TW200932531A - Laminate, heat-shrinkable film and heat-shrinkable label each obtained from the laminate, and container bearing the label - Google Patents

Laminate, heat-shrinkable film and heat-shrinkable label each obtained from the laminate, and container bearing the label Download PDF

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Publication number
TW200932531A
TW200932531A TW97144296A TW97144296A TW200932531A TW 200932531 A TW200932531 A TW 200932531A TW 97144296 A TW97144296 A TW 97144296A TW 97144296 A TW97144296 A TW 97144296A TW 200932531 A TW200932531 A TW 200932531A
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TW
Taiwan
Prior art keywords
layer
film
heat
resin
laminate
Prior art date
Application number
TW97144296A
Other languages
Chinese (zh)
Inventor
Yukihiro Tanaka
Takatoshi Muta
Takashi Hiruma
Jun Takagi
Original Assignee
Mitsubishi Plastics Inc
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Publication date
Application filed by Mitsubishi Plastics Inc filed Critical Mitsubishi Plastics Inc
Publication of TW200932531A publication Critical patent/TW200932531A/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/44—Number of layers variable across the laminate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2274/00—Thermoplastic elastomer material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • B32B2307/736—Shrinkable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2519/00—Labels, badges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2553/00—Packaging equipment or accessories not otherwise provided for

Landscapes

  • Laminated Bodies (AREA)
  • Details Of Rigid Or Semi-Rigid Containers (AREA)
  • Wrappers (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A laminate which comprises in the following order a first layer constituted of a resin composition comprising a polyester elastomer and/or a modified polyester elastomer; and a second layer constituted of a resin composition comprising a polyester resin. The laminate has an interlaminar peeling strength of 1 N/15-mm width or higher when examined by forming the laminate into a heat-shrinkable film, obtaining from the film a test piece having a size in which the dimension in a main shrinkage direction is 150 mm and that in the direction perpendicular to the main shrinkage direction is 15 mm, partly peeling off the second layer in the test piece from an end in the main shrinkage direction, clipping with the chucks of a tensile tester that part of the second layer which has been peeled off and that part of the first layer from which the second layer has been peeled, and conducting a 180 DEG peel test in the main shrinkage direction at a test speed of 100 mm/min. This laminate has excellent interlaminar adhesion. After having been processed into a heat-shrinkable film, the laminate has excellent shrinkage characteristics and transparency. The laminate is suitable for use in applications such as shrink packaging, shrink bundling, and shrink labels.

Description

200932531 六、發明說明： 【發明所屬之技術領域】 本發明係關於具有以含¥& ^200932531 VI. Description of the invention: [Technical field to which the invention pertains] The present invention relates to having a &

自曰糸彈十生#夕枝L .成之層的積層體，暨使用誃 之樹枭組成物所構 積層體之 .收縮性薄膜、熱收縮性標鐵、^ f溥膜、成形體、熱 言之，本發明_於具麵/及附有該標《之容器。更詳 即便以高溫處理仍不易剝離之屑$熱眭、透明性及外觀，且 ❹使用該積層體之熱收縮性薄層間接著性優異的積層體，暨 之容器。 、、熱收縮性標籤及附有該標籤 【先前技術】 ，<·巧茂义便用於包裝 之塑膠材料，可舉出聚乙烯、何料、卡片、容器及其他物品 對苯二甲酸乙二自旨、聚酸胺、聚丙稀、聚酯、聚苯乙稀、聚 ❹ 材料單獨使用之情況，大夕聚碳酸酯等各種材料，將該等 於聚酯樹脂之1種的聚乳酽^匕得充分的物性。例如，屬 衝擊性差的缺點，因此已知文由於單獨使用時具有脆弱而耐 其物性（參照專利文獻1)轉由對其混合軟質系樹脂以改善 又’作為改良以材科單體製4 * 法，已知有將異種材料積作之薄膜可能發生之缺點的手 中揭示有一種收縮樑鐵，其而成之薄膜。例如，專利文獻2 中間層的兩側，積層由特」係於由聚苯乙烯系樹脂所構成之 的外層。該收縮標籤係鞞定單體所形成之聚酯系樹脂所構成 。賴296 、由在聚酿系樹脂所構成的兩外層之 200932531 ，在著由聚苯乙烯系樹脂所構成之中間層，而具有收縮標 籤所要求之低溫收縮性、與為了使標籤容易自容器剝除而設 ./之㈣性優異的特徵。此外，由於該熱收縮性標簸 ，係、使聚本乙婦系樹脂所構成之中間層覆蓋於聚醋系樹脂所 構成之外層，故具有财溶劑性、耐熱性亦優異之特徵。然而， 使=收缩性標籤裝附於容器上之情況，由於該標籤裝附後 ;;輪送中的薄膜互相之摩擦、或人手指等所造成的拉 Ο抓等，會發生中間層與外層剝離之不佳狀況。 目此’此種積層薄膜中，通常係在防止剝離之目的下，採 用於外層與中間層之間形成具有接著性能之接著層的方 法。例如已揭示有-種熱收縮性多層薄膜，其係於聚苯乙稀 系樹月曰所構成之内層上，介隔著輯烴㈣脂所構成之接著 層而積層由聚g旨系樹脂所構成之外層（參照專利文獻⑺。 然^，若料散獻3之熱㈣性多層薄膜裝附於容器上， 在熱收縮步财會有㈣與外層祕之不佳狀況，無法獲得 充分的剝離防止效果所帶來的優異外觀。 (專利文獻1)曰本專利特開平9_1111〇7號公報 • (專利文獻2)曰本專利特開2002-351332號公報 . (專利文獻3)日本專利特開昭61-41543號公報 【發明内容】 (發明所欲解決之問題） 作為近來之傾向’積層薄膜例如當作為食品包裝用途而使 097144296 4 200932531 用之匱況因煮沸消毒、加溫等之目的，係於以積層薄膜包 裝食σ口之狀態下，於高溫環境下進行處理。此外，例如使用 作為裝附在寶特瓶或金屬罐等容器之熱收縮性薄膜的情 況’亦需要經過棵千^^ 、 你不Uabeling)步驟中之熱收縮步驟。因 此，於介在有接著層之積層薄膜中 ’具有即便於高溫環境下 處理仍可充分耐受之耐剝離性及優異外觀之積層薄膜的開 發需求係逐漸提向’⑫仍無法獲得可滿足之薄膜。 日本發月係為了解決上述問題*完成者，本發明之課題在於 提U優異耐熱性、透明性及外觀，且即便以高溫處理仍 不易剝離之層間接著性優異的積層體。 之另課喊在於提供使用上述積層薄膜之成形 σσ L伸薄膜’與適合於收縮包裝、收縮收束包裝或熱收縮 籤專途之熱收縮性薄膜、由該熱收縮性薄膜所構成之熱 ❿ 收縮性標籤’及附有該熱收縮性標籤之容器。 (解決問題之手段） 本月人針對在將聚酿系樹脂所構成之層與其他熱可塑 !·生树月曰所構成之層予以接著而成之積層體加工為薄膜狀並 進行制離》式驗之情況下難以剝離之接著性樹脂進行深入檢 寸、’、u果在使用含有既定之聚酯系彈性體的樹脂組成物的情 况’成功獲仔可解決上述習知技術問題的積層體，而完成本 發明。 亦即’本發明之課題為一種至少具備含有聚酯系彈性體作 097144296 200932531 為主成分之樹脂組成物、含有改質聚酯系彈性體作為主成分 之樹脂組成物、或該等樹脂組成物之混合樹脂組成物所構成 之第1層’與含有聚酯系樹脂作為主成分之樹脂組成物所構 - 成之第2層的積層體’將上述積層體至少於一方向延伸而製 作熱收縮性薄膜，由該熱收縮性薄膜以主收縮方向15〇唧、 垂直於主收縮方向的方向15mm之大小採取試驗片後，從該 试驗片之主收縮方向的薄膜端面剝離上述第2層之一部分 ©而分別於上述第2層上形成剝離部、於上述第1層上形成被 剝離部，將上述第2層之剝離部與上述第丨層之被剝離部以 拉伸試驗機之夾頭夾取，以相對於主收縮方向之試驗速度 1 OOmm/min進行180度剝離試驗時之層間剝離強度為 IN/15mm寬以上。 又’本發明之另-課題係藉由使用本發明之積層體的延伸 4膜、成形體、熱收縮性薄膜、熱收縮性標籤及附有該標籤 ®之容器所達成。 (發明效果） 本發明之積層體係具備含有聚g旨系彈性體、改質聚g旨系彈 • ㈣或該等之、混合樹脂組成物作為主成分之樹脂組成物所 • 誠的* 1層’與含有聚S旨系樹脂作為主成分之樹脂組成物 所構成之第2層，於成形為熱收縮性薄膜時，第1層與第2 層之間的層間剝離強度為1N /15 _寬以上。因此，根據本發 明，可獲得具有優異之耐熱性、透明性及外觀，且即便以高 097144296 6 200932531 溫處理仍不易剝離之層間 ^ ^ ώ 埯者性優異的積層體，且可提供於 加工為熱收縮性薄膜時具 ^ , 、，馒異之熱收縮特性及透明性，適 合於收縮包裝、收縮收束白 . lL + 装或收縮標籤等用途之積層體。 此外，若使用本發明之 ^ ^ 嘈體，可提供適合於收縮包裝、 •收縮收束包裝、收縮標錢箸 U ^ 用途之熱收縮性薄膜、熱收縮性Self-cultivating ten students #夕枝 L. The layered body of the layer, and the layered body of the composition of the tree 枭 .. Shrink film, heat shrinkable iron, ^ f film, formed body, It is to be noted that the present invention is a container having the surface/with the label. Further, even if it is treated at a high temperature, it is not easy to peel off the crumbs, heat, transparency, and appearance, and the laminate having excellent heat-shrinkability between the laminates and the laminate is used. , heat shrinkable label and the label [previous technology], <·Qiao Maoyi used for packaging plastic materials, can be cited polyethylene, what materials, cards, containers and other items When the materials are used alone, the polyacrylamide, the polypropylene, the polyester, the polystyrene, and the polyfluorene material are used alone, and various materials such as the Daxi polycarbonate are equal to one of the polyester resins. Get full physicality. For example, it is a disadvantage of poor impact, and therefore it is known that it is weak and resistant to physical properties when it is used alone (refer to Patent Document 1), and it is improved by mixing soft resin with it as a modified material. The method, which is known to have the disadvantage that the film of the dissimilar material is formed, reveals a shrinking beam iron which is formed into a film. For example, in both sides of the intermediate layer of Patent Document 2, the laminate is made of an outer layer made of a polystyrene resin. The shrink label is composed of a polyester resin formed by a monomer. Lai 296, 200932531, which consists of two outer layers of polystyrene resin, has an intermediate layer made of a polystyrene resin, and has the low temperature shrinkage required for the shrink label, and the label is easily peeled off from the container. In addition, the characteristics of (4) are excellent. In addition, since the intermediate layer made of the polyacetal resin is coated on the outer layer of the polyester resin, the heat shrinkability index is excellent in both the solvent property and the heat resistance. However, when the label is attached to the container, the label is attached, and the middle layer and the outer layer are generated due to the friction of the film in the rotation or the pulling of the finger or the like. The poor condition of stripping. In the case of such a laminated film, a method of forming an adhesive layer having an adhesive property between the outer layer and the intermediate layer is usually employed for the purpose of preventing peeling. For example, there has been disclosed a heat-shrinkable multilayer film which is attached to an inner layer composed of a polystyrene tree, and which is laminated with a layer formed of a hydrocarbon (tetra) resin. The outer layer is formed (see Patent Document (7). However, if the heat (four) multilayer film is attached to the container, the heat shrinkage will have a bad condition (4) and the outer layer is not good enough, and sufficient peeling cannot be obtained. (Patent Document 1) Japanese Patent Laid-Open No. Hei. No. 2002-351332. (Patent Document 3) Japanese Patent Laid-Open Japanese Patent Publication No. Sho 61-41543 (Claim of the Invention) (Problems to be Solved by the Invention) As a recent trend, a laminated film is used for food packaging purposes, for example, for sterilizing, heating, etc. by using 097144296 4 200932531 It is processed in a high-temperature environment in a state in which the sigma is packaged in a laminated film. In addition, for example, when it is used as a heat-shrinkable film attached to a container such as a PET bottle or a metal can, it is necessary to pass through a tree. ^, Not Uabeling) the step of heat shrinkage step. Therefore, in the laminated film having an adhesive layer, the development of a laminated film having a peeling resistance and an excellent appearance which can be sufficiently tolerated even under a high-temperature environment is gradually increasing to '12, and a satisfactory film cannot be obtained. . In order to solve the above problems, the present invention has an object of providing a laminate having excellent heat resistance, transparency, and appearance, and which is excellent in interlayer adhesion which is not easily peeled off even at a high temperature. The other lesson is to provide a formed σσ L stretch film using the above laminated film and a heat shrinkable film suitable for shrink packaging, shrink-wrap packaging or heat shrink labeling, and a heat absorbing film composed of the heat-shrinkable film. A shrinkable label' and a container with the heat shrinkable label attached thereto. (Means for Solving the Problem) This month, the layered body formed by laminating the layer composed of the poly-baked resin and other layers of thermoplastics and trees is processed into a film and separated. In the case of the test, the adhesive resin which is difficult to peel off is subjected to in-depth inspection, and 'the fruit is used in the case of using a resin composition containing a predetermined polyester-based elastomer', and the laminate of the above-mentioned conventional technical problems can be successfully obtained. The present invention has been completed. In other words, the object of the present invention is to provide a resin composition containing at least a polyester elastomer as 097144296 200932531 as a main component, a resin composition containing a modified polyester elastomer as a main component, or a resin composition. The laminated body of the second layer composed of the first resin layer composed of the mixed resin composition and the resin composition containing the polyester resin as a main component extends the laminated body at least in one direction to produce heat shrinkage. The test piece is taken from the heat-shrinkable film in a direction of 15 mm in the main shrinkage direction and 15 mm in the direction perpendicular to the main shrinkage direction, and then the second layer is peeled off from the film end face in the main shrinkage direction of the test piece. A part of the second layer is formed on the second layer, and a peeled portion is formed on the first layer, and the peeled portion of the second layer and the peeled portion of the second layer are sandwiched by a tensile tester. The interlaminar peeling strength at the 180-degree peeling test at a test speed of 100 mm/min with respect to the main shrinkage direction was IN/15 mm or more. Further, another subject of the present invention is achieved by using the laminate 4 film of the present invention, a molded article, a heat-shrinkable film, a heat-shrinkable label, and a container with the label. (Effect of the Invention) The laminated system of the present invention comprises a resin composition containing a poly-g-type elastomer, a modified poly-g-type bullet, (4) or the like, and a mixed resin composition as a main component. 'When the second layer composed of a resin composition containing a poly-S resin as a main component is formed into a heat-shrinkable film, the interlayer peel strength between the first layer and the second layer is 1 N / 15 _ wide the above. Therefore, according to the present invention, it is possible to obtain a laminate having excellent heat resistance, transparency, and appearance, and which is excellent in interlayer properties which are not easily peeled off by heat treatment at a high temperature of 097144296 6 200932531, and can be provided as processing. The heat-shrinkable film has the heat shrinkage characteristics and transparency of the film, and is suitable for shrink packaging, shrinking and converging white. lL + laminated or shrinkable labels and other applications. Further, if the ^ ^ carcass of the present invention is used, a heat-shrinkable film suitable for shrink packaging, shrink-wrap packaging, shrinkage, and U?

標戴及附有該標籤之容器。 T 【實施方式】 ❹ ❿ 以下，針對本發明之積屌 ,,,,^ ^ llL9 延伸薄膜、成形體、熱收縮 :標籤之容器，進行詳細說 性薄膜、熱收縮性標籤以及附有誃 人 明。 另外’本說明書中，「作為主士、 „ 馬王成分J係指在不妨礙構成各 層之树脂的作用•效果之篇图 圍内’容許含有其他成分之意 義。此外，此用語並不限制且體 “體的含有量，係佔各層之構成 成分整體的60質量％以上、較佳Α 7Λ讲θ 敕佳為7〇質量％以上、更佳為 80質量％以上且1〇〇質量％以下之成分。 [積層體] 本發明之積層體係至少具備：含有聚⑽彈性體作為主成 分之樹脂組成物、含有改質聚酯系彈性體作為主成分之樹脂 組成物、或該等樹脂組成物之混合樹脂組成物所構成的第i 層’與含有聚酯系樹脂作為主成分之樹脂組成物所構成的第 2層。’ 〈第1層〉 097144296 7 200932531 本發明之積層體的第1層係由以含有聚酯系彈性體作為 樹脂組成物、或含有藉由具極性基之改質劑而將聚酯系彈性 體予以改質之改質聚酯系彈性體的樹脂組成物、或該等之混 * 合樹脂組成物作為主成分之樹脂組成物所構成。藉由使用含 . 有聚酯系彈性體作為構成第1層的主成分之樹脂組成物、含 有改質聚g旨系雜體作為主成分之樹脂、或以該等樹脂之混 合树知組成物作為主成分之樹脂組成物，可抑制彈性體特有 ©之黏著力所造成之層間剝離，且可利用構成聚酯性彈性體之 聚酯成分與構成第2層之聚酯系樹脂的親和性，賦予更為強 固的層間剝離力。 上述聚S旨系彈性體係由具有低玻璃轉移溫度且表現烟彈 性（entropy elasticity)之柔軟聚醚單位、聚醋單位、聚 碳酸酯單位等所構成之軟鏈段，與防止塑性變形之結晶性為 硬質的高溶點聚醋嵌段單位所構成之硬鏈段所構成之嵌段 八聚口體3外’改質聚g旨性彈性體係例如將上述聚醋性彈 性體利用具有極性基之改質劑而改質者。 作為構成上述聚I系彈性體之硬鏈段，例如可舉出聚對苯 .一甲日單位、聚萘二甲酸丁二g旨單位、聚間苯二曱酸 • 丁二Sl單位等，或該等硬鏈段單位骨架共聚合而成者。另一 方面，作為軟鏈段，例如可舉出聚（四亞甲基氧化物）乙二 醇單位、聚（卜己_)單位、脂肪族聚碳酸g旨二醇單位 等’或該等軟鏈段單位骨架共聚合而成者4述共聚合體係 097144296 8 200932531 包含純嵌段絲合體、無規錢聚合體、轉（細 喪段共聚合體、多錢段共聚匈，或上述賴段或 鏈段，或者㈣妓合體為主”並於其舰上具有上= 鏈段或上述硬鏈段或其共聚合體之接枝共聚合體等，共聚二 之形態並無特別限定。又，其嵌段單位亦可為重複單元重: 數個。另外，作為改質聚醋系彈性體，例如可舉出對 Ο 段所構成之⑽系彈性體樹脂藉由具有極性劑之 ’ 改質者。 剛而 其中’作為聚酯系彈性體，較佳可使用聚對苯二甲酸丁一 酉旨-聚（四亞曱基氧化物）二醇共聚合體或聚對苯二甲酸 二酯-聚間苯二f酸丁二醋一聚（四亞曱基氧化物）:丁 合體。 轉共聚 ❹ 上述聚酯系彈性體中之硬鏈段的含有率，相對於硬鏈俨邀 軟鏈段總量係為50質量％以上，較佳為7〇質量％以 -j-，更隹 為75質量％以上，特佳為8〇質量％以上。若硬鏈段之含有率 為50質量％以上’則與構成第2層之聚酯系樹脂的親和性致 果可充分作用，且即便在高溫環境下，仍可保持聚酯系彈2 體之耐熱性，故不會發生在高溫環境下的層間接著強声 低，可充分保持積層體之形狀。 ％ 構成上述聚酯系彈性體之硬鏈段的聚對苯二甲酸 嘴1 丁二酷 單位等之重量（質量）平均分子量係400以上，較佳A n 4 !&gt;0〇〇 以上，更佳為2, 000以上，且為i〇, 〇〇Q以下，較隹 馮8,00〇 097144296 9 200932531 以下，更佳為6,000以下。若硬鏈段之重量（質量）平均分 子量為400 i 10, _之範圍，則可保持聚酿系彈性體之财 熱性，不發生於高溫環境下之層間接著強度的降低，可充分 保持積層體之形狀，故較佳。 另一方面’構成上述聚酯系彈性體之軟鏈段的聚伸烷基氧 二醇單位等之重量（質量）平均分子量係500以上，較佳為 800以上’更佳為1，〇〇〇以上，且為3, 〇〇〇以下較佳為&amp; 5〇q β以下，更佳為2, 000以下。若軟鏈段之分子量為5〇〇以上且 3, 000以下，則可充分獲得彈性體成分所特有之黏著力，可 k升層間剝離強度，故較佳。 若例示聚酯系彈性體之具體商品’可舉出rPrimall〇y A 系列」、「Primalloy B系列」（三菱化學股份有限公司製）、 「PELPRENE P系列」（東洋紡股份有限公司製）、「Hytrel」 (東麗•杜邦股份有限公司製）等。 ® 又，作為改質聚酯系彈性體之極性基，例如可舉出酸酐 基、羧酸基、羧酸酯基、羧酸氣化物基、羧酸醯胺基、羧酸 鹽基、確酸基、續酸酯基、續酸氯化物基、礦酸醯胺基、績 酸鹽基、環氧基、胺基、醯亞胺基或噚唑基等之官能基，其 中以酸酐基、羧酸基或羧酸酯基為佳。 若例示改質聚酯系彈性體之具體商品，可舉出例如 「Primalloy AP系列」（三菱化學股份有限公司製）等。 第1層所使用之含有聚酯系彈性體的樹脂組成物或含有 097144296 10 200932531 改i聚S旨系彈性體的樹月旨組成物，並不限於該等之單體，亦 可互相、混合聚酯系彈性體、互相混合改質聚醋系彈性體、或 混合2種類以上的該等之混合物等而使用。此情況，混合量 '可根據所使用之樹脂的特性而適當決定。 除了第1層為含有聚酯系彈性體的樹脂組成物及含有改 貝聚醋糸彈性體的樹脂組成物以外，例如亦可含有〇 1質量 %以上且40質量％以下之烴樹脂類、苯乙烯系樹脂類、聚酯 Ο 系樹脂類。含有烴樹脂類之情況，可抑制硬鏈段之結晶化， 賦予柔軟性與黏著性。又，含有苯乙烯系樹脂類之情況，可 提升聚酯系彈性體之耐熱性，賦予和構成第3層之聚苯乙烯 系樹脂的親和性。 〈第2層〉 本發明之積層體的第2層，係由含有聚酯系樹脂作為主成 分之樹脂組成物所構成。於第1層上積層第2層而作成積層 ❹體後’將該積層體至少於一方向延伸而製作熱收縮性薄膜之 情況，可對薄膜賦予剛性、耐斷裂性及低溫收縮性，並同時 抑制自然收縮。本發明中之較佳聚酯系樹脂係為二羧酸成分 • 與二醇成分所構成之聚酯系樹脂組成物或聚乳酸系樹脂組 • 成物。作為二羧酸成分與二醇成分所構成之聚酯系樹脂組成 物中所含有的二羧酸成分例，可舉出對苯二甲酸、間苯二甲 酸、2-乳化對苯二曱酸、2, 5-二氣對苯二曱酸、2-曱基對笨 二曱酸、4, 4-二苯乙烯二羧酸、4, 4-雙苯基二綾酸、鄰苯二 097144296 11 200932531 甲酸、2, 6-萘二羧酸、2, 7-萘二羧酸、雙苯曱酸、雙（對羧 基苯基）甲烷、蒽二羧酸、4, 4-二苯基醚二羧酸、4, 4-二苯 氧基乙烷二羧酸、5-Na磺化間苯二曱酸、伸乙基-雙-對苯 -甲酸等之芳香族二羧酸；己二酸、癸二酸、壬二酸、十二酸、 * 1，3-環己烷二羧酸、1, 4-環己烷二羧酸等之脂肪族二羧酸或 由該等之酯衍生物所衍生的成分。該等二羧酸成分可含有單 獨1種或含有2種以上。作為上述聚酯系樹脂，對苯二曱酸 〇 與乙二醇所形成之聚酯樹脂係較適合使用。 本發明中，較佳係聚酯系樹脂由二羧酸成分與二醇成分所 形成，而二羧酸成分及二醇成分之至少一者為2種以上之成 分所構成之混合物。本說明書中，含有2種以上成分之情 況，係以質量（莫耳«最多者作為第1成分，較該第1成 分更少量且於剩下的成分中最多者作為第2成分（以下則同 樣為第3成分、第4成分…）。藉由使二羧酸成分與二醇成 ® 分成為此種混合系統，可降低所得之聚酯系樹脂的結晶性， 故使用作為本發明之積層體的第2層之情況，可抑制第2 層之結晶化的進行，因而較佳。 . 作為較佳之二醇成分的混合物，例如可舉出使用乙二醇成 . 分作為第1成分，由1，4-丁二醇、新戊二醇、二乙二醇、 聚四亞甲基二醇及1,4-環己烷二曱醇所構成群組中選出之 至少1種所衍生之成分（較佳為1,4-環己烷二曱醇成分） 作為第2成分者。 097144296 12 200932531 又’作為較佳之二羧酸成分之混合物，例如可舉出使用對 苯二甲酸作為第1成分，由間苯二曱酸、1，4-環已烷二幾 酸、玻轴酸及已二酸成分所構成群組中選出之至少一種所衍 • 生的成分（較佳為間苯二甲酸成分）作為第2成分者。 上述第2成分以下之二叛酸成分及二醇成分的總量之含 有率’相對於上述二羧酸成分之總量〇〇〇莫耳％)與上述 二醇成分之總量（100莫耳％)之合計（ 200莫耳％)，係為 ❹10莫耳％以上、較佳為20莫耳％以上，且為50莫耳％以下、 較佳為40莫耳％以下。若上述第2成分以下的成分之含有率 為10莫耳％以上’則可將所得之聚酯的結晶化度抑制為低的 值。另一方面’若上述第2成分以下的成分之含有率為5〇 莫耳％以下，則可發揮第1成分之優點。 例如，當二羧酸成分為對苯二曱酸成分，而二醇成分之第 1成分為乙二醇成分、第2成分為1，4-環己烷二曱醇成分之 ❹情況，屬於第2成分之i，4_環己烷二甲醇成分之含有率相 對於屬於二羧酸成分之對苯二甲酸成分之總量（1〇〇莫耳％) 與乙二醇成分及丨，4—環己烷二甲醇成分之總量（100莫耳％) -的合計（200莫耳％)，係為1〇莫耳％以上、較佳為15莫耳％ • 以上、更佳為託莫耳％以上，且為50莫耳％以下、較佳為 40莫耳％以下、更佳為35莫耳％以下之範圍。藉由在此範園 中使用乙二醇成分及14—環己烧二甲醇成分作為二醇成 刀’所彳t之聚g旨的結晶性幾乎絲，且可提升耐斷裂性。 097144296 13 200932531 此外，於上述例中，二羧酸成分 刀1糸u對苯二曱酸成分作為 第1成分、以間苯二甲酸成分作為第2成分_成之情況， 屬於二減成分之間苯二甲酸成分與屬於二醇成分之U— 環己烧二曱醇成分之含有率，相對於辦笨二曱酸成分及間苯 '二甲酸成分之總量⑽.莫耳％)與乙二醇成分及U—環己 烧二甲醇成分之總量⑽莫耳％)之合計（2〇〇莫耳％)為 10莫耳％以上、較佳為15莫耳％以上、更佳為25莫耳％以上， β且為50莫耳％以下、較佳為40莫耳％以下、更佳為35莫耳％ 以下之範圍。 上述聚酯系樹脂之折射率（η1)係為156〇以上且158〇 以下，較佳為約1. 570。 上述聚酯系樹脂之固有黏度（IV)為〇 5dl/g以上、較佳 為0.6dl/g以上、更佳為〇.7dl/g以上，且為1 5dl/g以下、 較佳為1. 2dl/g以下、更佳為1. 〇dl/g以下。若固有黏度（iv) 為0· 5dl/g以上，可抑制薄膜強度特性與耐熱性之降低。另 一方面，若固有黏度為1. 5dl/g以下，則可防止隨延伸張力 增加而造成之斷裂。The container with the label attached. T [Embodiment] ❹ ❿ ❿ ❿ ❿ ❿ ❿ ❿ ❿ ❿ ❿ ❿ ❿ ❿ ❿ ❿ ❿ 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 Bright. In addition, in the present specification, "as a master, „Mawang's ingredient J means that it is allowed to contain other components in the picture of the effect of the resin that does not hinder the layers. In addition, the term "body content" is not limited to 60% by mass or more of the entire constituent components of each layer, and preferably θ Λ θ θ is preferably 7% by mass or more, more preferably 80% by mass or more. In addition, the laminated system of the present invention includes at least a resin composition containing a poly(10) elastomer as a main component and a resin composition containing a modified polyester elastomer as a main component. Or the second layer formed of the mixed resin composition of the resin composition and the resin composition containing the polyester resin as a main component. 'First layer> 097144296 7 200932531 The present invention The first layer of the laminate is a modified polyester elastomer containing a polyester elastomer as a resin composition or a polyester elastomer modified by a polar modifier. A resin composition containing the resin composition or the resin composition as a main component, and a resin composition containing a polyester elastomer as a main component constituting the first layer, and a resin composition. Modified polyg A resin composition containing a main component as a main component or a resin composition containing a composition of the resin as a main component, which can suppress interlaminar peeling caused by adhesion of an elastomer, and can be used as a polyester. The affinity between the polyester component of the elastomer and the polyester resin constituting the second layer imparts a stronger interlaminar peeling force. The polys-based elastic system has a low glass transition temperature and exhibits entropy elasticity. a soft segment composed of a soft polyether unit, a polyester unit, a polycarbonate unit, and the like, and a hard segment composed of a high-melting point polyester block unit which prevents the plasticity of plastic deformation from being hard. For example, the above-mentioned polyacetal elastomer is modified by using a modifier having a polar group as the hard segment of the poly-I-based elastomer. For example, a polyparaphenylene group, a one-day unit, a poly(naphthalene dicarboxylate) unit, a poly-m-phthalic acid-butadiene-S1 unit, or the like, or a hard-chain unit skeleton may be copolymerized. On the other hand, as a soft chain Examples of the segment include a poly(tetramethylene oxide) ethylene glycol unit, a poly(b) unit, an aliphatic polycarbonate, a glycol unit, or the like, or a copolymerization of the soft segment unit skeletons. The fourth embodiment of the copolymerization system 097144296 8 200932531 contains pure block silk, random money polymer, transfer (fine segment copolymer, multi-currency copolymerized Hungary, or the above-mentioned Lai segment or segment, or (d) complex The main body has a top = chain segment or a graft copolymer of the above hard segment or a copolymer thereof, and the form of the copolymerization is not particularly limited. Further, the block unit may be a repeating unit weight: Further, as the modified polyacetal elastomer, for example, the (10) elastomer resin which is composed of the ruthenium portion is modified by a polar agent. In the case of 'polyester elastomer, it is preferred to use polybutylene terephthalate-poly(tetramethylene oxide) diol copolymer or polyterephthalate-poly(m-phenylene terephthalate) Acid diced vinegar monopoly (tetrakisyl sulfhydryl oxide): butyl complex. The copolymerization ratio of the hard segment in the polyester-based elastomer is 50% by mass or more, preferably 7% by mass or less, based on the total amount of the soft chain-inviting soft segment. It is 75 mass% or more, and particularly preferably 8 mass% or more. When the content of the hard segment is 50% by mass or more, the affinity with the polyester resin constituting the second layer can be sufficiently effective, and the polyester elastomer can be maintained even in a high temperature environment. Since it is heat-resistant, it does not occur in a high-temperature environment, and then the sound is low, and the shape of the laminated body can be sufficiently maintained. % The weight (mass) average molecular weight of the polybutylene terephthalate 1 or the like which constitutes the hard segment of the polyester elastomer is 400 or more, preferably A n 4 !&gt; Preferably, it is more than 2,000, and it is i〇, 〇〇Q or less, which is less than von 8,00〇097144296 9 200932531, and more preferably 6,000 or less. If the weight (mass) average molecular weight of the hard segment is in the range of 400 i 10, _, the heat of the poly-branched elastomer can be maintained, and the interlaminar strength between the layers does not occur in a high-temperature environment, and the laminate can be sufficiently maintained. The shape is preferred. On the other hand, the weight (mass) average molecular weight of the polyalkylene glycol unit or the like constituting the soft segment of the polyester elastomer is 500 or more, preferably 800 or more, more preferably 1, 〇〇〇 The above is preferably 3, and the following is preferably &amp; 5〇q β or less, more preferably 2,000 or less. When the molecular weight of the soft segment is 5 Å or more and 3,000 or less, the adhesive strength peculiar to the elastomer component can be sufficiently obtained, and the peel strength between the layers can be increased, which is preferable. Specific examples of the polyester elastomers include "rPrimall〇y A series", "Primalloy B series" (manufactured by Mitsubishi Chemical Corporation), "PELPRENE P series" (made by Toyobo Co., Ltd.), and "Hytrel". (made by Toray DuPont Co., Ltd.). Further, examples of the polar group of the modified polyester elastomer include an acid anhydride group, a carboxylic acid group, a carboxylate group, a carboxylic acid vapor group, a carboxylic acid oxime group, a carboxylate group, and an acid. a functional group such as a carboxylic acid group, a phthalic acid group, a chlorinated acid group, a mineral acid amide group, an acid salt group, an epoxy group, an amine group, a guanidino group or a carbazolyl group. An acid group or a carboxylate group is preferred. For example, a "Primalloy AP series" (manufactured by Mitsubishi Chemical Corporation) or the like can be given as a specific product of the modified polyester elastomer. The resin composition containing the polyester elastomer used in the first layer or the composition of the 971144296 10 200932531 modified elastomer is not limited to the monomers, and may be mixed with each other. The polyester-based elastomer, the mixed-modified modified vinegar-based elastomer, or a mixture of two or more of these types or the like is used. In this case, the mixing amount ' can be appropriately determined depending on the characteristics of the resin to be used. In addition to the resin composition containing the polyester elastomer and the resin composition containing the modified polyacetate elastomer, the first layer may contain, for example, 1% by mass or more and 40% by mass or less of a hydrocarbon resin or benzene. Ethylene resin or polyester resin. In the case of containing a hydrocarbon resin, crystallization of the hard segment can be suppressed, and flexibility and adhesion can be imparted. Further, when the styrene-based resin is contained, the heat resistance of the polyester-based elastomer can be improved, and the affinity with the polystyrene-based resin constituting the third layer can be imparted. <Second layer> The second layer of the laminate of the present invention is composed of a resin composition containing a polyester resin as a main component. After the second layer is laminated on the first layer to form a laminated body, and the laminated body is stretched in at least one direction to form a heat-shrinkable film, rigidity, fracture resistance, and low-temperature shrinkage can be imparted to the film. Inhibits natural contraction. The preferred polyester resin in the present invention is a dicarboxylic acid component, a polyester resin composition composed of a diol component, or a polylactic acid resin group. Examples of the dicarboxylic acid component contained in the polyester resin composition composed of the dicarboxylic acid component and the diol component include terephthalic acid, isophthalic acid, and 2-emulsified terephthalic acid. 2, 5-di-p-benzoic acid, 2-mercapto-p-benzoic acid, stilbene dicarboxylic acid, 4,4-bisphenyl dinonanoic acid, phthalic acid 097144296 11 200932531 Formic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, bisbenzoic acid, bis(p-carboxyphenyl)methane, stilbene dicarboxylic acid, 4,4-diphenyl ether dicarboxylic acid , 4, 4-diphenoxyethane dicarboxylic acid, 5-Nasulfonated isophthalic acid, ethyl di-p-phenylene-carboxylic acid, etc.; aromatic dicarboxylic acid; adipic acid, bismuth An aliphatic dicarboxylic acid such as an acid, azelaic acid, dodecanoic acid, *1,3-cyclohexanedicarboxylic acid or 1,4-cyclohexanedicarboxylic acid or derived from such ester derivatives ingredient. These dicarboxylic acid components may be contained alone or in combination of two or more. As the polyester resin, a polyester resin formed of bismuth phthalate and ethylene glycol is preferably used. In the present invention, the polyester-based resin is preferably a dicarboxylic acid component and a diol component, and at least one of the dicarboxylic acid component and the diol component is a mixture of two or more components. In the present specification, when two or more types of components are contained, the mass is the highest component (the molar component is the first component, the smaller one is smaller than the first component, and the most component is the second component (the same applies to the following) When the dicarboxylic acid component and the diol are grouped into such a mixing system, the crystallinity of the obtained polyester resin can be reduced, and the laminate is used as the laminate of the present invention. In the case of the second layer, it is preferable to suppress the progress of crystallization of the second layer. As a preferable mixture of the diol components, for example, ethylene glycol is used as the first component, and 1 is used. At least one selected from the group consisting of 4-butanediol, neopentyl glycol, diethylene glycol, polytetramethylene glycol, and 1,4-cyclohexanedimethanol ( The 1,4-cyclohexanediketanol component is preferred as the second component. 097144296 12 200932531 Further, as a mixture of preferred dicarboxylic acid components, for example, terephthalic acid is used as the first component. From isophthalic acid, 1,4-cyclohexanedicarboxylic acid, glassy acid and adipic acid At least one component selected from the group (preferably an isophthalic acid component) is used as the second component. The content ratio of the total amount of the tickic acid component and the diol component below the second component The total of the total amount of the above-mentioned dicarboxylic acid component (% by mol) and the total amount of the above diol component (100 mol%) (200 mol%) is ❹10 mol% or more. Preferably, it is 20 mol% or more, and is 50 mol% or less, preferably 40 mol% or less. When the content of the component of the second component or less is 10 mol% or more, the degree of crystallization of the obtained polyester can be suppressed to a low value. On the other hand, when the content of the component of the second component or less is 5 莫 mol% or less, the advantage of the first component can be exhibited. For example, when the dicarboxylic acid component is a terephthalic acid component and the first component of the diol component is an ethylene glycol component and the second component is a 1,4-cyclohexanedikecan component, The content of i, 4_cyclohexane dimethanol component of the two components is relative to the total amount of the terephthalic acid component belonging to the dicarboxylic acid component (1% molar %) and the ethylene glycol component and hydrazine, 4 - The total amount (100 mol%) of the cyclohexanedimethanol component (200 mol%) is 1 mol% or more, preferably 15 mol% or more, more preferably Tomor % or more, and is 50 mol% or less, preferably 40 mol% or less, more preferably 35 mol% or less. By using the ethylene glycol component and the 14-cyclohexene dimethanol component in this garden, the crystallinity of the diol forming process is almost the same, and the fracture resistance can be improved. 097144296 13 200932531 In the above example, the dicarboxylic acid component knife 1糸u terephthalic acid component is used as the first component, and the isophthalic acid component is used as the second component. The content of the phthalic acid component and the U-cyclohexanol component belonging to the diol component is relative to the total amount of the stearic acid component and the meta-benzene 'dicarboxylic acid component (10). The total amount of the alcohol component and the total amount of the U-cyclohexane-diethanol component (10% by mole) is 2 mol% or more, preferably 15 mol% or more, more preferably 25 mol. The ear% or more, β is 50 mol% or less, preferably 40 mol% or less, more preferably 35 mol% or less. The refractive index (η1) of the polyester resin is 156 Å or more and 158 Å or less, preferably about 1.570. The polyester resin has an intrinsic viscosity (IV) of 〇5 dl/g or more, preferably 0.6 dl/g or more, more preferably 〇7 dl/g or more, and 15 dl/g or less, preferably 1. 2 dl / g or less, more preferably 1. 〇 dl / g or less. When the intrinsic viscosity (iv) is 0·5 dl/g or more, the deterioration of the film strength characteristics and heat resistance can be suppressed. On the other hand, if the intrinsic viscosity is 1.5 dl/g or less, the fracture due to the increase in the stretching tension can be prevented.

• 若例示上述聚酯系樹脂的具體商品，可舉出例如「PETG - c〇Plyester6763」、「Embrace LV」（Eastman Chemical 公司 製）及「PETGSKYGREENS2008」（SK Chemical 公司製）等。 作為本發明之積層體的第2層所使用之聚酯系樹脂，除了 由上述二羧酸成分與二醇成分所衍生之聚酯系樹脂以外，亦 097144296 14 200932531 可使1於2分子中具有鲮酸成分與醇成分之單體聚合而成 之聚ga系⑽日。尤其將乳酸聚縮合而成之聚乳酸’由賦予剛 性低皿收縮性、低自然收縮性而言，可適合使用。 適口作為構成第2層之聚酯系樹脂而使用之聚乳酸系樹 月曰係心D~乳酸或L~乳酸的同元聚合體或該等之共聚合 亦包含該等之混合物。更具體而言，係為構造單位為 D乳心之聚（D—乳酸）、構造單位為L-乳酸之聚（L-乳酸）、 Ο狀L-礼酸與D_乳酸之共聚合體的聚（DL_乳酸）、或該等 之混合物。 聚乳酸系樹脂為D-乳酸與L_乳酸之混合物的情況，D—乳 酸與L-乳酸之混合比較佳為D_乳酸/L_乳酸 =99· 8/0. 2〜75/25 或 D-乳酸/L-乳酸=〇. 2/99. 8〜25/75,更佳 係D-乳酸/L-乳酸=99. 5/〇·5〜8〇/2〇或D_乳酸几乳酸For example, "PETG-c〇Plyester6763", "Embrace LV" (manufactured by Eastman Chemical Co., Ltd.), and "PETGSKYGREENS2008" (manufactured by SK Chemical Co., Ltd.), etc., are exemplified as the specific products of the polyester resin. The polyester-based resin used in the second layer of the laminate of the present invention may be one or two molecules in addition to the polyester-based resin derived from the above dicarboxylic acid component and the diol component, and also 097144296 14 200932531. A poly-ga system (10) in which a monomer of a decanoic acid component and an alcohol component are polymerized. In particular, the polylactic acid which is obtained by polycondensing lactic acid is suitably used in terms of imparting low shrinkage and low natural shrinkage. A homopolymer which is a polylactic acid-based tree of the polyester resin constituting the second layer, which is used as the polyester resin of the second layer, or a homopolymer of L-lactic acid or the like, or a mixture thereof. More specifically, it is a polycondensation of a poly (D-lactic acid) having a structural unit of D-nucleus, a poly(L-lactic acid) having a structural unit of L-lactic acid, and a copolymer of L-lactate and D_lactic acid. (DL_lactic acid), or a mixture of such. The polylactic acid-based resin is a mixture of D-lactic acid and L-lactic acid, and the mixture of D-lactic acid and L-lactic acid is preferably D_lactic acid/L_lactic acid=99·8/0. 2~75/25 or D -Lactic acid/L-lactic acid=〇. 2/99. 8~25/75, more preferably D-lactic acid/L-lactic acid=99. 5/〇·5~8〇/2〇 or D_lactic acid

=0· 5/99· 5〜20/80。D-乳酸單獨或L—乳酸單獨所構成之聚乳 酸係顯示非常高的結晶性，且熔點高，有耐熱性及機械物性 優異之傾向。然而，當將本發明之積層體使用作為熱收縮性 薄膜之情況，通常係伴隨有使用印刷及溶劑之製袋步驟，故 為了提升印刷適性及溶劑密封性，必須適度降低構成材料本 身之結晶性。又，當結晶性過高之情況，於延伸時係進行配 向結晶化’而有收縮特性降低之傾向。由該等情況而士本 發明所使用之聚乳酸系樹脂的混合比較佳為乳酸^一乳 酸=99/1 〜85/15 或 D-乳酸/L-乳酸=1/99〜15/85。 097144296 15 200932531 本發明中，聚乳酸系樹脂係可混合 D-乳酸與L-乳酸的共聚合體而使用。此同共聚合比之 個乳酸系聚合體之卜乳睃與L-乳駿的二二中’只要將多 整為上述範圍内即可。板據使用用途，°比之平均值調 D-乳酸與L-乳酸之共聚合體比不同=合二種以上的 結晶性，藉此在成形為熱收縮性_#=系樹脂，調整 熱收縮特性之平衡。 3 /兄中取得耐熱性與 ❹ 本發月所使用之聚㈣㈣ 叛酸或脂肪族二醇、月旨肪族二㈣之2錢與㈣基 與乳酸系樹脂共聚合之「 、 口體。在此，作為 1m 基療酸」’可舉出乳酸之#興 異構體（相對於L—乳酸為D_乳酸 出桃之先予 酸）、乙醇酸、3-幾基丁酸、4_經基丁^ '礼酸為L-乳 2,基-3，kf基丁酸、2_輕=基-正丁酸、 酸、2-經基己内醋酸0 ^丁酸、2-甲基丁 内乂 Γ 官能脂肪麵基姻，以及己 =:、戊内，等之_。又，作為與乳酸系樹脂 4 口之月曰肪族二醇’可舉出乙二醇、I 4_丁二醇、】4— 環己燒二甲料。又’作為被共聚合之脂肪族讀酸，可舉 出珑賴、己二酸、辛二酸、癸二_及十二烧二酸等。乳 酸與α，基紐、脂肪族二醇或脂肪族二賴之共聚合體 的/、聚σ比，較佳為乳酸/ ( α _羥基鲮酸、脂肪族二酸或脂 肪族二羧酸）=90/10〜10/90之範圍，更佳為8〇/2〇〜2〇/8〇， 特佳為30/70〜70/30。若共聚合比為上述範圍内，可獲得剛 097144296 16 200932531 性、透明性、耐衝擊性等物性平衡良好的薄膜。 上述聚乳酸系樹脂係可利用縮合聚合法、開環聚合法等之 公知聚合法而製作。例如，若為縮合聚合法，可將D_乳酸、 • L-乳酸或該等之混合物進行直接脫水縮合聚合，獲得具有任 •意組成之聚乳酸系樹脂。又，於開環聚合法方面，可將屬於 乳酸之環狀二聚物的乳酸交醋，視需要在使用聚合調整劑等 之下’於既定觸媒之存在下進行開環聚合，藉此獲得具有任 ❹ 意組成之聚乳酸系樹脂。上述乳酸交酯中有屬於l-乳酸之 一聚物的DL-乳酸父S旨，藉由視需要將該等予以混合並聚 合’可獲得具有任意組成、結晶性之聚乳酸系樹脂。此外， 亦可在增大分子直之目的下，使用少量之鏈延長劑，例如二 異氰酸酯化合物、二環氧化合物、酸酐、醯氯（acid chloride)等。 上述聚乳酸系樹脂之重量（質量）平均分子量係為2〇, 〇〇〇 ❹以上、較佳為40, 000以上、更佳為以上，且為 400, 000以下、較佳為350, 000以下、更佳為〇〇〇以下。 若重量（質量）平均分子量為20, 000以上，可獲得適度的 - 樹脂凝集力，可抑制薄膜之強伸度不足或脆化。另一方面， - 若重量（質量）平均分子量為400, 000以下，則可降低熔融 黏度’以製造、生產性提升之觀點而言為佳。 作為上述聚乳酸系樹脂之市售品，例如可舉出 「NatureWorks」（NatureWorksLLC 公司製）、r LACEA」（三 097144296 17 200932531 井化學公司製）等。 第2層中所含之聚酯系樹脂相對於第2層之樹脂總量若含 有60質量％以上、較佳為70質量％以上、更佳為8〇質量^ 以上’則亦可含有聚g旨系樹脂以外之樹脂。若例示此種樹 -脂，可舉出例如聚烯烴系樹脂、聚苯乙烯系樹脂、聚碳酸酯 樹脂、丙烯酸系樹脂，其中以聚笨乙烯系樹脂為佳。 〈第3層〉 ® 本發明之積層體可於與第2層為相反侧之第1層上，且有 以與構成第2層之樹脂組成物不同組成的樹脂組成物所構 成之第3層。例如，若於第1層上設置以不同組成之聚酯系 樹脂組成物所構成的第3層，則可對第3層與第2層賦予不 同的結晶性，可調整積層體之聚酯的結晶化率。 作為第3層可使用之樹脂組成物，可舉出例如苯乙烯系樹 脂、聚碳酸酯系樹脂、聚醯胺系樹脂、聚烯烴系樹脂、聚（曱 基）丙烯酸酉旨樹脂、或含有與構成帛2層之聚醋系樹脂不同 的聚酯系樹脂等作為主成分之樹脂組成物等。其中，當第3 層係由含有苯乙烯系樹脂作為主成分之樹脂組成物所構成 之情況，由於可對積層體賦予充分的層間剝離強度，故適合 使用。 作為構成第3層之苯乙稀系樹脂，可適合使用苯乙烯系烴 與共耗二烯系煙之嵌段共聚合。作為苯乙烯紐，例如可舉 出聚苯乙烯、聚（對一間'或鄰-曱基苯乙烯）、聚（2, 4-、 097144296 18 200932531 2, 5-、3, 4-或3, 5-二甲基苯乙烯）、聚（對_第三丁基苯乙 稀）等之聚烷基苯乙烯；聚（鄰_、間—或對—氯化苯乙烯）、 聚（鄰-、間-或對-溴化苯乙烯）、聚（鄰_、間-或對-氟化 苯乙烯）、聚（鄰-甲基-對-氟化苯乙烯）等之聚鹵化苯乙烯； • 聚（鄰―、間-或對-氯化曱基苯乙烯）等之聚鹵化取代烷基 苯乙烯；聚（對-、間-或鄰-曱氧基苯乙烯）、聚（鄰_、間_ 或對-乙氧基苯乙烯）等之聚烷氧基苯乙烯；聚（鄰_、間一 ❹或對-羧基曱基苯乙烯）等之聚羧基烷基苯乙烯；聚（對-乙烯基苄基丙基醚）等之聚烷基醚苯乙烯；聚（對_三甲基 矽基苯乙烯）等之聚烷基矽基苯乙烯；以及聚乙烯基苄基二 甲氧基亞磷酸鹽等。該苯乙烯系烴嵌段亦可於嵌段内含有該 等之同元聚合體、共聚合體及/或苯乙烯系烴以外之可共聚 合的單體。 作為共軛二烯系烴之例，可舉出丁二烯、異戊二烯、2一 甲基-1，3-丁一稀、2, 3-一 甲基-1，3-丁 二烯、1，3-戊二烯、 1,3-己二稀等。共輛二浠系烴嵌段亦可於嵌段内含有該等之 同元聚合體、共聚合體及/或共扼二豨系煙以外之可共聚合 • 的單體。 - 作為第3層中可較佳使用之苯乙烯系烴與共軛二烯系烴 之嵌段共聚合體之一，可舉出苯乙烯系烴為苯乙烯而共軛二 烯系烴為丁二烯之苯乙烯-丁二烯系嵌段共聚合體（SBS)。 SBS較佳係苯乙烯/ 丁二烯的質量％比為（95〜6〇) / (5〜4〇) 097144296 19 200932531 左右’更佳為(93’V(7〜4〇)，4(9〇〜6〇)/(i〇 4〇) 左右。此外’ SBS之熔融流動速率（_)測定值（測定條 件：溫度20(TC、負重麵）為2g/1()分鐘以上較佳為 .分鐘以上，且為心/1〇分鐘以下、較佳為10g/10分鐘以下， • 更佳為8g/l0分鐘以下。 本發明中，作為苯乙烯系烴與共扼二缔系煙之谈段共聚合 體，亦適合使用苯乙烯一異戊二埽—丁二烯係嵌段共聚合體 ❹（SIBS)〇SIBS中，苯乙烯/異戊二婦/丁二稀之質量％比較 佳為（60〜90)/( 50〜4〇)/(5〜3〇)，更佳為（㈣5)/⑴撕 /(5〜25)，特佳為（6()~8())/(1()〜25)/(5~2())。此外， 遞之熔融流動速率（MFR)啦值（測定條件：溫度· t：、負重49N)係為2g/10分鐘以上、較佳為3g/i〇分鐘以 上’且為15g/10分鐘以下、較佳為1〇g/1〇分鐘以下更佳 為8g/10分鐘以下。若丁二婦含有量多而異戊二稀含有量 少，則有於擠出機内部等中被加熱之丁二婦引發交聯反應而 使膠狀物增加之情況。另—方面，若丁二稀含有量少而異戊 一烯a有里多，則有丁二烯之交聯反應受到抑制而使膠狀物 -被抑制之情況。 - 上述笨乙烯系樹脂並不限於單純物質，亦可為2種類以上 之混合物。例如上述苯乙烯系樹脂為现5與幻肪之混合物 之情況，SBS/SIBS之質量。/。比較佳為（9〇〜1〇) / (1〇~9〇) 左右，更佳為（80〜20) / ( 20〜80)左右，特佳為（7〇〜30) 097144296 20 200932531 / (30~70)左右。 第3層所含有之上述苯乙烯系樹脂的含有率，係為構成第 3層之樹脂組成物總量的50質量％以上，較佳為65質量°/〇以 -上，更佳為80質量％以上。惟，當含有GPPS之情況，由於 • GPPS之Tg(損失彈性模數E”之波峰溫度）係為100°C左右 之非常高的值’所混合之GPPS之含有率較佳為構成第3層 之樹脂總量的20質量％以下，更佳為15質量％以下，特佳為 Ο ίο質量％以下。 第3層所含有之上述苯乙烯系樹脂只要如上所述般含有 構成第3層之樹脂組成物總量的50質量％以上，亦可混合其 他樹脂。若例示此種可混合之樹脂，可舉出聚酯系樹脂、含 有聚醋系彈性體或改質聚醋系彈性體之樹脂、聚稀煙系樹 脂、丙烯酸系樹脂、聚碳酸酯樹脂等。其中較佳為聚醋系樹 脂、或含有聚㈣彈性體或改質聚料彈性體的樹脂，較佳 係以構成第3層之樹脂組成物總量的4〇質量％以下、更佳為 35質《以下、特佳為30質量％以下之含有率含有。…、 第3層所含有之苯乙婦系樹脂為苯乙稀系烴與 系煙之嵌段絲合體之情況，上㈣段 _為鲜制定之折射率⑽魏_2層所含有 =樹:組成物的折射率(nl)々〇〇2、更佳為±_ 此广將第3層之折射率⑽之 折射率（nl)之差娜於既定之範_，當將本發明之積層 097144296 21 200932531 體成形為熱收縮性薄膜之情況、與將薄膜之製造步驟中所產 生之薄膜的切斷片等混練於後述之第3層中而進行製膜之 情況，均可獲得具有良好透明性之薄膜。 丨述苯乙料烴與_二_烴之嵌段共聚合體 ，係可藉 由適當調整苯乙埽系烴與共輛二稀系烴之組成比而將其折 射率U2)調整為接近所需之值。因此，對應於第2層所使 用之聚醋系樹脂的折射率（nl)，調整第3層所使用之欲段 ❹共聚合體的苯乙㈣烴與驗二烯系烴的組成比，藉此可獲 得nl±0.02之範圍内的折射率（n2)。該既定之折射率可利 用苯乙烯系烴與共軛二烯系烴之嵌段共聚合體單純物質來 調整，亦可混合2種以上的樹脂來調整。 本發明中’第3層所含有之上述苯乙稀系樹脂之代的儲 存彈性模數（E )較佳為1. 〇〇xl〇9Pa以上，更佳為1 50x 109Pa以上。該0°C的儲存彈性模數（£’ ）係表示將上述笨 ® 乙嫜系樹脂成形為既定厚度的薄膜時之薄膜的剛性，亦即薄 膜的彈性強度。藉由具有l.〇〇xl〇9Pa以上之儲存彈性模數 (E’ ）’當將本發明之積層體成形為薄膜之情況，可獲得除 - 了透明性亦具備剛性之薄膜。該儲存彈性模數（E，）係萨 - 由上述本乙烯系經與共輥一烯系煙之嵌段共聚合體的單純 物質、2種以上之該共聚合體的混合物、或者在無損於透明 性之範圍内與其他樹脂混合而獲得。 當使用苯乙烯系烴與共軛二烯系烴之嵌段共聚合體的混 097144296 22 200932531 合系統、或該共聚合體與其他樹脂之混合系統作為第3層之 主成分的情況’係可藉由適當選擇負責耐斷裂性之共聚合體 或樹脂與負責剛性之共聚合體或樹脂，而獲得良好的結果。 亦即，藉由組合具有高耐斷裂性之苯乙烯系烴-共軛二烯系 煙之嵌段共聚合體、與具有高剛性之苯乙烯系烴-共輛二稀 系烴之嵌段共聚合體’或者藉由混合具有高耐斷裂性之苯乙 烯系烴-共軛二烯系烴之嵌段共聚合體、與具有高剛性之其 © 他種類之樹脂組成物，可進一步調整該等苯乙烯系烴—共軛 二烯系烴之合計組成或者進一步與其他種類樹脂之混合 物，使其滿足所需之折射率（n2)及之儲存彈性模數 (E，）。=0· 5/99· 5~20/80. The polylactic acid composed of D-lactic acid alone or L-lactic acid alone exhibits very high crystallinity, has a high melting point, and is excellent in heat resistance and mechanical properties. However, when the laminate of the present invention is used as a heat-shrinkable film, it is usually accompanied by a bagging step using printing and a solvent. Therefore, in order to improve printability and solvent sealing property, it is necessary to appropriately lower the crystallinity of the constituent material itself. . Further, when the crystallinity is too high, the alignment crystallization is carried out during stretching, and the shrinkage characteristics tend to be lowered. The mixing of the polylactic acid-based resin used in the present invention is preferably lactic acid = 99/1 to 85/15 or D-lactic acid/L-lactic acid = 1/99 to 15/85. 097144296 15 200932531 In the present invention, a polylactic acid-based resin can be used by mixing a copolymer of D-lactic acid and L-lactic acid. This is the same as the copolymerization ratio of the lactic acid-based polymer and the L-milk of the lactic acid-based polymer as long as it is within the above range. According to the use, the ratio of D-lactic acid to L-lactic acid is different from the average value = the crystallinity of two or more types is combined, whereby the heat shrinkage property is adjusted by heat shrinkage _#= resin. Balance. 3 / Brothers to obtain heat resistance and ❹ This month's use of poly (four) (four) tick or aliphatic diol, the month of the two (four) of the two money and the (four) base and lactic acid resin copolymerization, the mouth. Therefore, as the 1 m-based therapeutic acid "", the isomer of lactic acid (relative to L-lactic acid, D_lactic acid, pre-acid), glycolic acid, 3-methylbutyric acid, 4_jing Keding ^ 'Like acid is L-milk 2, ke -3, kf-butyric acid, 2 - light = keto-n-butyric acid, acid, 2-transpyridyl acetate 0 ^ butyric acid, 2-methyl butyl Internal 乂Γ Functional fat surface base, and _ =, 戊,, etc. _. Further, examples of the aliphatic diol diol which is a lactic acid-based resin include ethylene glycol, I 4 -butanediol, and 4-cyclohexene dimethyl hydride. Further, examples of the aliphatic acid-reading acid to be copolymerized include sputum, adipic acid, suberic acid, bismuth dihydrate, and dodecanedioic acid. The ratio of lactic acid to α, ketone, aliphatic diol or aliphatic conjugate, / σ ratio, preferably lactic acid / ( α _ hydroxy decanoic acid, aliphatic diacid or aliphatic dicarboxylic acid) = The range of 90/10~10/90 is more preferably 8〇/2〇~2〇/8〇, especially good 30/70~70/30. When the copolymerization ratio is within the above range, a film having a good balance of physical properties such as 097144296 16 200932531, transparency, and impact resistance can be obtained. The polylactic acid-based resin can be produced by a known polymerization method such as a condensation polymerization method or a ring-opening polymerization method. For example, in the case of a condensation polymerization method, D_lactic acid, L-lactic acid or a mixture of the above may be subjected to direct dehydration condensation polymerization to obtain a polylactic acid-based resin having an arbitrary composition. Further, in the ring-opening polymerization method, lactic acid which is a cyclic dimer of lactic acid may be subjected to ring-opening polymerization in the presence of a predetermined catalyst, if necessary, by using a polymerization regulator or the like. A polylactic acid-based resin having any desired composition. In the above-mentioned lactide, a DL-lactic acid parent which is a monomer of l-lactic acid is used, and if necessary, these are mixed and polymerized to obtain a polylactic acid-based resin having an arbitrary composition and crystallinity. Further, a small amount of a chain extender such as a diisocyanate compound, a diepoxide, an acid anhydride, an acid chloride or the like may be used for the purpose of increasing molecular straightness. The polylactic acid-based resin has a weight (mass) average molecular weight of 2 Å or more, preferably 4,000 or more, more preferably more than 400,000 or less, and preferably 1,500 or less. More preferably, the following. If the weight (mass) average molecular weight is 20,000 or more, a moderate - resin cohesive force can be obtained, and the film can be suppressed from being insufficient in elongation or embrittlement. On the other hand, if the weight (mass) average molecular weight is 400,000 or less, the melt viscosity can be lowered, which is preferable from the viewpoint of production and productivity improvement. For example, "NatureWorks" (manufactured by NatureWorks LLC), r LACEA (manufactured by Well Chemical Co., Ltd.), etc., may be mentioned as a commercial product of the above-mentioned polylactic acid-based resin. The polyester resin contained in the second layer may contain 60% by mass or more, preferably 70% by mass or more, more preferably 8 Å by mass or more, based on the total amount of the resin of the second layer. It is intended to be a resin other than resin. For example, a polyolefin resin, a polystyrene resin, a polycarbonate resin, or an acrylic resin is exemplified, and a polystyrene resin is preferred. <Layer 3> The laminate of the present invention may be on the first layer opposite to the second layer, and may have a third layer composed of a resin composition different from the resin composition constituting the second layer. . For example, when a third layer composed of a polyester resin composition having a different composition is provided on the first layer, different crystallinity can be imparted to the third layer and the second layer, and the polyester of the laminate can be adjusted. Crystallization rate. Examples of the resin composition usable in the third layer include a styrene resin, a polycarbonate resin, a polyamide resin, a polyolefin resin, a poly(decyl)acrylic resin, or a A resin composition or the like as a main component, such as a polyester resin having a different polyester resin having two layers. In the case where the third layer is composed of a resin composition containing a styrene resin as a main component, since the laminate can be provided with sufficient interlayer peel strength, it is suitably used. As the styrene-based resin constituting the third layer, a block copolymerization of a styrene-based hydrocarbon and a co-depleted diene-based tobacco can be suitably used. Examples of the styrene neodymium include polystyrene, poly(p-' or o-mercaptostyrene), poly(2, 4-, 097144296 18 200932531 2, 5-, 3, 4- or 3, Polyalkylstyrene such as 5-dimethylstyrene), poly(p-tert-butylstyrene), poly(o-, m- or p-chlorostyrene), poly(o--, Poly-halogenated styrene such as meta- or para-bromostyrene), poly(o-, m- or p-fluorinated styrene), poly(o-methyl-p-fluorinated styrene), etc.; Polyhalogenated substituted alkylstyrenes such as o-, m- or p-nonylphenyl styrene; poly(p-, m- or o-nonyloxystyrene), poly(o-_, _ Or polyoxyalkyl styrene of p-ethoxystyrene; poly (carboxyl styrene) such as poly(o-, m- or p-carboxydecyl styrene); poly(p-vinyl) Polyalkylether styrene such as benzyl propyl ether; polyalkyl fluorenyl styrene such as poly(p-trimethyldecyl styrene); and polyvinyl benzyl dimethoxy phosphite Wait. The styrene-based hydrocarbon block may contain a copolymerizable monomer other than the homopolymer, the copolymer, and/or the styrene hydrocarbon in the block. Examples of the conjugated diene hydrocarbons include butadiene, isoprene, 2-methyl-1,3-butadiene, and 2,3-monomethyl-1,3-butadiene. , 1,3-pentadiene, 1,3-hexadiene, and the like. The common diterpene hydrocarbon block may also contain copolymerizable monomers other than the homopolymer, the copolymer, and/or the conjugated fluorene in the block. - One of the block copolymers of a styrene-based hydrocarbon and a conjugated diene-based hydrocarbon which can be preferably used in the third layer, and examples thereof include a styrene-based hydrocarbon and a conjugated diene-based hydrocarbon. A styrene-butadiene block copolymer (SBS). The mass ratio of SBS is preferably styrene / butadiene is (95~6〇) / (5~4〇) 097144296 19 200932531 around 'better' (93'V (7~4〇), 4 (9 〇~6〇)/(i〇4〇) or so. In addition, the measurement value of the melt flow rate (_) of SBS (measurement conditions: temperature 20 (TC, load surface) is 2g/1 () minutes or more is preferably. More than a minute, and it is a heart/1 minute or less, preferably 10 g/10 minutes or less, and more preferably 8 g/l0 minute or less. In the present invention, as a styrene hydrocarbon and a conjugated cigarette The copolymer is also suitable for the use of styrene-isoamyl-butadiene-based block copolymer ❹(SIBS)〇SIBS, and the mass% of styrene/isoprene/butadiene is relatively good (60~ 90) / ( 50 ~ 4 〇) / (5 ~ 3 〇), better ((4) 5) / (1) tear / (5 ~ 25), especially good (6 () ~ 8 ()) / (1 () ～25)/(5~2()). Further, the melt flow rate (MFR) value (measurement condition: temperature·t:, load weight 49N) is 2 g/10 min or more, preferably 3 g/i. It is preferably 15 g/10 min or less, preferably 1 g/1 min or less, and more preferably 8 g/10 min or less. When the amount of Ding Er women is large and the content of isoprene is small, there is a case where the Ding Er woman is heated in the inside of the extruder to cause a cross-linking reaction to increase the gum. In other respect, if Ding Er When the amount of the rare content is small and the amount of the isoprene-ene is too large, the crosslinking reaction of the butadiene is suppressed and the jelly is suppressed. - The above-mentioned stupid vinyl resin is not limited to a simple substance. It is a mixture of two or more types. For example, the above styrene resin is a mixture of the current 5 and the illusion, and the mass of the SBS/SIBS is better. (9〇~1〇) / (1〇~9〇) Left and right, more preferably (80~20) / (20~80), especially good (7〇~30) 097144296 20 200932531 / (30~70). The above styrene resin contained in the third layer The content ratio is 50% by mass or more, preferably 65 mass%/〇-, more preferably 80% by mass or more, based on the total amount of the resin composition constituting the third layer. However, when GPPS is contained, • The Tg of the GPPS (the peak temperature of the loss elastic modulus E) is a very high value of around 100 °C. The content ratio of the mixed GPPS is higher. It is preferable that the total amount of the resin constituting the third layer is 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 5% by mass or less. The styrene resin contained in the third layer is contained as described above. The other resin may be mixed in an amount of 50% by mass or more based on the total amount of the resin composition of the third layer. Examples of such a resin that can be mixed include a polyester resin, a polyester-containing elastomer, or a modified polyester. An elastomer resin, a poly-smoke resin, an acrylic resin, a polycarbonate resin, or the like. Among them, a polyester resin or a resin containing a poly(tetra) elastomer or a modified polymer elastomer is preferably used, and preferably 4% by mass or less, more preferably 35% of the total amount of the resin composition constituting the third layer. The following is contained in the content ratio of 30% by mass or less. ..., the styrene resin contained in the third layer is a block of a styrene-based hydrocarbon and a smog, and the upper (four) segment _ is a freshly defined refractive index (10) and the 2-1 layer contains = tree: The refractive index (nl) 々〇〇2 of the composition, more preferably ± _ the difference between the refractive index (nl) of the refractive index (10) of the third layer is greater than the established value _, when the laminate of the present invention is 097144296 21 200932531 When a body is formed into a heat-shrinkable film, and a film obtained by kneading a cut film of a film produced in a film production step in a third layer to be described later to form a film, it is possible to obtain a film having good transparency. film. The block copolymer of styrene-diol and _di-hydrocarbon can be adjusted to adjust the refractive index U2) to the desired ratio by appropriately adjusting the composition ratio of the styrene-based hydrocarbon to the common di-basic hydrocarbon. The value. Therefore, the composition ratio of the styrene (tetra) hydrocarbon to the diene hydrocarbon to be used in the third layer is adjusted in accordance with the refractive index (nl) of the polyester resin used in the second layer. A refractive index (n2) in the range of nl ± 0.02 can be obtained. The predetermined refractive index can be adjusted by using a simple substance of a block copolymer of a styrene-based hydrocarbon and a conjugated diene hydrocarbon, or can be adjusted by mixing two or more kinds of resins. In the present invention, the storage elastic modulus (E) of the styrene-based resin contained in the third layer is preferably 1. 〇〇xl 〇 9 Pa or more, more preferably 1 50 x 109 Pa or more. The storage elastic modulus (£') at 0 °C indicates the rigidity of the film when the above-mentioned stupid ethyl acetal resin is formed into a film having a predetermined thickness, that is, the elastic strength of the film. When the laminated body of the present invention is formed into a film by a storage elastic modulus (E')' having a thickness of l.〇〇xl〇9Pa or more, a film having rigidity in addition to transparency can be obtained. The storage elastic modulus (E,) is a simple substance derived from the above-mentioned ethylene-based and copolymerized block copolymer of a copolymerized monoolefin, or a mixture of two or more of the copolymers, or without impairing transparency. It is obtained by mixing with other resins in the range. When a mixed system of a styrene-based hydrocarbon and a block copolymer of a conjugated diene hydrocarbon is used, 097144296 22 200932531, or a mixed system of the copolymer and another resin is used as a main component of the third layer, Good results are obtained by appropriately selecting a copolymer or resin responsible for the fracture resistance and a copolymer or resin responsible for rigidity. That is, by combining a block copolymer of a styrene-based conjugated diene-based cigarette having high fracture resistance and a block copolymer having a high rigidity of a styrene-co-diuretic hydrocarbon 'The styrene system can be further adjusted by mixing a block copolymer of a styrene-based conjugated diene hydrocarbon having high fracture resistance and a resin composition having high rigidity. The total composition of the hydrocarbon-conjugated diene hydrocarbons or a mixture with other kinds of resins to satisfy the desired refractive index (n2) and the storage elastic modulus (E,).

作為可賦予耐斷裂性之苯乙烯系烴_共軛二烯系烴的嵌段 聚口體，較佳者為純喪段SBS (pure bi〇ck別3)及無規 嵌段SBS (randomblockSBS)。其中’尤其以具有yc之儲 存彈性模數（E，）在L G_8pa以上且丨烏l()9pa以下， 而知失彈性模數（E”）之波峰溫度的至少—者為-赃以下 之黏彈性特性者為佳。若G。⑽儲存彈性魏為丨⑽咖 U藉由增加負責剛性的樹脂之摻合量㈣積層體成 形為相之情況，可_膜舒祕強度H面，損失 :=ί(Ε”）之波♦溫度卜低溫側之溫度係主要顯示 ===該特性係因延伸條件而變化，而在延伸前之狀態 下知失彈性模數（Ε”）之波峰溫度不存在於貴以下之情 097144296 23 200932531 況，當將積層體成形為薄膜時，可能難以對薄膜賦予充 斷裂性 分的 ，作為可賦予剛性之樹脂’可例示『c的儲存彈性模數 (E，）為2.00痛以上之苯乙埽系煙所構成之共聚人 體；例如控制餘構造的苯乙__料二料烴的奸 體;聚苯乙稀、苯乙烯系烴與脂肪族不綱酸‘ 二為控制嵌段構造之笨乙_^_二㈣烴嵌段 口 ^可舉出苯乙烯-丁二稀嵌段共聚合體的特性為代的 儲存弹性率（E，）為2.〇〇xl〇9Pa以上 的As the block polymer of the styrene-based hydrocarbon-conjugated diene hydrocarbon which can impart fracture resistance, it is preferably pure SBS (pure bi〇ck 3) and random block SBS (randomblock SBS). . Wherein, in particular, the storage elastic modulus (E,) having yc is above L G_8pa and the 丨 l (1 9pa or less), and the peak temperature of the known elastic modulus (E" is at least - 赃The viscoelastic property is better. If G. (10) storage elasticity Wei Wei (10) coffee U by increasing the amount of resin involved in the rigidity of the resin (4) the formation of the layered body as a phase, can be _ membrane relaxation strength H surface, loss: =ί(Ε)) Wave ♦ Temperature Bu temperature on the low temperature side mainly shows === This characteristic changes due to the extension condition, and the peak temperature of the lost elastic modulus (Ε") is not in the state before the extension In the case of forming a laminate into a film, it may be difficult to impart a fracture-producibility to the film, and as a resin capable of imparting rigidity, the storage elastic modulus of "c" may be exemplified (E, a comonomer consisting of phenethyl acetonide with a viscosity of 2.00 or more; for example, a trait of a benzene-based hydrocarbon containing a residual structure; a polystyrene, a styrene-based hydrocarbon, and an aliphatic non-acid The second is to control the block structure of the stupid B _ ^ _ (four) hydrocarbon block mouth ^ can be cited benzene Alkenyl - butadiene block copolymer assembly characteristics generation storage modulus (E,) than is 2.〇〇xl〇9Pa

的苯乙烯〜丁二烯的組成 滿足其之SBS (95,)/…0)左右。 整為笨乙稀/丁二歸=The composition of styrene ~ butadiene satisfies its SBS (95,) / ... 0). The whole is stupid Ethylene / Ding Ergui =

規共聚合趙之構造及各丧段部分的構造，較佳為A 規嵌段及錐形嵌段。更佳為，為 ^較佳為無 彈性模數Μ”）之波峰溫度為，收縮特性而使損失 下沒有明確的損失彈_ 乂上，特佳為在靴以 性率（E，，）之波♦严声s )之波峰溫度。當損失彈 況，幾乎顯示與聚苯乙 c為止均為表觀上不存在的情 予薄臈之㈣。又，彳。失㈣的儲存彈性模數雜，故可賦 在於抓以上，較模數（E”）之_溫度係存 峰溫度係主要影響收縮 上且崎以下之範圍。該波 啊以下之範圍，則自然該溫度在做以上且 097144296 . 、民溫收縮率均不會劇烈降 24 200932531 低0 滿足上述黏彈性特性之苯乙烯系烴-共軛二烯系烴共聚合 體的聚合方法示於下。以一般方法裝入苯乙烯或丁二烯之一 '部分並使聚合結束後，裝入苯乙烯單體與丁二烯單體之混合 • 物，使聚合反應繼續進行。藉此，聚合活性高的丁二稀係優 先聚合，最後產生由苯乙烯之單純單體所構成之嵌段。例 如，若先使苯乙烯同元聚合，於聚合結束後，裝入苯乙烯單 ❹ 體與丁二烯單體之混合物，使聚合繼續進行，則可獲得具有 於苯乙烯嵌段與丁二烯嵌段之中間使苯乙烯· 丁二烯單體比 依序變化之苯乙烯•丁二烯共聚合體部位的苯乙烯-丁二烯 嵌段共聚合體。藉由具有此種部位，可獲得具有上述黏彈性 特性之聚合物。此情況中，無法明確地確認到上述之丁二烯 嵌段與苯乙烯嵌段所造成的2個波峰，於表觀上僅看見存在 1個波峰。亦即，於純嵌段或丁二烯嵌段明確存在之無規嵌 ® 段SBS般的嵌段構造中，丁二烯嵌段所造成之Tg主要存在 於0°C以下，因此變得難以使0°C之儲存彈性模數（E’ ）成 為既定值以上。又，關於分子量係以熔融流動速率（MFR) - 測定值（測定條件：200°C、負重49N)為2g/10分鐘以上 . 且15g/10分鐘以下之範圍調整。該賦予剛性之苯乙烯-丁二 烯嵌段共聚合體之混合量係依其積層體的特性而適當調 整，較佳係調整為構成第3層之樹脂組成物總量的20質量％ 以上且80質量％以下，更佳為40質量％以上且70質量％以下 097144296 25 200932531 之範圍。若笨乙说— 成物她縣段共聚合體之混合量為樹脂組 :=8°質量%以下，則在將積層體成形為_ 大幅=薄膜之剛性，且可抑制耐斷裂性之降低。另一方 ㈣之20 烯嵌段共聚合體之混合量為樹脂組成物 &quot; 以上，則可對薄膜賦予充分的剛性。 第層所3有之苯乙締系樹脂的分子量，重 ❹ ❹ 以上、較佳為⑽屬以上= 為500,000以下、查吞社攻 以下為棚，000以下、更佳為3〇〇,〇〇〇 二::上:樹_ 若苯：:發生薄膜劣化之缺點偷 =乙=fc之重量(質量)平均分子量( 以下’則沒有調整流動特性之 點，故較佳。 Μ擠纽降低等缺 ，用苯乙稀系烴與脂肪族不飽和緩酸醋之共聚合體作為 樹脂之情況，作為與苯乙烯系煙絲合之脂肪族不 飽和缓酸醋，可舉出甲基（甲基）两埽酸醋、丁基（甲基） 丙細旨、2—乙基己基（甲基）丙_自旨、月桂基（甲i) 丙_旨、硬脂基（曱基）丙_旨。較佳為苯乙烯與丁基 (甲基）丙稀酸醋之共聚合體，更佳為笨乙稀在7G質量％ 以上且90請以τ之範圍，且Tg(損失彈性模數E”之波 峰溫度）在5(TC以上且9代以下、您融流動速率（猶）測 定值（測定條件：溫度2〇(TC、負重彻）在2洲分鐘以 097144296 26 200932531 上且15g/l0分鐘以下者。另外，上述（甲基）丙嫌酸酯係 表示丙烯酸酯及/或曱基丙烯酸醋。 苯乙烯系烴與脂㈣不飽和紐紅共聚合體在第3層 中之含有量，係依其組成比而適當決定。典型例子係相對於 構成第3層之樹脂組成物總量，調整為2〇質量％以上且70 質量％以下之範圍。若以上述共聚合體之含有率為質量％ 以下進行混合，當將本發明之積層體成形為薄膜之情況，可 © 大幅提昇薄膜之剛性，且可維持良好的耐斷裂性。又，若以 20質量％以上進行混合，則可對薄膜賦予充分的剛性。 本發明之積層體除了上述成分之外，在不明顯阻礙本發明 之效果的範圍内’亦可在改良•調整成形加工性、生產性及 成形後之薄膜的各物性之目的下，於各層中含有可塑劑及/ Ϊ黏。著賦予樹脂，其含量係相對於構成各層之樹脂總量為1 質量％以上、較佳為2質量％以上、更佳為3質量％以上，且 2 1〇質量％以下、較佳為8質量％以下、更佳為5質量。以下。 或㈣賦予樹脂之含有率相對於樹脂總量為 亦不县’觀融黏度之降低與耐熱溶融性的降低小， ' 自然收縮。此外，本發明之積層胃^ &quot; 劑及黏荃盹谓增體除了上述可塑 黏者賦予樹脂之外，亦可視目的， 加冬祷禾+如 ^各_途適當添 ，、、〇劑，例如紫外線吸收劑、光安定劑 安定劑、荽&amp;卡， n抗氧化劑、 者色劑、抗靜電劑、潤滑劑、無機填 〈層構成〉 具死材4。 097144296 27 200932531 本發明之積層體只要為至少具有第1層與第2層之2層以 上的構成，則層構成並無特別限定，例如可為第1層/第2 層之層構成或第2層/第1層/第2層、第2層/第1層/第2 層/第1層/第2層之層構成。較佳為在第2層相反側之第1 -層上，具有由與構成第2層之樹脂組成物不同組成的樹脂組 成物所構成之第3層之層構成，更佳為第3層係由含有聚苯 乙烯系樹脂作為主成分之樹脂組成物所構成的層。 ❹ 本發明中較佳之積層構成為由第2層/第1層/第3層/第 1層/第2層所構成之5層構成。释由採用此層構成，當將 本發明之積層體成形為熱收縮性薄膜之情況，可以良好生產 性、經濟性，獲得目的之薄膜剛性、收縮完成性、耐斷裂性 優異，且層間剝離受到抑制之適於收縮包裝、收縮收束包裝 或收縮標籤等用途的熱收縮性薄膜。 其次，針對本發明較佳實施形態之一的第2層/第1層/ ❹第3層/第1層/第2層之5層構成的積層體進行說明。惟， 只要沒有特別的問題’相關之說明記載亦可適用於其他的層 構成。 • 本發明之積層體中，關於第2層與第3層之厚度比，當將 .第2層定為1之情況’第3層係為2以上、較佳為3以上、 更佳為4以上，且為12以下、較佳為10以下、更佳為8 以下。又，第i層之厚度係為第2層厚度之5%以上、較佳 為1(U以上，且為150%以下、較佳為丨〇〇%以下、更佳為8⑽ 097144296 28 200932531 以下°若第1層之厚度為第2層厚度之5%以上1 良好的接著效果’又若為議以下（亦即第2層&lt; 可獲得 以下）之厚度，則不會造成透明性大幅降低。倍 本發明之積層體的總厚度並無特別限定，成形 薄膜前之厚度（無延伸狀態之厚度）係為5叫m :%性 佳為_ 以下，更佳為300 μ m以下，由處理性下’車交 言下限值為l〇#ra為佳。 觀點而 ❹ ❹ 本發明之積層體係經施行既定處理後之第1 間的剝㈣度具有既定之值者。亦即，將義體^少^之 向延伸’製作熱收縮性薄膜，由該熱收縮性薄膜以、方 向150mm、垂直於主收縮方向的方向15丽之大小採=輪方 片後，從賴驗片之主收縮方向的薄膜端面剝離試驗 層之-部分而分別於上述第2層上形成_部、於上、〔第2 層上形成被剝離部，將上述第2層之剝離部與上述第第1 被剝離部以拉伸試驗機之爽頭夾取，以㈣於主收端1層之 試驗速度lOOmm/min進行18〇度剝離試驗時之層間韌=向之 為1N/I5mm寬以上、較佳為2N/15mm寬以上、更佳為领/ =度 寬以上，且為20N/15mm寬以下、較佳為18N/15mm寬以下、 更佳為15N/15mm寬以下。本發明之積層體由於成形為熱收 縮性薄膜之情況的層間剝離強度為1N/15mm寬以上，故使用 時不會發生密封部分剝落等不良狀況。 〈重疊部之偏差寬度〉 097144296 29 200932531 其-人，針對本發明之積層體中的重疊部之偏差寬度，使用 圓式進行說明。另外，具有同一機能者係賦予同一元件符號 並省略說明。 _ 目1至圖5中’元件符號刚表示試驗片，係表示將本發 月=積層體至少於-方向延伸而製作熱收縮性薄膜，並切取 定大j之„式驗片。又，元件符號2表示第2層，元件符號 ^表不第1層，兀件符號6表示第3層，元件符號$表示重 且4 70件魏8w表示重疊部之重疊寬度，元件符號1〇 表示第2層2之端面’元件符號12表示第i層4之端面， 凡件符號14表示第3層6之端面，元件符號16表示密封部， 元件符號18表示偏差部，元件符號18w表示偏差寬度，元 件符號A表示—端側，元件符號B表示另—端側。另外，該 女而侧A之部分係與另—端側β之部分重疊，形成重疊部。 ® 1至圖4表示本發明較佳之實施態樣之圖式。圖i及圖 2係從上方依序積層第2層⑴、第1層⑷、第3層⑷ 之薄膜的重疊部⑷附近之剖面圖，圖3及圖4係從上方 依序積層第2層⑴、第1層⑷、第3層⑷、第i層⑷、 、曰（2)之薄膜的重疊部（8)附近之剖面圖。又，各圖 式中，（a)為顯示熱處理前之狀態的圖式，㈤為熱處理後 在重疊部（8)於薄膜的第2層⑴或第2層⑺及们 層⑷”第3層(6)之間產生偏差之狀態的圖式。圖5⑷ 表示將本發明之積層體至少於一方向延伸而製作熱收縮性 097144296 30 200932531 薄膜由销收縮性薄膜切m縮方向、垂直於主 縮方向之方向500_大小之矩形薄膜的試驗片（_)，圖 (b)係為說明在將試驗# (_)騎_密封俾使垂直 於主收縮方向之方向的一端側A之第2層⑺的面、與同 •方向之另—端侧B的第3層⑷的面或第2層⑺的面在 垂直於主收縮方向之方向上平行，製成積層薄膜 ，並在積層 &gt;膜上形成lQrom寬之重疊部（8)的狀態之圖式。 ©纟圖5所不’本發明之積層體係從所製造之薄膜捲筒以拉 取方向（MD)與直角方向⑽（亦即主收縮方向）235麵、 拉取方向（MD)(即垂直於主收縮方向之方向）_mm的大小 切出薄膜’將此定為試驗片（剛）。接著進行溶劑密封， 使垂直於試驗片（⑽）之主收縮方向的方向之一端側A的 第2層（2)之面與同方向之另一端側B的第3層（6)之面 或第2層⑺之面平行，於試驗面上形成lGmm寬之重疊部 (8)’於90°C、5秒鐘之條件下進行熱處理。本發明中「以 90°C、5秒鐘之條件進行熱處理」係意指於g(rc之蒸汽隧道 之中處理5秒鐘之狀態。 -於90C之條件下熱處理後，當回復至常溫之情況 ’試驗 .4中，於重疊部（8)被溶織封之第2層⑺的主收縮方 向之垂直方向（MD)的端面（1〇)或第2層及第1層 (4)之端面（1〇、12)、與第1層（4)及第3層（6)的 MD之端面（12、14)或第3層（6)之端面（14)之間的偏 097144296 31 200932531 差（18)之偏差寬度（I8w)’相對於重疊部（8)之重疊寬 度（8w)係為5%以内。 圖1係苐2層（2)與第3層（6)之間具有第1層（4) -之3種3層的薄膜之例。其顯示將由本發明之積層體所得之 . 試驗片（100)以90〇C進行熱處理後，回復至常溫時，於在 重疊部（8)被溶劑密封之第2層（2)之拉取方向（MD)的 端面（10)、與第1層（4)及第3層（6)之主收縮方向的 β垂直方向⑽）之端面（12、⑷之間產生偏差部（18)之 狀態。此情況，偏差寬度（1 gw)相對於重疊部（8)之重疊 寬度（8w)為5%以内。 圖2係與圖1同樣為3種3層之例，其顯示於上述熱處理 後，回復至常溫時，於在重疊部被溶劑密封之第2層 (2)及第1層（4)的主收縮方向之垂直方向（肋）的端面 (10、12)、與第3層（6)的主收縮方向之垂直方向（仙） 的端面（14)之間產生偏差部（18)之狀態。此情況中亦同， 偏差寬度（18w)相對於重疊部⑻之重疊寬度（8w)為 5%以内。 * ®3及4係表示第2層（2)、第1層⑷、第3層（6)、 ，第1層⑷、第2層（2)之3種5層之例。圖3係顯示上 述熱處理後’回復至常溫時，於在重疊部⑻被密封之第 2層（2)的主收縮方向之垂直方向的端面（1〇)，與第1層 (4)、第3層（6)、第！層⑷、第3層⑷的主收縮方 097144296 32 200932531 向之垂直方向的端面（12、14、12、10)之間產生偏差部（μ) 之狀態。圖4係顯示於上述熱處理後，回復至常溫時，於在 重疊部（8)被密封之第2層（2)及第1層（4)的主收縮 • 方向之垂直方向的端面（10、12)，與第3層（6)、第1層 • (4)、第2層（2)的主收縮方向之垂直方向的端面（14、 12、10)之間產生偏差部（18 )之狀態。此等情況中亦同， 偏差寬度（18w)相對於重疊部（8)之重疊寬度為 ❹ 5%以内。 S知之具有以聚酯系樹脂所構成之外層的積層薄膜，當施 以熱處理之情況，於外層與接著層之間、或接著層與内層之 間會觀察到剝離之現象，具有無法獲得良好外觀之問題。相 對於此，由本發明之積層體所構成之薄膜，即便經施以熱處 理，於第2層（外層）與第1&gt;f(接著層）之間或第μ (接 著層）與第3層（内層）之間仍不易發生剝離，可獲得優異 ❹之外觀。 、 本發明之積層體中’加熱處理後之層間剝離的容易度係可 藉由密封後之外層與接著層、或接著層與内層之間所產生之 •偏差來表示。亦即，本發明之積層體係至少於一方向延伸而 -製作熱收縮性薄膜，由該熱收縮性薄臈以主收縮方向 235mm垂直於主收縮方向之方向5〇〇丽的大小採取試驗片 後’ K驗片上形成lQmm寬之重疊部，使垂直於該試驗片 之主收縮方向的方向之一端侧的第2層之面、與同方向之另 097144296 33 200932531 -端側的第3層或第2層之面成為平行，於溶劑密封後，在 垂直於主收縮方向之方向上切出165丽之圓筒狀薄膜，以蒸 汽隧道於、5秒鐘之條件下使之㈣並回復至常溫 於上述重疊部被密封之垂直於主收縮方向之方向的第/層 •之端面、與第1層及第3層之端面之間的偏差寬度，或者垂 直於主收縮方向之方向的第2層及第！層之端面、與第3 層之端面之間的偏差寬度，係為上述重疊部之重疊寬度的 ❹5%以内，此為重要條件，而較佳為3%以内，更佳為找以内。 若熱處理後之重疊部的偏差為5%以内，則即便經熱處理 後’於-外層與接著層或接著層與㈣之間不會發生剝離， 可維持優異之外觀。 目〜叫丹巧乃叼之另一端側之第 2層的面···（略）···溶劑密封」係蚊本發明之積層體的層 β構成係例如圖3或圖4所示般於第1層⑷的兩面積層第 2層（2)，此情況，將—端側之第2層⑺的面與另一端 側之第2層⑺的面予以溶劑密封。 上述重疊縣”直於上述試驗片之域縮方向的方向 之—端的第2層之面、與同方向之另—端側的第3層或第2 層之面平行之方式，於試則上以寬重疊之部分。為 了將端側之第2層的面與另一端側之第3層或第2層的面 予以溶劑密封所使用之溶媒，可舉出戊貌、正己統、二乙基 醚、庚貌、辛燒、環己燒、醋酸異_旨、醋酸-正丁基醋、 097144296 34 200932531 醋酸-正丙基酯、四氯化碳、二曱苯、醋酸乙基酯、甲苯、 苯、曱基曱基酮、醋酸曱基酯、二氯曱烷、四氩呋喃、二哼 咮、丙酮、異丙醇、乙醇、甲醇，或由該等溶劑之至少2 •種溶劑所構成之混合溶劑。又，溶劑密封寬度至少為2mm 寬以上，較佳為3mm寬以上，且為7mm寬以下，較佳為5mm 以下。 又，本發明之積層體至少於1方向延伸而製作熱收縮性薄 〇 膜，由該熱收縮性薄膜以主收縮方向235丽、垂直於主收縮 方向的方向500匪之大小採取試驗片後，以垂直於該試驗片 之主收縮方向的方向之一端側的第2層之面、與同方向之另 一端側的第3層或第2層之面平行之方式，於試驗片上形成 10mm寬之重疊部，進行溶劑密封後，於垂直於主收縮方向 的方向切出30mm之圓筒狀薄膜（圓筒狀薄膜之圓周約為 225顏），接著在夾持該圓筒狀薄膜之各兩端部的狀態下，於 ® 95°C溫水中浸潰30秒鐘時，於上述重疊部中被密封之垂直 於主收縮方向的方向之第2層的端面、與第1層及第3層的 端面之間的偏差寬度，或垂直於主收縮方向之方向的第2 . 層及第1層的端面、與第3層的端面之間的偏差寬度，係上 . 述重疊部之重疊寬度的5%以内，較佳為3%以内，更佳為2% 以内。 本發明之積層體當以較上述條件更為嚴苛之條件進行處 理之情況，亦可維持優異的層間剝離強度。亦即，將本發明 097144296 35 200932531 之積層體至少於一方向進行延伸而製作熱收縮性薄膜，將所 得之熱收縮性薄膜於主收縮方向以235mm寬進行切片而製 作試驗片。接著，以垂直於試驗片之主收縮方向的方向之一 •端側的第2層之面、與同方向之另一端側的第3層或第2 _ 層之面平行之方式，於試驗片上形成10顏寬之重疊部，利 用例如THF與環己烷以體積量各半混合所成之溶劑進行接 著，製作圓筒狀薄膜。接著，於垂直於主收縮方向的方向， ❹切出30mm之圓筒狀薄膜（圓筒狀薄膜之圓周約225mm)，藉 由裁斷相對於該圓筒狀薄膜之溶劑接著部的相反側之圓周 部’製作於中心具有溶劑接著部之MD3〇丽xTD225腿的短片 狀薄膜。其後，於將短片狀薄膜之兩端部以寬13〇_固定之 2片金屬框上，將上述短片薄膜以主收縮方向鬆弛為143丽 之狀態央住’將固定著該薄膜之金屬框於95。〇之溫水浴中 浸潰30秒’之後，於23Ϊ之冷水中浸潰30秒後，將收縮 之薄膜從金屬框取下’藉由比較薄膜之溶劑接著部的狀態而 進行評估。 〈用途〉 • 本發明之積層體藉由延伸亦可提升拉伸強度、衝擊強度， - 故亦可適合使用作為延伸薄膜。又，於延伸後，亦可藉由調 整熱固疋溫度而使用作為熱收縮性薄膜。其他亦可適合使用 作為各種成形品。 其次，針對將本發明之積層體使用作為熱收縮性薄膜之情 097144296 36 200932531 況進行說明。 [熱收縮性薄膜] 本發明之熱收縮性薄臈係可藉由將本發明之積層體至少 於一方向進行延伸而獲得。本發明之熱收縮性薄膜中，藉由 . 在第2層中使用含有聚酯系樹脂之樹脂組成物作為主成 分，可對薄膜賦予剛性與耐斷裂性，並且可進行低溫收縮， 可抑制自然收縮。然而，若僅有聚酯系樹脂，則箨法獲得均 ❹勻的收縮，而有收縮不均等之收縮完成性不良的問題、或在 私籤用途發生主收縮方向及垂直方向之收縮所造成的外觀 不良之問題。 於是’熱收縮性薄膜係可藉由使由含有聚酯系樹脂的樹脂 組成物作為主成分所構成之第2層、與以和構成第2層之樹 脂組成物不同的組成之樹脂作為主成分的樹脂組成物所構 成之第3層積層，而解決上述問題。然而，由上述第2層與 第3層所構成之熱收縮性薄膜，由於係將不同組成之樹脂組 成物所形成的層予以積層，故於如標籤用途的進行製袋之情 況’會有於製袋的密封部分發生層間剝離，或由於在薄膜裂 • 附後之製品的輸送中之薄膜之間的摩擦或人類手指等之抓 -取’而使第2層與第3層剝離之問題。因此，本發明之埶: 雜薄膜係為了消除上述缺點，在第2層與第3層之間介在 著以含有聚i旨系彈性體或改質聚§旨系彈性體之樹脂組成 物、或該等樹驗成物之混合樹驗成物料主成分所構成 097144296 200932531 第1層’以提升層關離強度。 、、本發明之熱收縮性薄膜的總厚度並無特別限制，由儘可能 減夕=、料成本等之觀點而言，較薄者為佳，具體而言，延伸 後之厚度較佳為7Q&quot;m以下，更佳為以下，再更佳為 55以下’最佳為5。_以下。 ❹ 本&amp;明之熱收縮性薄膜於70°C溫水中浸潰10秒鐘時之主 收縮方向的熱收縮率為⑽以上且未滿3G%，較佳為1〇%以 上且28/°以下，更佳為12%以上且25%以下之範圍。又，本 發明之熱收縮性薄膜於啊溫水中浸潰歸鐘時之主收縮 方向的熱收縮率為20%以上，較佳為25%以上，更佳為3⑽ 以上，且為80%以下，較佳為75%以下更佳為7⑽以 下。 另外，本說明書中，「主收縮方向」^系指縱方向與橫方向 巾延伸方向大的方向’例如裝附於瓶之情況係為相當於盆外 周方向的方向。又，「與主收縮方向垂直之方向」係指縱方 向與橫方向中延伸方向小的方向。 若於腕及航溫水中浸潰10秒鐘時之主㈣方向的熱 .收縮率在上述範_，則於7(rc附近之低溫區域中，熱收 .縮性薄膜係具有例如暫時停留於容器上之程度的熱收縮 性，且於超過70°c之8〇ΐ附近的高溫區域中發生劇烈收 縮，其結果’在既定位置處，即便從容器之體部，在相較於 體部極為纖細的頭部或頂面’仍不會發生敵折或凸痕等之異 097144296 38 200932531 常狀況，且可獲得均勻的收縮，可獲得完美的收縮完成性。 若70°C附近之主收縮方向的熱收縮率未滿丨〇%，則由於熱 收縮力小，在例如將熱收縮性薄膜使用作為上述之容器用標 -籤之情況，無法暫時停留於容器上，故有在高溫狀態下，薄 膜於頂面方向往上滑之情況。另一方面，若7〇。匚附近之主 收縮方向的熱收縮率大於30%，則由於在低溫區域劇烈發生 熱收縮，故有無法在既定位置處進行熱收縮之情況。另一方 ❹面，若別。C附近之主收縮方向的熱收縮率未滿2〇%，則在上 述容器之頭部與頂面的熱收縮不充分，因此8〇。匸附近之主 收縮方向的熱收縮率為20%以上，較佳為25%以上，更佳為 30%以上。 將本發明之熱收縮性薄膜使用作為PET製容器用標籤之 情況，於8 0 °C溫水中浸们〇秒鐘時之垂直於主收縮方向的 方向之熱收縮率較佳為⑽以下，更佳為5%以下，特佳為 3%以下。又’於70 c溫水中浸潰1〇秒鐘時之垂直方向的熱 收縮率較佳為1〇%以下，更佳為5%以下，特佳為3%以下、。、、 若垂直方向之收縮率超過⑽，則於標籤用途中，收縮後於 -縱方向的收縮變得明顯，可能發生尺寸偏差或外觀上之缺 熱收縮性缚膜的透明性係由以JISK7105為美準 所測定之霧值來評估，露佶釦杜* ιλ 局丞早 霧值I佳為10%以下，更佳為8%以 下特佳為5%以下。甚靈估兔, 右霧值為10%以下，可獲得良好的透明 097144296 39 200932531 性，可進行完美的印刷等。 又，本發明之熱收縮性薄膜中，於第2層與第3層（較佳 係第3層）中再添加經回收之本發明的熱收縮性薄膜之情況 ’亦同’以JISK7105為基準所測定之霧值為10%以下，較佳 為⑽以下，更佳為⑽以下。若再添加回收製品後之霧值為 10%以下，則可維持再生薄膜之良好透明性。 於第3層中再生添加本發明之熱收縮性薄臈的回收製品 ❹之情況’第3層中所含之含有聚i㈣脂的樹脂組成物之含 有率，相對於構成第3層之樹脂組成物的總量為4〇質量％ 以下，較佳為35質量％以下，更佳為3〇質量％以下。又，第 3匕層中所含之含有聚S旨系彈性體或改質聚S旨系彈性體的樹 月曰組成物或該等之混合樹脂組成物之含有率，相對於構成第 3層之樹脂組成物的總量為1Q質量％以下，較佳為8質量％ &quot;乂下’更佳為6質量％以下。若含有聚醋系樹脂之樹脂組成 物:含有聚g旨系彈性體或改f㈣系彈性體的樹脂組成物或 該等之混合樹脂組成物的含有率為1〇質量％以下，則可抑制 與構成第3層之聚苯乙烯系樹脂的折射率差之乖離所造成 • 之透明性的明顯惡化，故較佳。 • (積層體及熱收縮性薄膜之製造方法） 本發月之積層體係將第1層與第2層同時或逐次積層而獲 得，而該第1層係以含有聚酯系彈性體之樹脂組成物、含有 改質聚酯系彈性體之樹脂組成物或該等之混合樹脂組成物 097144296 200932531 作為主成分所構成，該第2層_㈣輯脂作為主成分所 構成。又，在與第2層相反側之第}層上具有以與第2層不 同組成的樹脂組成物作為主成分所構成之第3層的情況，可 藉由將第1層、第2層及第3層同時或逐次積層而獲得。較 • 佳係藉由T字模法、管狀法等既存的方法，使用具備T字模 之擠出機’將本發明之積層體予以共擠出，藉此同時製作第 1層及第2層或第1層、第2層及第3層之方法。又，本發 ❹明之積層體亦可將構成各層之樹脂組成物各則材化後，使 用壓合法或輥握持（_ nip)法等進行積層並逐次製作。 本發明之熱收縮性薄膜係可藉由將本發明之積層體以既 疋溫度至少於一方向延伸而獲得。具體而言，係以冷卻輥、 空氣、水等進行冷卻後，以熱風、溫水、紅外線等之適當方 法進行再加熱，利用輥延伸法、拉幅延伸法、管狀延伸法、 長間隔延伸法等，同時或逐次進行單軸或雙軸延伸。在雙軸 ®延伸方面’可同時進行肋與TD方向之延伸，但以先將任一 方進行延伸之逐次雙軸延伸較為有效果，其順序不管肋或 TD任-者先進行均可。延伸溫度必須依構成薄膜之樹脂的 • 軟化溫度或熱收縮性積層薄膜被要求之用途而改變，大致上 -係控制於60°C (較佳為70。〇以上且13(TC以下（較佳為 120°C以下）之範圍。主收縮方向（TD)之延伸倍率係對應 於薄膜構成成分、延伸手段、延伸溫度、目的製品形態，而 於2倍以上、較佳為3倍以上、更佳為4倍以上，且7倍以 097144296 41 200932531 下較佳為6倍以下之範圍内適當決定。又，單軸延伸或雙 轴延伸係依目的製品之職所決定。 ❹ 於PET製容器用標籤般之需要大致一方向的收縮特性之 用途的情沉’在不阻礙收縮特性之範圍内於其垂直方向進行 L伸亦為有效的。其延伸溫度亦與pET以外之成分有關， 型!言為6Q°C以上且9G°C以下之範圍。此外，關於其 延伸倍率’雖尺寸越大則耐斷裂性越提升，但伴隨於此，熱 收縮率會上升，難以獲得良好的收縮完成性，因此較佳為 1.03倍以上且15倍以下。 又，本發明之熱收縮性薄膜係於延伸後，藉由在延伸薄膜 之分子配向未緩和之時間内快速進行薄膜之冷卻，可賦予收 縮性並且予以保持。 (熱收縮性標籤及附有該標籤之容器） 本發明之積層體係可藉由進行成 ❹積層印刷層、蒸鍍層等 恶要於成形後 敝積編㈣作输祕_^°尤食= (例如冰涼飲用水用或食品用之於食叩谷器 順瓶）用之熱收縮性襟鐵等之情況，即便為^瓶，較佳為 如中心縮小之圓枉、有角的四角柱 複雜之形狀(例 亦可邊、著於該形狀，可獲得 、角柱等）， 之容器。 痕等之附有完美標藏 097144296 42 200932531 ❹ 本發明之積層體係當成㈣触祕薄料具有優異之 低溫收縮性、收縮完成性，故除了加熱為高溫則發生變形之 塑膠成形品的熱收縮性標籤素材（基材）之外，可適當利用 ，為使用熱膨脹率或吸水性等係與本發明之積層體極^不同 .的材質（例如由金屬、料、玻璃、紙；聚乙烯、聚丙稀、 聚丁烯等之聚烯烴樹脂；聚甲基丙烯動旨系樹脂；聚碳_ 系樹脂·’聚對苯二曱酸乙二自旨、聚對笨二曱酸丁二醋等之^ 醋系樹脂；輯胺系樹脂所選出之至幻種）作 的包裝體（容器）之熱收縮性標籤素材（基材）。 材 作為構成可利用本發明之積層體的塑膠I裝體之材質，除 了上述樹脂之外，可舉出聚笨乙烯、橡豚 ’、 ⑽酸丁@旨共聚;^體 腈共聚合體、苯乙烯-順丁烯二酸酐共聚合體、 〇 稀-苯乙稀共聚合體（ABS)、（甲基）， ㈣ 共聚合體（MBS)、聚氯乙婦系樹脂、丁一烯本乙席 氰胺樹脂、環氧樹脂、不飽和聚_ θ、脲樹脂、三聚 留想你田十说田〇 聚石夕氧樹脂等’可 早獨使用或併用2種類以上。塑膠包袭體可為使用 之樹脂類的混合物所構成者，亦可為2居 種以上 (實施例） ㈢以上之積層體。 以下例示本發明之積層體、延伸 收縮性標籤及附有該標籤之容器的實施.、，、收縮性薄膜、熱 此等實施例之限制。另外 歹，’但本發明並不受 貫施例中戶斤示之測定值及評估係 097144296 43 200932531 如下所進行。實施例中，將積層體成形為薄臈時之拉取（行 進）方向（與主收縮方向垂直之方向）記為「肋」，與其垂 直之方向（主收縮方向）記為「TD」。 〈測定方法〉 (1)熱收縮率 將積層體成形為熱收縮性薄膜，對所得之薄膜以仙 30mm、TD l〇〇mm (原標線間隔）之大小切取 β將此試驗片於80。〇之溫水浴中分別浸潰1〇秒鐘厂於其後之 30秒鐘浸潰於23〇c之冷水後，測定標線間隔⑴，由下式 (1)算出收縮率。 》 收縮率（％) =100χ (100-A) /100 (2)透明性（總霧值） m之薄膜的霧值，評 以JISK7105為基準，測定厚度4〇以 估透明性。It is preferred that the structure of Zhao and the structure of each segment are preferably A-block and tapered block. More preferably, the peak temperature of ^ is preferably inelastic modulus Μ"), the shrinkage characteristic causes no loss of loss under the loss _ 乂, particularly preferably in the boot rate (E,,) Wave ♦ sound s) peak temperature. When the loss of the state of the bomb, almost shows that it is not apparently existing with polystyrene ethane c. (4). Also, 彳. Loss (four) storage elastic modulus Therefore, it can be assigned to grasp the above, and the temperature of the temperature system peak of the modulus (E") mainly affects the range of shrinkage and below. The following range of the wave, naturally the temperature is above and 097144296. The temperature shrinkage rate of the people will not drop drastically. 24 200932531 Low 0 Styrene hydrocarbon-conjugated diene hydrocarbon copolymers satisfying the above viscoelastic properties The polymerization method is shown below. After a part of styrene or butadiene is charged in a usual manner and the polymerization is completed, a mixture of a styrene monomer and a butadiene monomer is charged to continue the polymerization. Thereby, the butyl diene having a high polymerization activity is preferentially polymerized, and finally a block composed of a simple monomer of styrene is produced. For example, if styrene is first polymerized, a mixture of styrene monoterpene and butadiene monomer is charged after the end of the polymerization to continue the polymerization, and a styrene block and butadiene can be obtained. A styrene-butadiene block copolymer having a styrene-butadiene monomer ratio in the middle of the block. By having such a site, a polymer having the above viscoelastic properties can be obtained. In this case, it was not possible to clearly confirm the two peaks caused by the above butadiene block and the styrene block, and only one peak was apparently observed. That is, in the SBS-like block structure in which the pure block or the butadiene block is clearly present, the Tg caused by the butadiene block mainly exists below 0 ° C, so that it becomes difficult The storage elastic modulus (E') at 0 ° C was set to be equal to or higher than a predetermined value. Further, the molecular weight system is adjusted so that the melt flow rate (MFR) - measured value (measurement condition: 200 ° C, weight: 49 N) is 2 g/10 min or more and 15 g/10 min or less. The blending amount of the rigid styrene-butadiene block copolymer is appropriately adjusted depending on the characteristics of the laminate, and is preferably adjusted to 20% by mass or more and 80% of the total amount of the resin composition constituting the third layer. The mass% or less is more preferably 40% by mass or more and 70% by mass or less in the range of 097144296 25 200932531. If the mixing amount of the prepolymer of the county is the resin group: = 8 °% by mass or less, the laminated body is formed into _ large = the rigidity of the film, and the reduction of the fracture resistance can be suppressed. The other (4) of the 20-ene block copolymer is blended in a resin composition &quot; or more, the film can be sufficiently rigid. The molecular weight of the styrene-based resin of the first layer 3 is more than ❹ 、, preferably (10) or more = 500,000 or less, and the following is shed, 000 or less, more preferably 3 〇〇, 〇〇 〇二::上:树_ If Benzene:: The disadvantage of film degradation is stealing = B = weight of the fc (mass) average molecular weight (the following 'there is no point to adjust the flow characteristics, so it is better. When a copolymer of a styrene-based hydrocarbon and an aliphatic unsaturated vinegar is used as a resin, and as an aliphatic unsaturated vinegar mixed with a styrene-based tobacco, a methyl (methyl) oxime may be mentioned. Sour vinegar, butyl (methyl) propyl, 2-ethylhexyl (methyl) propyl, self-designed, lauryl (ethyl i), stearyl, stearyl It is a copolymer of styrene and butyl (meth) acrylate vinegar, more preferably 7 G mass% or more and 90 τ, and Tg (loss elastic modulus E) peak temperature) At 5 (TC or above and 9 generations or less, your melt flow rate (June) measured value (measurement conditions: temperature 2 〇 (TC, load-bearing) in 2 continents to 097144296 26 200932531 and 15g/l0min or less. In addition, the above (meth)propionic acid ester represents acrylate and/or mercapto acrylate. Styrene hydrocarbon and lipid (tetra) unsaturated neon red copolymer in the third The content of the layer is appropriately determined depending on the composition ratio. The typical example is adjusted to a range of 2% by mass or more and 70% by mass or less based on the total amount of the resin composition constituting the third layer. When the content of the composite is mixed in the mass% or less, when the laminated body of the present invention is formed into a film, the rigidity of the film can be greatly improved, and good fracture resistance can be maintained. By blending, it is possible to impart sufficient rigidity to the film. The laminate of the present invention can be improved, adjusted for moldability, productivity, and formed, in addition to the above-described components, within a range that does not significantly impede the effects of the present invention. For the purpose of the physical properties of the film, a plasticizer and/or a ruthenium are contained in each layer. The content of the resin is 1% by mass or more, preferably 2%, based on the total amount of the resin constituting each layer. The amount of the resin is preferably 3% by mass or more, more preferably 3% by mass or less, more preferably 8% by mass or less, more preferably 8% by mass or less, still more preferably 5% by mass or less, or (4) the content of the resin to be added is also relative to the total amount of the resin. The decrease in the viscosity of the non-prefective melt and the decrease in the heat-resistant meltability are small, 'natural shrinkage. In addition, the laminated stomach of the present invention and the adhesive additive are also visible in addition to the above-mentioned plastic adhesive imparting resin. Purpose, add winter prayer grass + such as ^ each _ appropriate addition,,, tincture, such as UV absorber, light stabilizer stabilizer, 荽 & card, n antioxidant, colorant, antistatic agent, lubricant In the case of the laminated body of the present invention, the layered structure of the present invention is not particularly limited as long as it has at least two layers of the first layer and the second layer. For example, the layer structure may be The layer structure of the first layer/the second layer or the layer of the second layer/first layer/second layer, the second layer/the first layer/the second layer/the first layer/the second layer. It is preferable that the first layer on the opposite side of the second layer has a layer of a third layer composed of a resin composition different in composition from the resin composition constituting the second layer, and more preferably a third layer. A layer composed of a resin composition containing a polystyrene resin as a main component.较佳 The preferred laminate in the present invention is composed of five layers of the second layer/first layer/third layer/first layer/second layer. When the laminate of the present invention is formed into a heat-shrinkable film, it can be produced with good productivity and economy, and the film is excellent in rigidity, shrinkage completion, and fracture resistance, and interlayer peeling is obtained. A heat-shrinkable film that is suitable for use in shrink wrap, shrink wrap, or shrink wrap. Next, a laminate of a second layer/first layer/third layer/first layer/second layer of five layers according to a preferred embodiment of the present invention will be described. However, as long as there is no particular problem, the description of the relevant description can be applied to other layer configurations. In the laminated body of the present invention, the thickness ratio of the second layer to the third layer is set to 1 when the second layer is set to 1. The third layer is 2 or more, preferably 3 or more, and more preferably 4 The above is 12 or less, preferably 10 or less, and more preferably 8 or less. Further, the thickness of the i-th layer is 5% or more of the thickness of the second layer, preferably 1 (U or more, and 150% or less, preferably 丨〇〇% or less, more preferably 8 (10) 097144296 28 200932531 or less. If the thickness of the first layer is 5% or more of the thickness of the second layer, and a good subsequent effect 'is less than the thickness of the second layer (i.e., the second layer can be obtained as follows), the transparency is not greatly lowered. The total thickness of the laminate of the present invention is not particularly limited, and the thickness before forming the film (thickness without extension) is 5 m:% is preferably _ or less, more preferably 300 μm or less, and is treated. The lower limit of the 'car quotation is better than l 〇 #ra. Opinion ❹ ❹ The first layer of stripping (four) degrees of the laminated system of the present invention has a predetermined value after the predetermined treatment is performed. ^The direction of the extension is made to produce a heat-shrinkable film. The heat-shrinkable film is taken from the direction of the direction of 150 mm and perpendicular to the direction of the main shrinkage direction. Part of the film end face peeling test layer is formed on the second layer, respectively, on the upper layer, on the second The peeled portion was formed on the layer, and the peeling portion of the second layer and the first peeled portion were taken up by the flat head of the tensile tester, and (4) at a test speed of 100 mm/min of the main receiving end layer. The interlayer toughness at the time of the peeling test is 1 N/I 5 mm or more, preferably 2 N/15 mm or more, more preferably more than the collar / = width, and is 20 N/15 mm or less, preferably 18 N/ 15 mm or less, and more preferably 15 N/15 mm or less. When the laminate of the present invention is formed into a heat-shrinkable film, the interlayer peeling strength is 1 N/15 mm or more, so that the sealing portion does not peel off during use. <Deviation width of the overlapping portion> 097144296 29 200932531 The width of the overlapping portion in the laminated body of the present invention is described by a circle. _ Item 1 to Fig. 5 'The symbol of the element just indicates the test piece, which means that the heat-shrinkable film is formed by extending the present month=layered body at least in the - direction, and the test piece is cut and cut. Further, the component Symbol 2 indicates layer 2, component symbol ^ is not the first layer, the symbol 6 indicates the third layer, the component symbol $ indicates the weight and 4 70 pieces Wei 8w indicates the overlapping width of the overlapping portion, and the component symbol 1 indicates the end face of the second layer 2 'the symbol 12 indicates The end face of the i-th layer 4, the symbol 14 indicates the end face of the third layer 6, the component symbol 16 indicates the seal portion, the component symbol 18 indicates the deviation portion, the component symbol 18w indicates the deviation width, and the component symbol A indicates the end face, the component symbol B denotes the other end side. Further, the female side A portion overlaps with the other end side β portion to form an overlapping portion. ® 1 to 4 show a preferred embodiment of the present invention. Fig. 2 and Fig. 2 are cross-sectional views showing the vicinity of the overlapping portion (4) of the film of the second layer (1), the first layer (4), and the third layer (4) sequentially from the top, and Fig. 3 and Fig. 4 sequentially stacking the second layer from above. (1) A cross-sectional view of the vicinity of the overlapping portion (8) of the film of the first layer (4), the third layer (4), the i-th layer (4), and the ytterbium (2). Further, in each of the drawings, (a) is a pattern showing a state before heat treatment, and (5) is a third layer (1) or a second layer (7) and a layer (4) of the film in the overlapping portion (8) after heat treatment. (6) A pattern in which a state of variation occurs between them. Fig. 5 (4) shows that the laminate of the present invention is extended in at least one direction to produce heat shrinkability 097144296 30 200932531 The film is cut by the pin shrink film in a m-direction, perpendicular to the main shrinkage The test piece (_) of the rectangular film of the direction 500_ direction, and the figure (b) is the 2nd layer which shows the end side A of the direction which is perpendicular to the main contraction direction by the test # (_) The surface of (7) is parallel to the surface of the third layer (4) of the other end side of the same direction B or the surface of the second layer (7) in a direction perpendicular to the main shrinkage direction to form a laminated film, and in the laminated layer > film The pattern of the state in which the overlap portion (8) of the lQrom width is formed. The layer system of the present invention is drawn from the film roll to be pulled in the direction of the film (MD) and the direction of the right angle (10) (ie, the main Shrinking direction) 235 face, pull direction (MD) (ie, perpendicular to the direction of the main shrinkage direction) _mm size cut out of the film This was designated as a test piece (just). Then, solvent sealing was performed so that the surface of the second layer (2) on one end side A perpendicular to the direction of the main shrinkage direction of the test piece ((10)) and the other end side B in the same direction were prepared. The surface of the third layer (6) or the surface of the second layer (7) is parallel, and a superimposed portion (8) of a width of 1 Gmm is formed on the test surface at a temperature of 90 ° C for 5 seconds. In the present invention, The heat treatment at 90 ° C for 5 seconds means that it is treated in g (the steam tunnel of rc for 5 seconds. - After heat treatment under the condition of 90C, when it returns to normal temperature test). In the fourth aspect, the end face (1〇) of the vertical direction (MD) of the main shrinkage direction of the second layer (7) in which the overlap portion (8) is melted and woven, or the end faces of the second layer and the first layer (4) (1〇) , 12), the offset between the end face (12, 14) of the MD of the first layer (4) and the third layer (6) or the end face (14) of the third layer (6) 097144296 31 200932531 Poor (18) The deviation width (I8w)' is within 5% of the overlapping width (8w) of the overlapping portion (8). Fig. 1 is a layer 1 between the 2 layers (2) and the 3rd layer (6). ) - an example of three 3-layer films. The display will The test piece (100) obtained by heat-treating the test piece (100) at 90 ° C and returning to the normal temperature, in the drawing direction (MD) of the second layer (2) sealed by the solvent in the overlapping portion (8) In the case where the end surface (10) and the end surface (12, (4) of the first layer (4) and the third layer (6) in the main contraction direction are perpendicular to the direction (10)), a state of the deviation portion (18) is generated. The deviation width (1 gw) is within 5% of the overlap width (8w) of the overlapping portion (8). Fig. 2 is an example of three types of three layers as in Fig. 1, which is shown after the above heat treatment, and returns to normal temperature. The end faces (10, 12) of the vertical direction (ribs) of the main shrinkage direction of the second layer (2) and the first layer (4) which are sealed by the solvent in the overlapping portion, and the main shrinkage of the third layer (6) A state in which the deviation portion (18) is generated between the end faces (14) of the vertical direction of the direction (sen). Also in this case, the deviation width (18w) is within 5% with respect to the overlapping width (8w) of the overlapping portion (8). * ® 3 and 4 are examples of three types of five layers of the second layer (2), the first layer (4), the third layer (6), the first layer (4), and the second layer (2). Fig. 3 is a view showing the end surface (1〇) in the vertical direction of the main shrinkage direction of the second layer (2) sealed in the overlapping portion (8) after the above heat treatment, and the first layer (4), 3 layers (6), the first! The main shrinkage of the layer (4) and the third layer (4) 097144296 32 200932531 A state in which a deviation portion (μ) is generated between the end faces (12, 14, 12, 10) in the vertical direction. Fig. 4 is a view showing an end face in the vertical direction of the main shrinkage direction of the second layer (2) and the first layer (4) which are sealed in the overlapping portion (8) after returning to the normal temperature after the above heat treatment (10, 12), a deviation portion (18) is generated between the end faces (14, 12, 10) perpendicular to the main shrinkage direction of the third layer (6), the first layer (4), and the second layer (2). status. Also in these cases, the width of the deviation (18w) is less than 5% of the overlap width of the overlapping portion (8). It is known that a laminated film having an outer layer composed of a polyester resin is subjected to heat treatment, and peeling is observed between the outer layer and the adhesive layer or between the adhesive layer and the inner layer, and a good appearance cannot be obtained. The problem. On the other hand, the film composed of the laminate of the present invention is subjected to heat treatment, between the second layer (outer layer) and the first &gt; f (sublayer) or the μ (sublayer) and the third layer ( Exfoliation is still less likely to occur between the inner layers), and an excellent enamel appearance can be obtained. The ease of peeling between the layers after the heat treatment in the laminate of the present invention can be expressed by the deviation between the outer layer and the adhesive layer after the sealing or between the subsequent layer and the inner layer. That is, the laminated system of the present invention is formed in at least one direction to produce a heat-shrinkable film, and the heat-shrinkable thin film is taken after the test piece by the size of the main shrinkage direction of 235 mm perpendicular to the direction of the main shrinkage direction of 5 'K test piece forms an overlap of lQmm width, so that the surface of the second layer on one end side perpendicular to the direction of the main contraction direction of the test piece, and the other layer in the same direction 097144296 33 200932531 - the third layer or the end side The surface of the two layers is parallel. After the solvent is sealed, a cylindrical film of 165 Å is cut in a direction perpendicular to the main shrinking direction, and the steam is tunneled for 5 seconds to return it to room temperature. The overlapping portion is sealed with a width of a first layer of the first layer and the third layer and a second layer of the end surface of the first layer and the third layer, or a second layer of the end surface of the first layer and the third layer The first! The width of the deviation between the end face of the layer and the end face of the third layer is within 5% of the overlap width of the overlap portion, which is an important condition, and is preferably within 3%, more preferably within the range. When the deviation of the overlapping portion after the heat treatment is within 5%, even if the peeling does not occur between the outer layer and the adhesive layer or the adhesive layer and (4) after the heat treatment, an excellent appearance can be maintained.目 叫 丹 丹 丹 丹 丹 丹 丹 丹 丹 丹 丹 丹 丹 丹 丹 丹 丹 丹 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂In the second layer (2) of the two-layer layer of the first layer (4), in this case, the surface of the second layer (7) on the end side and the surface of the second layer (7) on the other end side are solvent-sealed. On the test, the overlapped county "is parallel to the surface of the second layer of the end of the test piece in the direction of the direction of the direction of the direction of the test piece, and the surface of the third layer or the second layer of the other end of the same direction. The solvent used for solvent-sealing the surface of the second layer on the end side and the surface of the third layer or the second layer on the other end side is exemplified by morphine, n-hexyl, and diethyl. Ether, gemstone, octane, cyclohexane, acetic acid, acetic acid-n-butyl vinegar, 097144296 34 200932531 acetate-n-propyl ester, carbon tetrachloride, diphenylbenzene, ethyl acetate, toluene, Benzene, mercapto decyl ketone, decyl acetate, dichlorodecane, tetrahydrofuran, dioxane, acetone, isopropanol, ethanol, methanol, or at least 2 solvents of the solvents Further, the solvent sealing width is at least 2 mm width or more, preferably 3 mm width or more, and 7 mm width or less, preferably 5 mm or less. Further, the laminate of the present invention is stretched at least in one direction to produce heat shrinkability. Thin film, the heat shrinkable film is 235 in the main shrinking direction, perpendicular to the main shrinking direction After the test piece is taken in the direction of 500 匪, the surface of the second layer on one end side perpendicular to the direction of the main contraction direction of the test piece is parallel to the surface of the third layer or the second layer on the other end side in the same direction. In the manner of forming a 10 mm wide overlap on the test piece, after solvent sealing, a cylindrical film of 30 mm was cut in a direction perpendicular to the main shrinkage direction (the circumference of the cylindrical film was about 225), and then the clip was placed. An end surface of the second layer which is sealed in the overlapping direction in the direction perpendicular to the main shrinkage direction in the overlapping portion of the cylindrical film in the state of being held at 95 ° C in warm water for 30 seconds. The width of the deviation from the end faces of the first layer and the third layer, or the width of the second layer and the end face of the first layer and the end face of the third layer perpendicular to the direction of the main shrinkage direction are Preferably, the overlapping width of the overlapping portion is within 5%, preferably within 3%, and more preferably within 2%. The laminated body of the present invention may be treated under more severe conditions than the above conditions. Maintain excellent interlayer peel strength. That is, the invention 097144296 35 20093 The laminate of 2531 was stretched in at least one direction to form a heat-shrinkable film, and the obtained heat-shrinkable film was sliced at a width of 235 mm in the main shrinkage direction to prepare a test piece. Next, perpendicular to the main shrinkage direction of the test piece. One of the directions, the surface of the second layer on the end side, and the surface of the third layer or the second layer on the other end side in the same direction are formed so as to form an overlapping portion of 10 widths on the test piece, for example, using THF and The cyclohexane was mixed with a solvent obtained by mixing half by volume, and a cylindrical film was formed. Then, a cylindrical film of 30 mm was cut out in a direction perpendicular to the main shrinkage direction (the circumference of the cylindrical film was about 225 mm) was formed by cutting a circumferential portion ' on the opposite side to the solvent-attached portion of the cylindrical film to form a short film-like film of the MD3 brilliant xTD225 leg having a solvent-attached portion. Thereafter, the two ends of the short film-like film are framed by two metal frames fixed at a width of 13 〇, and the film of the short film is relaxed in a state of main shrinkage to a state of 143 glaze. The metal frame to which the film is to be fixed is fixed. At 95. After immersing in a warm water bath for 30 seconds, the film was taken out from the metal frame after being immersed in cold water of 23 Torr for 30 seconds, and the evaluation was carried out by comparing the state of the solvent of the film. <Application> The laminate of the present invention can also be used to extend tensile strength and impact strength by stretching, and thus can be suitably used as an extension film. Further, after stretching, it can also be used as a heat-shrinkable film by adjusting the heat-set temperature. Others are also suitable for use as various molded articles. Next, the case where the laminate of the present invention is used as a heat-shrinkable film will be described in the case of 097144296 36 200932531. [Heat-shrinkable film] The heat-shrinkable film of the present invention can be obtained by stretching the layered body of the present invention in at least one direction. In the heat-shrinkable film of the present invention, by using a resin composition containing a polyester resin as a main component in the second layer, rigidity and fracture resistance can be imparted to the film, and low-temperature shrinkage can be performed to suppress naturalness. shrink. However, if only the polyester resin is used, the shrinkage method is uniform, and the shrinkage completion property of the shrinkage unevenness is poor, or the main shrinkage direction and the vertical direction shrinkage are caused by the private label use. Poor appearance. Therefore, the heat-shrinkable film can be obtained by using a resin having a resin composition containing a polyester resin as a main component as a main component and a resin having a composition different from the resin composition constituting the second layer as a main component. The third layer of the resin composition is laminated to solve the above problems. However, since the heat-shrinkable film composed of the second layer and the third layer is laminated with a layer formed of a resin composition having a different composition, it may be used in the case of bag making for label use. The sealing portion of the bag is subjected to delamination, or the problem of peeling off the second layer and the third layer due to friction between the film in the conveyance of the film after the film is attached or the grasping of the human finger or the like. Therefore, in the present invention, in order to eliminate the above disadvantages, a hetero-film is interposed between a second layer and a third layer, and a resin composition containing an elastomer or a modified elastomer is used. The mixed tree of the tree test composition is composed of the main component of the material, which constitutes 097144296 200932531, the first layer 'to enhance the separation strength of the layer. The total thickness of the heat-shrinkable film of the present invention is not particularly limited, and is preferably as thin as possible, and the thickness after stretching is preferably 7Q&quot ; m or less, more preferably the following, and more preferably 55 or less 'best 5'. _the following.热 The thermal shrinkage film of the present heat-shrinkable film in the main shrinkage direction when immersed in warm water of 70 ° C for 10 seconds is (10) or more and less than 3 G%, preferably 1% or more and 28/° or less. More preferably, it is in the range of 12% or more and 25% or less. Moreover, the heat shrinkage ratio of the heat-shrinkable film of the present invention in the main shrinkage direction when immersed in warm water is 20% or more, preferably 25% or more, more preferably 3 (10) or more, and 80% or less. It is preferably 75% or less, more preferably 7 (10) or less. In the present specification, the "main contraction direction" means a direction in which the longitudinal direction is larger than the direction in which the transverse direction of the towel extends. For example, the case of being attached to the bottle is a direction corresponding to the outer circumferential direction of the bowl. Further, the "direction perpendicular to the main contraction direction" means a direction in which the longitudinal direction and the lateral direction are smaller. If the heat shrinkage rate in the main (four) direction when immersed in the wrist and the air temperature for 10 seconds is in the above range, then in the low temperature region near 7 (rc), the heat shrinkable film has, for example, temporarily stayed at a degree of heat shrinkage on the container, and severe shrinkage occurs in a high temperature region near 8 〇ΐ above 70 ° C. As a result, at a predetermined position, even from the body of the container, it is extremely larger than the body. The slender head or top surface 'will still not suffer from enemy folds or embossing, etc. 097144296 38 200932531 Normal condition, and uniform shrinkage can be obtained, and perfect shrinkage completion can be obtained. If the main shrinkage direction is near 70 °C When the heat shrinkage rate is less than 丨〇%, the heat shrinkage force is small, and when the heat shrinkable film is used as the above-mentioned container label, it is not possible to temporarily stay on the container, so that it is at a high temperature. The film slides upward in the direction of the top surface. On the other hand, if the heat shrinkage rate in the main shrinkage direction near the crucible is more than 30%, the heat shrinkage occurs in the low temperature region, so that it cannot be at a predetermined position. The case of heat shrinkage. If one side is covered, if the heat shrinkage rate in the main shrinkage direction near C is less than 2%, the heat shrinkage at the head and the top surface of the container is insufficient, so 8 〇. The heat shrinkage ratio is 20% or more, preferably 25% or more, and more preferably 30% or more. When the heat-shrinkable film of the present invention is used as a label for a PET container, it is immersed in warm water at 80 ° C. The heat shrinkage rate in the direction perpendicular to the main shrinkage direction in seconds is preferably (10) or less, more preferably 5% or less, particularly preferably 3% or less. Further, when immersed in 70 c of warm water for 1 sec. The heat shrinkage ratio in the vertical direction is preferably 1% by mole or less, more preferably 5% or less, particularly preferably 3% or less, and if the shrinkage ratio in the vertical direction exceeds (10), in the label use, after shrinking - The shrinkage in the longitudinal direction becomes conspicuous, and the dimensional deviation or the appearance of the heat-shrinkable bond film may be evaluated by the haze value measured by JIS K7105, and the dew 杜 ι ι ι ι ι The value I is preferably 10% or less, more preferably 8% or less, and particularly preferably 5% or less. The rabbit is evaluated, and the right haze value is 10% or less. Good transparency 097144296 39 200932531 can be obtained, and perfect printing can be performed. Further, in the heat-shrinkable film of the present invention, the second layer and the third layer (preferably the third layer) are further added and recovered. In the case of the heat-shrinkable film of the present invention, the haze value measured by JIS K7105 is 10% or less, preferably (10) or less, more preferably (10) or less. The haze value after adding the recovered product is 10 When it is less than %, the transparency of the regenerated film can be maintained. In the case where the recovered product of the heat-shrinkable thin enamel of the present invention is regenerated and added in the third layer, the resin composition containing the poly(i) sulphate contained in the third layer The content of the resin composition of the third layer is 4% by mass or less, preferably 35% by mass or less, and more preferably 3% by mass or less. Further, the content of the sapphire composition containing the poly S-based elastomer or the modified poly S-based elastomer contained in the third layer or the mixed resin composition is the same as the composition of the third layer The total amount of the resin composition is 1% by mass or less, preferably 8% by mass &quot;乂下' is more preferably 6% by mass or less. When the resin composition containing the polyacetal resin is a resin composition containing a poly-g-type elastomer or a modified f-(4)-based elastomer, or the content of the mixed resin composition is 1% by mass or less, it is possible to suppress It is preferable that the transparency of the polystyrene-based resin constituting the third layer is significantly deteriorated due to the deterioration of the transparency caused by the difference in refractive index. • (Manufacturing method of laminated body and heat-shrinkable film) The laminated system of this month is obtained by laminating the first layer and the second layer at the same time or successively, and the first layer is composed of a resin containing a polyester-based elastomer. The resin composition containing the modified polyester elastomer or the mixed resin composition 097144296 200932531 is composed of a main component, and the second layer (four) grease is composed of a main component. Further, in the case where the first layer on the opposite side to the second layer has a third layer composed of a resin composition having a composition different from that of the second layer as a main component, the first layer and the second layer can be The third layer is obtained simultaneously or successively. Preferably, the laminate of the present invention is coextruded by an existing method such as a T-die method or a tubular method using an extruder having a T-shaped mold to simultaneously produce the first layer and the second layer or the first Method of layer 1, layer 2 and layer 3. Further, in the laminate of the present invention, the resin compositions constituting each layer may be formed into a material, and then laminated by a pressing method or a roll holding method (_ nip) method or the like. The heat-shrinkable film of the present invention can be obtained by stretching the laminate of the present invention in at least one direction at a temperature of the enthalpy. Specifically, after cooling with a cooling roll, air, water, or the like, the film is reheated by a suitable method such as hot air, warm water, or infrared rays, and is subjected to a roll stretching method, a tenter stretching method, a tubular stretching method, and a long interval stretching method. Etc. Simultaneous or sequential uniaxial or biaxial stretching. In the case of the two-axis ® extension, the rib and the TD direction can be simultaneously extended, but the sequential biaxial stretching in which either one is extended first is effective, and the order can be performed regardless of the rib or the TD. The extension temperature must be changed depending on the softening temperature of the resin constituting the film or the use of the heat-shrinkable laminate film, and is generally controlled at 60 ° C (preferably 70 〇 or more and 13 (TC or less). The range of the stretching direction of the main shrinkage direction (TD) corresponds to the film constituent component, the stretching means, the extension temperature, and the desired product form, and is more than 2 times, preferably 3 times or more, and more preferably It is 4 times or more, and 7 times is appropriately determined within the range of 097144296 41 200932531, preferably 6 times or less. Further, the uniaxial extension or the biaxial extension is determined according to the purpose of the product. 标签 Labels for PET containers It is also effective to use the general purpose of the shrinkage characteristic in one direction. It is also effective to perform the L extension in the vertical direction without hindering the shrinkage characteristics. The extension temperature is also related to the components other than pET. In the range of 6Q ° C or more and 9 G ° C or less, the fracture resistance is increased as the size is larger, but the heat shrinkage rate increases, and it is difficult to obtain good shrinkage completion property. Preferably, the heat-shrinkable film of the present invention is capable of imparting shrinkage and imparting shrinkage by rapidly cooling the film after the molecular alignment of the stretched film is not relaxed after stretching. (Heat-shrinkable label and container with the label) The layered system of the present invention can be formed by depositing a layer of a printed layer, a vapor-deposited layer, etc. = (for example, in the case of cold drinking water or food for glutinous rice wares), heat shrinkable ferroniobium or the like, even if it is a bottle, it is preferably a rounded, angular square column Complicated shape (for example, in the shape, available in the shape, available, corner column, etc.), the container. The mark is attached with a perfect mark 097144296 42 200932531 ❹ The laminated system of the present invention is excellent as a (4) touch thin material In addition to the heat-shrinkable label material (base material) of the plastic molded article which is deformed by heating to a high temperature, the heat-shrinkable label material (base material) can be suitably used, and the thermal expansion coefficient or water absorbability is used, and the present invention is used. The material of the laminate is very different (for example, metal, material, glass, paper; polyolefin resin such as polyethylene, polypropylene, polybutene, etc.; polymethyl methacrylate resin; poly carbon _ resin@' a heat-shrinkable label of a package (container) made of a polyethylene terephthalate, a vinegar resin, or a polystyrene bismuth vinegar; Material (Substrate) The material of the plastic I package constituting the laminate of the present invention may be, in addition to the above-mentioned resin, polystyrene, rubber dolphins, and (10) acid butyl@ copolymer; Nitrile copolymer, styrene-maleic anhydride copolymer, bismuth-phenethylene copolymer (ABS), (methyl), (iv) copolymer (MBS), polyvinyl chloride resin, butadiene Ethyl cyanamide resin, epoxy resin, unsaturated poly_θ, urea resin, tripoly, and you can use it alone or in combination of two or more types. The plastic inclusion body may be composed of a mixture of resins to be used, or may be a laminate of two or more (Example) (3) or more. The following description exemplifies the embodiment of the laminate of the present invention, the stretchable shrinkable label, and the container with the label, the shrinkable film, and the heat. Further, 本, 'but the present invention is not subject to the measurement values and evaluation system shown in the example 097144296 43 200932531 as follows. In the embodiment, the pulling (running) direction (direction perpendicular to the main shrinking direction) when the laminated body is formed into a thin layer is referred to as "rib", and the direction perpendicular thereto (main shrinking direction) is referred to as "TD". <Measurement method> (1) Heat shrinkage ratio The laminate was formed into a heat-shrinkable film, and the obtained film was cut into β at a size of 30 mm and TD l〇〇mm (original line interval). After immersing in a warm water bath for 1 〇 second, the factory was immersed in cold water of 23 ° C for 30 seconds thereafter, and the line spacing (1) was measured, and the shrinkage rate was calculated by the following formula (1). 》 Shrinkage ratio (%) = 100 χ (100-A) / 100 (2) Transparency (total haze value) The haze value of the film of m is evaluated on the basis of JIS K7105, and the thickness is measured to evaluate the transparency.

評估基準： ◎:霧值為5%以下 〇：霧值大於5%且為1〇%以下 X :霧值大於10% (3)層間剝離強度 將積層體成形為熱收縮性薄膜，對所得之薄膜切取肋 15麵⑴50刪之大小，從TD端面_第2層之一部分， 分別於第2層上形成剝離部、其他層上形成被剝離部，將第 097144296 44 200932531 2層之剝離部與其他層之被剝離部分別夾於拉伸試驗機之 爽頭，對TD方向以試驗速度100mm/min進行180度剝離試 驗。將剝離試驗所得之負重成為某種程度之一定時的平均 -值，作為層間剝離強度。 - 評估基準： ◎:層間剝離強度為2N/15丽寬以上 〇：層間剝離強度為1N/I5mm寬以上且未滿2N/15mm ❹ X :層間剝離強度未滿1N/15mm (4)收縮時之剝離評估 〈收縮時之剝離評估1&gt; 將積層體成形為熱收縮性薄膜，將所得之薄膜切片為TD 235mm寬，於製袋機中將MD之薄膜兩端重疊10mm，將該薄 膜端面以各種溶劑予以密封，製作圓筒狀薄膜。將該圓筒狀 薄膜於垂直於寬度方向之方向上切出165mm，安裝於容量 ❹ 500mL之圓筒型寶特瓶，於蒸汽加熱方式之長3.2m (3區） 之收縮隧道中不旋轉地以約5秒鐘使之通過。各區中之隧道 内環境溫度係以蒸汽閥調整蒸汽量，定於70〜105°C之範圍 . (例如90°C )。將薄膜被覆後，以下述基準進行評估。 _ 評估基準： ◎:相對於薄膜兩端之重疊部份的重疊寬度，誤差寬度為 0%以上且未滿2%。 〇：相對於薄膜兩端之重疊部份的重疊寬度，誤差寬度為 097144296 45 200932531 2%以上且5%以下。 X:相對於薄膜兩端之重疊部份的重疊寬度，誤差寬度大 於5%，發生層間剝離。 〈收縮時之剝離評估2&gt;Evaluation criteria: ◎: The haze value is 5% or less 〇: the haze value is more than 5% and is 1% or less X: the haze value is more than 10% (3) Interlaminar peeling strength The laminated body is formed into a heat-shrinkable film, and the obtained The film cutting rib 15 surface (1) 50 is sized, and a peeling portion is formed on the second layer from one of the TD end faces and the second layer, and the peeled portion is formed on the other layer, and the peeling portion of the 097144296 44 200932531 2 layer and the other layer are formed. The peeled portions of the layers were respectively placed on the head of the tensile tester, and subjected to a 180-degree peel test at a test speed of 100 mm/min in the TD direction. The load-bearing weight obtained by the peeling test was made into a certain degree of timed average-value as the interlayer peel strength. - Evaluation criteria: ◎: Inter-layer peel strength is 2N/15 liters or more 〇: Inter-layer peel strength is 1N/I5mm width or more and less than 2N/15mm ❹ X: Inter-layer peel strength is less than 1N/15mm (4) Shrinkage Peel evaluation <peel evaluation 1 at the time of shrinkage> The laminate was formed into a heat-shrinkable film, and the obtained film was sliced to have a width of TD 235 mm. In the bag making machine, the ends of the film of the MD were overlapped by 10 mm, and the end faces of the film were various. The solvent was sealed to prepare a cylindrical film. The cylindrical film was cut out 165 mm in the direction perpendicular to the width direction, and mounted on a cylindrical PET bottle having a capacity of mL500 mL, and was not rotated in a shrink tunnel of 3.2 m (3 zones) of a steam heating method. Pass it in about 5 seconds. The ambient temperature in the tunnel in each zone is adjusted by steam valve and is set at 70~105 °C (for example, 90 °C). After the film was coated, it was evaluated on the basis of the following criteria. _ Evaluation criteria: ◎: The error width is 0% or more and less than 2% with respect to the overlapping width of the overlapping portions at both ends of the film. 〇: The error width is 097144296 45 200932531 2% or more and 5% or less with respect to the overlapping width of the overlapping portions at both ends of the film. X: Between the overlap widths of the overlapping portions at both ends of the film, the error width was more than 5%, and interlayer peeling occurred. <Peel Evaluation 2 at Contraction&gt;

將積層體成形為熱收縮性薄膜，將所得之薄膜切片為TD 235mm寬，將MD之薄膜兩端重疊i〇mm，以THF與環己燒體 積量各半混合而成之溶劑進行接著’製作圓筒狀薄膜。將該 ❹圓筒狀薄膜以MD 30mm切出’相對於溶劑接著部裁斷相反側 之圓周部，藉此製作於中心具有溶劑接著部之MD 3〇m軟丁d 225麵之短片狀薄膜。之後，於固定為寬度13〇咖之2根金 屬框上’將上述短片狀薄膜以弛為TD 143mm之狀態夾住。 、^將該固疋有薄膜之金屬框於95〇C之溫水浴中浸潰3〇 心之後於23 C之冷水中浸潰3〇秒。將收縮之薄獏從金屬 框取下’將薄膜之溶劑接著部的狀態以下述基準評估。 β 評估基準： Ο相對於薄膜兩端之重疊部份的重疊寬度，誤差寬度為 0%以上且未滿2%。 〇.相對於薄膜兩端之重疊部份的重疊寬度，誤差寬度為 2%以上且5%以下。 ‘ X相對於薄膜兩端之重疊部份的重疊寬度，誤差寬度大 於5%，發生層間剝離。 (實施例1) 097144296 46 200932531 以4〇質量％之苯乙烯系樹脂A (苯乙稀/丁The laminated body is formed into a heat-shrinkable film, and the obtained film is sliced to have a width of TD 235 mm, and the ends of the film of the MD are overlapped by i 〇 mm, and the solvent obtained by mixing the THF and the ring-burned volume in half is carried out. Cylindrical film. The cylindrical film of the crucible was cut out at a distance of 30 mm from MD to the circumferential portion on the opposite side with respect to the solvent-attached portion, thereby producing a short film-like film having a MD 3 〇m soft d 225 surface having a solvent-attached portion. Thereafter, the short film-like film was sandwiched in a state of TD 143 mm on the two metal frames fixed to the width of 13 〇. The metal frame of the solid film was dipped in a warm water bath of 95 ° C and then immersed in cold water of 23 C for 3 seconds. The shrinkage of the thin crucible was removed from the metal frame. The state of the solvent-attached portion of the film was evaluated on the basis of the following criteria. β Evaluation standard: 重叠 The width of the overlap with respect to the overlap of the two ends of the film, the error width is 0% or more and less than 2%.误差 The error width is 2% or more and 5% or less with respect to the overlapping width of the overlapping portions at both ends of the film. The overlapping width of ‘X with respect to the overlapping portions at both ends of the film, the error width is more than 5%, and interlayer peeling occurs. (Example 1) 097144296 46 200932531 4% by mass of styrene resin A (styrene/butyl)

❹作為第3 卩聚g旨系樹脂（二叛酸成分為對苯二曱酸1〇〇 如表1所示，以4 二烯=90/10(質量％)， 損失彈性模數E”之; 與60質量w 莫耳％，一醇成分為乙二 二醇70莫耳％、1，4-環己烷二甲醇30 莫耳％所構成之共聚合聚g旨（商品名pETG SKYG_s2〇〇8， sk化學公司製），以下稱為「簡」）作為第2層，以聚酯 系彈性體A (聚對苯二甲酸丁二醋_聚（氧化伸了基）二醇 共聚合體，聚對苯二甲酸丁二酯72質量％、聚（氧化伸丁基） 二醇28質量％，聚（氧化伸丁基）二醇聚合度13，商品名 ❹ PrimalloyA1900N，三菱化學公司製，以下稱為「τρΕΕ_Α」） 作為第1層，由3台之三菱重工業股份有限公司製之單軸擠 出機將各樹脂以设疋溫度210 °C〜2 3 0 °C之範圍予以熔融混 .合後，由3種5層鑄模共擠出，使各層之厚度成為第2層〆 第 1 層 /第 3 層 /第 1 層 /第 2 層=30/^/10^/12(^111/10// m/30 // m，以60 C之洗鑄輥拉取，使之冷卻固化，獲得寬 300mm、厚200//m之未延伸積層片。接著，以京都機械股份 有限公司製之薄膜拉幅機，以預熱溫度93。(：、延伸溫度90 097144296 47 200932531 °C於橫單軸方向延伸5.0倍後，以65°C進行熱處理，獲得 厚度40之熱收縮性薄膜。對所得之薄膜進行評估的結果 係示於表1。 - (實施例2) • 除了將實施例1中第1層所使用之樹脂組成物的構成改變 為聚醋系彈性體樹脂B (聚對苯二曱酸丁二酯-聚（氧化伸 丁基）二醇共聚合體，聚對苯二甲酸丁二酯74質量％、聚（氣 ❹化伸丁基）二醇26質量。/。，聚（氧化伸丁基）二醇聚合度 26，商品名Primall〇yA18〇〇NS，三菱化學公司製，以下稱 為「TPEE-B」）以外，以與實施例1同樣之手法獲得未延伸 積層片。進一步將該未延伸片以與實施例1同樣之手法進行 延伸，獲得熱收縮性積層薄膜。對所得之薄膜進行評估的姅 果係示於表1。 '° (實施例3) 〇 除了將實施例1中第丨層所使用之樹脂組成物的構成改變 為聚酯系彈性體樹脂c(聚對苯二曱酸丁二酯—聚（氧化伸 丁基）二醇共聚合體，聚對苯二曱酸丁二酯77質量％、聚（氧 - 化伸丁基）二醇23質量％，聚（氧化伸丁基）二醇聚合度 - 13 ’商品名PrimalloyB1900NS ’三菱化學公司製，以下稱 為「TPEE-C」）以外，以與實施例1同樣之手法獲得未延伸 積層片。進一步將該未延伸片以與實施例1同樣之手法進行 延伸，獲得熱收縮性積層薄膜。對所得之薄膜進行評估的結 097144296 48 200932531 果係不於表1。 (實施例4) 除了將實施例1中第1層所使用之樹脂組成物的構成改變 為聚酯系彈性體樹脂D (聚對苯二甲酸丁二酯—聚（氧化伸 丁基）—醇共聚合體’聚對苯二曱酸丁二酯84質量％、聚（氧 化伸丁基）二醇16質量％，聚（氧化伸丁基）二醇聚合度 13，商品名Primaii〇yB19i〇N，三菱化學公司製，以下稱為 β「TPEE-D」）以外，以與實_丨同樣之手法獲得未延:積 層片。進一步將該未延伸片以與實施例丨同樣之手法進行延 伸，獲得熱收縮性積層薄膜。對所得之薄膜進行評估的結果 係不於表1。 (實施例5) ❹ 除了將實施例1中第1層所使用之樹脂組成物的構成改變 為聚酯系彈性體樹脂Ε (聚對苯二曱酸丁二酯〜聚（氧化伸 丁基）二醇共聚合體，聚對苯二曱酸丁二酯71質量％、聚（氧 化伸丁基）二醇29質量％，聚（氧化伸丁基）二醇聚人产 13，商品名PELPRENE Ρ40Η，東洋紡公司剪，，、，π 又 衣以下稱為 「ΤΡΕΕ-Ε」）以外，以與實施例1同樣之手法獲得未延伸 層片。進一步將該未延伸片以與實施例1同樣之手法進^延 伸’獲得熱收縮性積層薄膜。對所得之薄膜進行評估的'结 係示於表1。 (實施例6) 097144296 49 200932531 除了將實施例1中第1層所使用之樹脂組成物的構成改變 為TPEE-B之30質量?^TPEE-C之70質量％的混合樹脂組成 物以外，以與實施例1同樣之手法獲得未延伸積層片。進一 步將該未延伸片以與實施例1同樣之手法進行延伸，獲得熱 收縮性積層薄膜。對所得之薄膜進行評估的結果係示於表 1 ° (實施例7) 除了將實施例1中第1層所使用之樹脂組成物的構成改變 為TPEE-B之40質量％與ΤΡΕΕ-C之60質量％的混合樹脂組成 物以外，以與實施例1同樣之手法獲得未延伸積層片。進一 步將該未延伸片以與實施例丨同樣之手法進行延伸，獲得熱 收縮性積層薄臈。對所得之薄膜進行評估的結果係示於表 1 ° (實施例8) 如表1所tf ’除了構成第3層之樹脂係使用將弧-八別 質量i SBS B 45 |量％、pETG 2〇質量％以及τρΕΕ—E 5質量 %所構成之混合樹餘成物、制雙軸㈣機予以混練並粒 狀化者’並將第1層所使用之樹脂組成物改變為TPEE-E以 外，以與實施例1同樣之手法獲得未延伸積層片。進-步將 該未延伸以埃實_丨同樣之手法崎㈣，獲得 性積層薄膜。對所得之薄_行評估的結果絲於表、卜 (比較例1) 097144296 50 200932531 如表1所示’以40質量％之SBS-Α與60質量％之SBs B 的混合樹脂作為第3層，以PETG作為第2層及第1層，由 3台之三菱重工業股份有限公司製單軸擠出機將各樹月旨以 -設定溫度21 (TC〜230°C之範圍熔融混合後，由3種5層鑄模 • 共擠出，使各層之厚度成為第2層/第1層/第3層/第j層^ 第2層=20;^111/10&quot;111/120//111/10//111/20;^111，以60。(3之堯鱗 輥拉取，使之冷卻固化，獲得寬300mm、厚18〇iajn之為延 ❹伸積層片。其次，以京都機械股份有限公司製之薄犋扳抨機 以預熱溫度93°C、延伸溫度9〇°C於橫單軸方向延伸5 〇件 後’以65。(：進行熱處理，獲得厚度36从m之熱收輪性積層 薄膜。對所得之薄膜進行評估的結果係示於表1。 e (比較例2) 除了將實施例1中第1層所使用之樹脂組成物的構成改變 為聚苯乙烯系彈性體樹脂A (聚苯乙烯-聚異戊二烯-聚苯乙 ®稀共聚合體’聚笨乙烯20質量❶/D ,商品名HYBRAR5125，❹ is the third 卩 poly g-based resin (the second treasant component is terephthalic acid 1 〇〇 as shown in Table 1, 4 is diene = 90/10 (% by mass), loss elastic modulus E" And copolymerization polyg of 60 mass% w %, monool component 70 mol% of ethylene glycol, 30 mol% of 1,4-cyclohexane dimethanol (trade name pETG SKYG_s2〇〇) 8, sk chemical company, hereinafter referred to as "simplified") as the second layer, polyester-based elastomer A (polybutylene terephthalate _ poly(oxidized stretch) diol copolymer, poly 72% by mass of butylene terephthalate, 28% by mass of poly(butylene oxide) diol, and a degree of polymerization of poly(oxybutylene) diol 13, trade name: Primalloy A1900N, manufactured by Mitsubishi Chemical Corporation, hereinafter referred to as "τρΕΕ_Α") As a first layer, each resin is melt-blended and mixed in a range of 210 ° C to 2 30 ° C in a single-axis extruder manufactured by Mitsubishi Heavy Industries, Ltd. Coextruded from three kinds of five-layer molds, the thickness of each layer becomes the second layer, the first layer/the third layer/the first layer/the second layer=30/^/10^/12 (^111/10// m/30 // m The film was pulled by a 60 C washing roll to be cooled and solidified to obtain an unstretched laminated sheet having a width of 300 mm and a thickness of 200/m. Then, a film tenter manufactured by Kyoto Machinery Co., Ltd. was used to preheat the temperature of 93. (:, extension temperature 90 097144296 47 200932531 °C was extended 5.0 times in the transverse uniaxial direction, and then heat-treated at 65 ° C to obtain a heat-shrinkable film having a thickness of 40. The results of evaluation of the obtained film are shown in the table. 1. (Example 2) • In addition to changing the composition of the resin composition used in the first layer of Example 1 to a polyester elastomer resin B (polybutylene terephthalate-poly(oxidation) a butyl diol copolymer, 74% by mass of polybutylene terephthalate, 26 masses of poly(p-butylene butyl) diol, and a polymerization degree of poly(oxybutylene) diol of 26, An unextended laminate sheet was obtained in the same manner as in Example 1 except that the product name is Primall® A18〇〇NS, manufactured by Mitsubishi Chemical Corporation (hereinafter referred to as “TPEE-B”). Further, the unstretched sheet was used in the same manner as in Example 1. The same method is used to extend and obtain a heat-shrinkable laminated film. The results of the evaluation of the film are shown in Table 1. '° (Example 3) The composition of the resin composition used in the first layer of Example 1 was changed to the polyester elastomer resin c (polyphenylene) Dibutyl phthalate-poly(butylene oxide) diol copolymer, 77% by mass of polybutylene terephthalate, 23% by mass of poly(oxy-butylene) diol, poly(oxidation) The unstretched laminated sheet was obtained in the same manner as in Example 1 except that the degree of polymerization of butyl diol was 13 'trade name: Primalloy B 1900 NS 'Mitsubishi Chemical Co., Ltd., hereinafter referred to as "TPEE-C"). Further, the unstretched sheet was stretched in the same manner as in Example 1 to obtain a heat-shrinkable laminated film. The results of the evaluation of the obtained film 097144296 48 200932531 are not shown in Table 1. (Example 4) The composition of the resin composition used in the first layer in Example 1 was changed to a polyester elastomer resin D (polybutylene terephthalate-poly(butylene oxide)-alcohol) Copolymer "polybutylene terephthalate 84% by mass, poly(butylene oxide) diol 16% by mass, poly(butylene oxide) diol polymerization degree 13, trade name Primaii〇y B19i〇N, In addition to the "T" "TPEE-D" manufactured by Mitsubishi Chemical Corporation, it is obtained in the same manner as the real one: the laminated sheet. Further, this unstretched sheet was stretched in the same manner as in Example , to obtain a heat-shrinkable laminated film. The results of the evaluation of the obtained film were not in Table 1. (Example 5) ❹ In addition to changing the composition of the resin composition used in the first layer of Example 1 to a polyester elastomer resin Ε (polybutylene terephthalate to poly(butylene oxide) a diol copolymer, 71% by mass of polybutylene terephthalate, 29% by mass of poly(butylene oxide) diol, and a poly(oxybutylene) glycol, 13 of which is sold under the trade name PELPRENE Ρ40Η. An unstretched layer sheet was obtained in the same manner as in Example 1 except that the Toyobo Co., Ltd. cut, and, π, and hereinafter referred to as "ΤΡΕΕ-Ε". Further, the unstretched sheet was further stretched in the same manner as in Example 1 to obtain a heat-shrinkable laminated film. The 'evaluation of the obtained film is shown in Table 1. (Example 6) 097144296 49 200932531 Except that the composition of the resin composition used in the first layer in Example 1 was changed to 30% by mass of TPEE-B, and 70% by mass of the mixed resin composition of TPEE-C, An unstretched laminate was obtained in the same manner as in Example 1. Further, this unstretched sheet was stretched in the same manner as in Example 1 to obtain a heat-shrinkable laminated film. The results of evaluation of the obtained film are shown in Table 1 (Example 7) except that the composition of the resin composition used in the first layer of Example 1 was changed to 40% by mass of TPEE-B and ΤΡΕΕ-C. An unstretched laminated sheet was obtained in the same manner as in Example 1 except for a mixed resin composition of 60% by mass. Further, the unstretched sheet was stretched in the same manner as in Example , to obtain a heat-shrinkable laminated sheet. The results of evaluation of the obtained film are shown in Table 1 ° (Example 8). As shown in Table 1 tf 'In addition to the resin layer constituting the third layer, the arc-eight-part mass i SBS B 45 |% by weight, pETG 2 was used.混合 mass% and τρΕΕ—E 5 mass% of the mixed tree residue, and the biaxial (four) machine is kneaded and granulated, and the resin composition used in the first layer is changed to TPEE-E. An unstretched laminated sheet was obtained in the same manner as in Example 1. The step-by-step method is to obtain a laminated film which is not extended by Essence _ 丨 the same hand saki (4). The results of the evaluation of the obtained thin line are shown in Table, (Comparative Example 1) 097144296 50 200932531 As shown in Table 1, '40% by mass of SBS-Α and 60% by mass of SBs B mixed resin as the third layer PETG is used as the second layer and the first layer, and each of the three uniaxial extruders manufactured by Mitsubishi Heavy Industries Co., Ltd. melts and mixes each of the trees at a set temperature of 21 (TC to 230 °C). 3 kinds of 5 layers of molds • Co-extrusion, so that the thickness of each layer becomes 2nd layer / 1st layer / 3rd layer / jth layer ^ 2nd layer = 20; ^111/10&quot;111/120//111/10 / / 111 / 20; ^ 111, to 60. (3 of the scale roller pull, so that it is cooled and solidified, to obtain a width of 300mm, thickness of 18 〇iajn for the extension of the stretch layer. Second, to Kyoto Machinery Co., Ltd. The thin tamper is made of a preheating temperature of 93 ° C and an extension temperature of 9 〇 ° C in a direction of a single uniaxial direction of 5 后 after the '65. (: heat treatment, to obtain a thickness of 36 from the heat of the wheel The film was evaluated. The results of evaluation of the obtained film are shown in Table 1. e (Comparative Example 2) The composition of the resin composition used in the first layer of Example 1 was changed to a polystyrene-based elastomer. Lipid A (polystyrene - polyisoprene - polystyrene copolymer ® lean body "polystyrene 20 mass ❶ / D, tradename HYBRAR5125,

Kuraray公司製，以下稱為「TPS-A」）以外，以與實施例1 同樣之手法獲得未延伸積層片。進一步將該未延伸片以與實 - 鉍例1同樣之手法進行延伸，獲得熱收縮性積層薄膜。對所 -得之薄膜進行評估的結果係示於表1。 (比較例3) 除了將實施例1中第1層所使用之樹脂組成物的構成改變 為聚苯乙稀系彈性體樹脂B (笨乙稀-乙烯-丁烯_苯乙稀共 097144296 51 200932531 聚合體，聚苯乙烁如μ θ 成化學公司製，_TUfteGH1Q41，旭化 同樣之手法獲得未：:：」)以外’以與實施例1 施例_之手法進行二;! 了將該未延伸片以與實 π u 丁乙伸獲侍熱收縮性積層薄膜。對所 付之薄膜進行評_結果麵於表卜 (比較例4) 除了將實施例1中笛1 a ❹ 層所使用之樹脂組成物的構成改變 =:本乙稀系彈性趙樹雁C (改質苯乙稀-乙㈣- ::聚合趙’聚笨乙烯3”量 — M1913，旭化成化學公 與實施m同樣之手法獲得去以下稱為「职」）以外，以 伸片以與實施例！同樣之=延伸積層片。進-步將該未延 薄膜。延伸，獲得熱收縮性積層 叶估的結果係示於表1。 ❿ 097144296 52 200932531 ο ο 〔I嵴〕 比較例 I &lt;3&gt; 〇 1—H c=&gt; 0 1 H 5 S s LT5 X · &lt;J5 ^ CO ◎ 3. 85 CO CD 〇 &lt;〇 o T—i S S s X 18.5 ^ CO ◎ w CO ◎ 00 CO &lt;N1 ◦ 〇&gt; F—H o &lt;〇 F &lt; S r*H (N1 o LO l〇 X d ◎ :· &lt;&gt;α ◎00 寸 〇 o &lt;=&gt; o r·· &lt; § CN1 &lt;NI 1—H LO ◎ :· X 0. 90 實施例 〇〇 C5 &lt;=&gt; 1 ~ '&lt; 〇 o LO LO OJ CM LO 〇3 〇二· 〇 1. 50 卜 5 S o cz&gt; § r—^ &lt;NI o LO ^ m 〇 1. 69 CO c=&gt; o &lt;=&gt; H S CNI oa r»H LT3 ^ CO 〇d ◎ 2. 00 LO &lt;=5 CD 1—^ CD o S S 05 〇3 ◎&quot;° ^ CO ◎ 2. 08 呀 Ο Ο 1—» o 〇&gt; r—&lt; 〇 S (ΝΪ 〇 in ◎ Ξ 〇 1. 08 CO ◦ &lt;=) τ—1 &lt;=&gt; o S &lt;N1 o LT5 ◎ Ξ CO 〇— 03 〇 1—Η o o S C&lt;l C&lt;l H LO ^ L〇 〇CO· ◎ :· 3@53 ◦ 〇 o o 5 S 7—H oa 〇 lO o ° CO 〇Ξ 〇 1. 58 TPEE-A ΤΡΕΕ-Β TPEE-C TPEE-D TPEE-E PETG TPS-A TPS-B TPS-C PETG SBS-A SBS-B PETG TPEE-E 70°Cxl0 秒（TD) 80°Cxl0 秒（TD) /^N 象s LO ^ 〇 03擊 I 霧值（％)JISK7105 層間剝離強度（N/15mm寬） 第1層 (質量《 第2層 (質量％) 第3層 (質量％) 1 熱收縮率（％) 收縮時之 剝離評估法1 - 9¾寸寸U60 200932531 (實施例9) 對於實施例3至8及比較例2至4中所使用之熱收縮性積 層薄膜，利用收縮時之剝離評估2的方法，評估剝離特性。 - 將評估結果示於表2。 ' [表 2] 收縮時之剝 實施例 比較例 離評估法2 3 4 5 6 7 8 2 3 4 95°Cx30 秒 ◎ ◎ 〇 〇 〇 〇 X X X 偏差寬度（％) 0. 5 0. 5 4. 5 2. 5 3. 5 4. 5 23. 0 32. 0 17. 5 ❹ 由表1可知，由本發明之積層體所得之熱收縮性薄膜（實 施例1〜8)，相較於未將第1層以含有聚酯系彈性體之樹脂 組成物構成的熱收縮性薄膜（比較例1)，層間剝離強度係 較大。又，由本發明之積層體所得之熱收縮性薄膜（實施例 1〜8)，相較於第1層為含有苯乙烯系樹脂之樹脂層的積層體 (比較例2〜4)，經熱收縮後亦可維持良好的層間剝離特 性。又，由表2可知，即便在熱收縮嚴苛之條件（收縮時之 ® 剝離評估2)中，由本發明之積層體所得的熱收縮性薄膜（實 施例3〜8)仍可抑制層間剝離。此外，由表1可知，由本發 明之積層體所得的熱收縮性薄膜（實施例1〜8)之透明性， -即便於第2層與第3層之間介在著含有聚酯系彈性體之樹脂 -組成物層，仍不會發生透明性之大幅降低，係具有作為標籤 用途之薄膜透明性而言充分的透明性。又，由實施例8可 知，關於在第3層中假定混合存在有回收製品之情況所嘗試 製成的薄膜，層間剝離強度仍無變化，在透明性方面亦為具 097144296 54 200932531 有作為標籤用途而言充足之透明性的薄膜。藉此，本發明之 積層體係具有較習知薄膜更優異之透明性、層間剝離強度， 最適合用於熱收縮性薄膜。 • (產業上之可利用性） 本發明之積層體由於兼具優異之層間剝離強度與透明 性，故可適當利用於需要熱收縮性之成形品，尤其是收縮標 籤等。 ❿ 以上針對本發明進行目前而言最為實用且較佳之實施形 態的說明，但本發明並不限於揭示在本案說明書中之實施形 態，在不違背閱讀本案申請專利範圍及說明書整體後可明白 之發明要旨或思想之範圍内，可進行適當變化，此種變化所 得之積層體、延伸薄膜、熱收縮性薄膜、成形體、熱收縮性 標籤、附有該標籤之容器當然亦包含於本發明之技術範圍 内。 ® 【圖式簡單說明】 圖1(a)及（b)為本發明之積層體的較佳實施態樣中，重疊 部附近之剖面圖（其〇。 _ 圖2(a)及（b)為本發明之積層體的較佳實施態樣中，重疊 — 部附近之剖面圖（其2)。 圖3(a)及（b)為本發明之積層體的較佳實施態樣中，重疊 部附近之剖面圖（其3)。 圖4(a)及（b)為本發明之積層體的較佳實施態樣中，重疊 097144296 55 200932531 部附近之剖面圖（其4)。 圖5(a)及（b)為說明本發明之積層體的較佳實施態樣 中，形成重疊部之狀態的說明圖。 •【主要元件符號說明】 • 2 第2層 4 第1層 6 第3層 ❹ 8 重疊部 8w 重疊寬度 10 第2層之端面 12 第1層之端面 14 第3層之端面 16 溶劑密封部 18 偏差部 ® 18w 偏差寬度 100 薄膜片 A 一端側 . B 另一端側 097144296 56An unstretched laminated sheet was obtained in the same manner as in Example 1 except that "manufactured by Kuraray Co., Ltd., hereinafter referred to as "TPS-A"). Further, the unstretched sheet was stretched in the same manner as in Example 1 to obtain a heat-shrinkable laminated film. The results of evaluation of the obtained film are shown in Table 1. (Comparative Example 3) The composition of the resin composition used in the first layer of Example 1 was changed to a polystyrene-based elastomer resin B (stupid ethylene-ethylene-butene-phenethyl 097144296 51 200932531) The polymer, polyphenylene bromide, such as μ θ, manufactured by Chemical Co., Ltd., _TUfte GH1Q41, the same method as Asahi Kasei obtained the following: "::") is performed in the same way as the embodiment 1 example; The sheet is stretched with a solid π u butadiene. The film to be evaluated was evaluated. The results are shown in Table (Comparative Example 4) except that the composition of the resin composition used in the layer 1 a ❹ layer of Example 1 was changed =: the present B-type elastic Zhao Shuyan C (modified) Benzene-B-(4-)-::aggregate Zhao's polystyrene 3" amount - M1913, Asahi Kasei Chemicals and the implementation of the same method to obtain m to go to the following "job"), to stretch the film and the examples! The same = extended laminate. The step is to extend the film without stretching. Extension, obtaining heat shrinkable laminate The results of leaf estimation are shown in Table 1. 097 097144296 52 200932531 ο ο [I嵴] Comparative Example I &lt;3&gt; 〇1—H c=&gt; 0 1 H 5 S s LT5 X · &lt;J5 ^ CO ◎ 3. 85 CO CD 〇&lt;〇o T—i SS s X 18.5 ^ CO ◎ w CO ◎ 00 CO &lt;N1 ◦ 〇&gt; F—H o &lt;〇F &lt; S r*H (N1 o LO l〇X d ◎ :· &lt;&gt ;α ◎00 〇o &lt;=&gt; or·· &lt; § CN1 &lt;NI 1 - H LO ◎ :· X 0. 90 Example 〇〇C5 &lt;=&gt; 1 ~ '&lt; 〇o LO LO OJ CM LO 〇3 〇二· 〇1. 50 卜5 S o cz&gt; § r—^ &lt;NI o LO ^ m 〇1. 69 CO c=&gt; o &lt;=&gt; HS CNI oa r »H LT3 ^ CO 〇d ◎ 2. 00 LO &lt;=5 CD 1—^ CD o SS 05 〇3 ◎&quot;° ^ CO ◎ 2. 08 呀Ο Ο 1—» o 〇&gt;r—&lt; 〇S (ΝΪ 〇in ◎ Ξ 〇 1. 08 CO ◦ &lt;=) τ—1 &lt;=&gt; o S &lt;N1 o LT5 ◎ Ξ CO 〇 — 03 〇1—Η oo S C&lt;l C&lt; l H LO ^ L〇〇CO· ◎ :· 3@53 ◦ 〇oo 5 S 7—H oa 〇lO o CO 〇Ξ 〇 1. 58 TPEE-A ΤΡΕΕ-Β TPEE-C TPEE-D TPEE-E PETG TPS-A TPS-B TPS-C PETG SBS-A SBS-B PETG TPEE-E 70°Cxl0 seconds (TD) 80°C×10 seconds (TD) /^N Image s LO ^ 〇03 II Fog value (%) JISK7105 Interlayer peel strength (N/15mm width) Layer 1 (Quality “Layer 2 (% by mass) Layer 3 ( (% by mass) 1 heat shrinkage rate (%) peeling evaluation method at the time of shrinkage 1 - 93⁄4 inch U60 200932531 (Example 9) For the heat shrinkable laminated film used in Examples 3 to 8 and Comparative Examples 2 to 4, use The method of peeling evaluation 2 at the time of shrinkage was evaluated for peeling characteristics. - The results of the evaluation are shown in Table 2. [Table 2] Peeling at the time of shrinkage Example Comparative Example Evaluation Method 2 3 4 5 6 7 8 2 3 4 95 ° C x 30 seconds ◎ ◎ 〇〇〇〇 XXX Deviation width (%) 0. 5 0. 5 4. 5 2. 5 3. 5 4. 5 23. 0 32. 0 17. 5 ❹ As can be seen from Table 1, the heat-shrinkable film obtained by the laminate of the present invention (Examples 1 to 8) is compared with the first A heat-shrinkable film (Comparative Example 1) composed of a resin composition containing a polyester-based elastomer in one layer had a large interlayer peel strength. Further, the heat-shrinkable film (Examples 1 to 8) obtained from the laminate of the present invention was heat-shrinked as compared with the laminate in which the first layer was a resin layer containing a styrene resin (Comparative Examples 2 to 4). Good interlaminar peeling characteristics can also be maintained afterwards. Further, as is apparent from Table 2, the heat-shrinkable film (Examples 3 to 8) obtained from the laminate of the present invention can suppress interlayer peeling even under the conditions of severe heat shrinkage (extrusion evaluation 2 at the time of shrinkage). Further, as is clear from Table 1, the transparency of the heat-shrinkable film (Examples 1 to 8) obtained from the laminate of the present invention is such that the polyester layer-containing elastomer is interposed between the second layer and the third layer. The resin-composition layer does not significantly reduce the transparency, and has sufficient transparency for the transparency of the film for label use. Further, as is understood from the eighth embodiment, the film which is attempted in the case where the recycled product is mixed in the third layer is not changed, and the peeling strength of the interlayer is not changed, and the transparency is also 097144296 54 200932531. A film that is sufficiently transparent. Thereby, the laminated system of the present invention has more excellent transparency and interlayer peeling strength than the conventional film, and is most suitable for use in a heat shrinkable film. (Industrial Applicability) Since the laminate of the present invention has excellent interlayer peel strength and transparency, it can be suitably used for a molded article requiring heat shrinkability, particularly a shrinkage label. The above is the most practical and preferred embodiment of the present invention, but the present invention is not limited to the embodiments disclosed in the present specification, and the invention can be understood without departing from the scope of the patent application and the specification as a whole. Appropriate changes can be made within the scope of the gist of the present invention. The laminate, the stretch film, the heat-shrinkable film, the molded body, the heat-shrinkable label, and the container with the label are of course included in the technology of the present invention. Within the scope. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 (a) and (b) are cross-sectional views showing a vicinity of an overlapping portion in a preferred embodiment of the laminated body of the present invention (hereinafter, _ Fig. 2 (a) and (b) In a preferred embodiment of the laminate of the present invention, a cross-sectional view (2) in the vicinity of the overlap portion is shown in Fig. 3(a) and (b) in a preferred embodiment of the laminate of the present invention. A cross-sectional view of the vicinity of the portion (Fig. 4). Fig. 4 (a) and (b) are cross-sectional views (4) of the vicinity of the 097144296 55 200932531 portion in a preferred embodiment of the laminated body of the present invention. (a) and (b) are explanatory views for explaining a state in which an overlapping portion is formed in a preferred embodiment of the laminated body of the present invention. • [Description of main component symbols] • 2 2nd layer 4 1st layer 6 3rd layer ❹ 8 Overlap 8w Overlap width 10 End face of the second layer 12 End face of the first layer 14 End face of the third layer 16 Solvent seal 18 Deviation part 18 WW Deviation width 100 Film piece A One end side. B The other end side 097144296 56

Claims (1)

200932531 七、申請專利範圍： 1. 一種積層體，係至少具有第i層與第2層者，該第工 層係以含有聚g旨系彈性體之樹脂組成物、含有改質聚醋系彈 性體之樹脂組成物、或該等樹脂組成物之混合樹脂組成物作 為主成分所構成，該第2層係以含有聚醋系樹脂之樹脂組成 物作為主成分所構成；其特徵為， 將上述積層體至少於一方向延伸而製作熱收縮性薄膜，由 ® 4熱收縮性薄膜以主收縮方向15Q_、垂直於主收縮方向 15mm之大小採取試驗片後，從該試驗片之主收縮方向的薄 膜端面剝離上述第2層之一部分而分別於上述第2層上形成 剝離部、於上述第1層上形成被剝離部，將上述第2層之剝 離部與上述第1層之被剝離部以拉伸試驗機之夾頭夾取，以 相對於主收縮方向之試驗速度1〇〇mm/min進行18〇度剝離試 驗時之層間剝離強度為1N/I5mm寬以上。 2. 如申請專利範圍第1項之積層體，其中，於與上述第2 層所積層的上述第1層之面相反側的上述第1層之面上，係 具有第3層’其係以與構成上述第2層之樹脂組成物相異之 - 組成的熱可塑性樹脂組成物作為主成分所構成。 ' 3·如申請專利範圍第2項之積層體，其中，將上述積層體 至少於一方向延伸而製作熱收縮性薄膜，由該熱收縮性薄膜 以主收縮方向235mm、垂直於主收縮方向的方向500顏之大 小採取試驗片後，將垂直於該試驗片之主收縮方向的方向之 097144296 57 200932531 端側的第2層之面、與同方向之另-端侧的第3層之面或 第2層之面，以平行之方式於試驗片上形成1〇丽寬之重疊 部’以溶劑密封後，於垂直於主收縮方向的方向切出 165mm *長之圓筒狀薄膜，於蒸汽通道（steamtunnel)中以9(TC、 '5秒鐘之條件下使之收縮並恢復至常溫時，上述重疊部中被 U*封之垂直於主收縮方向的方向之第2層的端面、與第1 層及第3層的端面之間之偏差寬度，或者垂直於主收縮方向 ®的方向之第2層及第1層的端面、與第3層的端面之間之偏 差寬度，係上述重疊部之重疊寬度的5%以内。 4.如申請專利範圍第2項之積層體，其中，將上述積層體 至少於一方向延伸而製作熱收縮性薄膜，由該熱收縮性薄膜 以主收縮方向235mm、垂直於主收縮方向的方向500mm之大 小採取試驗片後，將垂直於該試驗片之主收縮方向的方向之 ❹一端側的第2層之面、與同方向之另一端侧的第3層或第2 層之面以平行之方式於試驗片上形成i〇mm寬之重疊部， 以溶劑密封後，切出主收縮方向之圓周為225咖、垂直於主 收縮方向的方向之長度為30mm之圓筒狀薄膜，接著在夾持 此圓筒狀薄膜之各兩端部的狀態下，於95°C溫水中浸潰30 ❼時，上述重疊部中被密封之垂直於主收縮方向的方向之第 2層的端面、與第！層及第3層的端面之間之偏差寬度，或 者垂直於主收縮方向的方向之第2層及第1層的端面、與第 3層的％面之間之偏差寬度，係上述重疊部之重疊寬度的5% 097144296 58 200932531 以内。 5·如申請專利範圍第2至4項中任—項之積層體，其令 主 上述第3層係以含有聚苯乙埽系樹脂之樹驗成物作為 成分而構成之層。 … 積層體，其中，上述聚苯乙烯 烯系烴之嵌段共聚合體，或苯 共聚合體之混合物。 6.如申請專利範圍第5項之 系樹脂係苯乙烯系烴與共輕二 乙稀糸經與共輛》二稀系煙之嵌 〇 7.如申請專利範圍第2至6項中任一項之積層體，其中， 上述第3層係相對於構成第3層之樹脂組成物的總量，以 40質量％以下之含有率含有下述成分之層：含有構成第2層 之聚醋系樹脂的樹脂組成物、含有構成第Μ之聚醋系彈性 體的樹脂組成物、含有改質聚㈣、彈性體的樹脂組成物、或 該等之混合樹脂組成物。 8. 如申請專利範圍第i至7項中任一項之積層體，其中， ❹上述聚醋系樹脂係含有二魏成分與二醇成分，上述二竣酸 成分及上述二醇成分之至少一者係以2種以上之成分所構 成，上述2種以上之成分中，除去最多成分之成分的合計含 ，有率，相對於上述二羧酸成分之總量（1〇〇莫耳％)與上述 二醇成分之總量（1〇〇莫耳％)的合計（2〇〇莫耳％)，係為 10莫耳％以上且50莫耳％以下。 9. 如申凊專利範圍第1至8項中任一項之積層體，其以 JIS K7105為基準之霧值為以下。 097144296 59 200932531 10. —種延伸薄膜，其特徵為，係將申請專利範圍第1至 9項中任一項之積層體至少於一方向上延伸而成。 11. 一種熱收縮性薄膜，其特徵為，係將申請專利範圍第 - 1至9項中任一項之積層體至少於一方向上延伸而成，於80 • °C之溫水中浸潰10秒時之主收縮方向的熱收縮率為20%以 上。 12. —種成形體，其特徵為，係將申請專利範圍第1至9 ❹ 項中任一項之積層體、申請專利範圍第10項之延伸薄膜、 申請專利範圍第11項之熱收縮性薄膜成形而成。 13. —種熱收縮性標籤，其特徵為，係使用申請專利範圍 第11項之熱收縮性薄膜作為基材而成。 14. 一種容器，其特徵為，係附有申請專利範圍第13項之 熱收縮性標籤。200932531 VII. Patent application scope: 1. A laminated body having at least an i-th layer and a second layer, the working layer is a resin composition containing a poly-g-type elastomer, and contains a modified poly- vine elastic The resin composition of the body or the mixed resin composition of the resin composition is composed of a main component, and the second layer is composed of a resin composition containing a polyester resin as a main component; The laminate is formed in at least one direction to form a heat-shrinkable film, and the film is taken from the main shrinkage direction of the test piece after the test piece is taken from the heat shrinkable film of the 4th heat shrinkable film in the main shrinkage direction 15Q_ and perpendicular to the main shrinkage direction of 15 mm. The end surface is peeled off from one of the second layers, and a peeling portion is formed on the second layer, and a peeled portion is formed on the first layer, and the peeled portion of the second layer and the peeled portion of the first layer are pulled The chuck of the tensile testing machine was clamped, and the interlayer peeling strength at the time of the 18-inch peeling test at a test speed of 1 mm/min with respect to the main shrinkage direction was 1 N/I 5 mm or more. 2. The laminate according to claim 1, wherein the first layer on the side opposite to the surface of the first layer stacked on the second layer has a third layer The thermoplastic resin composition having a composition different from that of the resin composition constituting the second layer is composed of a main component. The laminate according to the second aspect of the invention, wherein the laminate is formed in at least one direction to form a heat-shrinkable film having a main shrinkage direction of 235 mm and perpendicular to the main shrinkage direction. After the test piece is taken in the direction of the face 500, the surface of the second layer on the end side of 097144296 57 200932531 perpendicular to the direction of the main contraction direction of the test piece, and the third layer on the other end side in the same direction or On the surface of the second layer, a 1 mm wide overlap portion was formed on the test piece in a parallel manner. After sealing with a solvent, a cylindrical film of 165 mm * length was cut in a direction perpendicular to the main shrinkage direction, in a steam passage ( In the steamtunnel, the end face of the second layer in the direction perpendicular to the main contraction direction of the U* seal in the overlap portion is contracted by 9 (TC, '5 seconds and returned to the normal temperature), and the first The width of the deviation between the end faces of the layer and the third layer, or the width of the second layer and the end face of the first layer perpendicular to the direction of the main shrinkage direction®, and the end face of the third layer are the overlapping portions Within 5% of the overlap width. The laminate according to the second aspect of the invention, wherein the laminate is formed in at least one direction to form a heat-shrinkable film, and the heat-shrinkable film is taken in a direction of a main shrinkage direction of 235 mm and a direction perpendicular to the main shrinkage direction of 500 mm. After the test piece, the surface of the second layer on the one end side perpendicular to the direction of the main shrinkage direction of the test piece, and the surface of the third layer or the second layer on the other end side in the same direction were tested in parallel. An overlap of i〇mm width is formed on the sheet, and after sealing with a solvent, a cylindrical film having a circumference of 225 coffee in the main contraction direction and a length of 30 mm perpendicular to the main contraction direction is cut out, and then the cylinder is clamped. In the state of each end portion of the film, when 30 ❼ is immersed in warm water of 95 ° C, the end face of the second layer which is sealed in the direction perpendicular to the main shrinkage direction in the overlapping portion, and the first layer and the The width of the deviation between the end faces of the three layers, or the width of the second layer and the end face of the first layer perpendicular to the direction of the main shrinkage direction, and the % face of the third layer are the overlapping widths of the overlapping portions. 5% 097144296 58 200932531 5. The laminate according to any one of the items 2 to 4 of the patent application, wherein the third layer of the main layer is a layer composed of a test composition containing a polystyrene resin as a component. And a mixture of the above-mentioned polystyrene-based hydrocarbon block copolymers or benzene copolymers. 6. Resin-based styrene-based hydrocarbons and co-light diethyl ruthenium according to claim 5 The laminated body of any one of the second aspect of the present invention, wherein the third layer is relative to the total amount of the resin composition constituting the third layer, A layer containing a resin composition constituting the second layer of the vinegar-based resin, a resin composition containing the polyester-containing elastomer constituting the second layer, and a modified poly(4) at a content ratio of 40% by mass or less. A resin composition of an elastomer or a mixed resin composition of the above. 8. The laminate according to any one of the items of the present invention, wherein the polyester resin contains a diWey component and a diol component, and at least one of the dicarboxylic acid component and the diol component. The composition is composed of two or more kinds of components, and the total content of the components of the above-mentioned two or more components is the total content of the components excluding the most components, and the total amount (% by mole) of the dicarboxylic acid component is The total amount (2% by mole) of the total amount of the above diol components (2% by mole) is 10 mol% or more and 50 mol% or less. 9. The laminate according to any one of claims 1 to 8, which has a haze value of JIS K7105 or less. 097144296 59 200932531 10. An extended film which is characterized in that the laminate of any one of claims 1 to 9 is extended at least in one direction. A heat-shrinkable film which is obtained by extending at least one of the laminates of any one of claims 1 to 9 and immersed in warm water of 80 ° C for 10 seconds. The heat shrinkage rate in the main shrinkage direction of the time is 20% or more. 12. A molded body characterized in that it is a laminate of any one of claims 1 to 9 of the patent application, an extended film of claim 10, and a heat shrinkage of claim 11 The film is formed. A heat-shrinkable label comprising the heat-shrinkable film of claim 11 as a substrate. A container characterized by being provided with a heat shrinkable label of claim 13 of the patent application. 097144296 60097144296 60
TW97144296A 2007-11-14 2008-11-14 Laminate, heat-shrinkable film and heat-shrinkable label each obtained from the laminate, and container bearing the label TW200932531A (en)

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