of the in-plane hysteresis in the width direction caused by heating after the extrusion of the resin sheet ( The following is sometimes only described as the method of reducing the "in-plane hysteresis value"). The influence of the peripheral speed ratio and the heating conditions are described below.

<關於圓周速度比的影響> <About the influence of peripheral speed ratio>

圓周速度比是指第2冷卻輥13以外的任意的冷卻輥及拉取輥相對於第2冷卻輥13的圓周速度的比，之後第2冷卻輥的圓周速度係表示為V2，第3冷卻輥的圓周速度係表示為V3，拉取輥的圓周速度係表示為V4。 The peripheral speed ratio refers to the ratio of the peripheral speeds of any cooling rolls and take-up rolls other than the second cooling roll 13 to the peripheral speeds of the second cooling roll 13, and then the peripheral speed of the second cooling roll is expressed as V2, and the third cooling roll The peripheral speed system of is denoted as V3, and the peripheral speed of the pulling roll is denoted as V4.

如以下所述地根據規定的條件來評價第3冷卻輥14相對於第2冷卻輥13的圓周速度比(V3/V2)與面內遲滯值的關係。 The relationship between the peripheral speed ratio (V3/V2) of the third cooling roll 14 to the second cooling roll 13 and the in-plane hysteresis value was evaluated based on predetermined conditions as described below.

上述從第3冷卻輥14剝離的樹脂的溫度係調整成相對於聚碳酸酯的玻璃轉移溫度(Tg)為-2℃至+15℃的範圍。 The temperature of the resin peeled from the third cooling roll 14 is adjusted to a range of -2°C to +15°C with respect to the glass transition temperature (Tg) of the polycarbonate.

樹脂與第3冷卻輥14接觸的樹脂的溫度係由於樹脂會在第3冷卻輥被冷卻，因此會比從第3冷卻輥14剝離的樹脂的溫度還高。也就是說，樹脂與第3冷卻輥14接觸的樹脂的溫度會比相對於聚碳酸酯的玻璃轉移溫度(Tg)為-2℃至+15℃還高，例如會在相對於玻璃轉移溫度(Tg)為+20℃附近。在此情況下，推測即便增加第3冷卻輥14的圓周速度比(V3/V2)且對擠出樹脂板施加較大的拉伸應力，但因為是樹脂的分子不易配向的高溫度區域的樹脂的溫度，因此不會顯著增加面內遲滯值(參照後述的實施例14)。 The temperature of the resin at which the resin contacts the third cooling roll 14 is higher than the temperature of the resin peeled from the third cooling roll 14 because the resin is cooled by the third cooling roll. In other words, the temperature of the resin in contact with the third cooling roller 14 will be higher than the glass transition temperature (Tg) of polycarbonate from -2°C to +15°C, for example, it will be higher than the glass transition temperature (Tg) relative to the glass transition temperature ( Tg) is around +20°C. In this case, it is assumed that even if the peripheral speed ratio (V3/V2) of the third cooling roll 14 is increased and a large tensile stress is applied to the extruded resin sheet, it is because it is a resin in a high temperature region where the molecules of the resin are not easily aligned. Therefore, the in-plane hysteresis value will not be significantly increased (refer to Example 14 described later).

評價拉取輥15相對於第2冷卻輥13的圓周速度比(V4/V2)與面內遲滯值的關係後，結果得知其圓周速度比(V4/V2)越大，面內遲滯值會越增加。 After evaluating the relationship between the peripheral speed ratio (V4/V2) of the drawing roll 15 to the second cooling roll 13 and the in-plane hysteresis value, it was found that the greater the peripheral speed ratio (V4/V2), the greater the in-plane hysteresis value. The more it increases.

其原因被認為是因為將樹脂從第3冷卻輥14剝離時的樹脂溫度調整成稍微高於聚碳酸酯的玻璃轉移溫度(Tg)的溫度，具體來說就是將樹脂從第3冷卻輥14剝離時的樹脂溫度調整成相對於該玻璃轉移溫度(Tg)為-2℃~+15℃的範圍，增加拉取輥15的圓周速度比，對擠出樹脂板施加較大的拉伸應力，藉以達到樹脂的分子易於配向的溫度區域。 The reason is thought to be that the resin temperature when the resin is peeled from the third cooling roll 14 is adjusted to a temperature slightly higher than the glass transition temperature (Tg) of the polycarbonate. Specifically, the resin is peeled from the third cooling roll 14 The resin temperature is adjusted to the range of -2°C~+15°C relative to the glass transition temperature (Tg), and the peripheral speed ratio of the drawing roll 15 is increased to apply greater tensile stress to the extruded resin sheet. Reach the temperature region where the molecules of the resin are easy to align.

接著研討加熱擠出樹脂板時的面內遲滯值下降的程度。 Next, the extent to which the in-plane hysteresis value decreases when the resin sheet is heated and extruded is discussed.

在樹脂從第3冷卻輥14剝離時的樹脂溫度比聚碳酸酯的玻璃轉移溫度(Tg)還低的情況下使第2冷卻輥13與拉取輥15的圓周速度比(V4/V2)逐漸增加時，可知面內遲滯值會逐漸增加，但加熱後的面內遲滯值的下降率會增加(參照後述的比較例1、2)。 When the resin temperature when the resin is peeled from the third cooling roll 14 is lower than the glass transition temperature (Tg) of the polycarbonate, the peripheral speed ratio (V4/V2) of the second cooling roll 13 and the drawing roll 15 is gradually increased. When increasing, it can be seen that the in-plane hysteresis value gradually increases, but the rate of decrease in the in-plane hysteresis value after heating increases (refer to Comparative Examples 1 and 2 described later).

在樹脂從第3冷卻輥14剝離時的樹脂溫度相對於聚碳酸酯的玻璃轉移溫度(Tg)為-2℃~15℃的範圍的情況下使第2冷卻輥13與拉取輥15的圓周速度比(V4/V2)逐漸增加時，面內遲滯值會逐漸增加，但加熱時的面內遲滯值的下降量並沒有顯著變化(參照後述的實施例10、11、12)。 When the resin temperature when the resin is peeled from the third cooling roll 14 relative to the glass transition temperature (Tg) of the polycarbonate is in the range of -2°C to 15°C, the circumference of the second cooling roll 13 and the drawing roll 15 When the speed ratio (V4/V2) gradually increases, the in-plane hysteresis value gradually increases, but the amount of decrease in the in-plane hysteresis value during heating does not change significantly (see Examples 10, 11, and 12 described later).

其原因被認為是因為藉由將樹脂從第3冷卻輥14剝離時的樹脂溫度調整成相對於聚碳酸酯的玻璃轉移溫度(Tg)為-2℃~15℃的範圍，增加拉取輥15的圓周速度比，對擠出樹脂板施加較大的拉伸應力，樹脂的分子會配向，或是由於在加熱溫度比聚碳酸酯的玻璃轉移溫度(Tg)還低的溫度下實施，樹脂的配向難以緩和。 The reason is considered to be that by adjusting the resin temperature when the resin is peeled from the third cooling roll 14 to the glass transition temperature (Tg) of polycarbonate in the range of -2°C to 15°C, the drawing roll 15 is increased. The peripheral speed ratio of the extruded resin sheet is greater, the molecules of the resin will be aligned, or because the heating temperature is lower than the glass transition temperature (Tg) of polycarbonate, the resin’s The alignment is difficult to ease.

由此來看，為達到本發明之目的，可知只要將從第3冷卻輥14剝離時的樹脂溫度控制在相對於聚碳酸酯的玻璃轉移溫度(Tg)為-2℃~15℃的範圍內並調整冷卻輥13與拉取輥15的圓周速度比來控制面內遲滯值即可。 From this point of view, in order to achieve the purpose of the present invention, it can be seen that the temperature of the resin when peeling from the third cooling roll 14 is controlled within the range of -2°C to 15°C relative to the glass transition temperature (Tg) of the polycarbonate. It is only necessary to adjust the peripheral speed ratio of the cooling roller 13 and the take-up roller 15 to control the in-plane hysteresis value.

具體來說，例如將拉取輥與第2冷卻輥的圓周速度比(V4/V2)設定為0.98以上1.01以下。 Specifically, for example, the peripheral speed ratio (V4/V2) of the drawing roll and the second cooling roll is set to 0.98 or more and 1.01 or less.

還有，第2冷卻輥13與拉取輥15的圓周速度比大於 1.01時，有面內遲滯值大於600nm的傾向(參照後述的比較例5)；小於0.98時，有面內遲滯值小於50nm的傾向(參照後述的比較例6)。從將面內遲滯值設定在較佳的範圍內之觀點來看，第2冷卻輥13與拉取輥15的圓周速度比更佳為0.985~0.995(參照後述的實施例10)。 Also, the peripheral speed ratio of the second cooling roll 13 to the take-up roll 15 is greater than At 1.01, the in-plane hysteresis value tends to be greater than 600 nm (see Comparative Example 5 described later); when it is less than 0.98, the in-plane hysteresis value tends to be less than 50 nm (see Comparative Example 6 described later). From the viewpoint of setting the in-plane hysteresis value in a preferable range, the circumferential speed ratio of the second cooling roll 13 to the drawing roll 15 is more preferably 0.985 to 0.995 (refer to Example 10 described later).

還有，液晶顯示器保護板的面內遲滯值大於600nm時，在透過偏光太陽眼鏡等偏光濾光片觀看的情況下，可見光範圍的各波長的穿透率的差增加，因此難以辨識各種顏色。另一方面，小於50nm時，可見光範圍的全波長下的穿透率大幅下降，變成全黑的影像而難以辨識。在50nm~600nm的範圍內，數值越大影像越明亮，數值越小顏色越減輕。尤其是在將面內遲滯值設定為80nm~350nm時，亮度與顏色的平衡良好且視認性優異，故而較佳。 Also, when the in-plane hysteresis value of the liquid crystal display protection plate is greater than 600 nm, when viewed through a polarizing filter such as polarized sunglasses, the difference in transmittance of each wavelength in the visible light range increases, making it difficult to recognize various colors. On the other hand, when it is less than 50 nm, the transmittance at all wavelengths in the visible light range is greatly reduced, and it becomes a completely black image that is difficult to recognize. In the range of 50nm~600nm, the larger the value, the brighter the image, and the smaller the value, the lighter the color. In particular, when the in-plane hysteresis value is set to 80 nm to 350 nm, the balance of brightness and color is good, and visibility is excellent, so it is preferable.

<加熱條件> <heating conditions>

關於本發明的加熱條件，係設定為75℃~100℃的範圍，但在進行測定時，係使用75℃、5小時與100℃、5小時中之一。上述加熱環境係參考形成一般的硬化被膜的過程中的加熱溫度及時間，較佳為能夠承受該加熱環境而維持遲滯。 Regarding the heating conditions of the present invention, the range of 75°C to 100°C is set, but when the measurement is performed, one of 75°C, 5 hours and 100°C, 5 hours is used. The above-mentioned heating environment refers to the heating temperature and time in the process of forming a general cured film, and it is preferable to withstand the heating environment while maintaining the hysteresis.

具體來說，藉由將試片放置於被管理在100℃±3℃或75℃±3℃的烘箱內5小時來進行測定。 Specifically, the measurement is performed by placing the test piece in an oven controlled at 100°C±3°C or 75°C±3°C for 5 hours.

如上所述，在上述的擠出樹脂板之製造方法中，較佳為以所製造的擠出樹脂板具有下列特性的方式進行控制。 As described above, in the above-mentioned method of manufacturing an extruded resin sheet, it is preferable to control so that the manufactured extruded resin sheet has the following characteristics.

擠出樹脂板係以在將擠出樹脂板於75℃至100℃的溫度下加熱5小時時，以於加熱前後在寬度方向的至少一部分中使面內遲滯值為50~600nm且使加熱前後的面內遲滯值的下降率小於15%的方式來控制製造步驟為佳。 The extruded resin sheet is used to heat the extruded resin sheet at a temperature of 75°C to 100°C for 5 hours, so that the in-plane hysteresis value is 50 to 600 nm in at least a part of the width direction before and after heating, and before and after heating The decrease rate of the in-plane hysteresis value is less than 15% to control the manufacturing steps.

再者，擠出樹脂板係以在加熱前後於寬度方向的至少一部分中使面內遲滯值為80~350nm的方式來控制製造步驟為佳。 In addition, the extruded resin plate is preferably used to control the manufacturing process such that the in-plane hysteresis value is 80 to 350 nm in at least a part of the width direction before and after heating.

再者，擠出樹脂板係以使加熱前後的面內遲滯值的下降率小於10%的方式來控制製造步驟為佳。 In addition, the extruded resin sheet is preferably used to control the manufacturing process so that the decrease rate of the in-plane hysteresis value before and after heating is less than 10%.

本發明之擠出樹脂板由於具有上述特性，因此經由在65℃~110℃的溫度下加熱1~30小時的步驟，能夠製造出適用於液晶顯示器保護板等的擠出樹脂板。 Since the extruded resin sheet of the present invention has the above-mentioned characteristics, it is possible to manufacture an extruded resin sheet suitable for liquid crystal display protection plates and the like through a step of heating at a temperature of 65°C to 110°C for 1 to 30 hours.

<用途> <Use>

本發明之擠出樹脂板的表面性良好，且可抑制翹曲發生，即便加熱至高溫高溫，面內遲滯值的下降率也小，具有適當的面內遲滯值，因此該擠出樹脂板及加熱該擠出樹脂板的樹脂板能夠使用在各種用途上，尤其是特別適用於銀行等金融機關的ATM、自動販賣機、行動電話、行動資訊終端(PDA)、數位聲訊播放機、行動遊戲機、平板型個人電腦、複印機、傳真、汽車導航等數位資訊設備的觸控面板的保護板；液晶顯示器保護板。 The extruded resin sheet of the present invention has good surface properties and can suppress the occurrence of warpage. Even if heated to high temperature and high temperature, the reduction rate of the in-plane hysteresis value is small and has an appropriate in-plane hysteresis value. Therefore, the extruded resin sheet and The resin sheet that heats the extruded resin sheet can be used for various purposes, especially suitable for ATMs, vending machines, mobile phones, mobile information terminals (PDAs), digital audio players, and mobile game consoles in financial institutions such as banks. , Tablet PCs, copiers, faxes, car navigation and other digital information equipment touch panel protection board; LCD display protection board.

[實施例] [Example]

以下表示實施例，以更詳細地說明本發明。然而，本發明不受到這樣的實施例的任何限制。 Examples are shown below to illustrate the present invention in more detail. However, the present invention is not limited in any way by such embodiments.

以下述方法測定擠出樹脂板的物性。 The physical properties of the extruded resin plate were measured by the following method.

[玻璃轉移溫度(Tg)] [Glass transition temperature (Tg)]

在減壓下(1kPa)將所得到的擠出樹脂板以80℃乾燥24小時後，切出10mg的試片，以鋁盤密封，使用示差掃描熱量計(「DSC-50」，Rigaku股份有限公司製)，進行30分鐘以上的氮氣置換。之後，在10ml/分鐘的氮氣氣流中，暫時以20℃/分鐘的速度從25℃升溫至200℃，保持10分鐘，冷卻到25℃(1次掃描)。接著，以10℃/分鐘的速度升溫至200℃(2次掃描)，從2次掃描所得到的結果以中點法算出玻璃轉移溫度(Tg)。還有，在因含有2種以上的樹脂而得到多個玻璃轉移溫度時，採用來自主成分的樹脂的值作為玻璃轉移溫度。 After drying the obtained extruded resin sheet at 80°C for 24 hours under reduced pressure (1kPa), a 10 mg test piece was cut out, sealed with an aluminum pan, and a differential scanning calorimeter ("DSC-50", Rigaku Co., Ltd.) was used. Made by the company), nitrogen replacement is performed for more than 30 minutes. After that, in a nitrogen gas flow of 10 ml/min, the temperature was temporarily increased from 25°C to 200°C at a rate of 20°C/min, held for 10 minutes, and cooled to 25°C (1 scan). Next, the temperature was raised to 200°C at a rate of 10°C/min (2 scans), and the glass transition temperature (Tg) was calculated by the midpoint method from the results of the 2 scans. In addition, when a plurality of glass transition temperatures are obtained by containing two or more kinds of resins, the value of the resin derived from the main component is adopted as the glass transition temperature.

[線膨脹係數] [Linear expansion coefficient]

線膨脹係數係定義為每單位溫度變化的長度變化率，線膨脹係數係使用熱機械分析裝置(「TMA4000」Bruker AXS股份有限公司製)並根據JIS K7197進行測定。亦即，使用鑽石鋸以對將各測定的樹脂壓製成形的片狀擠出樹脂板形成平滑的端面，加工成一邊的長度為5mm×5mm、高度10mm的方柱狀，將已加工的各試料以5mm×5mm的面與石英板接觸的方式放置在石英板上，將圓筒狀的棒放置於其上，施加5g的壓縮負重進行固定。接著，在空氣環境下，以升溫速度3℃/分鐘從25℃(室溫)升溫至各試料的玻璃轉移溫度(Tg)的-10℃，再冷卻至25℃(室溫)(掃描1次)。而且，以升溫速度3℃/分鐘從25℃(室溫)升溫至各試料的玻璃轉移溫度(Tg)的+20℃(掃描2次)。測定2次掃描時的各溫度下的膨脹率，求得30℃~80℃的範圍的 平均線膨脹係數。 The coefficient of linear expansion is defined as the rate of change in length per unit temperature change, and the coefficient of linear expansion is measured in accordance with JIS K7197 using a thermomechanical analyzer ("TMA4000" manufactured by Bruker AXS Co., Ltd.). That is, a diamond saw was used to form a smooth end surface on a sheet-like extruded resin plate formed by pressing each measured resin, and processed into a square column with a length of 5mm×5mm and a height of 10mm. The processed samples Place a 5mm×5mm surface on the quartz plate in such a way that the surface is in contact with the quartz plate, place a cylindrical rod on it, and apply a compression load of 5g to fix it. Next, in an air environment, the temperature was raised from 25°C (room temperature) to -10°C of the glass transition temperature (Tg) of each sample at a heating rate of 3°C/min, and then cooled to 25°C (room temperature) (scanning once) ). In addition, the temperature was increased from 25°C (room temperature) to +20°C (2 scans) of the glass transition temperature (Tg) of each sample at a temperature increase rate of 3°C/min. Measure the expansion rate at each temperature in 2 scans, and find the range of 30℃~80℃ Average linear expansion coefficient.

[翹曲量] [Warpage amount]

將實施例及比較例的擠出樹脂板以與擠出流動方向平行的方向為短邊、與擠出流動方向垂直的方向為長邊的方式切成長方形，製作短邊65mm、長邊110mm的試片。以含甲基丙烯酸樹脂的層朝上的方式將所製作的試片放置在平台上，在溫度23℃、相對濕度50%的環境中放置24小時。之後，使用測隙規測定試片與平台的間隙的最大值，將此值定為初期翹曲量。接著，在設定成溫度85℃、相對濕度85%的環境試驗機中，以含甲基丙烯酸樹脂的層朝上的方式將前述試片放置在玻璃平台上，在此狀態下放置72小時後，在相對濕度50%、23℃環境下放置4小時。之後，與前述同樣地進行測定，將此值定為高溫高濕後的翹曲量。以含甲基丙烯酸樹脂的層朝上的方式將試片放置在平台上，將向下凸的翹曲的符號定為+，將向上凸的翹曲的符號定為-。翹曲量係以±0.5mm以下為合格。 The extruded resin sheets of the Examples and Comparative Examples were cut into rectangles with the short side as the short side in the direction parallel to the extrusion flow direction and the long side as the direction perpendicular to the extrusion flow direction, to produce a short side of 65mm and a long side of 110mm. Audition. Place the produced test piece on the platform with the layer containing the methacrylic resin facing up, and place it in an environment with a temperature of 23° C. and a relative humidity of 50% for 24 hours. After that, use a feeler gauge to measure the maximum value of the gap between the test piece and the platform, and set this value as the initial warpage. Next, in an environmental testing machine set to a temperature of 85°C and a relative humidity of 85%, the aforementioned test piece was placed on a glass platform with the methacrylic resin-containing layer facing up. After leaving it in this state for 72 hours, Place it at a relative humidity of 50% and 23°C for 4 hours. After that, the measurement was performed in the same manner as described above, and this value was defined as the amount of warpage after high temperature and high humidity. The test piece was placed on the platform with the methacrylic resin-containing layer facing upward, and the sign of the downward convex warpage was set as +, and the sign of the upward convex warpage was set as -. The amount of warpage is within ±0.5mm as qualified.

[加熱條件] [Heating conditions]

試片係使用自走鋸(running saw)切斷，製作100mm見方的試片。加熱係將試片放入管理成100℃±3℃的烘箱內5小時。 The test piece was cut using a running saw to produce a 100mm square test piece. In the heating system, the test piece is placed in an oven controlled at 100°C±3°C for 5 hours.

[遲滯值的測定] [Determination of Hysteresis Value]

試片係使用自走鋸切斷，製作100mm見方的試片。將試片在23℃±3℃的環境下放置10分鐘以上，使用Photonic Lattice股份有限公司製WPA-100(-L)測定遲滯 值，測定位置係測定試片的中央附近。 The test piece is cut with a self-propelled saw to make a 100mm square test piece. Place the test piece at 23°C±3°C for more than 10 minutes, and measure the hysteresis using WPA-100(-L) manufactured by Photonic Lattice Co., Ltd. Value, the measurement position is near the center of the measurement test piece.

又，對經過上述加熱條件的試片同樣地進行測定。 In addition, the same measurement was performed on the test piece subjected to the above-mentioned heating conditions.

遲滯的變化率係由下式求出。 The rate of change of the hysteresis is obtained by the following equation.

變化率(%)=([加熱前的遲滯值]-[加熱後的遲滯值])/[加熱前的遲滯值]×100 Change rate (%)=([Hysteresis value before heating]-[Hysteresis value after heating])/[Hysteresis value before heating]×100

[裝備偏光太陽眼鏡時的目視評價方法] [Visual evaluation method when equipped with polarized sunglasses]

試片係使用自走鋸切斷，製作100mm見方的試片。 The test piece is cut with a self-propelled saw to make a 100mm square test piece.

接著在距離眼睛35cm的位置設置液晶顯示裝置並顯示影像，然後將實施例及比較例之加熱前的試片在液晶顯示裝置與眼睛之間之距離眼睛30cm的位置設置成平行於顯示裝置的畫面，使試片的含甲基丙烯酸樹脂的層側朝向眼睛的方向。 Then set up the liquid crystal display device at a distance of 35 cm from the eyes and display the image, and then set the pre-heated test strips of the examples and comparative examples to be parallel to the screen of the display device at a distance of 30 cm between the liquid crystal display device and the eyes. , Orient the methacrylic resin-containing layer side of the test piece toward the eye.

首先，未裝備偏光太陽眼鏡並通過試片的厚度方向對影像進行目視觀察。 First, the polarized sunglasses were not equipped and the image was visually observed through the thickness direction of the test piece.

接著，裝備偏光太陽眼鏡並以臉部朝向影像的狀態下將頭向左右傾斜，如上所述地對影像進行目視觀察。 Next, the polarized sunglasses were equipped and the head was tilted left and right with the face facing the image, and the image was visually observed as described above.

之後，除了將加熱前的試片變更為加熱後的試片以外，與上述同樣地進行，針對未裝備偏光太陽眼鏡的情況及裝備偏光太陽眼鏡的情況以目視觀察影像。 After that, except for changing the test piece before heating to the test piece after heating, the same procedure was performed as described above, and the image was visually observed for the case of not equipped with polarized sunglasses and the case of equipped with polarized sunglasses.

○：影像的外觀未隨著有無裝備偏光太陽眼鏡而發生顯著的變化，能夠沒有問題地辨識影像。 ○: The appearance of the image does not change significantly with or without polarized sunglasses, and the image can be recognized without problems.

×：與未裝備偏光太陽眼鏡的情況相比，影像的外觀在裝備偏光太陽眼鏡的情況下將頭傾斜至某個角度時成為暗的影像，或是觀察到深的著色而難以看到影像。 ×: Compared with the case of not equipped with polarized sunglasses, the appearance of the image becomes a dark image when the head is tilted to a certain angle with polarized sunglasses, or a deep coloration is observed and it is difficult to see the image.

[表面性] [Surface]

在設置有螢光燈的室內，以肉眼觀察擠出樹脂板的兩面，以下面的基準評價表面性。 In a room where a fluorescent lamp was installed, both sides of the extruded resin plate were visually observed, and the surface properties were evaluated based on the following criteria.

○：在擠出樹脂板表面上未觀察到振動紋。 ○: No vibration marks are observed on the surface of the extruded resin plate.

△：在擠出樹脂板表面上觀察到振動紋，但不明顯。 △: Vibration marks are observed on the surface of the extruded resin plate, but are not noticeable.

×：振動紋在擠出樹脂板表面上是明顯的。 ×: Vibration marks are conspicuous on the surface of the extruded resin plate.

[樹脂溫度] [Resin temperature]

在從第3冷卻輥14剝離的位置，以紅外線輻射溫度計測定擠出樹脂板16整體的溫度，將如此進行而測得的溫度稱為樹脂溫度(TT)。 At the position peeled from the third cooling roll 14, the temperature of the entire extruded resin sheet 16 is measured with an infrared radiation thermometer, and the temperature measured in this way is referred to as the resin temperature (TT).

[甲基丙烯酸樹脂A] [Methacrylic resin A]

準備KURARAY股份有限公司製「PARAPET(註冊商標)HR」(在溫度230℃、3.8kg負重下的MFR=2.0cm3/10分鐘)作為甲基丙烯酸樹脂A。 As methacrylic resin A, "PARAPET (registered trademark) HR" manufactured by KURARAY Co., Ltd. (MFR at a temperature of 230°C and a load of 3.8 kg = 2.0 cm 3 /10 minutes) was prepared.

[甲基丙烯酸樹脂B] [Methacrylic resin B]

準備藉由甲基丙烯酸甲酯與甲基丙烯酸-8-三環[5.2.1.02,6]癸酯的自由基聚合所得到的共聚物作為甲基丙烯酸樹脂B。 The copolymer obtained by radical polymerization of methyl methacrylate and methacrylic acid-8-tricyclo[5.2.1.0 2,6 ]decyl ester is prepared as methacrylic resin B.

還有，將甲基丙烯酸-8-三環[5.2.1.02,6]癸酯在甲基丙烯酸甲酯與甲基丙烯酸-8-三環[5.2.1.02,6]癸酯的總劑量中所佔的摻入比率(質量百分率)稱為TC比率。 Also, the total dose of methacrylic acid-8-tricyclo[5.2.1.0 2,6 ]decyl ester in methyl methacrylate and methacrylic acid-8-tricyclo[5.2.1.0 2,6]decyl ester The incorporation ratio (mass percentage) accounted for in is called the TC ratio.

[樹脂組成物(1)] [Resin composition (1)]

在製造例中，使用下述所示的甲基丙烯酸樹脂及SMA樹脂。 In the production example, the following methacrylic resin and SMA resin were used.

<甲基丙烯酸樹脂> <Methacrylic resin>

甲基丙烯酸樹脂係準備上述KURARAY股份有限公司製「PARAPET(註冊商標)HR」(與甲基丙烯酸樹脂A相同)作為甲基丙烯酸樹脂。 Methacrylic resin system "PARAPET (registered trademark) HR" (same as methacrylic resin A) manufactured by Kuraray Co., Ltd. was prepared as a methacrylic resin.

<SMA樹脂> <SMA resin>

能夠由以下的方法取得SMA樹脂。 The SMA resin can be obtained by the following method.

藉由WO2010/013557所記載的方法，能夠得到作為苯乙烯-順丁烯二酸酐-MMA共聚物之SMA樹脂。 By the method described in WO2010/013557, SMA resin as a styrene-maleic anhydride-MMA copolymer can be obtained.

將使用的SMA樹脂的質量組成比及重量平均分子量(Mw)示於表1。 Table 1 shows the mass composition ratio and weight average molecular weight (Mw) of the SMA resin used.

Figure 106109081-A0202-12-0041-8
Figure 106109081-A0202-12-0041-8

<質量組成比> <mass composition ratio>

根據下述步驟，使用13C-NMR法求得SMA樹脂的共聚合組成。 According to the following procedure, the copolymerization composition of the SMA resin was obtained using the 13 C-NMR method.

13C-NMR光譜係使用核磁共振裝置(日本電子公司製GX-270)，將1.5g的SMA樹脂溶解於1.5ml的氘代氯仿中來調製試料溶液，在室溫環境下以累計次數4000~5000次的條件進行測定，根據測定的結果求得以下的值。 13 C-NMR spectroscopy system uses a nuclear magnetic resonance device (GX-270 manufactured by JEOL Ltd.) to prepare a sample solution by dissolving 1.5 g of SMA resin in 1.5 ml of deuterated chloroform. The accumulative number is 4000~ The measurement was performed under the condition of 5000 times, and the following values were obtained from the measurement results.

‧[苯乙烯單元中的苯環(碳數6)的碳峰(127、134、143ppm附近)的積分強度]/6 ‧[Integrated intensity of the carbon peaks (around 127, 134, and 143 ppm) of the benzene ring (carbon number 6) in the styrene unit]/6

‧[順丁烯二酸酐單元中的羰基部分(碳數2)的碳峰(170ppm附近)的積分強度]/2 ‧[Integrated intensity of the carbon peak (near 170ppm) of the carbonyl part (carbon number 2) in the maleic anhydride unit]/2

‧[MMA單元中的羰基部分(碳數1)的碳峰(175ppm附近)的積分強度]/1 ‧[Integrated intensity of the carbon peak (near 175ppm) of the carbonyl part (carbon number 1) in the MMA unit]/1

從上述值的面積比，求得試料中的苯乙烯單元、順丁烯二酸酐單元、MMA單元的莫耳比。從所得到的莫耳比與各個單體單元的質量比(苯乙烯單元：順丁烯二酸酐單元：MMA=104：98：100)，求得SMA樹脂中的各單體的質量組成。 From the area ratio of the above value, the molar ratio of the styrene unit, the maleic anhydride unit, and the MMA unit in the sample was determined. From the obtained molar ratio and the mass ratio of each monomer unit (styrene unit: maleic anhydride unit: MMA=104:98:100), the mass composition of each monomer in the SMA resin was obtained.

<重量平均分子量(Mw)> <Weight average molecular weight (Mw)>

根據下述步驟，使用GPC法求得SMA樹脂的Mw。 According to the following procedure, the Mw of the SMA resin is obtained by the GPC method.

使用四氫呋喃作為溶析液、以及使用串聯TOSOH股份有限公司製的TSKgel SuperMultipore HZM-M的2根與SuperHZ4000者作為管柱。使用具備示差折射率偵檢器(RI偵檢器)之TOSOH股份有限公司製的HLC-8320(型號)作為GPC裝置。將4mg的SMA樹脂溶解於5ml的四氫呋喃中來調製試料溶液。將管柱烘箱的溫度設定在40℃，在溶析液流量0.35ml/分鐘下注入試料溶液20μl，測定層析。以GPC測定分子量在400~5000000的範圍內的標準聚苯乙烯10點，製成表示滯留時間與分子量的關係的檢量線。根據此檢量線確定Mw。 Tetrahydrofuran was used as the eluent, and two of TSKgel SuperMultipore HZM-M manufactured by TOSOH Co., Ltd. and SuperHZ4000 were used as the column. The HLC-8320 (model) manufactured by TOSOH Co., Ltd. equipped with a differential refractive index detector (RI detector) was used as the GPC device. 4 mg of SMA resin was dissolved in 5 ml of tetrahydrofuran to prepare a sample solution. The temperature of the column oven was set at 40°C, 20 μl of the sample solution was injected at a flow rate of 0.35 ml/min of the eluent, and the chromatography was measured. 10 points of standard polystyrene with a molecular weight in the range of 400 to 5,000,000 were measured by GPC, and a calibration curve showing the relationship between residence time and molecular weight was prepared. Determine Mw according to this calibration curve.

將樹脂組成物(1)中之SMA樹脂在甲基丙烯酸樹脂A與SMA樹脂的總量中所佔的摻入比率(質量百分率)稱為SMA比率。 The incorporation ratio (mass percentage) of the SMA resin in the resin composition (1) in the total amount of the methacrylic resin A and the SMA resin is called the SMA ratio.

[聚碳酸酯] [Polycarbonate]

準備Sumika Styron Polycarbonate股份有限公司製「SD POLYCA(註冊商標)PCX」(在溫度300℃、1.2kg負重下的MFR=6.7g/10分鐘、玻璃轉移溫度(Tg)=150℃、線膨脹係數=6.93×10-5/K)作為聚碳酸酯。 Prepare "SD POLYCA (registered trademark) PCX" manufactured by Sumika Styron Polycarbonate Co., Ltd. (MFR at a temperature of 300°C and a load of 1.2 kg = 6.7g/10 minutes, glass transition temperature (Tg) = 150°C, coefficient of linear expansion = 6.93×10 -5 /K) as polycarbonate.

[實施例1] [Example 1]

(擠出樹脂板之製造方法) (Method of manufacturing extruded resin board)

將TC比率20質量%的甲基丙烯酸樹脂B(玻璃轉移溫度：120度、線膨脹係數：7.30×10-5/K)以65mmφ單軸擠出機[東芝機械股份有限公司製]熔融，將聚碳酸酯以150mmφ單軸擠出機[東芝機械股份有限公司製]熔融，透過多重分歧管型模頭將兩者積層。將積層的樹脂(擠出樹脂板16、熔融狀態的熱塑性樹脂積層體)夾在如圖1所示之第1冷卻輥12與第2冷卻輥13之間並捲繞至第2冷卻輥13後，藉由捲繞至第3冷卻輥14來進行冷卻，利用拉取輥15拉取製造擠出樹脂板16製造。樹脂溫度(TT)係藉由控制第2冷卻輥13及第3冷卻輥14的溫度而調整至150℃。又，將第2冷卻輥13與拉取輥15的圓周速度比(V4/V2)調整成0.995，將第2冷卻輥13與第3冷卻輥14的圓周速度比(V3/V2)調整成1.005，使含聚碳酸酯的層側與第3冷卻輥14側相接。將含甲基丙烯酸樹脂的層的厚度定為0.075mm，將含聚碳酸酯的層的厚度定為0.925mm。將製造條件及所得到的擠出樹脂板的評價結果的評價結果示於表2。 Methacrylic resin B (glass transition temperature: 120°C, linear expansion coefficient: 7.30×10 -5 /K) with a TC ratio of 20% by mass was melted in a 65mmφ single-screw extruder [manufactured by Toshiba Machine Co., Ltd.], and The polycarbonate is melted by a 150mmφ single-screw extruder [manufactured by Toshiba Machine Co., Ltd.], and the two are laminated through a multi-branch tube die. The laminated resin (extruded resin sheet 16, molten thermoplastic resin laminate) is sandwiched between the first cooling roll 12 and the second cooling roll 13 as shown in FIG. 1 and wound to the second cooling roll 13 , It is cooled by winding to the third cooling roll 14, and the extruded resin sheet 16 is produced by pulling it with the pulling roll 15. The resin temperature (TT) was adjusted to 150°C by controlling the temperature of the second cooling roll 13 and the third cooling roll 14. In addition, the circumferential speed ratio (V4/V2) of the second cooling roll 13 and the drawing roll 15 is adjusted to 0.995, and the circumferential speed ratio (V3/V2) of the second cooling roll 13 to the third cooling roll 14 is adjusted to 1.005 , The polycarbonate-containing layer side is brought into contact with the third cooling roll 14 side. The thickness of the methacrylic resin-containing layer was set to 0.075 mm, and the thickness of the polycarbonate-containing layer was set to 0.925 mm. Table 2 shows the evaluation results of the production conditions and the evaluation results of the obtained extruded resin sheet.

[實施例2~4] [Examples 2~4]

除了使用具有表2的「含甲基丙烯酸樹脂的層」一欄中所記載的TC比率的甲基丙烯酸樹脂B來代替TC比率20質量%的甲基丙烯酸樹脂B並將樹脂溫度(TT)如表2所記載地進行調整之外，係與實施例1同樣地製造擠出樹脂板。將製造條件及所得到的擠出樹脂板的評價結果示於表2。 Except for using methacrylic resin B with a TC ratio described in the column of "Methacrylic resin containing layer" in Table 2 instead of methacrylic resin B with a TC ratio of 20% by mass, and the resin temperature (TT) as Except for adjusting as described in Table 2, an extruded resin sheet was produced in the same manner as in Example 1. Table 2 shows the production conditions and the evaluation results of the obtained extruded resin sheet.

[實施例5] [Example 5]

使用SMA比率20質量%的樹脂組成物(1)來代替TC比率20質量%的甲基丙烯酸樹脂B並如表2所記載，與實施例1同樣地製造擠出樹脂板。 The resin composition (1) with an SMA ratio of 20% by mass was used instead of the methacrylic resin B with a TC ratio of 20% by mass, and as described in Table 2, an extruded resin sheet was produced in the same manner as in Example 1.

[實施例6~15、比較例2~6] [Examples 6-15, Comparative Examples 2-6]

除了使用具有表2的「含甲基丙烯酸樹脂的層」所記載的SMA比率的樹脂組成物(1)來代替SMA比率20質量%的樹脂組成物(1)並如表2所記載地改變各條件以外，係與實施例5同樣地製造擠出樹脂板。將製造條件及所得到的擠出樹脂板的評價結果示於表2。 Except that the resin composition (1) having the SMA ratio described in the "methacrylic resin-containing layer" of Table 2 was used instead of the resin composition (1) with the SMA ratio of 20% by mass, and each was changed as described in Table 2. Except for the conditions, an extruded resin sheet was produced in the same manner as in Example 5. Table 2 shows the production conditions and the evaluation results of the obtained extruded resin sheet.

[比較例1] [Comparative Example 1]

除了使用甲基丙烯酸樹脂A來代替TC比率20質量%的甲基丙烯酸樹脂B以外，係如表2所記載，與實施例1同樣地製造擠出樹脂板。將製造條件及所得到的擠出樹脂板的評價結果示於表2。 Except that methacrylic resin A was used instead of methacrylic resin B with a TC ratio of 20% by mass, as described in Table 2, an extruded resin plate was produced in the same manner as in Example 1. Table 2 shows the production conditions and the evaluation results of the obtained extruded resin sheet.

Figure 106109081-A0202-12-0045-9
Figure 106109081-A0202-12-0045-9

在表2中，針對各個實施例及比較例，顯示作為含甲基丙烯酸樹脂的層而使用的樹脂或樹脂組成物的種類、樹脂溫度(TT)、圓周速度比(V3/V2)、圓周速度比(V4/V2)、玻璃轉移溫度(Tg)、含甲基丙烯酸樹脂的層的線膨脹係數、擠出樹脂板的線膨脹比(SR)、初期及高溫高濕後的翹曲量、加熱前後的遲滯、加熱前後的遲滯的變化率及表面性之測定結果。 Table 2 shows the type of resin or resin composition used as the layer containing methacrylic resin, resin temperature (TT), peripheral speed ratio (V3/V2), peripheral speed for each example and comparative example. Ratio (V4/V2), glass transition temperature (Tg), linear expansion coefficient of methacrylic resin-containing layer, linear expansion ratio (SR) of extruded resin sheet, initial warpage and after high temperature and high humidity, heating The measurement results of the hysteresis before and after, the rate of change of the hysteresis before and after heating, and the surface properties.

在實施例1至4中，製造積層有含TC比率20~60質量%的甲基丙烯酸樹脂B的層與含聚碳酸酯的層之 擠出樹脂板來進行試驗。如表2所示，在使用實施例3的含TC比率45%的甲基丙烯酸樹脂B的層的情況下，若考慮到玻璃轉移溫度(Tg)、線膨脹係數比(SR)、翹曲量以及遲滯值及變化率，此為最佳的結果。 In Examples 1 to 4, a layer containing a methacrylic resin B with a TC ratio of 20 to 60% by mass and a layer containing polycarbonate were produced. The resin board was extruded for testing. As shown in Table 2, in the case of using the layer of methacrylic resin B with a TC ratio of 45% in Example 3, considering the glass transition temperature (Tg), linear expansion coefficient ratio (SR), and the amount of warpage As well as the hysteresis value and rate of change, this is the best result.

在實施例5至14中，製造積層有含SMA比率20~100質量%的樹脂組成物(1)的層與含聚碳酸酯的層之擠出樹脂板來進行試驗。如表2所示，在使用實施例7、9的含SMA比率70質量%的樹脂組成物(1)的層的情況下，遲滯值及變化率為良好，翹曲量的絕對值亦小，此為最佳的結果。 In Examples 5 to 14, an extruded resin sheet in which a layer containing a resin composition (1) having an SMA ratio of 20 to 100% by mass and a polycarbonate-containing layer were laminated was produced and tested. As shown in Table 2, when the layer of the resin composition (1) containing 70% by mass of SMA of Examples 7 and 9 was used, the hysteresis value and the rate of change were good, and the absolute value of the warpage was also small. This is the best result.

又，在實施例1~9中，將圓周速度比(V4/V2)恆定為0.995。 In addition, in Examples 1 to 9, the peripheral velocity ratio (V4/V2) was constant at 0.995.

在實施例10~14中，使用含SMA比率70質量%的樹脂組成物(1)的層，將樹脂溫度(TT)固定在155℃，將圓周速度比(V4/V2)定為0.98~1.01。 In Examples 10-14, a layer containing a resin composition (1) with an SMA ratio of 70% by mass was used, the resin temperature (TT) was fixed at 155°C, and the peripheral speed ratio (V4/V2) was set at 0.98 to 1.01 .

另一方面，在比較例1中，玻璃轉移溫度(Tg)低，而高溫高濕後的翹曲大。在比較例2、3中，降低樹脂溫度(TT)後，成為翹曲量大的擠出樹脂板，而且加熱前後的面內遲滯值的下降率大。 On the other hand, in Comparative Example 1, the glass transition temperature (Tg) was low, but the warpage after high temperature and high humidity was large. In Comparative Examples 2 and 3, after lowering the resin temperature (TT), an extruded resin sheet with a large amount of warpage was obtained, and the rate of decrease in the in-plane hysteresis value before and after heating was large.

在比較例4中，提高樹脂溫度(TT)後，成為表面性差的擠出樹脂板。在比較例5中，提高圓周速度比(V4/V2)後，成為遲滯值高的擠出樹脂板。在比較例6中，降低圓周速度比(V4/V2)後，成為遲滯值低的擠出樹脂板。 In Comparative Example 4, after raising the resin temperature (TT), it became an extruded resin sheet with poor surface properties. In Comparative Example 5, after increasing the peripheral speed ratio (V4/V2), it became an extruded resin sheet with a high hysteresis value. In Comparative Example 6, after lowering the peripheral speed ratio (V4/V2), it became an extruded resin sheet with a low hysteresis value.

[產業上之可利用性] [Industrial availability]

本發明之製造方法所得到的擠出樹脂板係例 如能夠用於液晶顯示器保護板或觸控面板的保護蓋，適用於車載用顯示裝置、行動電話、智慧型手機、電腦、電視等。 Examples of extruded resin sheets obtained by the manufacturing method of the present invention For example, it can be used as a protective cover for LCD protection panels or touch panels, and is suitable for automotive display devices, mobile phones, smart phones, computers, TVs, etc.

還有，本發明不限於上述實施的形態，可在不脫離要點的範圍內適當地進行變更。 In addition, the present invention is not limited to the embodiment described above, and can be appropriately modified within a range that does not deviate from the gist.

Claims (15)

一種擠出樹脂板之製造方法，其係在含有聚碳酸酯的層的至少一面上積層有含有甲基丙烯酸樹脂的層之擠出樹脂板之製造方法，其中，該含有甲基丙烯酸樹脂的層的玻璃轉移溫度在115℃以上，該製造方法包含下述步驟：在熔融狀態下將在該含有聚碳酸酯的層的至少一面上積層有該含有甲基丙烯酸樹脂的層之熱塑性樹脂積層體從T字模擠出，在第1冷卻輥與第2冷卻輥之間夾住該熱塑性樹脂積層體，藉由將該熱塑性樹脂積層體捲繞至該第2冷卻輥之後捲繞至第3冷卻輥來進行冷卻，利用拉取輥拉取該熱塑性樹脂積層體；在該熱塑性樹脂積層體從最後捲繞的冷卻輥剝離的位置，將樹脂整體的溫度設定成相對於該含有聚碳酸酯的層的玻璃轉移溫度為-2℃~+15℃的範圍，將該拉取輥的圓周速度(V4)與該第2冷卻輥的圓周速度(V2)的圓周速度比(V4/V2)設定為0.98以上1.01以下。 A method for manufacturing an extruded resin sheet, which is a method for manufacturing an extruded resin sheet in which a layer containing methacrylic resin is laminated on at least one surface of a layer containing polycarbonate, wherein the layer containing methacrylic resin The glass transition temperature is 115°C or higher. The manufacturing method includes the following steps: in a molten state, the thermoplastic resin laminate in which the methacrylic resin-containing layer is laminated on at least one surface of the polycarbonate-containing layer is obtained from T-die extrusion, sandwich the thermoplastic resin laminate between the first cooling roll and the second cooling roll, and wind the thermoplastic resin laminate to the second cooling roll and then to the third cooling roll. After cooling, the thermoplastic resin laminate is pulled by a pull roll; at the position where the thermoplastic resin laminate is peeled from the last cooling roll wound, the temperature of the entire resin is set relative to the glass of the polycarbonate-containing layer The transition temperature is in the range of -2°C to +15°C, and the peripheral speed ratio (V4/V2) of the peripheral speed (V4) of the pulling roll and the peripheral speed (V2) of the second cooling roll (V4/V2) is set to 0.98 or more and 1.01 the following. 如請求項1之擠出樹脂板之製造方法，其中該含有聚碳酸酯的層的線膨脹係數(S1)與該含有甲基丙烯酸樹脂的層的線膨脹係數(S2)的差(S2-S1)、與該含有聚碳酸酯的層的線膨脹係數(S1)之比((S2-S1)/S1)為-10%~+5%。 The method for manufacturing an extruded resin sheet according to claim 1, wherein the difference (S2-S1) between the linear expansion coefficient (S1) of the polycarbonate-containing layer and the linear expansion coefficient (S2) of the methacrylic resin-containing layer ), the ratio ((S2-S1)/S1) to the linear expansion coefficient (S1) of the polycarbonate-containing layer is -10%~+5%. 如請求項1或2之擠出樹脂板之製造方法，其中該含有甲基丙烯酸樹脂的層含有來自甲基丙烯酸甲酯的結構單元40~80質量%且含有來自以下述通式(I)表示的甲基丙烯酸酯的結構單元20~60質量%；
Figure 106109081-A0305-02-0051-1
 (式中，Cy係表示脂環式烴基)。 The method for manufacturing an extruded resin sheet according to claim 1 or 2, wherein the methacrylic resin-containing layer contains 40 to 80% by mass of structural units derived from methyl methacrylate and is represented by the following general formula (I) The structural unit of methacrylate is 20-60% by mass;
Figure 106109081-A0305-02-0051-1
 (In the formula, Cy represents an alicyclic hydrocarbon group). 如請求項3之擠出樹脂板之製造方法，其中該通式(I)中之Cy為多環脂肪族烴基。 The method for manufacturing an extruded resin sheet according to claim 3, wherein Cy in the general formula (I) is a polycyclic aliphatic hydrocarbon group. 如請求項1或2之擠出樹脂板之製造方法，其中該含有甲基丙烯酸樹脂的層含有：甲基丙烯酸樹脂5質量%以上小於80質量%、與包含來自以下述通式(II)表示的芳香族乙烯化合物的結構單元及來自以下述通式(III)表示的酸酐的結構單元而成的共聚物20質量%以上；
Figure 106109081-A0305-02-0051-2
 (式中：R1及R2係各自獨立地表示氫原子或烷基)；
Figure 106109081-A0305-02-0051-3
 (式中：R3及R4係各自獨立地表示氫原子或烷基)。 The method for producing an extruded resin sheet according to claim 1 or 2, wherein the layer containing methacrylic resin contains: methacrylic resin 5 mass% or more and less than 80 mass%, and containing from the following general formula (II) 20% by mass or more of a copolymer composed of structural units of the aromatic vinyl compound and structural units derived from the acid anhydride represented by the following general formula (III);
Figure 106109081-A0305-02-0051-2
 (In the formula: R 1 and R 2 each independently represent a hydrogen atom or an alkyl group);
Figure 106109081-A0305-02-0051-3
 (In the formula: R 3 and R 4 each independently represent a hydrogen atom or an alkyl group). 如請求項5之擠出樹脂板之製造方法，其中該共聚物含 有50~84質量%的該來自芳香族乙烯化合物的結構單元、含有15~49質量%的該來自酸酐的結構單元以及含有1~25質量%的甲基丙烯酸酯單體。 The method for manufacturing an extruded resin sheet of claim 5, wherein the copolymer contains There are 50 to 84% by mass of the structural unit derived from the aromatic vinyl compound, 15 to 49% by mass of the structural unit derived from the acid anhydride, and 1 to 25% by mass of the methacrylate monomer. 如請求項6之擠出樹脂板之製造方法，其中該甲基丙烯酸酯單體為甲基丙烯酸甲酯。 The method for manufacturing an extruded resin sheet according to claim 6, wherein the methacrylate monomer is methyl methacrylate. 一種擠出樹脂板，其係藉由如請求項1至7中任一項之製造方法所得到的擠出樹脂板，其中，將該擠出樹脂板在75℃下加熱5小時時，於加熱前後在寬度方向的至少一部分中，面內遲滯值為50~600nm，於該加熱前後的該遲滯值的下降率小於15%。 An extruded resin sheet, which is an extruded resin sheet obtained by the manufacturing method of any one of claims 1 to 7, wherein the extruded resin sheet is heated at 75°C for 5 hours. In at least a part of the width direction before and after, the in-plane hysteresis value is 50 to 600 nm, and the rate of decrease of the hysteresis value before and after the heating is less than 15%. 一種擠出樹脂板，其係藉由如請求項1至7中任一項之製造方法所得到的擠出樹脂板，其中，將該擠出樹脂板在100℃下加熱5小時時，於加熱前後在寬度方向的至少一部分中，面內遲滯值為50~600nm，於該加熱前後的該遲滯值的下降率小於15%。 An extruded resin sheet, which is an extruded resin sheet obtained by the manufacturing method of any one of claims 1 to 7, wherein the extruded resin sheet is heated at 100°C for 5 hours. In at least a part of the width direction before and after, the in-plane hysteresis value is 50 to 600 nm, and the rate of decrease of the hysteresis value before and after the heating is less than 15%. 一種擠出樹脂板，其係藉由如請求項1至7中任一項之製造方法所得到的擠出樹脂板，其中，將該擠出樹脂板在75℃~100℃下加熱5小時時，於加熱前後在寬度方向的至少一部分中，面內遲滯值為50~600nm，於該加熱前後的該遲滯值的下降率小於15%。 An extruded resin sheet, which is an extruded resin sheet obtained by the manufacturing method according to any one of claims 1 to 7, wherein the extruded resin sheet is heated at 75°C to 100°C for 5 hours In at least a part of the width direction before and after heating, the in-plane hysteresis value is 50 to 600 nm, and the rate of decrease of the hysteresis value before and after heating is less than 15%. 如請求項8至10中任一項之擠出樹脂板，其中於該加熱前後在寬度方向的至少一部分中，面內遲滯值為80 ~350nm。 The extruded resin sheet according to any one of claims 8 to 10, wherein in at least a part of the width direction before and after the heating, the in-plane hysteresis value is 80 ~350nm. 如請求項8至10中任一項之擠出樹脂板，其中於該加熱前後的該遲滯值的下降率小於10%。 The extruded resin sheet according to any one of claims 8 to 10, wherein the reduction rate of the hysteresis value before and after the heating is less than 10%. 如請求項8至10中任一項之擠出樹脂板，其係進一步在至少一表面上具備抗刮性層。 The extruded resin sheet according to any one of claims 8 to 10, which is further provided with a scratch-resistant layer on at least one surface. 一種擠出樹脂板之製造方法，其係藉由如請求項1至7中任一項之製造方法得到擠出樹脂板，並進一步包含將該擠出樹脂板在65℃~110℃的溫度下加熱1~30小時之步驟，於該加熱前後在寬度方向的至少一部分中，面內遲滯值為50~600nm，於該加熱前後的該遲滯值的下降率小於15%。 A method for manufacturing an extruded resin board, which is obtained by the manufacturing method as claimed in any one of claims 1 to 7, and further comprises heating the extruded resin board at a temperature of 65°C to 110°C In the step of heating for 1 to 30 hours, in at least a part of the width direction before and after the heating, the in-plane hysteresis value is 50 to 600 nm, and the rate of decrease of the hysteresis value before and after the heating is less than 15%. 一種擠出樹脂板，其係在含有聚碳酸酯的層的至少一面上積層有含有甲基丙烯酸樹脂的層之擠出樹脂板，其中，該含有甲基丙烯酸樹脂的層的玻璃轉移溫度在115℃以上，在75℃下加熱5小時時，於加熱前後在寬度方向的至少一部分中，面內遲滯值為50~600nm，於該加熱前後的該遲滯值的下降率小於15%，該含有聚碳酸酯的層的線膨脹係數(S1)與該含有甲基丙烯酸樹脂的層的線膨脹係數(S2)的差(S2-S1)、與該含有聚碳酸酯的層的線膨脹係數(S1)之比((S2-S1)/S1)為-10%~+5%。 An extruded resin sheet, which is an extruded resin sheet in which a layer containing methacrylic resin is laminated on at least one side of a layer containing polycarbonate, wherein the glass transition temperature of the layer containing methacrylic resin is 115 ℃ or higher, when heating at 75℃ for 5 hours, in at least a part of the width direction before and after heating, the in-plane hysteresis value is 50~600nm, and the rate of decrease of the hysteresis value before and after heating is less than 15% The difference (S2-S1) between the linear expansion coefficient (S1) of the carbonate layer and the linear expansion coefficient (S2) of the methacrylic resin-containing layer, and the linear expansion coefficient (S1) of the polycarbonate-containing layer The ratio ((S2-S1)/S1) is -10%~+5%.
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