TW581724B - Multilayer structure - Google Patents

Abstract

Disclosed is a multilayer structure having (A) a polycarbonate resin layer, (B) an adhesive resin layer and (C) a glass layer, wherein at least one of the glass layer and the adhesive resin layer comprises an ultraviolet ray-absorbing component, and preferably, the polycarbonate resin layer has terminal hydroxyl groups in an amount of 8 mole % or less of moles of the repeating unit of its polymer chain. The multilayer structure is lightweight and excellent in impact resistance and the like, and also is reduced in the yellowing and in the decrease of transparency in the case of being used outdoors for a long period of time.

Description

581724 A7581724 A7

五、發明說明（1 ) 技術領域 經濟部智慧財產局員工消費合作社印製 本發明係關於可利用在汽車、飛機等之窗玻璃，建築 物、學校、商店等之窗、展示窗、屋頂等之多層結構物； 曰羊曰之’係有關聚碳酸酯系樹脂及玻璃層利用粘著樹脂層 一體化而成，耐候性經改良之多層結構物。 先行技術 汽車、建築物、學校、商店等之窗、屋頂、透明壁材 ，向來係用無機玻璃爲之。然而，近年來由於汽車燃料費 之提升，建築物窗材之耐衝擊性、重量減輕、取用性等， 有取代無機玻璃的輕量材料之要求。又，汽車之窗玻璃及 天窗玻璃’公共建築等，爲求防止無機玻璃板在破損時玻 璃之飛散，有將二片玻璃板以聚乙烯醇縮丁醛等之粘著性 樹脂爲中間層作爲貼合玻璃板使用。 然而，無機玻璃板、貼合玻璃板中玻璃比重仍高，爲 輕量化有降低其厚度之必要，而從用途所需之強度特性， 玻璃板之薄片化自屬有限。因此，近來有取代無機玻璃板 改用比重低之聚甲基丙烯酸甲酯或聚碳酸酯系樹脂板之提 議，已見採用於公共建築之窗戶或屋頂等。 聚甲基丙烯酸甲酯之耐衝擊性未必充分，故近來聚碳 酸酯系樹脂受到矚目。然而，聚碳酸酯系樹脂之表面硬度 ，擦拭硬度等不充分，易起表面損傷，使用範圍受到限制 。爲提升其表面硬度、耐擦傷性，有於聚碳酸酯系樹脂板 之表面以矽酮系樹脂等之硬質樹脂作被覆處理，或蒸鍍以V. Description of the Invention (1) Technical Field Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The present invention relates to window glass, windows, display windows, roofs, etc. that can be used in automobiles, aircrafts, etc. Multi-layered structure; "Yangyue Zhi" is a multilayered structure in which the polycarbonate resin and glass layer are integrated by using an adhesive resin layer with improved weather resistance. Advanced technology Windows, roofs, and transparent wall materials for automobiles, buildings, schools, and shops have always been made of inorganic glass. However, in recent years, due to the increase in automobile fuel costs, the impact resistance, weight reduction, and accessibility of building window materials have demanded lightweight materials that replace inorganic glass. In addition, in order to prevent the scattering of inorganic glass plates when the window glass and sunroof glass of public buildings are damaged, there are two glass plates with an adhesive resin such as polyvinyl butyral as an intermediate layer. Use with laminated glass. However, the specific gravity of glass in inorganic glass plates and laminated glass plates is still high. It is necessary to reduce the thickness in order to reduce the weight. However, from the strength characteristics required for applications, the thinning of glass plates is limited. Therefore, recently, there have been proposals to replace inorganic glass plates with polymethyl methacrylate or polycarbonate resin plates with low specific gravity, and they have been used in windows or roofs of public buildings. Polymethyl methacrylate may not have sufficient impact resistance, and polycarbonate resins have recently attracted attention. However, the surface hardness and wiping hardness of polycarbonate-based resins are not sufficient, and they are prone to surface damage, and the use range is limited. In order to improve the surface hardness and scratch resistance, the surface of the polycarbonate resin plate is coated with a hard resin such as a silicone resin or vapor-deposited to

It---*--------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公复） -4 - 581724 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（2) 氧化矽等或金屬氧化物等之改良方法的提議。 然而，此類有表面被覆層之形成的聚碳酸酯系樹脂板 其耐久性仍不充分，迄今未能取代無機玻璃板。爲此，有 結合玻璃板之優點的硬度、耐擦傷性及聚碳酸酯系樹脂之 透明性、強度尤其是特優之耐衝擊性的多層板之提議。例 如，於2至8毫米左右之聚碳酸酯.系樹脂板的一面，將1 至2毫米左右之玻璃板，中介以例如聚乙烯醇縮丁醛、乙 烯-醋酸乙烯酯共聚物、聚氨酯、聚碳酸酯-有機矽氧烷 (嵌段）共聚物等之粘著樹脂層合成多層結構物（層合體 )已見提議。 這些多層結構物，對於衝擊或貫穿，較之無機玻璃板 單獨材料，呈示顯著較佳抗性，同時，藉由變更無機玻璃 板及聚碳酸酯系樹脂厚度之比，可以設計出物性與輕量化 得以平衡之材料，係爲一大特徵。 又，該多層結構物，係以上述之三層結構爲基礎，長 久使用或因使用場所之故，由於玻璃板與聚碳酸酯系樹脂 的基本物性之差別，有時可見應力龜裂、霧化、剝離等。 此時，亦可於上述多層結構物之聚碳酸酯系樹脂層上，更 中介以粘著樹脂層將玻璃板層合成對稱型之多層結構物。 再者，依目的，可設其它之任意樹脂層，例如聚甲基丙烯 酸甲酯等之硬質樹脂，彈性樹脂層等的種種提議，亦已見 提出。 這些以無機玻璃板/聚碳酸酯系樹脂板爲基本結構之 板狀多層結構物（層合體），係具如上述之優異特性。但 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公H ^ »r ---------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 581724It --- * ---------- Order --------- line (Please read the precautions on the back before filling this page) This paper size applies to Chinese national standards (CNS) A4 specification (210 X 297 public reply) -4-581724 A7 B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (2) Proposals for improvement methods such as silicon oxide or metal oxides. However, the polycarbonate-based resin sheet having such a surface coating layer has insufficient durability, and has so far failed to replace the inorganic glass sheet. For this reason, there are proposals for a multilayer board which combines the hardness and scratch resistance of a glass plate with the transparency and strength of a polycarbonate-based resin, and particularly excellent impact resistance. For example, on the side of a polycarbonate resin sheet of about 2 to 8 mm, a glass sheet of about 1 to 2 mm is interposed with, for example, polyvinyl butyral, ethylene-vinyl acetate copolymer, polyurethane, poly It has been proposed to synthesize multilayer structures (laminates) of adhesive resin layers such as carbonate-organosiloxane (block) copolymers. These multilayer structures show significantly better resistance to impact or penetration than the individual materials of the inorganic glass plate. At the same time, by changing the thickness ratio of the inorganic glass plate and polycarbonate resin, physical properties and weight reduction can be designed. A balanced material is a major feature. In addition, the multilayer structure is based on the three-layer structure described above. For long-term use or because of the place of use, due to the difference in basic physical properties between the glass plate and the polycarbonate resin, stress cracks and fogging may be seen. , Peeling, etc. In this case, the polycarbonate resin layer of the multilayer structure may be laminated with a glass plate layer to form a symmetrical multilayer structure through an adhesive resin layer. Furthermore, according to the purpose, various other resin layers, such as hard resins such as polymethyl methacrylate, and elastic resin layers, have been proposed. These plate-like multilayer structures (laminates) having an inorganic glass plate / polycarbonate resin plate as a basic structure have excellent characteristics as described above. But this paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 male H ^ »r --------------- Order --------- line (please (Please read the notes on the back before filling out this page) 581724

經濟部智慧財產局員工消費合作社印製 五、發明說明（3) 是，這些多層結構物，大部份係使用於汽車、建築物之窗 材等以面向屋外爲主。爲此，多層結構物深受來自太陽之 紫外線的作用，聚碳酸酯系樹脂層會有變黃之發生。因此 ’時間過後產生變色，外觀惡化，並且透明度下降而令其 使用範圍大受限制。 爲此’亦有於聚碳酸酯系樹脂板之成型時配合以紫外 線吸收劑者。然而，爲防止變黃，有必要添加紫外線吸收 劑至相當程度，而有因添加劑導致.聚碳酸酯系樹脂板產生 者色之情事。又，聚碳酸酯系樹脂之熔融粘度高，成型溫 度高’易起紫外線吸收劑之升華等，合用之紫外線吸收劑 之選擇範圍狹窄，係其缺失。 本發明之目的，係在上述現況底下，提供聚碳酸酯系 樹脂及玻璃板中介以粘著樹脂層一體化而成之重量輕、耐 衝擊性等優異之多層結構物，其於戶外使用，經長久使用 亦少有變黃或透明性之減降。 發明之揭示 爲達本發明之目的，本發明人等對聚碳酸酯系樹脂及 玻璃之多層結構物的耐候性之改良，進行了精心探討。結 果發現，當於特定之層添加以紫外線吸收成分（劑）時， 有優異效果，而完成本發明。 亦即，本發明係關於， (1 )由聚碳酸酯系樹脂層（A )、粘著樹脂層（B )、玻璃層（C )所成之多層結構物，係於玻璃層或粘著 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -6^ ί Γ I----- I------^ « — — — — — — I— (請先閱讀背面之注意事項再填寫本頁) 581724Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (3) Yes, most of these multi-layered structures are used in cars, windows of buildings, etc., and they are mainly oriented to the outside. For this reason, the multilayer structure is deeply affected by the ultraviolet rays from the sun, and the polycarbonate resin layer may turn yellow. As a result, discoloration occurs after the time has elapsed, and the appearance is deteriorated, and transparency is reduced, so that its use range is greatly restricted. For this purpose, there is also a case where a polycarbonate-based resin plate is molded with an ultraviolet absorbent. However, in order to prevent yellowing, it is necessary to add an ultraviolet absorbent to a considerable extent, and the polycarbonate resin sheet may be colored due to the additives. In addition, the polycarbonate resin has a high melt viscosity and a high molding temperature, and it is liable to cause sublimation of an ultraviolet absorber, etc., and the selection range of the combined ultraviolet absorber is narrow, which is lacking. The object of the present invention is to provide a multilayer structure with light weight and excellent impact resistance integrated with a polycarbonate resin and a glass plate interposed by an adhesive resin layer under the above-mentioned current conditions. Long-term use also has little yellowing or loss of transparency. DISCLOSURE OF THE INVENTION In order to achieve the object of the present invention, the present inventors have carefully studied the improvement of the weather resistance of a multilayer structure of polycarbonate resin and glass. As a result, it was found that when an ultraviolet absorbing component (agent) is added to a specific layer, an excellent effect is achieved, and the present invention has been completed. That is, the present invention relates to (1) a multilayer structure made of a polycarbonate-based resin layer (A), an adhesive resin layer (B), and a glass layer (C), which is connected to the glass layer or the adhesive layer. Paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -6 ^ Γ Γ I ----- I ------ ^ «— — — — — — I— (Please read first (Notes on the back then fill out this page) 581724

五、發明說明（4) 樹脂層之至少其一含有紫外線吸收成分的多層結構物。 (請先閱讀背面之注意事項再填寫本頁) (2 )於玻璃層（A )及粘著樹脂層（b )兩者均含 紫外線吸收成分之（1 )所記載的多層結構物。 (3 )玻璃層（A )係蘇打石灰氧化砂系玻璃，而含 於玻璃之紫外線吸收成分係鈽之（.1 )或（2 )所記載之 多層結構物。 (4 )含有粘著樹脂層（b )之紫外線吸收成分，係 苯并***系化合物及/或三嗪系化合物之（1 )至（3 ) 之任一所記載的多層結構物。 (5 )粘著樹脂層（B )係選自乙烯一醋酸乙烯酯共 聚物，聚醋酸乙烯酯，乙烯一（甲基）丙烯酸酯共聚物， 聚氨酯，聚酯-聚氨酯共聚物，聚碳酸酯一有機矽氧烷共 聚物，聚乙烯醇縮丁醛樹脂之至少一層所成的（1 )至（ 4 )之任一所記載的多層結構物。 (6 )用於聚碳酸酯樹脂層（’ A )之聚碳酸酯其末端 羥基之量，係占聚合鏈之重複單位的8莫耳％以下者之（ 1 )至（5 )之任一所記載的多層結構物。 經濟部智慧財產局員工消費合作社印製 (7 )粘著樹脂層（B )係有二層，其中靠近聚碳酸 酯系樹脂層（A )之側係聚碳酸酯-聚有機矽氧烷共聚物 之（1 )至（6 )之任一所記載的多層結構物。 (8 )又於聚碳酸酯系樹脂層（A )之側中介以粘著 樹脂層設有玻璃層而成之（1 )至（7 )之任一所記載的 多層結構物。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 5817245. Description of the invention (4) At least one of the resin layers is a multilayer structure containing an ultraviolet absorbing component. (Please read the precautions on the back before filling out this page.) (2) Both the glass layer (A) and the adhesive resin layer (b) contain the multilayer structure described in (1) of the ultraviolet absorbing component. (3) The glass layer (A) is a soda lime oxidized sand-based glass, and the ultraviolet absorbing component contained in the glass is a multilayer structure as described in (.1) or (2). (4) The multilayer structure according to any one of (1) to (3) of the benzotriazole-based compound and / or the triazine-based compound, the ultraviolet-absorbing component containing the adhesive resin layer (b). (5) The adhesive resin layer (B) is selected from the group consisting of ethylene-vinyl acetate copolymer, polyvinyl acetate, ethylene- (meth) acrylate copolymer, polyurethane, polyester-polyurethane copolymer, and polycarbonate- The multilayer structure according to any one of (1) to (4), which is an organosiloxane copolymer and at least one layer of a polyvinyl butyral resin. (6) The amount of the terminal hydroxyl groups of the polycarbonate used in the polycarbonate resin layer ('A) is any one of (1) to (5) below 8 mol% of the repeating unit of the polymer chain. The multilayer structure described. (7) The adhesive resin layer (B) printed by the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs has two layers, of which the polycarbonate-polyorganosiloxane copolymer is on the side near the polycarbonate resin layer (A). The multilayer structure according to any one of (1) to (6). (8) The multilayer structure according to any one of (1) to (7), wherein a glass layer is provided on the side of the polycarbonate resin layer (A) through an adhesive resin layer. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 581724

經濟部智慧財產局員工消費合作社印製 五、發明說明（5) 【面之簡單說明 第1圖係本發明之多層結構物之一例的不思剖視圖。 圖中符號1示聚碳酸酯系樹脂層，符號2不粘著樹脂 層，符號3示玻璃層。 MMZ m佳實施形熊 以下詳細說明。 I ·構成本發明之多層結構物的成分 (1 )聚碳酸酯系樹脂層 作爲構成本發明之多層結構體的主要層之聚碳酸酯系 樹脂（P C )者無特殊限制，可列舉多種。通常，可用二 價酚與碳酸酯前驅物反應製成之芳族聚碳酸酯。易言之， 寸一 ί貝與碳酸酯則驅物，以溶液法或熔融法，亦即，二 價酚與光氣之反應，二價酚與碳酸二苯酯等之酯交換法反 應而製造者均可使用。 二價酚者可列舉多種，尤可舉2 ，2 —雙（4 一羥基 苯基）丙烷〔雙酚A〕，雙（4一羥基苯基）甲烷，1 ， 1 一雙（4 —羥基苯基）乙烷’ 2，2 —雙（4 一羥基一 3’5-二甲基苯基）丙烷，4，4’ 一二羥基聯苯，雙 (4 一羥基苯基）環烷烴，雙（4 · 一羥基苯基）氧化物， 雙（4 —羥基苯基）硫化物，雙（4 一羥基苯基）碩，雙 (4 一羥基苯基）亞硕，雙（4 一羥基苯基）醚，雙（4 -羥基苯基）甲酮等，或其鹵素取代物等。 特佳之二價酚爲雙（羥基苯基）烷烴系，尤其是以雙 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -8 - M --------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 581724 Α7 Β7 五、發明說明（6) 酚A爲主原料者。又，碳酸酯前驅物可係羰基鹵化物，碳 基酯，或鹵代甲酸酯等，具體言之·，可係光氣，二價酚之 二鹵代甲酸酯、碳酸二苯酯、碳酸二甲酯、碳酸二乙酯等 。此外，二價酚可列舉氫醌、間苯二酚、兒茶酚等。這些 二價酚可個別單獨使用，亦可二種以上混合使用。 又，聚碳酸酯樹脂亦可具分枝結構，分枝劑有1 ，1 ，1一參（4一羥基苯基）乙烷，α，α’ ，α” 一參（ 4 一羥基苯基）一 1 ，3，5 -三異丙基苯，均苯三酚， 偏苯三酸，靛紅雙（鄰甲酚）等。又，爲調節分子量，可 用酚，對三級丁基酚，對三級辛基酚，對異丙基苯基酚， 對癸基酚等。 又，用於本發明之聚碳酸酯系樹脂，亦可係具有聚碳 酸酯部及聚有機矽氧烷部之隨機共聚物，嵌段共聚物，或 合該共聚物之聚碳酸酯樹脂。又，亦可係在對酞酸等之二 官能羧酸、或其酯衍生物等之酯前驅物的存在下進行聚碳 酸酯之聚合而得之聚酯-聚碳酸酯樹脂。又，亦可用種種 聚碳酸酯樹脂之混合物。適用於本發明之聚碳酸酯系樹脂 ，從機械強度及成型性之觀點，其粘度平均分子量係以在 10，000至100，000爲合適，以在 15， 0〇0至40， 000爲佳，以在20， 000至 30,000爲特佳。 再者，聚碳酸酯樹脂板中末端羥基之量，係在聚合鏈 之重複單位的8莫耳％以下，以在6莫耳％以下爲佳，更 佳者爲在4莫耳％以下，從耐候性之觀點來說係爲尤佳。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -9- 卜—r-----裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 581724 A7Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (5) [Simplified description of the surface] Figure 1 is a sectional view of an example of the multilayer structure of the present invention. In the figure, reference numeral 1 indicates a polycarbonate resin layer, reference numeral 2 indicates a non-adhesive resin layer, and reference numeral 3 indicates a glass layer. The MMZ m best implementation is described in detail below. I. Components constituting the multilayer structure of the present invention (1) Polycarbonate-based resin layer The polycarbonate-based resin (P C) constituting the main layer of the multilayer structure of the present invention is not particularly limited, and various types can be listed. In general, aromatic polycarbonates can be made by reacting a divalent phenol with a carbonate precursor. In other words, Cinyi shellfish and carbonate are used to drive the product, which is produced by solution method or melting method, that is, the reaction of divalent phenol and phosgene, and the transesterification method of divalent phenol and diphenyl carbonate. Anyone can use it. Divalent phenols can be exemplified by various types, and in particular, 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxybenzene) ) 'Ethane' 2,2-bis (4-monohydroxy-3'5-dimethylphenyl) propane, 4,4'-dihydroxybiphenyl, bis (4-monohydroxyphenyl) cycloalkane, bis ( 4 · monohydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl), bis (4-hydroxyphenyl), bis (4-hydroxyphenyl) Ethers, bis (4-hydroxyphenyl) methanone, etc., or halogen substitutes thereof. The best divalent phenols are bis (hydroxyphenyl) alkanes, especially for the size of the double paper, which is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) -8-M -------- Order --------- line (please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 581724 Α7 Β7 V. Description of the invention (6) Phenol A as the main raw material . Further, the carbonate precursor may be a carbonyl halide, a carbon ester, or a haloformate, and specifically, may be phosgene, a dihaloformate of a divalent phenol, diphenyl carbonate, Dimethyl carbonate, diethyl carbonate, etc. Examples of the divalent phenol include hydroquinone, resorcinol, and catechol. These divalent phenols may be used alone or in combination of two or more. In addition, the polycarbonate resin may have a branching structure, and the branching agent is 1, 1, 1, 1- (4-hydroxyphenyl) ethane, α, α ', α "-1 (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, pyrogallol, trimellitic acid, isatin bis (o-cresol), etc. In addition, in order to adjust the molecular weight, phenol, p-tertiary butylphenol, p Tertiary octylphenol, p-isopropylphenylphenol, p-decylphenol, etc. The polycarbonate resin used in the present invention may also be a random resin having a polycarbonate portion and a polyorganosiloxane portion. Copolymers, block copolymers, or polycarbonate resins containing the copolymers, or may be polymerized in the presence of a bifunctional carboxylic acid such as terephthalic acid or an ester precursor thereof. Polyester-polycarbonate resin obtained by polymerizing carbonates. Mixtures of various polycarbonate resins can also be used. Polycarbonate resins suitable for the present invention have an average viscosity from the viewpoint of mechanical strength and moldability. The molecular weight is preferably between 10,000 and 100,000, more preferably between 15,000 and 40,000, and between 20,000 and 30,000. In addition, the amount of terminal hydroxyl groups in the polycarbonate resin plate is 8 mol% or less, preferably 6 mol% or less, and more preferably 4 mol% or less in repeating units of the polymer chain. From the viewpoint of weather resistance, the following are particularly preferred. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -9- Bu —r ----- packing ----- --- Order --------- (Please read the notes on the back before filling this page) 581724 A7

經濟部智慧財產局員工消費合作社印製 五、發明說明（7) 通常係於聚碳酸酯樹脂層配合以抗氧化劑等添加劑， 利用擠出成型成膜。於該成膜當中，亦可於成爲玻璃層之 側的一面上將聚碳酸酯一有機矽氧烷共聚物等之粘著樹脂 層共擠出成型成爲具粘著樹脂之多層膜。膜厚以1至1 〇 毫米爲佳，以2至6毫米左右爲更佳。又，於聚碳酸酯系 樹脂，亦可含光安定劑或容許範圍內之紫外線吸收劑。又 ’製造方法亦可採用射出成型、射出壓縮成型等。 (2 )玻璃層Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (7) Generally, the polycarbonate resin layer is compounded with additives such as antioxidants and formed into a film by extrusion. In this film formation, an adhesive resin layer such as a polycarbonate-organosiloxane copolymer or the like can also be co-extruded on the side that becomes the glass layer to form a multilayer film with an adhesive resin. The film thickness is preferably 1 to 10 mm, and more preferably about 2 to 6 mm. In addition, the polycarbonate resin may contain a light stabilizer or an ultraviolet absorber within an allowable range. Also, the manufacturing method may be injection molding, injection compression molding, or the like. (2) glass layer

用於本發明之玻璃層（C )之玻璃，僅須係無機玻璃 即無特殊限制，可用通常之窗用玻璃板。此類玻璃板，係 將矽砂、蘇打灰、石灰石、芒硝等主原料以一定比例調配 後’混合以適當比例之玻璃屑（碎玻璃），必要時添加副 原料氧化鋁、氧化鎂、氧化鈣、氧.化鐵、氧化鎳、氧化鈷 、氧化鈦、硒等，於窯槽中在1， 5 0 0至1， 6 0 0 °C 完全熔解，玻璃化成均勻之素玻璃。其次，從該素玻璃以 浮層法（於熔融金屬之表面成型）等製得平板玻璃，再經 二次加工即可製得磨光板玻璃。 (3 )粘著樹脂層 用於結合玻璃板及聚碳酸酯系樹脂膜之粘著樹脂’無 特殊限制，可用以往使用中之樹脂。粘著樹脂可列示乙烯 -醋酸乙烯酯共聚物，聚醋酸乙烯酯，乙烯-（甲基）丙 烯酸酯共聚物，聚氨酯，聚酯一聚氨酯共聚物，聚碳酸酯 L --------訂--------- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -10- 經濟部智慧財產局員工消費合作社印製 581724 A7 — B7 五、發明說明（8) -聚有機矽氧烷嵌段共聚物、隨機共聚物，聚乙烯醇縮丁 醛等。 於此，乙烯-醋酸乙烯酯共聚物，係以醋酸乙烯酯成 分在5至6 0質量％者爲佳。又，聚碳酸酯-有機矽氧烷 共聚物，其聚有機矽氧烷之含量係以2至7 0質量％爲佳 ，以2 0至6 0質量％爲更佳。亦即，以聚矽氧烷含量高 而質軟，成爲彈性樹脂者爲佳。聚矽氧烷之聚矽氧烷嵌段 單位，可任意係「矽-氧-矽」結合爲中介之主鏈結合者 ’或以「矽-碳」結合爲中介之主鏈結合物等。 這些聚碳酸酯-有機矽氧烷共聚物之製法，可係將聚 碳酸酯係聚物之二氯甲烷溶液，與末端爲酚之二甲基矽氧 烷等’或矽氧烷與碳結合之二羥基化合物在三乙胺觸媒之 存在下，必要時加入雙酚A之鹼性水溶液而反應之已知方 法。 這些粘著樹脂，可係馬來酐、富馬酸等不飽和羧酸， 或其衍生物作化學改質之樹脂，或使其含化學改質樹脂。 再者’爲提升與玻璃板之粘著性，亦可加入3 -氨基丙基 二甲基乙氧基矽烷，3 -氨基丙基甲基二乙氧基矽烷，乙 烯基三乙氧基矽烷等之耦合劑。 又’該粘著樹脂當係軟質（彈性率在1，〇 〇 〇百萬 帕以下）樹脂，於玻璃板與聚碳酸酯系樹脂間之緩衝粘著 之觀點而言爲較佳。作爲該軟質粘著樹脂者，有良好使用 於無機玻璃之貼合的粘著中間層之聚乙烯醇縮丁醛。但若 將該聚乙烯醇縮丁醛就此用作本發明之粘著樹脂層時，於 „----,--------------訂--------- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -TT- 經濟部智慧財產局員工消費合作社印製 581724 A7 __ B7 五、發明說明（9) 無機玻璃之貼合固無問題，但於聚碳酸酯系樹脂板之層合 時則會有問題。 此乃於聚乙烯醇縮丁醛膜中配合有可塑劑，該可塑劑 在層合後會往聚碳酸酯系樹脂遷移，而成爲聚碳酸酯系樹 脂板之白化、透明性下降之原因。此時，可以使用無聚乙 烯醇縮丁醛樹脂層與聚碳酸酯系樹脂層間的可塑劑遷移之 虞的，例如，聚碳酸酯-聚有機矽氧烷共聚物，聚氨酯等 之其它粘著樹脂。亦即，將粘著樹脂層製成二層以上。 I I ·本發明之多層結構物 以下，對本發明之多層結構物，基於其製法逐步說明 。第1圖係本發明之多層結構物之示意剖視圖。第1圖中 ’ 1係聚碳酸酯系樹脂板，2係粘著樹脂層，3係玻璃層 。本發明之多層結構物，係如第1圖（1 )所示，基本上 係由聚碳酸酯系樹脂層（A ) 1、玻璃層（C ) 3及粘著 樹脂層（B ) 2所構成。而其中之玻璃層（C )、粘著樹 脂層（B )之至少其一，較佳者爲兩者均含有紫外線吸收 成分（劑），此爲本發明的特徵之所在。 首先’玻璃板係，例如，以矽砂爲主成分，將蘇打灰 、石灰石、碳、芒硝熔融，於該熔融物添加含有作爲紫外 線吸收成分之各種成分的玻璃料，通常係著色玻璃料，而 製造。具體言之，可以蘇打石灰氧化矽系玻璃爲例。於此 ’作爲紫外線吸收成分者，僅須係於形成玻璃板後可減降 紫外線之透過者而無特殊限制，可以含鈽者爲例。鈽成分 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -12- ，卜 -------------訂--------- (請先閱讀背面之注意事項再填寫本頁) 581724 A7 B7 經 濟 部 智 慧 財 產 局 員 工 消 費 合 作 社 印 製 苯并***系者可舉2 -（3 -三級丁基一 5一甲基一 2 -羥基苯基）一 5 -氯化苯并***，2一3 ，5 —二三 級丁基—2 —羥基苯基）一 5 -氯化苯并***，2 — ( 5 —甲基一 2 —經基苯基）苯并三u坐，2 — (3 ，5 — 一二 級丁基一 2 -羥基苯基）苯并三d坐，The glass used in the glass layer (C) of the present invention is not limited as long as it is an inorganic glass, and ordinary glass plates for windows can be used. This type of glass plate is prepared by mixing the main raw materials such as silica sand, soda ash, limestone, and thenardite at a certain ratio, and mixing the glass chips (broken glass) with an appropriate ratio, and adding auxiliary materials such as alumina, magnesium oxide, and calcium oxide if necessary Oxygen, iron, nickel oxide, cobalt oxide, titanium oxide, selenium, etc. are completely melted in the kiln at 1,500 to 1,600 ° C, and the glass is converted into a homogeneous plain glass. Next, flat glass is prepared from the plain glass by a floating layer method (molded on the surface of a molten metal), etc., and then polished to obtain a polished plate glass. (3) Adhesive resin layer There are no particular restrictions on the adhesive resin 'used to bond glass plates and polycarbonate resin films, and resins used in the past can be used. Adhesive resins can be listed as ethylene-vinyl acetate copolymer, polyvinyl acetate, ethylene- (meth) acrylate copolymer, polyurethane, polyester-polyurethane copolymer, polycarbonate L ------- -Order --------- (Please read the notes on the back before filling in this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -10- Intellectual Property of the Ministry of Economic Affairs Printed by the Bureau's Consumer Cooperatives 581724 A7 — B7 V. Description of the Invention (8)-Polyorganosiloxane block copolymer, random copolymer, polyvinyl butyral, etc. Here, the ethylene-vinyl acetate copolymer is preferably one having a vinyl acetate content of 5 to 60% by mass. The content of the polyorganosiloxane in the polycarbonate-organosiloxane copolymer is preferably 2 to 70% by mass, and more preferably 20 to 60% by mass. That is, those having a high polysiloxane content and being soft in quality are preferred as the elastic resin. The polysiloxane block unit of polysiloxane can be arbitrarily a "silicon-oxygen-silicon" bond as an intermediary main chain bonder 'or a "silicon-carbon" bond as an intermediary main chain bonder. These polycarbonate-organosiloxane copolymers may be prepared by combining a dichloromethane solution of a polycarbonate-based polymer with dimethylsiloxane, etc. at the end of phenol, or a combination of silicone and carbon. A known method of reacting a dihydroxy compound in the presence of a triethylamine catalyst by adding an alkaline aqueous solution of bisphenol A as necessary. These adhesive resins may be unsaturated carboxylic acids such as maleic anhydride, fumaric acid, or the like, or their derivatives may be chemically modified resins, or they may contain chemically modified resins. Furthermore, in order to improve the adhesion to the glass plate, 3-aminopropyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, vinyltriethoxysilane, etc. can also be added. Its couplant. The adhesive resin is preferably a soft (elasticity of 1,000 MPa or less) resin, and is preferable from the viewpoint of buffer adhesion between a glass plate and a polycarbonate resin. As such a soft adhesive resin, there is polyvinyl butyral which is an adhesive intermediate layer which is well used for bonding of inorganic glass. However, if the polyvinyl butyral is used as the adhesive resin layer of the present invention, the order is made in --------, -------------- --- (Please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -TT- Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 581724 A7 __ B7 V. Description of the invention (9) There is no problem in the bonding and fixing of inorganic glass, but there will be problems in the lamination of polycarbonate resin plates. This is a plasticizer mixed with polyvinyl butyral film. The plasticizer will migrate to polycarbonate resin after lamination, which will cause the whitening and transparency of the polycarbonate resin board to decrease. At this time, a polyvinyl butyral resin-free layer and a polymer can be used. For the migration of plasticizers between carbonate resin layers, for example, other adhesive resins such as polycarbonate-polyorganosiloxane copolymers, polyurethanes, etc. That is, the adhesive resin layer is made into two or more layers. II · Multilayer structure of the present invention Hereinafter, the multilayer structure of the present invention will be described step by step based on its manufacturing method. Figure 1 The schematic cross-sectional view of the multilayer structure of the present invention. In the first figure, the '1 series polycarbonate resin plate, the 2 series adhesive resin layer, and the 3 series glass layer. The multilayer structure of the present invention is shown in FIG. 1 (1 As shown in Figure), it basically consists of a polycarbonate resin layer (A) 1, a glass layer (C) 3, and an adhesive resin layer (B) 2. Among them, the glass layer (C) and the adhesive resin layer (B) At least one, and preferably, both of them contain ultraviolet absorbing components (agents), which is a feature of the present invention. First, the glass plate system, for example, uses silica sand as the main component, and soda ash , Limestone, carbon, and thenardite are melted, and a glass frit containing various components as an ultraviolet absorbing component is added to the melt, and is usually a colored glass frit. Specifically, soda lime silica glass can be used as an example. Here 'As a UV absorbing component, it is only necessary to be a person who can reduce the transmission of UV rays after forming a glass plate without special restrictions, and can include 钸 as an example. 钸 Composition This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) -12- Bu ------------- Order --------- (Please read the notes on the back before filling out this page) 581724 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs For benzotriazoles, 2- (3-tert-butyl-5, methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2-3,5-tert-butyl —2 —Hydroxyphenyl) 5-chlorobenzotriazole, 2- (5-methyl-1—2-phenylphenyl) benzotriazole, 2- (3,5—primary and secondary butyl A 2-hydroxyphenyl) benzotrid,

五、發明說明（W 係以.於玻璃原料中添加1至2 ，紫外線吸收成分亦可係鈦成 吸收紫外線者。 含紫外線吸收成分之熔融 、下拉法、上拉法等製成玻璃 光玻璃板。本申請案之多層結 玻璃所成，而於汽車用之窗玻 亦可作和緩之曲面加工。玻璃 作適當決定，於本發明之多層 量化之目的，不宜過厚，以〇 〇· 7至3毫米左右爲更佳。 其次，粘著樹脂可以上述 之紫外線吸收成分（劑）無特 ***系，三嗪系，苯甲酸酯系 用苯并***系、三嗪系爲佳。 質量％之氧化鈽而製造。又 分、著色成分等之複合而能 玻璃，可藉浮層法、壓鑄法 板。又必要時可予硏磨成拋 構物’標準者爲平板狀之板 璃、屋頂材料等之情況下， 板之厚度可依用途、大小等 結構物，因有無機玻璃的輕 • 5至4毫米爲佳，以 樹脂爲之，用於該粘著樹脂 殊限制。具體言之，有苯并 ，二苯甲酮系等，其中以使 一（2 —羥基—5 三級辛基苯基）苯并***’ （2_羥基_3 ，5 — 三級戊基苯基）苯并***’2, 2，一亞甲基雙（4 一 1 ，1 ，3 ，3 —四甲基丁基）—6 — 〔 （ 2 H —苯并 唑一 2 —基）苯基〕），2, 2，一亞甲基雙〔6_〔 ^紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱 ---r---.-------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 581724 Α7 __ Β7 五、發明說明（11) (2 Ή、苯并***一 2一基）苯基〕〕等。 三嗪系者可舉2，4一雙（2， 一羥基苯基）一6— 芳基一 1 ，3，5 -三嗪型（日本專利特開平8 — 239368號公報）等。 又’苯甲酸酯系者可擧2 ，4 一二三級丁基苯基一 3 ’ 5 -二三級丁基一 4 一羥基苯甲酸酯，十六基—3 ，5 一二三級丁基一 4 一羥基苯甲酸酯等。 二苯甲酮系者可舉2 ，4 一二羥基二苯甲酮，2 —羥 基一 4 一甲氧基二苯甲酮，5，5·’ 一亞甲基雙（2 —羥 基一 4 -甲氧基二苯甲酮）等。這些紫外線吸收劑於必要 時亦可使用多數個。 這些紫外線吸收劑之配合比率，以占粘著樹脂成分之 〇·01至3質量％爲佳，以〇·05至2質量％左右爲 更佳。紫外線吸收劑之配合量不足0 · 0 1質量％時，耐 候性不充分，又，超過3質量％時無法期待其效果之相對 提升。又，本發明係異於將紫外線吸收劑添加於聚碳酸酯 系樹脂，粘著樹脂比較上成型溫度低，可與耐熱性、升華 性等無關而從寬廣範圍加以選擇，是其特徵。而且，由於 粘著樹脂層厚度低，即使添加量較高，亦有不致提高成本 的附加效果。 又，於粘著樹脂層，必要時亦可於紫外線吸收劑配合 以光安定劑、著色劑等。在此，光安定劑者，有受阻胺系 光安定劑，苯甲酸苯酯系光安定劑等。該受阻胺系或苯甲 酸苯酯系光安定劑之具體例可舉雙（2，2，6 ，6 -四 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） L --------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 581724V. Description of the invention (W is based on the addition of 1 to 2 to the glass raw material. The ultraviolet absorbing component can also be titanium to absorb ultraviolet light. The glass containing light absorbing component is melted, pulled down, and pulled up to make a glass light glass plate. .The multilayer junction glass of this application is used, and the window glass for automobile can also be used for gentle curved surface processing. The glass is appropriately determined. For the purpose of the multilayer quantification of the present invention, it should not be too thick. About 3 millimeters is more preferred. Second, the adhesive resin can have the above-mentioned ultraviolet absorbing components (agents) without triazole, triazine, and benzotriazole, and triazine. It can be produced by dysprosium oxide. It can be divided into different colors and other components to make glass. It can be produced by floating layer method or die-casting method. It can also be honed into a paraboloid if necessary. In the case of roofing materials, etc., the thickness of the board can be based on the structure of the application and size. It is preferably 5 to 4 millimeters in weight due to the inorganic glass. Resin is the only material used for this adhesive resin. Specifically, With benzo and benzophenone Etc. in which mono (2-hydroxy-5 tertiary octylphenyl) benzotriazole '(2-hydroxy_3,5-tertiary pentylphenyl) benzotriazole'2, 2,1 Methylenebis (4--1,1,3,3-tetramethylbutyl) -6 [[(2H-benzoxazol-2-yl) phenyl]), 2,2,1-methylene Double [6_ 〔^ paper size applies to China National Standard (CNS) A4 specifications (210 X 297 public love --- r ---.--------- order ---------- --- line (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 581724 Α_ _7 Β7 V. Description of the invention (11) (2 pyrene, benzotriazole-1 2-1 ) Phenyl]] etc. For triazines, 2,4-bis (2,1-hydroxyphenyl) -6-aryl-1,3,5-triazine type (Japanese Patent Laid-Open No. 8-239368) Gazette), etc. For those who are benzoate, 2,4-tert-butylphenyl-3'5-tert-tert-butyl-4 4-hydroxybenzoate, hexadecyl-3, 5 1,2 tertiary butyl-4 monohydroxybenzoate, etc. For benzophenone series, 2,4-dihydroxydiphenyl Ketones, 2-hydroxy-4 4-methoxybenzophenone, 5,5'-methylenebis (2-hydroxy-4 -methoxybenzophenone), etc. These UV absorbers are used when necessary A plurality of them can also be used. The blending ratio of these ultraviolet absorbers is preferably from 0.01 to 3% by mass of the adhesive resin component, and more preferably from about 0.05 to 2% by mass. The blending amount of the ultraviolet absorber If it is less than 0.1% by mass, the weather resistance will be insufficient, and if it exceeds 3% by mass, the relative improvement of the effect cannot be expected. In addition, the present invention is different from adding a UV absorber to a polycarbonate resin and adhering it. The resin has a relatively low molding temperature, and can be selected from a wide range irrespective of heat resistance, sublimation properties, and the like. In addition, since the thickness of the adhesive resin layer is low, even if the amount of addition is high, there is an additional effect that the cost is not increased. In addition, a light stabilizer, a coloring agent, etc. may be blended with the ultraviolet absorber to the adhesive resin layer if necessary. Here, the light stabilizers include hindered amine light stabilizers, phenyl benzoate light stabilizers, and the like. Specific examples of the hindered amine-based or phenylbenzoate-based light stabilizers include double (2, 2, 6, 6-four paper sizes applicable to China National Standard (CNS) A4 (210 X 297 mm) L- ------- Order --------- Line (Please read the precautions on the back before filling this page) 581724

經濟部智慧財產局員工消費合作社印製 五、發明說明（θ 甲基.-4 一哌啶基）癸二酸酯，琥珀酸與ν -（ 2 -羥基 丙基）一2 ，2 ，6 ，6 —四甲基一 4 一羥基暖啶之縮合 物，肆（2 ，2 ，6 ，6 —四甲基一4 — njd定基），1 ， 2，3’4一 丁烷四羧酸酯，N，N,—雙（2，2，6 ’ 6_四甲基一4 一哌啶基）六亞甲基二胺與1 ，2 -二 溴化乙院之聚縮合物，雙（2，2 ，6 ，6 —四甲基哌啶 基）己二酸酯，雙（2 ，2 ，6 ，. 6 —四甲基哌啶基）富 馬酸酯，聚〔〔6 —（1 ，1 ，3 ，3 —四甲基丁基）醯 亞胺基一 1，3，5 —三嗪一 2，4 一 二基〕〔（2,2 ’ 6 ’ 6 —四甲基一 4 一哌啶基）醯亞胺基〕六亞甲基〔 (2 ’ 2 ’ 6 ，6 —四甲基一 4 一哌π定基）醒亞胺〕〕， 含4 —羥基一 2 ，2 ，Θ ，6 —四甲基一 1 —哌啶乙醇之 二甲基琥珀酸酯聚合物，2，4 一二三級丁基苯基一 3， 5 -二三級丁基一 4 一羥基苯甲酸酯，4 一辛基苯基一 3 ，5 -二三級丁基一 4 —羥基苯甲酸酯，正十六基一 3， 5 -二三級丁基- 4 -羥基苯甲酸酯等。這些光安定劑之 配合量亦依上述紫外線吸收劑予以配合。 本發明所用之粘著樹脂層，係於乙係-醋酸乙烯酯共 聚物，聚氨酯，聚醋酸乙烯酯，乙烯-（甲基）丙烯酸酯 共聚物，聚酯-聚氨酯共聚物，聚碳酸酯-聚有機矽氧烷 共聚物，聚乙烯醇縮丁醛等，配合以必要量之紫外線吸收 劑，及所欲之添加劑以擠出成型、碾壓成型、吹膜成型 等薄膜或板片成型方法成型爲膜狀。該粘著樹脂膜之厚度 ，係以0 · 1至2毫米爲佳，以〇 · 2至0 · 8毫米左右 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -15- IT I -I I I--·1111111 ^ -----I--- (請先閱讀背面之注意事項再填寫本頁) 581724 經濟部智慧財產局員工消費合作社印製 A7 __B7_ 五、發明說明（θ 爲佳.。 本發明之多層結構物，一般係於具目的多層結構物之 形狀的玻璃板及聚碳酸酯系樹脂板之間中介以粘著樹脂膜 ’***橡膠袋或真空裝置，充分真空脫氣後，於脫氣狀態 下就此移往加熱裝置，藉由加熱至中間層粘著樹脂軟化， 達粘著溫度而製造。又，粘著樹脂層可如第1圖（2 )所 示，係使上述之粘著樹脂層以二層爲之。 又’於聚碳酸酯系樹脂層之表面，亦可以已知之矽酮 系樹脂等爲提升硬度、耐擦傷性等之表面特性，作被覆處 理。亦即，一般使用時，相對於外面，內面之性能稍低亦 可充分耐用。 又，本發明之多層結構物，基本上係由聚碳酸酯系樹 脂層（A )，粘著樹脂層（B )，玻璃層（C )所構成。 但是，爲求多層結構物之性能安定、提升，有時係以構成 爲如第1圖（3 )所示，於聚碳酸酯系樹脂層（A ) 1側 將粘著樹脂層（B ’ ) 2 2 - 1. 2 2 — 2，玻璃層（ C ’ ）3 3 —體化，以聚碳酸酯系樹脂層爲中心而對稱爲 佳。此時，亦可有各層厚度之適度變更。又，粘著樹脂層 (B ’ ）及玻璃層（C ’ ）在本發明係必要成分，紫外線 吸收成分則否。此乃由於本發明之多層結構物，幾乎均使 用於面向太陽之情況，聚碳酸酯系樹脂層之劣化通常僅發 生於單面。 以下利用實施例以及比較例更具體說明本發明，但本 發明並非以之作爲任何限制。 ---r-----------------訂- ------- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -16- 經濟部智慧財產局員工消費合作社印製 581724 A7 __B7 五、發明說明（14 〔實施例1至7，比較例1至6，參考例1，2〕 爲形成表1至表3所示之層結構、層厚度，用下述各 原料聚合、真空脫氣後，隨粘著層於1 〇 〇至1 8 0°C之 範圍設定貼合溫度條件，維持加熱後，緩緩冷卻得多層結 構物。又，比較例5係如表2之腳注所示，將厚度加以變 更。 所得之多層結構物之耐候性，係以Sun Shine Weather Meter 〔測試條件：6 3 t：，降雨條件4 8 0小時〕作耐候 測試，測試前後之Υ I係依j I S Κ 7 1 0 5作測定 。測定結果與多層結構物之面密度一倂，示於表1、表2 及表3。 ①聚碳酸醋系樹脂（A )板 •PC1:粘度平均分子量22， 000之雙酚A聚碳酸 酯樹脂’末端羥基量，相對於聚合鏈之重複單位，爲4莫 耳％。 •PC2:粘度平均分子量22, 000之雙酚A聚碳酸 酯樹脂’末端羥基量，相對於聚合鏈之重複單位，爲6莫 耳％。 •PC3:粘度平均分子量22，000之雙酚A聚碳酸 酯樹脂’末端羥基量，相對於聚合'鏈之重複單位，爲1 〇 莫耳％。 • PC4 :粘度平均分子量22，000之雙酚A聚碳酸 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -17- ---^---^--------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 581724 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（1今 酯樹脂，末端羥基量’相對於聚合鏈之重複單位，爲1 4 莫耳％。 又，末端羥基之量，係依特開平1 _ 7 4 2 3 1號公 報所記載之方法加以調整，用1 Η 一 n M R，基於末端構造 (對三級丁基苯基）1 · 3 p p m及基於羥基末端的 6 · 7 p p m之波峰面積加以算出。 ② 玻璃板 將氧化鈽、氧化鈦各以1 · 5質量％添加於基本的蘇 打石灰氧化矽系玻璃原料，得紫外線吸收性玻璃板（玻璃 U )，以及無紫外線吸收性之玻璃板（玻璃）。 ③ 粘著樹脂 (1 ) EVA :醋酸乙烯酯含量4 0質量％之乙烯醋 酸乙烯酯共聚物 (2) EVA1:於醋酸乙烯酯含量40質量％之乙 烯醋酸乙烯酯共聚物含1 · 〇質量％之苯并***系紫外線 吸收劑：Tinuvin 329 〔 2 - 2， 一羥基一 5 ’ 一三級辛基 酚〕苯并***〕（汽巴特用化學品公司製） (3) EVA2:於醋酸乙烯酯含量40質量％之乙 烯醋酸乙烯酯共聚物含1 · 〇質量％之三嗪系紫外線吸收 劑：Tlnuvin 1 5 77 (汽巴特用化學品公司製） (4 ) P V B ··聚乙烯醇縮丁醛 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------^--------- (請先閱讀背面之注意事項再填寫本頁) 581724 A7 B7 五、發明說明（， VA3Dds· sd·lulcis·zvs· 0 0 9“ °6Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (θ methyl.-4 monopiperidinyl) sebacate, succinic acid and ν-(2-hydroxypropyl) -2, 2, 6, Condensate of 6-tetramethyl-1, 4-hydroxypiperidine, (2, 2, 6, 6, 6-tetramethyl-1, 4-njd amidinyl), 1,2,3'4-butanetetracarboxylic acid ester, Polycondensation product of N, N, —bis (2,2,6'6-tetramethyl-4 piperidinyl) hexamethylenediamine and 1,2-dibromoethyl bromide, bis (2, 2,6,6-tetramethylpiperidinyl) adipate, bis (2,2,6, .6-tetramethylpiperidinyl) fumarate, poly [[6 — (1,1 , 3,3-tetramethylbutyl) fluorenimino-1,3,5-triazine-2,4-diyl] [(2,2 '6' 6 -tetramethyl-4 4-piperidine Amidinyl) imino] hexamethylene [(2'2'6,6-tetramethyl-1,4-piperidinyl) imine]], containing 4-hydroxy-2,2,2, Θ, 6- Tetramethyl-1, piperidine ethanol dimethyl succinate polymer, 2,4,2 tertiary butylphenyl-3,5-di 4-butyl-4-hydroxybenzoate, 4-octylphenyl-3,5-di-tertiary-butyl-4-hydroxybenzoate, n-hexadecyl-3,5-tertiary-butyl -4-hydroxybenzoate and the like. The blending amount of these light stabilizers is also blended in accordance with the above-mentioned ultraviolet absorber. The adhesive resin layer used in the present invention is based on ethylene-vinyl acetate copolymer, polyurethane, polyvinyl acetate, ethylene- (meth) acrylate copolymer, polyester-polyurethane copolymer, polycarbonate-poly Organosiloxane copolymer, polyvinyl butyral, etc., combined with the necessary amount of ultraviolet absorber, and the desired additives are formed by extrusion molding, roll molding, blown film molding and other film or sheet molding methods Membrane. The thickness of the adhesive resin film is preferably from 0. 1 to 2 mm, and from about 0.2 to 0. 8 mm. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -15 -IT I -II I-- · 1111111 ^ ----- I --- (Please read the notes on the back before filling this page) 581724 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 __B7_ V. Description of the invention (Θ is better.) The multilayer structure of the present invention is generally interposed between a glass plate and a polycarbonate resin plate having the shape of the multilayer structure of interest, and is inserted into a rubber bag or a vacuum device through an adhesive resin film. After vacuum degassing, it is moved to the heating device in the degassed state, and is manufactured by heating until the intermediate layer adhesive resin is softened to the adhesion temperature. The adhesive resin layer can be shown in Figure 1 (2) The above-mentioned adhesive resin layer is made of two layers. On the surface of the polycarbonate-based resin layer, a silicone resin can also be known to improve the surface properties such as hardness and scratch resistance. Handling, that is, the nature of the inner side relative to the outer side in general use It is also slightly durable enough to be sufficiently durable. In addition, the multilayer structure of the present invention is basically composed of a polycarbonate resin layer (A), an adhesive resin layer (B), and a glass layer (C). The stability and improvement of the performance of the multilayer structure may be configured as shown in Fig. 1 (3), and the resin layer (B ') 2 2-1 will be adhered to the polycarbonate resin layer (A) 1 side. 2 2-2, glass layer (C ') 3 3 is integrated, and it is better to focus on the polycarbonate resin layer. At this time, the thickness of each layer can be changed appropriately. Also, the adhesive resin layer (B ') and glass layer (C') are essential components in the present invention, but not ultraviolet absorbing components. This is because the multilayer structure of the present invention is almost always used when facing the sun. Degradation usually occurs only on one side. The following examples and comparative examples are used to describe the present invention in more detail, but the present invention is not intended to limit it. --- r --------------- --Order- ------- (Please read the notes on the back before filling out this page) This paper size applies Chinese national standards CNS) A4 specifications (210 X 297 mm) -16- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 581724 A7 __B7 V. Description of the invention (14 [Examples 1 to 7, Comparative Examples 1 to 6, Reference Example 1, 2] In order to form the layer structures and layer thicknesses shown in Tables 1 to 3, the following materials are used for polymerization and vacuum degassing, and then the bonding temperature is set in the range of 1000 to 180 ° C with the adhesive layer. The conditions are such that after heating, the multi-layer structure is slowly cooled. In Comparative Example 5, the thickness is changed as shown in the footnote of Table 2. The weather resistance of the obtained multi-layer structure is based on the Sun Shine Weather Meter [test conditions: 6 3 t :, rain conditions 480 hours] for the weather resistance test, and before and after the test I is based on j IS κ 7 1 0 5 Determination. The measurement results are shown in Table 1, Table 2 and Table 3 together with the areal density of the multilayer structure. ①Polycarbonate resin (A) board • PC1: Bisphenol A polycarbonate resin with a viscosity average molecular weight of 22,000. The amount of terminal hydroxyl groups is 4 mol% relative to the repeating unit of the polymer chain. • PC2: Bisphenol A polycarbonate resin 'terminal hydroxyl group with a viscosity average molecular weight of 22,000 is 6 mol% relative to the repeating unit of the polymer chain. • PC3: Bisphenol A polycarbonate resin 'terminal hydroxyl content with a viscosity average molecular weight of 22,000 is 10 mole% relative to the repeating unit of the polymerized chain. • PC4: Bisphenol A polycarbonate with a viscosity average molecular weight of 22,000. This paper is sized for China National Standard (CNS) A4 (210 X 297 mm) -17- --- ^ --- ^ ----- --------- Order --------- line (please read the notes on the back before filling out this page) 581724 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (1) For ester resins, the amount of terminal hydroxyl groups is 14% by mole relative to the repeating unit of the polymer chain. The amount of terminal hydroxyl groups is determined by the method described in Japanese Patent Application Laid-Open No. 1 _ 7 4 2 3 For the adjustment, 1 Η 1 n MR was used to calculate the peak area based on the terminal structure (p-tert-butylphenyl) of 1 · 3 ppm and the hydroxyl terminal based on the peak area of 6 · 7 ppm. ② The glass plate was made of thorium oxide and titanium oxide. Adding 1.5% by mass to basic soda-lime-silica-based glass raw materials, ultraviolet-absorbing glass plates (glass U) and non-ultraviolet-absorbing glass plates (glass) are obtained. ③ Adhesive resin (1) EVA: Ethylene vinyl acetate copolymer with 40% by mass of vinyl acetate (2) EVA1: 40% by mass of vinyl acetate % Ethylene vinyl acetate copolymer contains 1.0% by mass of a benzotriazole-based ultraviolet absorber: Tinuvin 329 [2-2, monohydroxy-5 '-tertiary octylphenol] benzotriazole] (steam (3) EVA2: ethylene vinyl acetate copolymer with a vinyl acetate content of 40% by mass and a triazine-based ultraviolet absorber containing 1.0% by mass: Tlnuvin 1 5 77 (Chembat Chemical (4) PVB ·· Polyvinyl butyral The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -------- ^ ------ --- (Please read the notes on the back before filling this page) 581724 A7 B7 V. Description of the invention (， VA3Dds · sd · lulcis · zvs · 0 0 9 “° 6

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本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱) -TST 581724 A7 B7 五、發明說明（17) 經濟部智慧財產局員工消費合作社印製 一破 鎰 ΛΛ PQ > 1 1 1 1 〇〇 寸 〇\ 〇 r—< Csl τ—Η 〇〇 < Η 寸 If 海 < > ω 1 寸 u 1 < > m If 趦 〇〇 寸 〇〇 r- csi τ—( (N1 σ\ cn U CU cn 1 寸 U Ph 1 1 1 寸 cn m un cn r—Η \〇 〇〇 CN1 ±Λ 經 < > ω u CU 00 寸 u Ph u Oh < > ω If 澎 ο 〇\ ” < r 1 < CNl f —Η 4J jf 澎 OQ > 〇< u Cu 00 cn U Dh U Qh cn PQ > IS 澎 in ο 〇\ i i v 1 Η CO r^· 暖 W % < 寸 ο 寸 o CO 寸 o 寸 o Η 来 /^v 米 vt 陌 Η-Η 担 m ¥n , fi , If Ε- t# , _ 逝 U cx K , _ 卜 _ _ 瑯 _ 鹄 W 侧 R _ 馨 采_00· 0 = 3 Λ d ,米wcxlH 鹄澎：LOf^鎰丑* --------------------訂---------*5^ ·- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -ΖΌ - 581724 A# 17 五、發明說明（1等 表3， 參考例1 參考例2 比較例6 層 材料 厚度 m 毫米 權 玻璃婀 1 玻璃U 玻蕩U 玻璃 接著舯甲 0,4 EVA1 EVA1 PVB 接»層乙 0,4 一 SPC SPC PC層 2 PC3 PC3 PC1 接著層丙 0,4 一 SPC SPC 接著層丁 0,4 EVA PVB 玻璃層 1 — ' 玻璃 玻璃 多層之厚度（毫米） 3,4 5,6 5,6 面密度（公斤/平方米） 5,3 9,0 9,0 耐候性評估（YI) 初期 1-0 1,2 1,2 耐候試驗後 6.0 5,0 7,3 (請先闐讀背面之*ϋ項再填寫本頁》 經濟部%1财產曷員X清費合作社印製 從表1、表2之結果可知，本發明之多屢結權物，義 之比較例5的贴合玻_，其面密度小而輕•又，耐候性亦 明顯優於比較例·再者，從參考例1、2以及比較例6可 知，聚碳__樹脂的末端羥基之量，以相對於聚合鍵之重 複單位在8莫耳％以下者，其耐候性佳。 產業上之利用锸域 適 度 尺 張 紙 本 10 (21 格 Μ Μ 咖 581724 A7 B7 五、發明說明（19) 本發明之多層結構物（層合體），由於外面係以無機 玻璃形成，具有與無機玻璃相當之硬度、耐擦傷性；且因 聚碳酸酯系樹脂而質輕又兼具耐衝擊性，故有優異性能。 並且，於聚碳酸酯系樹脂實質上無紫外線吸收劑之配合， 可得聚碳酸酯系樹脂板的變黃之減少與透明性之確保，而 爲耐候性顯著良好之多層結構物。因而，結合聚碳酸酯系 樹脂之耐衝擊性，可貢獻於汽車用車門玻璃、天窗玻璃等 之對汽車的輕量化。又，亦可擴展用途至於建築物、學校 等之窗戶^商店之樹窗、屋頂材料等。 ---?-----------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 public love) -TST 581724 A7 B7 V. Description of the invention (17) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 镒 ΛΛ PQ > 1 1 1 1 〇〇inch 0 \ 〇r— < Csl τ—Η 〇〇 < Ηinch If sea < > ω 1 inch u 1 < > m If 趦 〇〇inch〇〇r- csi τ— ((N1 σ \ cn U CU cn 1 inch U Ph 1 1 1 inch cn m un cn r—Η \ 〇〇〇CN1 ± Λ Warp < > ω u CU 00 inch u Ph u Oh < > ω If Pengο 〇 \ ”< r 1 < CNl f —Η 4J jf Peng OQ > 〇 < u Cu 00 cn U Dh U Qh cn PQ > IS Pengin ο 〇 \ iiv 1 Η CO r ^ · Warm W% < inch ο inch o CO inch o inch o Η 来 / ^ v 米 vt MoΗ-t Ηm ¥ n, fi, If Ε- t #, _ Pass U cx K, _ 卜 _ _ 朗 _鹄 W side R _ 馨 采 _00 · 0 = 3 Λ d, mwcxlH 鹄 peng: LOf ^ 镒 ugly * -------------------- Order --- ------ * 5 ^ ·-(Please read the precautions on the back before filling out this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -ZΌ-581724 A # 17 V. Description of the invention (Class 1 Table 3, Reference Example 1 Reference Example 2 Comparative Example 6 Layer Material Thickness mm Millimeter Weight Glass 婀 1 Glass U Glass D U Glass and then armor 0,4 EVA1 EVA1 PVB connection »layer B 0,4-SPC SPC PC layer 2 PC3 PC3 PC1 followed by layer C 0,4-SPC SPC followed by layer 0,4 EVA PVB glass layer 1 — 'thickness of glass glass multilayer ( Mm) 3,4 5,6 5,6 Area density (kg / m2) 5,3 9,0 9,0 Weatherability evaluation (YI) Initial 1-0 1,2 1,2 After weathering test 6.0 5, 0 7,3 (Please read the * on the back before filling out this page. ”Printed by Table 1 and Table 2 from the results of Table 1 and Table 2 of the Ministry of Economic Affairs% 1 Property Agent X Clearance Cooperatives. The laminated glass of Comparative Example 5 has a small surface density and light weight. Also, the weather resistance is significantly better than that of Comparative Example. Furthermore, it can be seen from Reference Examples 1, 2 and Comparative Example 6 that polycarbonate __ resin The amount of the terminal hydroxyl group is 8 mol% or less relative to the repeating unit of the polymer bond, and the weather resistance is good. Industrial use: Moderate ruled paper 10 (21 grid Μ Ｍ 581724 A7 B7 V. Description of the invention (19) Because the multilayer structure (layered body) of the present invention is formed of inorganic glass, it has the same properties as inorganic glass. Glass has comparable hardness and abrasion resistance, and it is excellent in performance due to its light weight and impact resistance due to the polycarbonate resin. In addition, the polycarbonate resin has virtually no UV absorber and can be obtained. Polycarbonate resin sheet reduces yellowing and ensures transparency, and is a multilayer structure with significantly better weather resistance. Therefore, combined with the polycarbonate resin's impact resistance, it can contribute to automotive door glass and sunroof Lightweight of glass and other cars. It can also be extended to windows of buildings, schools, etc. ^ shop windows, roof materials, etc. ---? ------------- ---- Order --------- line (please read the notes on the back before filling this page) Printed on the paper by the Intellectual Property Bureau of the Ministry of Economic Affairs, Employees' Cooperatives, this paper applies the Chinese National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

581724581724 夂、申請專利範圍 第89124956號專利申請案 中文申請專利範圍修正本 民國93年1月14日修正 1 · 一種多層結構物，其特徵爲由聚碳酸酯系樹脂層 (A )、粘著樹脂層（b )、玻璃層（C )所成，其玻璃 層或粘著樹脂層之至少一層含有紫外線吸收成分。 2 ·如申請專利範圍第χ項之多層結構物，其中玻璃 層（A )以及粘著樹脂層.（b )兩者皆含紫外線吸收成分 3 .如申請專利範圍第χ項或第2項之多層結構物， 其中玻璃層（A )係蘇打石灰氧化矽系玻璃，而玻璃所含 之紫外線吸收成分係姉。 4 ·如申請專利範圍第1項之多層結構物，其中含於 粘著樹脂層（B )之紫外線吸收成分係苯并***系化合物 及/或三嗪系化合物。 經濟部智慧財產局員工消費合作社印製 5 ·如申請專利範圍第1項之多層結構物，其中粘著. 樹脂層（B )係選自乙烯-醋酸乙烯酯共聚物，聚醋酸乙 烯酯，乙烯一（甲基）丙烯酸酯共聚物，聚氨酯，聚酯-聚氨酯共聚物，聚碳酸酯-有機矽氧烷共聚物，聚乙烯醇 縮丁醛樹脂之至少一層所成。 6 .如申請專利範圍第1項之多層結構物，其中用於 聚碳酸酯樹脂層（A )之聚碳酸酯樹脂的末端羥基量，相 對於聚合鏈之重複單位係在8莫耳％以下。 本紙張尺度適用中國國家標準（CNS ) A4規格（2】0Χ297公釐） 581724 ABCD 六、申請專利範圍 7 .如申請專利範圍第1項之多層結構物，其中粘著 樹脂層（B)係由二層構成，其中聚碳酸酯系樹脂層（A )側係聚碳酸酯-聚有機矽氧烷共聚物層。 8 .如申請專利範圍第1項之多層結構物，其中更於 聚碳酸酯系樹脂層（A )側中介以粘著樹脂層設有玻璃層 而成。 _·ι裝 II (請先閱部背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) Α4規格（2】0Χ 297公釐） -2-夂 、 Patent Application No. 89124956 Chinese Patent Application Amendment Chinese Patent Application Amendment January 14, 1993 Amendment 1. A multilayer structure characterized by a polycarbonate resin layer (A) and an adhesive resin layer (B) At least one of the glass layer or the adhesive resin layer formed by the glass layer (C) contains an ultraviolet absorbing component. 2. If the multilayer structure of item χ of the scope of patent application, where the glass layer (A) and the adhesive resin layer. (B) both contain ultraviolet absorbing components 3. If the scope of the application of the patent scope of item χ or 2 A multilayer structure, in which the glass layer (A) is a soda lime silica glass, and the ultraviolet absorbing component contained in the glass is a sister. 4. The multilayer structure according to item 1 of the patent application scope, wherein the ultraviolet absorbing component contained in the adhesive resin layer (B) is a benzotriazole-based compound and / or a triazine-based compound. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5 · If the multilayer structure of the first patent application scope is applied, the adhesive layer. The resin layer (B) is selected from ethylene-vinyl acetate copolymer, polyvinyl acetate, ethylene At least one layer of mono (meth) acrylate copolymer, polyurethane, polyester-polyurethane copolymer, polycarbonate-organosiloxane copolymer, and polyvinyl butyral resin. 6. The multilayer structure according to item 1 of the scope of patent application, wherein the amount of terminal hydroxyl groups of the polycarbonate resin used for the polycarbonate resin layer (A) is 8 mol% or less relative to the repeating unit of the polymer chain. This paper size is applicable to Chinese National Standard (CNS) A4 specification (2) 0 × 297 mm. 581724 ABCD 6. Application scope of patent 7. For the multilayer structure of the first scope of patent application, the adhesive resin layer (B) consists of The two-layer structure includes a polycarbonate-based resin layer (A) and a polycarbonate-polyorganosiloxane copolymer layer. 8. The multilayer structure according to item 1 of the scope of patent application, wherein the polycarbonate resin layer (A) is further provided with a glass resin layer through an adhesive resin layer. _ · Ι Pack II (Please read the notes on the back of the ministry before filling out this page) Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives This paper is printed in accordance with Chinese National Standards (CNS) Α4 specifications (2) 0 × 297 mm -2-