TW201000588A - Adhesive film - Google Patents

Adhesive film Download PDF

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Publication number
TW201000588A
TW201000588A TW098115952A TW98115952A TW201000588A TW 201000588 A TW201000588 A TW 201000588A TW 098115952 A TW098115952 A TW 098115952A TW 98115952 A TW98115952 A TW 98115952A TW 201000588 A TW201000588 A TW 201000588A
Authority
TW
Taiwan
Prior art keywords
adhesive
mass
adhesive film
acrylate
vinyl chloride
Prior art date
Application number
TW098115952A
Other languages
Chinese (zh)
Other versions
TWI448528B (en
Inventor
Seiji Saita
Kohji Kubo
Daisuke Yoshimura
Yosuke Suzuki
Original Assignee
Denki Kagaku Kogyo Kk
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Publication date
Application filed by Denki Kagaku Kogyo Kk filed Critical Denki Kagaku Kogyo Kk
Publication of TW201000588A publication Critical patent/TW201000588A/en
Application granted granted Critical
Publication of TWI448528B publication Critical patent/TWI448528B/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J107/00—Adhesives based on natural rubber
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J121/00—Adhesives based on unspecified rubbers
    • 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
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/12—Layered products comprising a layer of natural or synthetic rubber comprising natural rubber
    • 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
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
    • 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
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
    • C09J109/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
    • C09J123/28—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/006—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/04—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/245—Vinyl resins, e.g. polyvinyl chloride [PVC]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • 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
    • B32B2405/00—Adhesive articles, e.g. adhesive tapes
    • 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
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber 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
    • B32B2509/00—Household appliances
    • 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
    • B32B2605/00—Vehicles
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2407/00—Presence of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2427/00—Presence of halogenated polymer
    • C09J2427/006—Presence of halogenated polymer in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2451/00—Presence of graft polymer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention provides an adhesive film, which renders less softening agents being transferred from substrate to the adhesive, with excellent adhesion, rewinding and retentivity, and little of the paste resided in the adhesion bodies. The adhesive film comprises substrate of vinyl chloride resin composition as well as adhesive layer in at least one side of the film. The adhesive layer comprises adhesive base consisting of natural rubber and/or styrene rubber, grafted polymer consisting of methacrylate with alkyl group and natural rubber and/or, as well as softening agent. The composition comprises 0.3 to 4 weight % softening agent relative to the adhesive of the adhesive layer, the grafted polymer is 10 to 50 parts of mass relative to 100 parts of adhesive base of natural rubber and/or methacrylate, the Mooney viscosity of the grafted polymer analysed in basis of method of JIS K 6300 is 60-90 Ms1+4 (100 DEG C).

Description

201000588 六、發明說明： 【發明所屬之技術領域】 本發明係有關一種黏著薄膜，例如適用於：將黏著薄 膜成形爲膠帶狀而綑綁汽車之線束等電線·電纜的捆用膠 帶、在黏著薄膜之表面呈示文字及圖形的標記膜。 【先前技術】 汽車、鐵路、飛機、船舶、住家、工廠等中之各種電 器產品所使用的絕緣膠帶等之各種黏著薄膜，係具有適度 (的柔軟性與延展性，在阻燃性、機械性強度、耐熱變形性、 電絕緣性以及成形加工性等方面優異，更且，從較爲廉價 之理由，而使用在以含有氯乙烯樹脂之樹脂組成物作爲原 料之基材的單面上經塗布黏著劑之氯乙烯系黏著薄膜。 在黏著薄膜之基材中，一般係爲了使基材軟化而調配 軟化劑。然而，隨著時間經過，會有軟化劑從基材轉移到 黏著劑層之情形。軟化劑轉移到黏著劑層時，黏著劑因軟 化而從作成捲體之製品的側面擠出並產生沾黏（側邊沾 u 黏）、或者因黏著劑之凝聚力或黏著力降低而成爲黏著薄膜 從被黏著體剝離之原因。而且，當黏著薄膜剝離時，部分 黏著劑以及軟化劑殘留在被黏著體中，而有污染被黏著體 的情形。 作爲意圖抑制如此軟化劑的轉移之黏著薄膜，已提案 在軟質基材與黏著劑層之間設有硬化型底層塗料之黏著薄 膜（例如：專利文獻1以及專利文獻2)。然而，該等之黏著 薄膜係將糊面以基材分隔物保護、或者，如基材之背面（非 形成糊面之面）不進行表面處理並捲成圓捲狀時，使經重疊 201000588 之一方的黏著薄膜的黏著劑層之表面與另一方之黏著薄膜 的背面成爲直接接觸，而在黏著薄膜間產生軟化劑的移 動。因此’糊面與背面如不進一步加以保護，則將有無法 充分地抑制軟化劑的移動之問題點。 【專利文獻1】日本特開平11-263946號公報 【專利文獻2】日本特開2002-146274號公報 【發明内容】 本發明之目的係提供一種從基材轉移至黏著劑的軟化 劑較少，黏著力、回捲力以及維持力優異且在被黏著體上 少有糊渣殘留之黏著薄膜。 本發明係爲達成上述目的而具有下述要點者。 (1) 一種黏著薄膜，其係由氯乙烯系樹脂組成物構成之基 材、以及在基材之至少一面上形成的黏著劑層所構成之黏 著薄膜，該黏著劑層含有： (i) 由天然橡膠及/或苯乙烯-丁二烯橡膠構成之黏著基劑； (ii) 由具有烷基之（甲基）丙烯酸酯與天然橡膠及/或苯乙烯-丁二烯橡膠接枝聚合而成之接枝聚合物；以及 (iii) 軟化劑， 其中 (A) 相對於構成黏著劑層之黏著劑而言，軟化劑之調配量爲 0.3至4質量％ ; (B) 相對於由天然橡膠及/或苯乙烯-丁二烯橡膠構成之黏著 基劑100質量份而言，接枝聚合物之調配量爲10至50質 201000588 (C)接枝聚合物之門尼黏度（依據ns Κ 6 300之門尼黏度）爲 60 至 90Msl+4(100°C )。 (2) 如上述（1)之黏著薄膜，其中相對於樹脂成分總量而言， 氯乙烯系樹脂組成物含有5 0質量％以上之氯乙烯樹脂。 (3) 如上述（1)之黏著薄膜，其中接枝聚合物爲由60至80質 量％的苯乙烯-丁二烯橡膠與20至40質量％的具有烷基之 (甲基）丙烯酸酯接枝聚合而成。 (4) 如上述（1)之黏著薄膜，其中具有烷基之（甲基）丙烯酸酯 係選自於由（甲基）丙烯酸甲酯、（甲基）丙烯酸正丁酯、（甲 基）丙烯酸2-乙基己酯以及該等之混合物所成組群。 (5) 如上述（1)之黏著薄膜，其中軟化劑係酞酸二異壬酯。 (6) 如上述（1)之黏著薄膜，其中相對於氯乙烯系樹脂組成物 之樹脂成分總量而言，基材中所含的軟化劑爲15至45質 量％。 如依本發明即可獲得一種黏著薄膜，其係從基材轉移 至黏著劑的軟化劑較少，黏著力、回捲力以及維持力優異 且在被黏著體上少有糊渣殘留之黏著薄膜。 【實施方式】 本發明之黏著薄膜，其係由氯乙烯系樹脂組成物構成 之基材、以及在基材之至少一面上形成的黏著劑層所構 成，而該黏著劑層係由含有下述者之黏著劑而形成： 相對於黏著劑而言，0.3至4質量％的軟化劑；以及， 由具有烷基之（甲基）丙烯酸酯與天然橡膠及/或苯乙烯 -丁二烯橡膠接枝聚合而成之接枝聚合物。 201000588 < I.基材> 作爲構成基材之氯乙烯系樹脂組成物，只要含有作爲 樹脂成分之主成分的氯乙烯系樹脂者即無特別限制。氯乙 烯系樹脂係指以往習知之氯乙烯的單一聚合物之同聚物樹 脂、或以往習知之各種共聚物樹脂，而無特別限定者。 上述共聚物樹脂可使用以往習知之共聚物樹脂，其代 表例係如：氯乙烯-乙酸乙烯酯共聚物樹脂、氯乙烯-丙酸 乙烯酯共聚物樹脂等之氯乙烯與乙烯酯類的共聚物樹脂； " 氯乙烯-丙烯酸丁酯共聚物樹脂、氯乙烯-丙烯酸2-乙基己 酯共聚物樹脂等之氯乙烯與丙烯酸酯類的共聚物樹脂；氯 乙烯-乙烯共聚物樹脂、氯乙烯-丙烯共聚物樹脂等之氯乙 烯與烯烴類的共聚物樹脂；氯乙烯·丙烯腈共聚物樹脂等。 特佳者，宜使用氯乙烯之單一聚合物的同聚物樹脂、氯乙 烯-乙烯共聚物樹脂、氯乙烯-乙酸乙烯酯共聚物樹脂等。 共聚物樹脂中，共聚之單體含量並無特別限定，可因應成 形加工性等所要求之品質而決定。 相對於氯乙烯系樹脂組成物之樹脂成分總量而言，氯 乙烯樹脂之比率係如50質量％以上，以80質量％以上爲 佳，以90至100質量％更佳。另外，可因應必要而添加阻 燃劑、安定劑、抗老化劑、顏料以及無機質塡充劑等。 作爲氯乙烯樹脂，可適用軟質的氯乙烯樹脂。軟質的 氯乙烯樹脂係可列舉如：在黏度平均聚合度爲900至1300 之氯乙烯樹脂中添加適量的安定劑或軟化劑等者。氯乙烯 樹脂之該聚合度少於900時，基材因柔軟而有成爲低耐熱 201000588 性物之情形。另一方面，該聚合度超出13 00時，因氯乙嫌 樹脂系樹脂組成物之添加劑的分散性變差而有黏著薄膜t 柔軟性變差之情形。該聚合度係使200g之樹脂溶解於50ml 之硝基苯中，再將該聚合物溶液於30 t之恆溫槽中以毛細 管（UBERODE)型黏度計測定比黏度，並經〗IS K6720-2求算 而得者。 <軟化劑> 基材中可調配使基材軟化用之軟化劑。可使用於基材 之軟化劑種類雖無特別限定，惟可採用習知之軟化劑。其 中一例係黏著劑手冊（日本黏著工業會，第3版，第69頁） 中記載之DOP(苯二酸二辛酯）、DINP(苯二酸二異壬酯）、 DINA(己二酸二異壬酯）、DBP(苯二酸二丁酯）、TOTM (偏苯 三酸三2-乙基己酯）、DIDP(苯二酸二異癸酯）等二元酸酯； 液狀聚異丁烯、液狀異戊二烯、液狀丁烯等液狀橡膠；芳 香族系加工用油、環烷系加工用油、鏈烷烴系油、蓖麻油、 妥爾油（tall oil)等之一般軟化劑。該等可單獨使用，亦可 將二種以上組合使用。相對於氯乙烯系樹脂組成物之樹脂 成分總量而言，軟化劑之比例宜爲1 5至45質量％，而以 1 5至30質量％更佳。該軟化劑少於1 5質量％時，基材會有 變硬的情形。反之，該軟化劑超出4 5質量％時，在基材之 製造中，會有基材折斷或基材收縮等的問題發生。 基材之厚度雖無特別限制，惟以1 0至500 # m爲佳， 以12至200ym更佳，又以15至ΙΟΟμιη爲特佳。而且， 基材可具有單層之型態，亦可具有複數層之型態。 201000588 基材中，可依所需而施行背面處理、抗靜電處理、底 塗層處理等之各種處理。 <π.黏著劑層> 本發明中，用以形成黏著劑層之黏著劑係包含：相對 於黏著劑而言，0.3至4質量％之軟化劑；以及由具有烷基之 (甲基）丙烯酸酯與天然橡膠及/或苯乙烯-丁二烯橡膠（以下 簡稱爲SBR)接枝聚合而成之接枝聚合物。 <黏著基劑> 黏著劑含有作爲黏著基劑之天然橡膠及/或苯乙烯-丁 二烯橡膠。 天然橡膠可廣泛地使用作爲黏著組成物之基劑。而 且，SBR係代表性之廣用橡膠，其耐老化性、耐蠕變 (anti-creep)特性、耐塑化劑特性等爲優異。天然橡膠、SBR 可使用市售品。 SBR可使用習知乃至慣用之SBR。同時，SBR中作爲 單體成分之苯乙烯與丁二烯的比例並無特別限制。SBR之 種類或等級無特別限制，可使用各種種類或等級之SBR。 <軟化劑> 黏著劑層中所調配之軟化劑可採用與基材中所使用者 爲相同之上述習知之軟化劑。 黏著劑層中之軟化劑含有率，相對於黏著劑而言’以 0.3至4質量％爲佳，以1至3質量％更佳。軟化劑之含有 率少於0.3質量％時，則無法抑制軟化劑從氯乙烯系樹脂組 成物所構成之基材轉移而使黏著劑之凝聚力降低，或隨著 201000588 貼合時間的經過而增加黏著力使得在剝離黏著薄膜時會產 生糊渣殘留的情形。反之，如該軟化劑之含有率超出4質 量％時，則與經時時間無關而在初期的黏著劑中發生凝聚力 不足，且當剝離黏著薄膜時會產生糊渣殘留的情形。經由 使軟化劑以上述之特定量存在於黏著劑中，軟化劑從基材 朝黏著劑的轉移能以化學平衡之原理抑制。 本發明中之軟化劑含量係經由下述方法測定。 裝置名稱：氣相層析儀（GC日本電子公司製造） C 試驗方法：將黏著薄膜之黏著劑以正己烷剝離、萃取 後，在40°C下進行乾燥而測定。 <接枝聚合物> 本發明中之接枝聚合物，其黏著特性不易發生劣化’ 且耐軟化劑性優異，對於因軟化劑的轉移而使黏著劑之凝 聚力的降低更具有抑制效果。而且，由於將具有烷基之（甲 基）丙烯酸酯進行接枝因而可謀求對各種被黏著體的密合 性、回捲力的提升、亦可謀求在低溫時之操作性的效率化。 / 1相對於由天然橡膠及/或SBR所構成之黏著基劑100質量 份，接枝聚合物之調配量爲10至50質量份，以20至50 質量份爲佳。接枝聚合物少於1 0質量份時，對於各種被黏 著體會有無法獲得適當的黏著力、回捲力的情形。反之， 接枝聚合物超出50質量份時，接枝聚合物會過硬而有無法 使用作爲黏著劑的情形。 接枝聚合物係經由在該接枝聚合物之分子構造中兼具 極性高之構成分子（具有烷基之（甲基）丙烯酸酯）與極性低 -10- 201000588 之構成分子（天然橡膠、SBR)兩者，即可發揮對難以附著在 作爲黏著薄膜的被黏著體之密合性以及高的回捲力。因 此，由於必須將兩構成分子適當地分配，因此在接枝聚合 物中宜進行聚合使天然橡膠及/或SBR成爲60至80質量％ 以及具有烷基之（甲基）丙烯酸酯成爲20至40質量％。更佳 者係使65至75質量％之天然橡膠及/或SBR與25至35質 量％之具有烷基之（甲基）丙烯酸酯進行聚合。 該（甲基）丙烯酸烷酯係如：（甲基）丙烯酸甲酯（以下簡 f 稱爲Μ Μ A )、（甲基）丙烯酸乙酯、（甲基）丙烯酸正丙酯、（甲 基）丙烯酸異丙酯、（甲基）丙烯酸正丁酯、（甲基）丙烯酸2_ 乙基己酯、（甲基）丙烯酸苯甲酯、（甲基）丙烯酸環己酯、（甲 基）丙烯酸異辛酯、（甲基）丙烯酸正辛酯、（甲基）丙烯酸壬 酯、（甲基）丙烯酸異壬酯、（甲基）丙烯酸十一烷酯、（甲基） 丙烯酸異十一烷酯、（甲基）丙烯酸十二烷酯、（甲基）丙烯酸 異十三烷酯、（甲基）丙烯酸十四烷酯等。該等可一種使用 或將二種以上倂用。其中以（甲基）丙烯酸甲酯、（甲基）丙烯 ί 酸正丁酯、（甲基）丙烯酸2-乙基己酯爲適用。 本發明中之接枝聚合物的門尼黏度爲 60至 90Msl+4(100°C)，以 70 至 90Msl+4(100°C)爲佳。接枝聚合 物之門尼黏度少於6 0 M s 1 + 4 (1 0 0 °C )時，對於黏著劑之流動 性的抵抗力弱而有無法獲得高凝聚力之情形。反之，門尼 黏度超出90Msl+4(100°C)時，會有黏著劑之凝聚力過高的 情形。作爲調整門尼黏度之方法係如習知之方法，並無特 別限定。其例可列舉如：經由開口輥、班伯里混練機 -11 - 201000588 (Banbury Mixer)、捏合機等之單純的混練等，其中 門尼黏度之容易度而言，較佳者爲以開口輥進行單 之方法。門尼黏度之測定係依據Π S - K 6 3 0 0者。 <添加劑> 黏著劑中可依所需而調配各種添加劑，例如：塑 紫外線吸收劑、抗氧化劑等之各種安定劑；賦黏劑 劑；著色劑；抗靜電劑；發泡劑以及界面活性劑等 的各種添加劑。 ί ' 賦黏劑中所使用之賦黏樹脂可在考量軟化點、 分之相溶性等之後加以選擇。其例可列舉如：萜烯 松香樹脂、氫化松香樹脂、色滿·節樹脂、苯乙烯系 脂肪族系以及脂環族系等之石油樹脂、萜烯-酚樹脂 苯樹脂、其他之脂肪族烴樹脂或芳香族烴樹脂等。 脂之軟化點爲6 5至1 7 0 °C，以8 0至1 5 0 °C爲佳。相 著劑100質量份，賦黏樹脂之調配量爲50至200質 以100至150質量份之範圍爲佳。賦黏樹脂較少時 C ' " 薄膜中會有無法發揮高黏著力的情形。反之，賦黏 多時，黏著薄膜會有黏著力過高的情形。 <111黏著薄膜> 本發明之黏著薄膜係由氯乙烯系樹脂組成物構 材、以及在該基材之至少一面上形成的黏著劑層所 通常，黏著劑層僅於基材之單面形成，然亦可於雙酉 黏著薄膜可使用塗布法等慣用之方法，經由在基材 一面上形成黏著劑層而製造。同時，黏著劑層可經 以調整 純混練 化劑、 ‘，塡充 之習知 與各成 樹脂、 樹脂、 、二甲 賦黏樹 對於黏 量份， ，黏著 樹脂較 成之基 構成。 '形成。 之至少 剝離基 -12- 201000588 材（剝離襯片）保護。而且，黏著薄膜在無損及本發明之效 果的範圍下可具有其他之層（例如：中間層、底塗層等）。 基材成形之手段雖無特別限定，惟可將上述之各種材 料使用慣用之熔融混練等或各種混合裝置（單軸或雙軸擠 出機、滾輪、班伯里混練機、各種捏合機等）進行混合使各 成分均勻分散’再將該混合物以壓延成形機於基材上成 形’並裁成所要之膠帶寬度而製得。壓延成形中之滾輪排 列方式可採用例如：L型、倒L型、Z型等之習知方式，而 且，滾輪溫度一般設定在150至200 °C，以160至180之範 圍爲佳。 將構成黏著劑層之黏著劑塗布在基材之手段並無特別 限定者，例如可使用：壓花滾輪式塗布機、反向滾輪式塗 布機、接觸滾輪式塗布機、浸泡式滾輪塗布機、棒塗布機、 刮刀式塗布機、噴塗機。黏著劑層於乾燥後之厚度，可在 不損及黏著性與操作性之範圍下適當地選擇，黏著劑層之 厚度例如爲5至100//m，以10至50ym爲佳。低於此厚 度時則有減低黏著力以及回捲力的情形。反之，如大於此 厚度時則會有塗布性能變差且容易產生糊渣殘留的情形。 本發明之黏著薄膜經由捲成圓捲狀，即可製成爲具有 回捲成圓捲狀之狀態或型態的黏著膠帶（回捲成圓捲狀之 黏著薄膜）’未回捲成圓捲狀時，可製作爲黏著片。 將黏著薄膜形成於黏著膠帶時，經由將剝離劑塗布在 黏著薄膜之背面（非形成糊面之面）而設置背面處理層，即 使將黏著膠帶釋成圓捲狀’亦可確實地阻礙黏著薄膜間之 -13- 201000588 軟化劑的移動。同樣地，經由使剝離襯片之 著劑層之表面並積層，由於剝離襯片介於一 黏著劑層表面與另一方黏著薄膜背面之間， 阻礙黏著薄膜間之軟化劑的移動。 [實施例] 以下，根據實施例與比較例而更詳加說 本發明並不受該等實施例所限定。 實施例中所使用之材料分別爲以下所示 (1) 氯乙烯樹脂：ΤΗ_ 1000(大洋聚氯乙烯公司 1100)、ΤΗ- 1 300(大洋聚氯乙烯公司製造：聚 (2) 軟化劑：DINP(DIC公司製造） (3) 賦黏劑：C5C9系石油樹脂（ESSO化學公 9 4〇C ) (4) 安定劑：Ca-Zn系安定劑（水澤化學公司製 (5) 改質劑：MBS(日本合成橡膠公司製造） (6) 將MMA與天然橡膠接枝聚合而成之； MEGAPOLY 30(ASIATIC 公司製造：將 30 質 70質量％之天然橡膠接枝聚合而成之接枝聚 (7) 將MMA與天然橡膠接枝聚合而成之 MEGAPOLY 50(ASIATIC 公司製造：將 50 質 50質量％之天然橡膠接枝聚合而成之接枝聚 (8) 將 MMA與 SBR接枝聚合而成之g SGMM-30(電氣化學工業公司製造：將30質 70質量％之SBR接枝聚合而成之接枝聚合物 剝離面接觸黏 方黏著薄膜之 因而可確實地 明本發明，然 者。 製造：聚合度 合度1 300) 司製造；軟化點 [造） 接枝聚合物： 量％之MMA與 合物） 接枝聚合物： 量％之Μ Μ A與 合物） I枝聚合物： 量％之Μ Μ A與 I ) -14- 201000588 (9) 將（甲基）丙烯酸丁酯與SBR接枝聚合而 物：SGBM-30(電氣化學工業公司製造：將30】 丙烯酸丁酯與70質量％之SBR接枝聚合而 物） (10) 將丙烯酸丁酯與SBR接枝聚合而成之 SGBA-30(電氣化學工業公司製造：將30質I 酯與70質量％之SBR接枝聚合而成之接枝聚 ί 成之接枝聚合 鼋量％之（甲基） 成之接枝聚合 接枝聚合物： t %之丙烯酸丁 :合物） -15- 201000588 [表1] 實施例 1 2 3 4 5 6 7 8 9 基材 PVC TH-1000(聚合度 1100) 100 100 100 100 100 100 100 100 - TH-13CXX 聚合度 1300) - 100 軟化劑 DINP質量％ 25 25 25 25 25 25 25 25 30 黏著劑 天然橡膠 MS1+4(100°C) ： 45 100 100 100 100 100 100 - 50 100 SBR MS1+4(100°C) : 30 - - - - - - 100 50 MEGAPOLY30 MS1+4(100°C): 80 20 50 - - - - 20 20 20 MEGAPOLY50 MS1+4(100°C) ： 90 - - 20 - - - - - SGMM-30 MS1+4(100°C) ： 80 - - - 20 - - - - - SGBM-30 MS1+4(100°C) ： 70 - - - - 20 - - 琴 - SGBA-30 MS1+4(100°C) ： 60 - - - - - 20 - - - 軟化劑含量 DINP質量％ 2 0.6 1.9 2.3 2.3 2.4 3 2.5 4 特性値 初期黏著力 (N/10mm) 對SUS 2 3 1.8 3 3 3.5 1.7 1.9 11 對PE 1.7 1.6 1.5 1.7 1.7 2 1.5 1.8 1.7 對PVC 1.7 2 1.6 2.7 2.7 3 1.6 1.8 1.9 對PET 2.5 2.7 2.4 3.2 3.2 3.5 2 2.7 2.7 對SUS經時 黏著力之變化 (N/10mm) 初期(貼合30分鐘後） 2 3 1.8 3 3 3.5 1.7 1.9 2.1 貼合1個月後 2.1 3 1.9 3 3.2 3.7 2.1 2.3 2.5 -20°C (貼合30分鐘後） 2.5 2.8 2.6 3.2 3.5 4.1 2.3 2.8 2.5 維持力 落下時間(分鐘） 300 350 350 400 350 350 350 320 280 回捲力 (N/10mm) 製造7天後 6.2 7 6 6 6 6 6 6.6 6.5 SUS剝離 有無初期剝離 良 良 良 良 良 良 良 良 良 1個月後 良 良 良 良 良 良 良 良 良 SUS糊渣殘留 貼合30分鐘後 良 良 良 良 良 良 良 良 良 貼合1個月後 良 良 良 良 良 良 良 良 良 -16- 201000588 [表2] 比較例 1 2 3 4 5 6 基材 PVC TH-1000(聚合度 1100) 100 100 100 100 100 100 軟化劑 DINP質量％ 25 25 25 25 25 25 黏著劑 天然橡膠 MS1+4(100°C) ： 45 100 100 100 100 100 100 SBR MS1+4(100°C) : 30 - - - - - - MEGAPOLY30 MS1+4(100°C) ： 50 - - > 20 - - MEGAPOLY30 MS1+4(100°C) ： 80 - 8 60 - - 20 MEGAPOLY30 MS1+4(100°C) ： 95 - - - 琴 20 - 軟化劑含量 DINP質量％ 6 4 2 2.5 1.8 6 特性値 初期黏著力 對SUS 0.5 0.7 4.5 2.5 1.8 1.5 (N/10mm) 對PE 0.2 0.3 4 2 1.6 1.5 對PVC 0.5 0.7 4.2 2 2 1.7 對PET 0.5 0.7 4.8 2.4 2 1.8 對SUS經時 初期(貼合30分鐘後） 0.5 0.7 4.5 2,5 1.8 1.5 黏著力之變化 貼合1個月後 3.2 3.5 4.7 5 2 3 (N/10mm) -20°C(貼合30分鐘後） 0.8 1.2 5 3 2,2 3.5 維持力 落下時間(分鐘） 30 100 400 200 400 10 回捲力 (N/10mm) 製造7天後 2 3 15 9 5 4 SUS mm 有無初期剝離 不佳 不佳 良 良 不佳 良 1個月後 良 不佳 良 良 不佳 不佳 SUS糊渣殘留 貼合30分鐘後 不佳 不佳 良 不佳 良 不佳 貼合1個月後 不佳 不佳 良 不佳 良 不佳201000588 6. TECHNOLOGICAL FIELD OF THE INVENTION The present invention relates to an adhesive film which is suitable, for example, for forming an adhesive film into a tape shape and binding a wire for a wire harness such as a wire harness of a car, and a tape for bonding the film. A marking film with text and graphics on the surface. [Prior Art] Various adhesive films such as insulating tape used in various electrical products such as automobiles, railways, airplanes, ships, homes, factories, etc., have moderate (softness and ductility, flame retardancy, mechanical properties). It is excellent in strength, heat deformation resistance, electrical insulating properties, and moldability, and is coated on one side of a substrate containing a resin composition containing a vinyl chloride resin as a raw material for the reason of being inexpensive. A vinyl chloride-based adhesive film for an adhesive. In a substrate for an adhesive film, a softener is generally added to soften the substrate. However, as time passes, there is a case where the softener is transferred from the substrate to the adhesive layer. When the softener is transferred to the adhesive layer, the adhesive is squeezed from the side of the product made into the roll due to softening and is sticky (side adhesive), or becomes adhesive due to the cohesive force or adhesive force of the adhesive. The reason why the film is peeled off from the adherend. Moreover, when the adhesive film is peeled off, part of the adhesive and the softener remain in the adherend, and the contaminated adherend In the case of an adhesive film which is intended to suppress the transfer of such a softener, an adhesive film having a curable primer is provided between the soft substrate and the adhesive layer (for example, Patent Document 1 and Patent Document 2). The adhesive film is such that the paste is protected by the substrate separator, or if the back surface of the substrate (the surface which is not formed into a paste) is not surface-treated and rolled into a circular shape, the adhesion of one of the overlapped 201000588 is made. The surface of the adhesive layer of the film is in direct contact with the back surface of the other adhesive film, and the movement of the softener is generated between the adhesive films. Therefore, if the paste surface and the back surface are not further protected, the softening may not be sufficiently suppressed. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2002-146274. SUMMARY OF THE INVENTION The object of the present invention is to provide a transfer from a substrate to an adhesive. The agent has less softener, adhesive force, rewinding force and adhesive film which are excellent in maintaining power and have little residue on the adherend. In order to achieve the above object, the following points are obtained: (1) An adhesive film comprising a substrate composed of a vinyl chloride resin composition and an adhesive film formed of an adhesive layer formed on at least one side of the substrate. The adhesive layer comprises: (i) an adhesive base composed of natural rubber and/or styrene-butadiene rubber; (ii) a (meth) acrylate having an alkyl group and natural rubber and/or styrene a graft polymer obtained by graft-polymerizing a butadiene rubber; and (iii) a softener, wherein (A) the amount of the softener is from 0.3 to 4% by mass relative to the adhesive constituting the adhesive layer (B) The graft polymer is formulated in an amount of 10 to 50 masses 201000588 (C) of the graft polymer relative to 100 parts by mass of the adhesive base composed of natural rubber and/or styrene-butadiene rubber. The Mooney viscosity (based on ns Κ 6 300 Mooney viscosity) is 60 to 90 Msl + 4 (100 ° C). (2) The adhesive film according to the above (1), wherein the vinyl chloride resin composition contains 50% by mass or more of the vinyl chloride resin based on the total amount of the resin component. (3) The adhesive film according to (1) above, wherein the graft polymer is 60 to 80% by mass of styrene-butadiene rubber and 20 to 40% by mass of (meth) acrylate having an alkyl group The branches are aggregated. (4) The adhesive film according to (1) above, wherein the (meth) acrylate having an alkyl group is selected from the group consisting of methyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylic acid. 2-Ethylhexyl ester and mixtures of such mixtures are grouped. (5) The adhesive film according to (1) above, wherein the softening agent is diisononyl phthalate. (6) The adhesive film according to the above (1), wherein the softener contained in the substrate is from 15 to 45% by mass based on the total amount of the resin component of the vinyl chloride resin composition. According to the present invention, an adhesive film can be obtained which is less adhesive agent for transferring from the substrate to the adhesive, and has an excellent adhesive force, a rewinding force, and a retaining force, and an adhesive film which has little residue on the adherend. . [Embodiment] The adhesive film of the present invention comprises a base material composed of a vinyl chloride resin composition and an adhesive layer formed on at least one surface of the base material, and the adhesive layer contains the following Formed by an adhesive: 0.3 to 4% by mass of a softener relative to the adhesive; and, by a (meth) acrylate having an alkyl group and a natural rubber and/or styrene-butadiene rubber A graft polymer obtained by polymerizing branches. 201000588 <I. Substrate> The vinyl chloride resin composition constituting the substrate is not particularly limited as long as it contains a vinyl chloride resin as a main component of the resin component. The chloroethylene-based resin is a homopolymer resin of a conventional single-polymer of vinyl chloride or a conventional copolymer resin, and is not particularly limited. As the above copolymer resin, a conventional copolymer resin can be used, and a representative example thereof is a copolymer of vinyl chloride and vinyl ester such as a vinyl chloride-vinyl acetate copolymer resin or a vinyl chloride-vinyl propionate copolymer resin. Resin; " vinyl chloride-butyl acrylate copolymer resin, vinyl chloride-2-ethylhexyl acrylate copolymer resin, vinyl chloride and acrylate copolymer resin; vinyl chloride-ethylene copolymer resin, vinyl chloride - a copolymer resin of vinyl chloride and olefin such as a propylene copolymer resin; a vinyl chloride/acrylonitrile copolymer resin or the like. Particularly preferred is a homopolymer resin of a single polymer of vinyl chloride, a vinyl chloride-ethylene copolymer resin, a vinyl chloride-vinyl acetate copolymer resin, or the like. In the copolymer resin, the monomer content of the copolymerization is not particularly limited, and can be determined in accordance with the quality required for the formability and the like. The ratio of the vinyl chloride resin to the total amount of the resin component of the vinyl chloride resin composition is, for example, 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass to 100% by mass. Further, a flame retardant, a stabilizer, an anti-aging agent, a pigment, and an inorganic chelating agent may be added as necessary. As the vinyl chloride resin, a soft vinyl chloride resin can be applied. Examples of the soft vinyl chloride resin include those in which an appropriate amount of a stabilizer or a softener is added to a vinyl chloride resin having a viscosity average degree of polymerization of 900 to 1300. When the degree of polymerization of the vinyl chloride resin is less than 900, the substrate may be soft and have a low heat resistance of 201000588. On the other hand, when the degree of polymerization exceeds 130,000, the dispersibility of the additive of the resin composition of the vinyl chloride resin is deteriorated, and the flexibility of the adhesive film t is deteriorated. The degree of polymerization is such that 200 g of the resin is dissolved in 50 ml of nitrobenzene, and the specific solution is measured by a capillary (UBERODE) type viscometer in a 30 t thermostat, and is obtained by IS K6720-2. Count it. <Softener> A softener for softening the substrate can be blended in the substrate. The type of the softening agent to be used for the substrate is not particularly limited, and a conventional softening agent can be used. One of them is DOP (dioctyl phthalate), DINP (diisononyl phthalate), and DINA (dipic acid) described in the Adhesive Handbook (Japan Adhesive Industry Association, 3rd edition, page 69). Diester esters such as isodecyl ester), DBP (dibutyl phthalate), TOTM (tris-2-ethylhexyl trimellitate), DIDP (diisononyl phthalate); liquid polyisobutylene Liquid rubber such as liquid isoprene or liquid butene; general softening of aromatic processing oil, naphthenic processing oil, paraffinic oil, castor oil, tall oil, etc. Agent. These may be used singly or in combination of two or more. The proportion of the softener is preferably from 15 to 45 mass%, more preferably from 15 to 30 mass%, based on the total amount of the resin component of the vinyl chloride resin composition. When the softener is less than 15% by mass, the substrate may be hardened. On the other hand, when the softener exceeds 45 mass%, problems such as breakage of the substrate or shrinkage of the substrate may occur in the production of the substrate. Although the thickness of the substrate is not particularly limited, it is preferably from 10 to 500 #m, more preferably from 12 to 200 μm, and particularly preferably from 15 to ΙΟΟμιη. Moreover, the substrate may have a single layer type or a plurality of layers. 201000588 In the substrate, various treatments such as back treatment, antistatic treatment, and undercoat treatment can be performed as needed. <π.Adhesive layer> In the present invention, the adhesive for forming the adhesive layer contains: 0.3 to 4% by mass of the softener relative to the adhesive; and A graft polymer obtained by graft polymerization of acrylate with natural rubber and/or styrene-butadiene rubber (hereinafter abbreviated as SBR). <Adhesive base> The adhesive contains natural rubber and/or styrene-butadiene rubber as an adhesive base. Natural rubber can be widely used as a base for an adhesive composition. Further, SBR is a representative rubber which is excellent in aging resistance, anti-creep characteristics, plasticizer resistance, and the like. Commercially available products can be used for natural rubber and SBR. SBR can use conventional or even conventional SBR. Meanwhile, the ratio of styrene to butadiene as a monomer component in SBR is not particularly limited. The type or grade of the SBR is not particularly limited, and various types or grades of SBR can be used. <Softener> The softener formulated in the adhesive layer may be the same as the above-mentioned conventional softener as used in the substrate. The content of the softener in the adhesive layer is preferably from 0.3 to 4% by mass, more preferably from 1 to 3% by mass, based on the adhesive. When the content of the softener is less than 0.3% by mass, the softener cannot be inhibited from shifting from the substrate composed of the vinyl chloride resin composition, and the cohesive force of the adhesive is lowered, or the adhesion is increased as the bonding time of 201000588 is passed. The force causes a residue to remain when the adhesive film is peeled off. On the other hand, when the content of the softener exceeds 4% by mass, the cohesive force is insufficient in the initial adhesive regardless of the elapsed time, and the slag remains when the adhesive film is peeled off. By allowing the softening agent to be present in the adhesive in the above specified amount, the transfer of the softening agent from the substrate to the adhesive can be inhibited by the principle of chemical equilibrium. The softener content in the present invention is determined by the following method. Device name: Gas chromatograph (manufactured by GC Nippon Electronics Co., Ltd.) C Test method: The adhesive of the adhesive film was peeled off and extracted with n-hexane, and then dried at 40 ° C to measure. <Graft polymer> The graft polymer of the present invention is less susceptible to deterioration in adhesion characteristics and has excellent softener resistance, and has a suppressing effect on the reduction of the cohesive force of the adhesive due to the transfer of the softener. In addition, since the (meth) acrylate having an alkyl group is grafted, the adhesion to various adherends and the rewinding force can be improved, and the operability at low temperatures can be improved. The compounding amount of the graft polymer is from 10 to 50 parts by mass, preferably from 20 to 50 parts by mass, based on 100 parts by mass of the adhesive base composed of natural rubber and/or SBR. When the graft polymer is less than 10 parts by mass, proper adhesion and rewinding force may not be obtained for various adherends. On the other hand, when the graft polymer exceeds 50 parts by mass, the graft polymer may be too hard to be used as an adhesive. The graft polymer is composed of a constituent molecule having a high polarity (a (meth) acrylate having an alkyl group) and a molecule having a low polarity - 10 201000588 in the molecular structure of the graft polymer (natural rubber, SBR) Both of them can exhibit adhesion to the adherend which is difficult to adhere to the adhesive film and high rewinding force. Therefore, since it is necessary to appropriately disperse the two constituent molecules, it is preferred to carry out polymerization in the graft polymer so that the natural rubber and/or SBR becomes 60 to 80% by mass and the (meth) acrylate having an alkyl group becomes 20 to 40. quality%. More preferably, 65 to 75 mass% of the natural rubber and/or SBR is polymerized with 25 to 35 mass% of the alkyl (meth) acrylate. The (meth)acrylic acid alkyl ester is, for example, methyl (meth)acrylate (hereinafter referred to as Μ Μ A ), ethyl (meth) acrylate, n-propyl (meth) acrylate, (methyl) Isopropyl acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, isooctyl (meth)acrylate Ester, n-octyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, isoundecyl (meth)acrylate, ( Dodecyl (meth)acrylate, isotridecyl (meth)acrylate, tetradecyl (meth)acrylate, and the like. These may be used alone or in combination of two or more. Among them, methyl (meth)acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth)acrylate are suitable. The graft polymer of the present invention has a Mooney viscosity of 60 to 90 Msl + 4 (100 ° C), preferably 70 to 90 Msl + 4 (100 ° C). When the Mooney viscosity of the graft polymer is less than 60 M s 1 + 4 (100 ° C), the resistance to the fluidity of the adhesive is weak and high cohesion cannot be obtained. Conversely, when the Mooney viscosity exceeds 90 Msl + 4 (100 ° C), there is a case where the cohesive force of the adhesive is too high. The method of adjusting the Mooney viscosity is a conventional method, and is not particularly limited. Examples thereof include simple kneading by an open roll, a Banbury kneading machine -11 - 201000588 (Banbury Mixer), a kneading machine, etc., and in terms of ease of Mooney viscosity, an open roll is preferred. The method of making a single. The Mooney viscosity is determined by Π S - K 6 3 0 0. <Additives> Various additives such as various plasticizers such as plastic ultraviolet absorbers and antioxidants; tackifiers; colorants; antistatic agents; foaming agents and interfacial activity can be formulated as needed in the adhesive. Various additives such as agents. ί ' The tackifying resin used in the adhesive can be selected after considering the softening point, the compatibility, and the like. Examples thereof include a terpene rosin resin, a hydrogenated rosin resin, a chroman resin, a styrene aliphatic system, and an alicyclic petroleum resin, a terpene-phenol resin benzene resin, and other aliphatic hydrocarbons. Resin or aromatic hydrocarbon resin. The softening point of the fat is from 6 5 to 170 ° C, preferably from 80 to 150 ° C. The amount of the tackifying resin is from 50 to 200, preferably from 100 to 150 parts by mass, based on 100 parts by mass of the treating agent. When the tackifying resin is small, C ' " may not be able to exert high adhesion in the film. On the other hand, when the adhesion is long, the adhesive film may have an excessive adhesion. <111 Adhesive film> The adhesive film of the present invention is composed of a vinyl chloride resin composition member and an adhesive layer formed on at least one side of the substrate. Generally, the adhesive layer is only one side of the substrate. Alternatively, the double-twist adhesive film may be produced by forming an adhesive layer on one side of the substrate by a conventional method such as a coating method. At the same time, the adhesive layer can be adjusted to adjust the pure mixing agent, ‘, the conventional knowledge and the resin, the resin, the dimethyl viscous tree for the viscosity component, and the adhesive resin. 'form. At least the release base -12- 201000588 material (release liner) protection. Moreover, the adhesive film may have other layers (e.g., an intermediate layer, an undercoat layer, etc.) without departing from the effects of the present invention. The means for forming the substrate is not particularly limited, but various materials described above may be used by conventional melt-kneading or various mixing devices (single-axis or twin-screw extruders, rollers, Banbury kneaders, various kneaders, etc.). The mixing is carried out to uniformly disperse the components, and then the mixture is formed on a substrate by a calendering machine and cut to a desired tape width. The roller arrangement in the calendering can be carried out by a conventional method such as an L type, an inverted L type, or a Z type, and the roller temperature is generally set at 150 to 200 ° C, preferably in the range of 160 to 180. The means for applying the adhesive constituting the adhesive layer to the substrate is not particularly limited, and for example, an embossing roller coater, a reverse roller coater, a contact roller coater, a immersion roller coater, or the like can be used. Bar coater, knife coater, sprayer. The thickness of the adhesive layer after drying can be appropriately selected within a range not impairing adhesion and workability, and the thickness of the adhesive layer is, for example, 5 to 100 / / m, preferably 10 to 50 μm. Below this thickness there is a case where the adhesion and the rewinding force are reduced. On the other hand, if it is larger than this thickness, the coating property may be deteriorated and the residue may be easily generated. The adhesive film of the present invention is formed into a roll shape, and is formed into an adhesive tape (rewinding into a roll-shaped adhesive film) in a state of rewinding into a roll shape, and is not rolled into a roll shape. When made, it can be made into an adhesive sheet. When the adhesive film is formed on the adhesive tape, the backing treatment layer is provided by applying a release agent to the back surface of the adhesive film (the surface on which the paste is not formed), and even if the adhesive tape is released into a roll shape, the adhesive film can be surely hindered. Between -13- 201000588 The movement of softeners. Similarly, by laminating the surface of the release liner layer, since the release liner is interposed between the surface of one of the adhesive layers and the back surface of the other adhesive film, the movement of the softener between the adhesive films is inhibited. [Examples] Hereinafter, the present invention is not limited by the examples and the comparative examples, and the present invention is not limited by the examples. The materials used in the examples are as follows: (1) Vinyl chloride resin: ΤΗ_1000 (Ocean polyvinyl chloride company 1100), ΤΗ-1 300 (manufactured by Ocean Polyvinyl Chloride Co., Ltd.: poly(2) softener: DINP (Manufactured by DIC) (3) Adhesive: C5C9 petroleum resin (ESSO Chemical Co., Ltd. 9 4〇C) (4) Stabilizer: Ca-Zn stabilizer (made by Mizusawa Chemical Co., Ltd. (5) Modifier: MBS (Manufactured by Japan Synthetic Rubber Co., Ltd.) (6) Grafting and polymerizing MMA with natural rubber; MEGAPOLY 30 (manufactured by ASIATIC: Grafting polymerization of 30% by mass of natural rubber grafted polymerized (7) MEGAPOLY 50 obtained by graft-polymerizing MMA with natural rubber (manufactured by ASIATIC Co., Ltd.: grafting polymerization of 50% by mass of 50% by mass of natural rubber) (8) Grafting polymerization of MMA and SBR SGMM-30 (manufactured by Electric Chemical Industry Co., Ltd.: The grafted polymer obtained by graft-polymerizing 30 mass% of 70% by mass of SBR is in contact with the adhesive-adhesive film, and thus the present invention can be clearly confirmed. Degree of cooperation 1 300) Manufactured; softening point [made] grafted polymer: % MMA and compound) Graft polymer: 5% by weight Μ A and compound) I branch polymer: 5% by weight Μ A and I ) -14- 201000588 (9) butyl (meth) acrylate and SBR graft polymerization: SGBM-30 (manufactured by Electric Chemical Industry Co., Ltd.: 30) butyl acrylate grafted with 70% by mass of SBR) (10) Graft polymerization of butyl acrylate and SBR SGBA-30 (manufactured by Electric Chemical Industry Co., Ltd.: Graft polymerization of 30% of I ester and 70% by mass of SBR by graft polymerization) Branch polymer: t% butyl acrylate: hydrate) -15- 201000588 [Table 1] Example 1 2 3 4 5 6 7 8 9 Substrate PVC TH-1000 (degree of polymerization 1100) 100 100 100 100 100 100 100 100 - TH-13CXX Degree of Polymerization 1300) - 100 Softener DINP Mass % 25 25 25 25 25 25 25 25 30 Adhesive Natural Rubber MS1+4 (100 ° C) : 45 100 100 100 100 100 100 - 50 100 SBR MS1 +4(100°C) : 30 - - - - - - 100 50 MEGAPOLY30 MS1+4(100°C): 80 20 50 - - - - 20 20 20 MEGAPOLY50 MS1+4(100°C) : 90 - - 20 - - - - - SGMM-30 MS1+4(100°C) : 80 - - - 20 - - - - - SGBM-30 MS1+4(100°C) : 70 - - - - 20 - - Piano - SGBA-30 MS1+ 4(100°C) : 60 - - - - - 20 - - - Softener content DINP mass % 2 0.6 1.9 2.3 2.3 2.4 3 2.5 4 Characteristics 値 Initial adhesion (N/10mm) to SUS 2 3 1.8 3 3 3.5 1.7 1.9 11 to PE 1.7 1.6 1.5 1.7 1.7 2 1.5 1.8 1.7 to PVC 1.7 2 1.6 2.7 2.7 3 1.6 1.8 1.9 to PET 2.5 2.7 2.4 3.2 3.2 3.5 2 2.7 2.7 Change in SUS time-dependent adhesion (N/10mm) (after 30 minutes of bonding) 2 3 1.8 3 3 3.5 1.7 1.9 2.1 After 1 month of fitting 2.1 3 1.9 3 3.2 3.7 2.1 2.3 2.5 -20 ° C (after 30 minutes of bonding) 2.5 2.8 2.6 3.2 3.5 4.1 2.3 2.8 2.5 Maintenance force drop time (minutes) 300 350 350 400 350 350 350 320 320 280 Rewinding force (N/10mm) After 7 days of manufacture 6.2 7 6 6 6 6 6 6.6 6.5 SUS peeling with or without initial peeling Good good good good good good After 1 month, Liangliang Liangliangliangliangliangliang SUS paste residue fit for 30 minutes, Liangliangliangliangliangliangliangliang fits for 1 month, Liangliangliangliangliangliangliang-16 - 20100058 8 [Table 2] Comparative Example 1 2 3 4 5 6 Substrate PVC TH-1000 (degree of polymerization 1100) 100 100 100 100 100 100 Softener DINP% by mass 25 25 25 25 25 25 Adhesive natural rubber MS1+4 (100 °C) : 45 100 100 100 100 100 100 SBR MS1+4(100°C) : 30 - - - - - - MEGAPOLY30 MS1+4(100°C) : 50 - - > 20 - - MEGAPOLY30 MS1+4 (100°C) : 80 - 8 60 - - 20 MEGAPOLY30 MS1+4(100°C) : 95 - - - Piano 20 - Softener content DINP mass% 6 4 2 2.5 1.8 6 Characteristics 値 Initial adhesion to SUS 0.5 0.7 4.5 2.5 1.8 1.5 (N/10mm) For PE 0.2 0.3 4 2 1.6 1.5 For PVC 0.5 0.7 4.2 2 2 1.7 For PET 0.5 0.7 4.8 2.4 2 1.8 For SUS over time (after 30 minutes of bonding) 0.5 0.7 4.5 2 , 5 1.8 1.5 Change in adhesion After 1 month, 3.2 3.5 4.7 5 2 3 (N/10mm) -20°C (after 30 minutes of bonding) 0.8 1.2 5 3 2,2 3.5 Maintenance drop time (minutes ) 30 100 400 200 400 10 Rewinding force (N/10mm) After 7 days of manufacturing 2 3 15 9 5 4 SUS mm Whether there is initial poor peeling, poor good, good good, good good, good after 1 month, good, good, poor, poor, SUS paste After 30 minutes, the residual bonding poor poor poor good good good poor poor poor poor bonding after 1 month Poor Good

表1、表2中，「初期黏著力」係依JIS Z 0237之基準 而測定。將黏著薄膜放置在溫度設定爲23 ±2°C、溼度設定 爲50±5%RH之評定試驗室中24小時以上之後，以2000g 之滾輪往返2次使黏著薄膜貼合在各種被黏著體（S US、 PE、PET)上，測定30分鐘後之180度剝離強度（N/10mm)。 -17- 201000588 以1N/I0mm以上爲佳。 表1、表2中，「對SUS經時黏著力之變化 02 3 7之基準而測定。將黏著薄膜放置在溫度雷 °C、溼度設定爲50±5%RH之評定試驗室中24 後，以2000g之滚輪往返2次使黏著薄膜貼合右 板上，分別測定3 0分鐘後、1個月後之1 8 0 (Ν/lOmm)。另外，將黏著薄膜放置在經設定爲 定試驗室中24小時以上之後，以2000g之滾輪 ， 黏著薄膜貼合在SUS304鋼板上，測定30分鐘 剝離強度（Ν/lOmm)。均以1N/I0mm以上爲佳。 表1、表2中，「維持力」係依〗IS Z 02 37 定。將黏著薄膜靜置在溫度設定爲2 3 ±2 °C、 50±5%RH之評定試驗室中24小時以上之後，ΐ 鋼板作爲被黏著體，將20x20mm尺寸之黏著 此。其後，在40 °C之氣體環境下，在重力方fi 之重量，將砝碼的落下時間（分鐘）以n = 3以上 I.... 表之數値爲平均値。300分鐘以上爲佳。 表1、表2中，「回捲力」係依JISZ0237 定。將黏著薄膜靜置在溫度設定爲23±2°C、 50±5%RH之評定試驗室中24小時以上之後，將 15.8m/分鐘之速度回捲約 3秒鐘時的數値以 定。上述表之數値爲平均値。以6至8N/10分 佳。 表1、表2中，「剝離」係依JIS G 4305之3 」係依JIS Z έ定爲23±2 小時以上之 三SUS304鋼 度剝離強度 2 0 ± 2 °C之評 往返2次使 後之180度 之基準而測 溼度設定爲 g 用 SUS304 薄膜貼合於 句垂掛500g 測定。上述 之基準而測 溼度設定爲 黏著薄膜以 n = 3以上測 鐘之範圍爲 g準而測定。 -18- 201000588 將黏著薄膜放置在溫度設定爲23±2°C 、溼度設定爲 50±5 %RH之評定試驗室中24小時以上之後，將黏著薄膜壓 接在SUS304鋼板上，以肉眼觀察初期30分鐘後、7天後 之貼合狀態，並以下述基準評定其優劣。壓接方法係依JIS K6253之基準而使用200g之滾輪，以壓接速度5mm/s往返 1次進行壓接。 良：無剝落者 不佳：有剝落者 表1、表2中，「糊渣殘留」係依JIS G 4305之基準而 測定。將黏著薄膜靜置在溫度設定爲23±2°C、溼度設定爲 5 0±5 % RH之評定試驗室中24小時以上之後，將黏著薄膜壓 接在SUS 3 04鋼板上，在初期30分鐘後、1個月後，將黏 著薄膜朝180°方向以300mm/分鐘之速度剝離，以肉眼觀察 剝離後之SUS 3 04鋼板表面，並以下述基準評定其優劣。壓 接方法係依JIS K 6253之基準而使用200g之滾輪，以壓接 速度5mm/s往返1次進行壓接。 良：無糊渣殘留者 不佳：有糊渣殘留者 (實施例1) ⑴將聚合度1100之氯乙烯樹脂（大洋聚氯乙烯公司製造； ΤΗ-1000ΠΟ0質量份、作爲軟化劑之DINP(DIC公司製造）25 質量份、作爲賦黏劑之C5C9系石油樹脂（ESSO化學公司製 造；軟化點94 °C)10質量份、作爲改質劑之MBS(日本合成橡 膠公司製造）2質量份、作爲安定劑之Ca-Zn系安定劑（水澤 -19- 201000588 化學公司製造）2質量份、St酸（日本油脂公司製造）0.2質量 份、MMA(鐘淵化學公司製造）2質量份以漢塞混合機 (Henschel Mixer)進行混合，並經由壓延成形（滾輪溫度爲 145至180°C)而形成厚度120/zm之薄片。該薄片以規定之 長度（20m)捲繞而得者在120°C之條件下進行8小時之退火 後得到基材。 (ii) 在調配有天然橡膠100質量份（門尼黏度=45)、MMA30 質量％與天然橡膠70質量％接枝聚合而成之接枝聚合物 f (ASIATIC公司製造；MEGAPOLY 30)20質量份（門尼黏度 = 8 0)、DINP(DIC公司製造）2質量％之混合物中，將作爲賦 黏樹脂之萜烯樹脂（安原化學公司製造；YS樹脂PX-1 000) 100質量份、作爲抗老化劑之4-乙基6-第三丁基酚（川口化 學工業公司製造；ANT AGE W-5 00)2質量份溶解於甲苯使成 爲30質量％之基劑後調入上述混合液中，藉此而得到黏著 劑。 (iii) 在反向滾輪式塗布機中將黏著劑塗布在基材之單面 I 上’經過乾燥步驟，即形成乾燥後之厚度爲20 # m之黏著 劑層，裁切成寬度25mm之膠帶狀，得到黏著薄膜。 (實施例2至9) 除了將黏著劑以及基材之組成各變換成如表1所示者 之外，其餘依照實施例1製造黏著薄膜。 (比較例1至6) 除了將黏著劑之組成各變換成如表2所示者之外，其 餘依照實施例1製造黏著薄膜。 -20- 201000588 由表1、2而可明瞭，如依本發明， (SUS、PE、PVC、PET)中之初期黏著力（貼 異。而且，即使在SUS中之黏著力的經時 鐘後至1個月後，-20 °C之低溫）中，亦可維 可知由上述情形即可易於得到一種從基材 軟化劑較少，黏著力、回捲力以及維持力 體上少有糊渣殘留之黏著薄膜。 【圖式簡單說明】 ， 無。 【主要元件符號說明】 姐 。 j\\\ 各種被黏著體 3 0分鐘後）優 化（初期30分 高的黏著力。 移至黏著劑的 異且在被黏著 -21 -In Tables 1 and 2, "initial adhesion" was measured in accordance with JIS Z 0237. After the adhesive film was placed in an evaluation laboratory having a temperature of 23 ± 2 ° C and a humidity of 50 ± 5% RH for 24 hours or more, the adhesive film was attached to various adherends by using a 2000 g roller twice. On the S US, PE, PET), the 180-degree peel strength (N/10 mm) after 30 minutes was measured. -17- 201000588 It is better to be 1N/I0mm or more. In Tables 1 and 2, "the change in the adhesion of SUS over time is measured according to the reference of 02 3 7. The adhesive film is placed in the evaluation chamber of the temperature Thunder °C and the humidity is set to 50 ± 5% RH 24, The adhesive film was attached to the right plate with a roller of 2000 g twice, and the temperature was measured after 30 minutes and after 1 month (1/100 mm). In addition, the adhesive film was set in the test chamber. After 24 hours or more, the adhesive film was attached to a SUS304 steel plate with a roll of 2000 g, and the peel strength (Ν/lOmm) was measured for 30 minutes, preferably 1 N/I0 mm or more. In Tables 1 and 2, "maintenance" According to IS Z 02 37. After the adhesive film was allowed to stand in an evaluation laboratory having a temperature of 2 3 ± 2 ° C and 50 ± 5% RH for 24 hours or more, the ΐ steel plate was used as an adherend, and this was adhered to a size of 20 x 20 mm. Thereafter, in a gas atmosphere of 40 ° C, the weight of the gravity side fi, the weight drop time (minutes) is n = 3 or more I.... The number of tables is 値. More than 300 minutes is better. In Tables 1 and 2, the "rewinding force" is determined in accordance with JIS Z0237. After the adhesive film was allowed to stand in an evaluation laboratory having a temperature of 23 ± 2 ° C and 50 ± 5% RH for 24 hours or more, the speed of 15.8 m / minute was rewinded for several seconds. The number in the above table is the average 値. It is preferably 6 to 8N/10. In Tables 1 and 2, "peeling" is based on JIS G 4305 3". According to JIS Z, it is set to 23 ± 2 hours or more. SUS304 steel peel strength 2 0 ± 2 °C The measured humidity was set to g on the basis of 180 degrees, and was measured by attaching a SUS304 film to a sentence of 500 g. The above-mentioned reference humidity is set such that the adhesive film is measured with a range of n = 3 or more. -18- 201000588 After placing the adhesive film in an evaluation laboratory with a temperature setting of 23±2°C and a humidity setting of 50±5 %RH for 24 hours or more, the adhesive film was crimped onto the SUS304 steel plate to observe the initial stage with the naked eye. The bonding state after 30 minutes and 7 days, and the merits and demerits were evaluated on the basis of the following criteria. The crimping method was carried out by using a 200 g roller in accordance with JIS K6253 and crimping at a crimping speed of 5 mm/s. Good: No peeling off. Poor: Exfoliating. In Tables 1 and 2, "residual residue" is determined in accordance with JIS G 4305. After the adhesive film was allowed to stand in an evaluation laboratory having a temperature of 23 ± 2 ° C and a humidity of 50 ± 5 % RH for 24 hours or more, the adhesive film was pressure-bonded to the SUS 3 04 steel plate for 30 minutes in the initial period. After that, one month later, the adhesive film was peeled off at a speed of 300 mm/min in the 180° direction, and the surface of the SUS 3 04 steel sheet after peeling was visually observed, and the merits and the like were evaluated on the basis of the following criteria. The crimping method was carried out by using a 200 g roller in accordance with JIS K 6253 and crimping at a crimping speed of 5 mm/s. Good: Poor residue without slag residue: Residue of slag residue (Example 1) (1) Vinyl chloride resin having a polymerization degree of 1100 (manufactured by Ocean Polyvinyl Chloride Co., Ltd.; ΤΗ-1000 ΠΟ 0 parts by mass, DINP as softener) (manufactured by the company), 25 parts by mass, C5C9-based petroleum resin (manufactured by ESSO Chemical Co., Ltd.; softening point: 94 °C), 10 parts by mass, and 2 parts by mass of MBS (manufactured by Nippon Synthetic Rubber Co., Ltd.) as a modifier 2 parts by mass of Stabilizer Ca-Zn stabilizer (manufactured by Mizusawa-19-201000588 Chemical Co., Ltd.), 0.2 parts by mass of St acid (manufactured by Nippon Oil & Fats Co., Ltd.), and 2 parts by mass of MMA (manufactured by Kaneka Chemical Co., Ltd.) The machine (Henschel Mixer) was mixed and formed into a sheet having a thickness of 120/zm via calendering (roller temperature of 145 to 180 ° C.) The sheet was wound at a predetermined length (20 m) to obtain a temperature of 120 ° C. The substrate was obtained after annealing for 8 hours under conditions (ii) a graft polymer obtained by graft-polymerizing 100 parts by mass of natural rubber (Mooney viscosity = 45), MMA 30% by mass, and 70% by mass of natural rubber. f (Manufactured by ASIATIC; MEGAPOLY 30) 20 parts by mass (Monnier viscosity = 80), 2% by mass of a mixture of DINP (manufactured by DIC Corporation), 100% by mass of a terpene resin (manufactured by Anhara Chemical Co., Ltd.; YS resin PX-1 000) as a tackifying resin 2 parts by mass of 4-ethyl 6-tert-butylphenol (manufactured by Kawaguchi Chemical Industry Co., Ltd.; ANT AGE W-5 00) as an anti-aging agent, dissolved in toluene to make a base of 30% by mass, and then transferred to the above mixture. In the liquid, the adhesive is obtained by this. (iii) Applying the adhesive to the single side I of the substrate in the reverse roller coater'. After the drying step, the thickness of the dried layer is 20 #m. The agent layer was cut into a tape shape having a width of 25 mm to obtain an adhesive film. (Examples 2 to 9) The same procedure as in Example 1 was carried out except that the composition of the adhesive and the substrate were changed as shown in Table 1. Adhesive film (Comparative Examples 1 to 6) An adhesive film was produced in accordance with Example 1 except that the composition of the adhesive was changed to that shown in Table 2. -20- 201000588 It can be understood from Tables 1 and 2, According to the invention, the initial adhesion in (SUS, PE, PVC, PET) is different. Even in the SUS adhesion force after the clock to 1 month later, -20 ° C low temperature), it can be known from the above situation can easily get a less softener from the substrate, adhesion, back Rolling force and adhesion film with little residual residue on the body. [Simple description of the figure], No. [Description of main components] Sister. j\\\ Various adhesives after 30 minutes) Optimization (Initial 30 High adhesion. Moved to the adhesive and is stuck -21 -

Claims (1)

201000588 七、申請專利範圍： 1. 一種黏著薄膜，其係由氯乙烯系樹脂組成学 材、以及在基材之至少一面上形成的黏著劑, 黏著薄膜，該黏著劑層含有： u)由天然橡膠及/或苯乙烯-丁二烯橡膠構月 劑； (ii)由具有烷基之（甲基）丙烯酸酯與天然橡膠 烯·丁二烯橡膠接枝聚合而成之接枝聚合物； r (iii)軟化劑， 其中 (A) 相對於構成黏著劑層之黏著劑而言，軟化 爲〇. 3至4質量％ ; (B) 相對於由天然橡膠及/或苯乙烯-丁二烯橡 著基劑100質量份而言，接枝聚合物之調配量 質量份， (C) 接枝聚合物之門尼黏度（依據IIS K 6300 ^ ( 爲 60 至 90Msl+4(100°G )。 2. 如申請專利範圍第1項之黏著薄膜，其中相 分總量而言，氯乙烯系樹脂組成物含有50質 氯乙烯樹脂。 3 .如申請專利範圍第1項之黏著薄膜，其中接 由60至80質量％的苯乙烯-丁二烯橡膠與20 的具有烷基之（甲基）丙烯酸酯接枝聚合而成 4.如申請專利範圍第1項之黏著薄膜，其中具： 基）丙烯酸酯係選自於由（甲基）丙烯酸甲酯、 办構成之基 罾所構成之 ζ之黏著基 !及/或苯乙 以及 劑之調配量 膠構成之黏 爲10至50 己門尼黏度） 對於樹脂成 量％以上之 枝聚合物爲 至40質量％ ) 寻烷基之（甲 (甲基）丙烯 -22- 201000588 酸正丁酯、（甲基）丙烯酸2-乙基己酯以及該等之混合物 所成組群。 5 .如申請專利範圍第1項之黏著薄膜，其中軟化劑係酞酸 二異壬酯。 6.如申請專利範圍第1項之黏著薄膜，其中相對於氯乙嫌 系樹脂組成物之樹脂成分總量而言，基材中所含的軟化 劑爲1 5至4 5質量％。 -23- 201000588 四、指定代表圖： (一) 本案指定代表圖為：無。 (二) 本代表圖之元件符號簡單說明： 姐。 <M、、 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式：201000588 VII. Patent application scope: 1. An adhesive film consisting of a vinyl chloride resin and an adhesive formed on at least one side of the substrate, an adhesive film containing: u) natural a rubber and/or styrene-butadiene rubber constituting agent; (ii) a graft polymer obtained by graft polymerizing a (meth) acrylate having an alkyl group with a natural rubber olefin-butadiene rubber; (iii) a softening agent, wherein (A) is softened to 〇. 3 to 4% by mass relative to the adhesive constituting the adhesive layer; (B) relative to natural rubber and/or styrene-butadiene rubber For the 100 parts by mass of the base, the mass fraction of the graft polymer, (C) the Mooney viscosity of the graft polymer (according to IIS K 6300 ^ (60 to 90 Msl + 4 (100 ° G). 2 For example, in the adhesive film of claim 1, in the total amount of the phase, the vinyl chloride resin composition contains 50-type vinyl chloride resin. 3. The adhesive film according to claim 1 of the patent, wherein 60 Up to 80% by mass of styrene-butadiene rubber and 20 (alkyl) having alkyl groups The acrylate is graft-polymerized. 4. The adhesive film according to claim 1, wherein the acrylate is selected from the group consisting of methyl (meth) acrylate and ketone. Adhesive base! and / or styrene and the formulation of the amount of adhesive to form a viscosity of 10 to 50 henmeni viscosity) for the amount of resin above the amount of branch polymer to 40% by mass) Propylene-22- 201000588 n-butyl acid ester, 2-ethylhexyl (meth)acrylate, and mixtures thereof. 5. Adhesive film according to claim 1, wherein the softening agent is 6. The adhesive film according to claim 1, wherein the softener contained in the substrate is 15 to 5 with respect to the total amount of the resin component of the vinyl chloride resin composition. 4 5 mass%. -23- 201000588 IV. Designated representative map: (1) The representative representative of the case is: No. (2) The symbolic symbol of the representative figure is simple: Sister. <M,, V. If there is In the chemical formula, please reveal the chemical formula that best shows the characteristics of the invention.
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TWI448528B (en) 2014-08-11
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KR20110011680A (en) 2011-02-08
BRPI0912720A2 (en) 2015-10-13

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