TW201016812A - Surface protective film - Google Patents
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- TW201016812A TW201016812A TW098130714A TW98130714A TW201016812A TW 201016812 A TW201016812 A TW 201016812A TW 098130714 A TW098130714 A TW 098130714A TW 98130714 A TW98130714 A TW 98130714A TW 201016812 A TW201016812 A TW 201016812A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
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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
- 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
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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
- C09J125/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
- C09J125/02—Homopolymers or copolymers of hydrocarbons
- C09J125/04—Homopolymers or copolymers of styrene
- C09J125/08—Copolymers of styrene
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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
- 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
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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
- 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
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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
- 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
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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
- 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
- C09J7/241—Polyolefin, e.g.rubber
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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
- 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]
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- 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
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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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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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
- 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
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
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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
- C09J2423/00—Presence of polyolefin
- C09J2423/006—Presence of polyolefin in the substrate
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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
- C09J2453/00—Presence of block copolymer
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/1336—Illuminating devices
- G02F1/133602—Direct backlight
- G02F1/133606—Direct backlight including a specially adapted diffusing, scattering or light controlling members
- G02F1/133607—Direct backlight including a specially adapted diffusing, scattering or light controlling members the light controlling member including light directing or refracting elements, e.g. prisms or lenses
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2202/00—Materials and properties
- G02F2202/28—Adhesive materials or arrangements
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
Description
201016812 六、發明說明： 【發明所屬之技術領域】 本發明係關於表面保護膜。 【背景技術】 以往至今，為了保護光學裝置、金屬板、經塗裝之金 屬板、樹脂板、玻璃板等各種構件之表面，膜狀基材的— 面積層有黏著劑層而成之表面保護膜（一般來說有時亦稱 為保護帶（protect tape)、遮蓋帶（masking tape)、或表面保 濩片等）係廣泛地被使用。尤其近年來於液晶顯示器用之光 學構件係使用有表面保護膜。光學構件方面有如稜鏡片或 擴散膜等於表面呈凹凸形狀者。為了不損傷此凹凸，於使 用前係以其表面（尤其是凹凸的外表面）之表面保護膜來進 行保護，但將表面保護膜貼附於此種凹凸形狀之表面時， 因為無法獲得較大之接觸面積，故必須形成黏著力強之黏 著劑層。 然而，一般來說，表面保護膜係以將長條狀的膜捲繞 成輥狀而成之捲繞體形態來工業化地製造。丨為此種捲繞 體之表面保護膜方面，雖然已知捲繞體的回捲（rewind)所 需之力道（展開力）大且經時之展開力的上昇容易變大，但 仍強烈要求展開力小亦即可容易進行捲繞體之回捲。 又，表面保護膜因為於使用後會被剝離除去，故係要 求順暢的剝離性及不會有因殘糊所造成之被貼附物汚染。 另一方面’稜鏡片、擴散膜等素材係大多使用丙稀酸 系之樹脂及聚碳酸醋系之樹脂等極性聚合物。該等光學片 201016812 係於貼附表面保護膜後由光學裝 裝置製造商售出，有時在其 運搬、保管中等會暴露於高溫。 、 此時’尤其當被貼附物之矣 <表面呈凹凸形狀的情況時， 由於時間及溫度等外因會造成、 化成有被貼附物與黏著劑層之 間接觸面積增加因而黏著力上昇，所謂黏著宄進之問題。 /又來說’黏著劑係廣泛使用丙烯酸系黏著劑，但丙 烯酸系黏著劑隨著時間造成 取疋黏者力的上昇尤其顯著。 因此，尤其在適用於光學片之表面保護膜的情況時， 構成表面保護膜之黏著劑層中係主要使用有橡膠系黏著 劑而非丙稀酸系黏著劑。藉此謀求避免隨著時間造成之黏 t力的增大，且滑順地將表面保護膜從光學片之透鏡部（稜 鏡）表面剝離。 然而，橡膠系黏著劑，—舻φ 1又來說，因為是溶液塗佈型， 故有 >谷劑乾舞時之環请两绝这处旦 哀見污杂及能量浪費等問題，同時亦必 須要對廣泛使用之烯炉其分 歸基材層的背面（與積層有黏著劑芦 ❹201016812 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a surface protective film. [Background Art] In order to protect the surface of various members such as an optical device, a metal plate, a coated metal plate, a resin plate, and a glass plate, the surface layer of the film-like substrate has an adhesive layer. Films (generally referred to as protective tapes, masking tapes, or surface-protecting sheets, etc.) are widely used. In particular, in recent years, a surface protective film has been used for an optical member for a liquid crystal display. The optical member is such that the cymbal or the diffusion film is equal to the surface having a concave-convex shape. In order not to damage the unevenness, the surface protective film is protected by a surface protective film (especially the outer surface of the uneven surface) before use, but when the surface protective film is attached to the surface of the uneven shape, since it is not possible to obtain a large Since the contact area is large, it is necessary to form an adhesive layer having a strong adhesion. However, in general, the surface protective film is industrially produced in the form of a wound body in which a long film is wound into a roll. In the case of the surface protective film of such a wound body, although it is known that the force (expansion force) required for rewinding of the wound body is large and the expansion force over time tends to become large, it is strongly required. The unwinding force can also easily rewind the winding body. Further, since the surface protective film is peeled off after use, it is required to have smooth peelability and no contamination by the paste due to the residual paste. On the other hand, a material such as a ruthenium film or a diffusion film is often made of a polar polymer such as an acrylic resin or a polycarbonate resin. These optical sheets 201016812 are sold by an optical device manufacturer after being attached to a surface protective film, and sometimes exposed to high temperatures during transportation and storage. At this time, especially when the surface of the attached object is in a concave-convex shape, the contact area between the attached object and the adhesive layer is increased due to external factors such as time and temperature, and the adhesive force is increased. The so-called problem of adhesion. / In other words, the adhesive is widely used in acrylic adhesives, but the increase in the adhesiveness of the acrylic adhesive over time is particularly remarkable. Therefore, particularly in the case of a surface protective film suitable for an optical sheet, a rubber-based adhesive is mainly used in the adhesive layer constituting the surface protective film instead of the acrylic-based adhesive. Thereby, it is sought to avoid an increase in the adhesive force with time, and the surface protective film is smoothly peeled off from the surface of the lens portion (prism) of the optical sheet. However, the rubber-based adhesive, 舻φ 1 is also a solution-coated type, so there is a problem when the glutinous rice is dry and danced, and there is a problem such as contamination and energy waste. It is also necessary to divide the back side of the substrate layer for the widely used olefin furnace (with the adhesive layer reed with the laminate)
之側相反側的那_ ® ^ ΑΑ- JLI ^ 進仃離型處理。又，若為熱熔型之黏 著劑，則前者之問題可解^+ π、4、 畸了解4或低減，但無法避免背面之離 型處理。 對於改善回捲性此一 ..,. 诔喊，例如有人提出一種表面保 濩联之製造方法，對積層有由具有"固以上之分子内雙鍵 聚有機夕氧貌與聚稀烴系樹脂所構成之基材層、黏著 層而成之積層+ a 、基材層表面照射電子線或γ線（專利文 獻1) 〇 出種表面保護媒’其係將含有聚稀煙系 201016812 樹腊之表層與含有#可塑性彈性體之黏#劑層卩共擠出 法加以積層成膜之後，藉由塗佈法於表層之背面形成離型 層所得者（專利文獻2)。 、又，有人提出一種回捲性優異之表面保護膜，其係由 以下方式所得：使用以苯乙烯系彈性體作為主成分之黏著 劑層來取代天然鲁膠，再藉由與稀燦奢^ 者，並且其基材層之背面係經摩擦處理（專利文獻3)。 方面，對於抑制黏著亢進此一課題，例如，將導 it級炫基之聚乙烯亞胺混人基材層，並使之滲出於黏 劑層表面，藉此來韻對被貼附物之初期黏著力，同時 嘗试抑制黏著亢進（專利文獻4)。 :而’貼附有表面保護膜之稜鏡片在構裝於製品中之 月 般係以數十片為單位重疊保管。 此情況時’有時會因配置於上方之棱鏡片的荷重會使 配置於下方之稜鏡片 凸的頂。p受到破壞而光學品質變 認為此係原因在於，該頂部會因為荷重而滲入表 -黏黏著劑層而到達表面保護膜之基材，而超出每 界HIT能達成之上述荷重的分散、緩和效果的限 界。為了解決此問題，五Λ切Α 加厚即可。缺a Α ° <為將黏著劑層的厚度充分地 Ρ 了。然而，若將黏著劑層的眉& u 用的劑層的厚度增厚，則從製造費 用的觀點來看只會不利，或 層的、合一透鏡。卩（稜鏡）滲入至黏著劑 層的冰度會變大而隨著時 虞。 嗖云黏者力的上昇有變大之 基於此理由 亦有使用有苯乙烯系彈性體來取代天然 201016812 橡膠之表面保護膜的例子。伽 例如’專利文獻5中係揭示一 種表面保護膜’其中係使用有 ’从本乙烯系彈性體作為主成The _ ® ^ ΑΑ - JLI ^ on the opposite side of the side is removed. Further, in the case of a hot-melt type of adhesive, the former problem can be solved by ^+π, 4, or by 4 or less, but the release treatment of the back side cannot be avoided. For improving the rewindability, this one..,. screams, for example, has proposed a manufacturing method of surface protection, which has a multi-molecular double-bonded organic oxide and polyhydrocarbon system. A substrate layer composed of a resin and an adhesive layer + a , and a surface of the substrate layer is irradiated with an electron beam or a γ-ray (Patent Document 1). A surface-protecting medium which contains a poly-smoke system 201016812 After the surface layer and the viscous agent layer containing the #plastic elastomer are co-extruded to form a film, the release layer is formed on the back surface of the surface layer by a coating method (Patent Document 2). Further, a surface protective film excellent in rewindability has been proposed, which is obtained by using an adhesive layer containing a styrene-based elastomer as a main component instead of a natural ruthenium, and The back surface of the base material layer is subjected to rubbing treatment (Patent Document 3). On the other hand, in order to suppress the adhesion of the adhesive, for example, a polyethyleneimine mixed with a base layer is mixed with a base material layer and allowed to permeate the surface of the adhesive layer, thereby beginning to be attached to the adhesive layer. At the same time, it is attempted to suppress adhesion (Patent Document 4). On the other hand, the ruthenium to which the surface protective film is attached is stored in a stack of several tens of pieces in a month. In this case, there is a case where the load placed on the prism sheet above is placed on the top of the convex sheet which is disposed below. The optical quality of p is destroyed and the reason for this is that the top penetrates into the surface-adhesive layer due to the load and reaches the substrate of the surface protective film, and the dispersion and relaxation effect of the above-mentioned load can be achieved beyond the HIT of each boundary. Limit of the limit. In order to solve this problem, the five-inch cut can be thickened. Abs a Α ° <To fully reduce the thickness of the adhesive layer. However, if the thickness of the layer for the eyebrow & u of the adhesive layer is increased, it is only disadvantageous from the viewpoint of manufacturing cost, or a layered, unitary lens. The enthalpy of 卩(稜鏡) infiltrates into the adhesive layer becomes large and becomes awkward. The increase in the viscosity of the cloud has increased. For this reason, there is also an example of using a styrene-based elastomer to replace the surface protective film of the natural 201016812 rubber. For example, 'Patent Document 5 discloses a surface protective film' in which the use of the present ethylene-based elastomer as a main component is used.
分之厚度10/zm以上的黏菩麻L ^ J黏者劑層。亦記載著說藉此可同時 滿足充分之對被貼附物之保鳍 v ^你硬機能與適當的黏著特性。 專利文獻1 :日本專利牡1，μ，。。 專利文獻2 專利文獻3 專利文獻4 專利文獻5 【發明内容 t〜将開平2_252783號公報 曰本專利特開2003-41216號公報 曰本專利特開平07-6231 1號公報 ❹ 曰本專利特開平09-1 88857號公報 曰本專利特開2000-80330號公報 然而，上述以往技術有著以下所述之問題。 即使藉由專利文獻1、或3 矣 4 J之表面保護膜，僅以背面 處理的話係無法充分地減低展 饮阀刀’而有捲繞體之回捲性 不足且作業性降低之虞。 以專利文獻2之離型處理法雖於基材之背面較粗的情 況時亦可確保充分的拉取性，但離㈣會轉印於黏著劑 層，而對被貼附物之黏著性會有降低之虞。 專利文獻4所揭示之表面保護臈在極端之高溫環境 (例如’熱帶地區或亞熱帶地區)下保存時，滲出於表面之 聚乙稀亞胺的量與在通常環境下保存的情況不同，有無法 發揮充分之黏著亢進抑制效果之虞。 又，專利文獻5所揭示之表面保護膜即使在粗糙不平 的狀態例如’尤其是當貼附於稜鏡片的稜鏡面，而與該稜 鏡面側相反側之表面（亦即，表面保護臈外側之表面）壓有 201016812 所明魚眼等犬起物時，從保護稜鏡部之凹凸 -觀點來看仍有更需要改良的地方。 卩讓 ' 本發明之目的係提供一種表面保護膜，其係用 T解決上述先前技術之缺點並確保適#的初期㈣力，同 日、展開性優異且剝離後對被貼附物之殘糊受到防止。 又，谁而本發明之目的係提供一種稜鏡 膜，其確保適當的初 衣肩保說 月黏著力同時在極端之高溫（例如70 C )環境下黏者几進同時獲得抑制。 又，本發明之又一目的在於提供一種表面保護膜 面，而於與該稜鏡面側 才文銳 外側之表面心 (亦即，表面保護膜之 所謂魚眼等突起物時，亦可保 凹凸頂部形狀。 更稷鏡邛之 本發明人等努力探討之結果 佶用且女—4 △ 效凡裙田於黏者劑層中 使用具有方香族烯基聚合 共聚物嵌段之牿““ 族烯基_共軛雙晞 初期η 段共聚物’可獲得能確保適當之 初期黏者力同時展開性優異 受到防止之表面㈣胳 』離後對被貼附物之殘糊 明。 艾叔纣之結果而完成本發 本發明之黏著劑組成物，其特徵人 聚合物（i〇， 於3有聚合物⑴與 该聚合物⑴為：含下述聚合 段B，且具右w、a j 欺仅A及下述聚合物嵌 i具有以通式[A_B]n(式中， B表示带人私々 表不聚合物嵌段A， 表丁聚3物嵌段B’n表示卜3之整數）所示構造之共聚 201016812 物⑴或其氫化物， 該聚合物（ii)為：含下述聚合物嵌段A及下述聚合物 散段B，且具有以通式A-B-A(式中之記號表示與上述相同 意義）或通式（Α·Β)χ-Υ(式中，X表示2以上之整數，γ表示 偶合劑殘基，其他記號表示與上述相同意義）所示構造之共 聚物（II)或其氫化物， 該聚合物（i)及上述聚合物（ii)整體之芳香族締基化合 物單位含有率（St(A+ B))為30〜50重量％， 該聚合物（i)及上述聚合物（ii)中個別所含之聚合物喪 段A的總量與聚合物嵌段b的總量之重量比（A: ^為$ . 95〜25 : 75之範圍内； 聚合物嵌段A為： 芳香族烯基化合物單位為連續且以芳香族稀基化人 物單位作為主體之聚合物嵌段， 聚合物嵌段B為： 無規地包含有共輛雙烯單位與芳香族烯基化合物單 位之芳香族烯基隸雙烯共㈣隸，且料㈣基化合 物單位含有率（St(b))為1〇〜35重量％之聚合物嵌段。 #本發明之表面保護膜係具有基材層、與上述本發明之 黏著劑組成物所構成之黏著劑層。 藉由使用本發明之黏著劑組成物，本發明之表面保護 膜展開性優異且剝離後對被貼附物之殘糊受到防止。 較佳為於上述表面保護膜中， 該基材層為聚烯烴基材層， 201016812 該黏著劑組成物進一步含有増勘劑，且 該黏著劑層於_50°c〜80。〇測定動 久助黏彈性所得之tan6 為取大時之溫度為_1()充〜2(TC。 因此上述表面保護膜彳具有u㈣ 期黏著力。 較佳為於上述表面保護膜中， 該基材層為聚蜂煙基材層， 該黏著劑組成物進-步含有増黏劑、及苯乙稀系喪段 相補強劑， 該聚=»物（!)、該聚合物（ii)及苯乙烯系嵌段相補強劑 中之芳香族烯基化合物單位重量相對於該黏著劑層之重 量的比例（芳香族烯基化合物單位含有率）為2〇〜5〇重量％。 因此’可更佳地抑制經時黏著力的亢進。 較佳為於上述表面保護膜中，該黏著劑層在7CTC時之 儲藏彈性模數G，為4 5xlG5pa〜6 Gxl〇5pa。 因此’可更佳地抑制經時黏著力的亢進。 較佳為’上述表面保護膜’當用於保護稜鏡片之棱鏡 面的表面，而貼附於該稜鏡面，且在701之環境氣氛下負 重〇.3N/cm2之荷重24小時的情況時，黏著劑滲入至該稜 鏡面的稜鏡頂角之深度為黏著劑層厚度的1%以上、未滿 40% 〇 因此可確保適當之黏著力同時，較佳地抑制稜鏡的損 傷。 較佳為’上述表面保護膜，當用於保護稜鏡片之稜鏡 10 201016812 面’而貼附於該稜鏡面，且於與該稜鏡面側相反側之表面 壓有直控40〇em、高度i2ym之突起物的情況時，黏著 劑渗入至該稜鏡面的稜鏡頂角之深度為該黏著劑層厚度 的1%以上、未滿1〇〇0/〇。 因此可確保適當之黏著力同時’較佳地抑制稜鏡的損 傷。A layer of sticky Bodhisattva L ^ J adhesive layer with a thickness of 10/zm or more. It is also stated that it can satisfy the full fins of the attached objects at the same time v ^ your hard function and proper adhesion characteristics. Patent Document 1: Japanese Patent No. 1, μ,. . Patent Document 2 Patent Document 3 Patent Document 4 Patent Document 5 [Summary of the Invention] [Twenty-seventh Patent Publication No. 2003-41216, Japanese Patent Laid-Open Publication No. 2003-41216 Japanese Laid-Open Patent Publication No. 2000-80330. However, the above prior art has the following problems. Even if the surface protective film of Patent Document 1, or 3, J J is used, it is not possible to sufficiently reduce the spread valve knives by the back surface treatment, and the rewinding property of the wound body is insufficient and the workability is lowered. The release treatment method of Patent Document 2 can ensure sufficient pullability when the back surface of the substrate is thick, but is transferred to the adhesive layer from (4), and the adhesion to the attached material is There is a reduction in ambiguity. When the surface protection disclosed in Patent Document 4 is stored in an extremely high temperature environment (for example, 'tropical area or subtropical area'), the amount of polyethyleneimine permeated on the surface is different from that in a normal environment. Give full play to the effect of adhesion and inhibition. Further, the surface protective film disclosed in Patent Document 5 has a surface on the side opposite to the side of the kneading surface even when it is in a rough state such as, in particular, a surface which is attached to the kneading surface of the crotch sheet (that is, the surface is protected from the outer side of the crucible) When there is a dog-like object such as the fisheye of 201016812, there is still a need for improvement from the viewpoint of the unevenness of the protection of the crotch. The object of the present invention is to provide a surface protective film which solves the above-mentioned disadvantages of the prior art with T and ensures the initial (four) force of the appropriate one. On the same day, the spreadability is excellent, and the residue of the attached object is peeled off after peeling. prevent. Further, the object of the present invention is to provide a ruthenium film which ensures proper adhesion of the vestibule and simultaneously suppresses adhesion at an extreme high temperature (e.g., 70 C) environment. Further, another object of the present invention is to provide a surface protective film surface which can be embossed when the surface of the outer surface of the surface of the surface is sharp (i.e., a so-called fisheye such as a surface protective film) The shape of the top. The effect of the inventors of the present invention is to explore the results of the use of the female - 4 △ effect of the skirt in the adhesive layer using a square aromatic polymer copolymer block "" family The alkenyl group _ conjugated biguanide initial η segment copolymer can be obtained by ensuring an appropriate initial viscosity and excellent surface stability while preventing the surface from being affixed to the attached object. As a result, the adhesive composition of the present invention is completed, which is characterized in that the polymer (i) has a polymer (1) and the polymer (1): contains the following polymerization section B, and has a right w, aj bully only A and the following polymer embedding i have the general formula [A_B]n (wherein B represents a person with a private polymer and a polymer block A, and the dimeric polymer block B'n represents an integer of 3) Copolymerization of 201016812 (1) or its hydride, the polymer (ii) is: containing the following polymer Block A and the following polymer dispersion B, and have the general formula ABA (the symbol in the formula represents the same meaning as above) or the general formula (Α·Β) χ-Υ (wherein, X represents an integer of 2 or more , γ represents a coupling agent residue, other symbols represent a copolymer (II) having the structure shown in the above-mentioned meaning) or a hydride thereof, the polymer (i) and the above-mentioned polymer (ii) as a whole aromatic conjugate compound The unit content rate (St(A+B)) is 30 to 50% by weight, the total amount of the polymer stagnation A contained in the polymer (i) and the above polymer (ii) and the polymer block b The weight ratio of the total amount (A: ^ is in the range of 95 to 25: 75; the polymer block A is: a polymer having a unit of aromatic alkenyl compound as a main component and being a monomer of aromatic dilute group The block, the polymer block B is: a unit containing a total of a diene unit and an aromatic alkenyl compound unit of an aromatic alkenyl group, and a unit content of the (4) group compound (St ( b)) is a polymer block of 1 to 35% by weight. #The surface protective film of the present invention has a substrate layer, and the present invention described above The adhesive layer composed of the adhesive composition is excellent in the spreadability of the surface protective film of the present invention by using the adhesive composition of the present invention, and the residue of the adherend after the peeling is prevented. In the surface protective film, the base material layer is a polyolefin base material layer, 201016812. The adhesive composition further contains a scooping agent, and the adhesive layer is at _50°c~80. The tan6 obtained by measuring the long-term viscoelasticity is measured. In order to take a large temperature, the temperature is _1 () charge ~ 2 (TC. Therefore, the surface protective film has a u (four) period adhesion. Preferably, in the above surface protective film, the substrate layer is a poly-bee substrate layer The adhesive composition further comprises a bismuth adhesive, and a styrene-based stimulating agent, the poly(»), the polymer (ii) and the styrenic block phase reinforcing agent. The ratio of the unit weight of the aromatic alkenyl compound to the weight of the pressure-sensitive adhesive layer (unit content of the aromatic alkenyl compound) is 2 〇 to 5 〇 by weight. Therefore, it is better to suppress the increase in the adhesion over time. Preferably, in the surface protective film, the elastic modulus G of the adhesive layer at 7 CTC is 4 5 x 1 G5pa to 6 Gxl 〇 5pa. Therefore, it is better to suppress the increase in the adhesion over time. Preferably, the above-mentioned surface protective film is used to protect the surface of the prism surface of the cymbal sheet, and is attached to the ruthenium surface, and when the load of the load of 7013 N/cm 2 is 24 hours under the ambient atmosphere of 701, The depth at which the adhesive penetrates into the dome angle of the crucible is 1% or more and less than 40% of the thickness of the adhesive layer, thereby ensuring proper adhesion and preferably suppressing damage of the crucible. Preferably, the above-mentioned surface protection film is attached to the kneading surface when used to protect the 稜鏡 10 201016812 surface of the cymbal sheet, and has a direct control 40 〇 em, height on the surface opposite to the kneading surface side. In the case of the protrusion of i2ym, the depth of the dome angle in which the adhesive penetrates into the surface of the crucible is 1% or more of the thickness of the adhesive layer, and is less than 1〇〇0/〇. Therefore, it is possible to ensure proper adhesion while at the same time 'suppressing damage to the tendon.
較佳為，上述表面保護膜，當用於保護稜鏡片之稜鏡 面時’基材層的外側表面具有〇.7〜2.〇仁m之表面粗度Ra、 3 # m以上之波紋度（waviness motif)平均高度、及35〇 # m 以上且600 a m以下之波紋度平均長度。 藉此可確保適當的黏著力同時即使在粗糙不平狀態 例如，尤其是當貼附於稜鏡片之稜鏡面而於與該稜鏡面側 相反侧之表面（即表面保護膜的外侧表面）壓有所謂魚眼等 突起物時，亦可保護稜鏡部之凹凸的頂部形狀。 較佳為，上述表面保護膜用於保護擴散膜之表面。 本發明之表面保護膜展開性優異且剥離後對被貼附 物之殘糊受到防止。 再者，本發明之-態様之表面保護膜係可確保適當的 初期黏著力同時在極端之高溫(例如7〇。〇環境下黏著宄進 亦獲得抑制。 再者，本發明之一態様之表面保護膜即使在粗輪不平 Γ心例如’尤其是當貼稜 4 ^ , 卜側表面）壓有所謂魚 艮專犬起物時’亦可保護稜鏡部之凹凸 11 201016812 【實施方式】 <本明書申之記號定義> 本說明書中用以表示數値範圍之記號「〜」只要沒有 特別限定，則該數値範圍係包含其兩端之數値。 本說明書中，「芳香族烯基化合物單位含有率」此一 用語等中所用之聚合物的重複單位的「含有率」係指、換 算成重複單位所來自之單艘而得之重量比，亦即，上述重 複單位所來自之單體的重量對於用以形成上述聚合物之 總單體的重量之比（重量％)，即聚合物之芳香族烯基化合〇 物含量[alkenyl aromatic compound content]。此處，「用 以形成上述聚合物之總總單體之重量」係近似於上述聚合 物之重量。又，同様地，本說明書中，所謂聚合物嵌段之 重複單位的「含有率」係指換算成重複單位所來自之單體 而得之重量比’亦即’上述重複單位所來自之單體的重量 對於用以形成上述聚合物嵌段之總單體的重量之比（重量 /〇) °此處「用以形成上述聚合物嵌段之總總單體之重量」 係近似於上述聚合物嵌段之重量。 〇 本說明書中，「乙烯基鍵之含有率」係指使用紅外線 吸收光譜法以摩雷羅氏（Morello)法所算出之1,2-乙烯基鍵 及3,4-乙烯基鍵之總含有率。 <黏著劑組成物> 本發明之黏著劑組成物係含有下述聚合物（i)及下述 聚合物（ii)。 本說明書中，「聚合物（i)」為含下述聚合物嵌段A及 12 201016812 下述聚合物嵌段B，且具有以通式[AB]n(式中，a表示聚 合物欲段A、B表示聚合物嵌段b、η表示1〜3之整數）所 示構造之共聚物（I)或其氫化物。 本說明書中，「聚合物（ii)」為含下述聚合物嵌段A 及下述聚合物嵌段B’且具有通式Α_Β·Α(式中之記號表示 與上述相同意義）或通式（Α_Β)χ·γ(式中，χ表示2以上之 整數，Υ表不偶合劑殘基，其他之記號表示與上述相同意 義）所示構造之共聚物（11)或其氫化物。 又本說明書中，由上述聚合物（i)與上述聚合物（Π)所 構成之組成物有時僅稱為「共聚物組成物」。 本發明之黏著劑組成物中，上述聚合物⑴及上述聚合 物（ι〇整鱧之芳香族烯基化合物單位含有率為3〇〜5〇重量 %， 上述聚合物（i)與上述聚合物（ii)中所含之聚合物嵌段 A的總量與聚合物嵌段B的總量之重量比在5: 95〜25:乃 之範圍内。 本說明書中，「聚合物钱段A」為芳香族婦基化合物 =位為連續且以芳香族職化合物單位為主體之聚合物 本說明書中，「聚合物嵌段B」為無 =單位與芳香族職化合物單位之芳香族稀基^ 烯共聚物嵌段，且芸乐缺咏健儿，、挑雙 單位含㈣（st(_ 董量/〇之聚合物嵌段。 <聚合物嵌段A> 13 201016812 如上述，「聚合物嵌段A」為芳香族烯基化合物單位 為連續且以芳香族烯基化合物單位為主體之聚合物嵌段 「芳香族烯基化合物單位」係指來自芳香族稀基化合 物之重複單位。「芳香族烯基化合物」可舉出例如：苯乙 烯、第三丁基苯乙烯、甲基苯乙烯、對甲基苯乙烯對 乙烯基葱、N，Nd基·對胺基乙基苯乙稀及乙烯基频 等。其中，基於工業上易於取得原料之理由，「 基化合物單位」為苯乙烯單位為佳。 烯 「聚合物嵌段A」必須以芳香族烯基化合物單位為主 要之重複單位來構成。具體而言，該芳香_基化合物單 位含有率為8〇重量％以上。藉由將芳香族稀基化合物單位 含有率提…〇重量％以上，有可使得黏著劑組成物之熱 可塑性提高’且黏著劑組成物之循環使用可更容易之優 點。可含有未滿20重量％夕益田夕父备 篁0之範圍之芳香族烯基化合物單位 以外的重複單位可舉出來自可與芳香㈣基化合物共聚 合之化合物之重複單位，例如：來自共軛雙烯化合 基）丙烯酸酸酯化合物之重複單位。1 (甲 初疋重複單位。其中，基於與芳香族烯 =化合物之共聚合性高之理由較佳為M丁二烯、異戊二 <聚合物嵌段B> 如上所述，「聚合物截段B」為無規地包含有 :單位與芳香族稀基化合物單位之芳香族稀基共輕^ 共聚物漱段，且芳香族締基化合物單位含： 201016812 10〜35重量％之聚合物嵌段。 /所謂構成「聚合物嵌段B」之「共輛雙烯化合物單位 係指’來自共輕雙稀化合物之重複單位。「共概雙稀化人」 物」可舉出例如：1，3-丁二稀、異戊二稀、2,3-二甲基_13口 丁二稀、1，3-戊二烯、2_甲基·辛二烯、以· ， 環己二烯、4 5- - r其1 2 土 ，— 辛二稀、3_ 丁基义3·辛二稀、 月桂稀（myrcene)及氯丁二烯 m 0 τ Φ 0 琊寺其中，基於聚合反應性高 業上易於取得原料之理由，「共概雙烯化合物單位」 ，3T —烯單位及異戊二稀單位之群中至少！種之重 複卓位為佳。 ^聚合物嵌段B」係必須以共輕雙烯化合物單位為主 ^重複單位來制。由發揮本㈣之絲之觀點來看較 佳為共軛雙烯化合物單位含 内。 ，手在65〜90重量％之範圍 又’ 「聚合物嵌段B從猶媒士 」從獲侍本發明之效果之觀點來 方香族稀基化合物單位令右i 率（（b))必須為10〜35重 量之範圍内，且較佳為13〜33 重置之範圍内’更佳為 了 ΐ/β之範圍内。芳香族稀基化合物單位含有率若 ^滿^重量％未滿，則有時展開性會變重，且使用性會變 差。另一方面，若超過35舌田0/ α1 ^ # . ,. . ^ 1 0 ’則黏著劑組成物之柔軟 性差而無法確保對於表面保 著力。 膜术說為重要之充分的黏 又聚口物叙段B」再不妨礙本發明效果的範圍内， 亦可含有共軛雙烯化合物 及方香族烯基化合物單位 15 201016812 以外之重複單位。 又’ 「聚合物嵌段B」，由發揮本發明效果之觀點來 看’乙烯基鍵含有率在50〜90%之範圍内為佳，在6〇〜80% 之範圍内更佳。又，藉由使乙烯基鍵含有率成為5〇%以上， 而有可構成黏著性（tackiness)與黏著力平衡優異之黏著劑 組成物此一優點。 <共聚物⑴〉 「共聚物（I)」為含下述聚合物嵌段A及下述聚合物喪 段B ’且具有以通式[A_B]n(式中，a表示聚合物嵌段a、 B表示聚合物嵌段B、n表示1〜3之整數）所示構造之共聚 物。 因為「n」表示1〜3之整數’故可知「式[A-B]n所示 構造」可舉出例如：A-B、A-B-A-B、及A-B-A-B-A-B所 表示之構造。該等嵌段共聚物中，A及B分別在重複中可 為相同或相異。 [A-B]n所表示之構造中，從確實發揮聚合物嵌段b之 效果的觀點來看，末端之聚合物嵌段B占共聚物整體之2 重量乂以上為佳。又，即使一部分的共聚物（I)的末端具有 -A之構造，但當末端之聚合物嵌段a之含有率未滿共聚 物（I)整體之2重量。/。時，亦可發揮與末端為聚合物嵌段b 時相同之效果。亦即，上述構造可視為實質上末端為聚合 物嵌段B者。 η必須為1〜3之整數。藉由使η為此範圍内，而工業 生產性會變得良好。又，從提升黏著力及材料強度之觀點 201016812 來看，η較佳為1〜2, 所示構造之共聚物」 段共聚物。 更佳為丨。亦即，作為「具有通式[Α-Β]η 尤佳為具有以通式Α_Β所示構造之嵌 〇共聚物⑴或其氫化物（聚合物⑴），芳香族稀基化合物 :位含有率為30〜50重量之範圍内為佳，更佳為η，重 量％。藉由使芳香族烯基化合物單位含有率在此範圍内， 可構成兼具適度之保持力與對於被貼附物表面凹凸之追 隨性且展開性優異之黏著劑組成物。 聚合物⑴之分子量並無特別限制，重量平均分子量較 佳為3萬〜50萬，更佳為8萬〜3〇萬，尤佳為ι〇萬〜2〇萬。 藉由使重量平均分子量為3萬〜5〇萬之範圍，可使得聚合 物⑴之工業生產變得容易，進而由聚合物⑴與共聚物（II) 或其氫化物（聚合物（ii))所構成之共聚物組成物之工業生 產亦變得容易。重量平均分子量若未滿3 [則將聚合物 脫溶劑、乾㉟之步驟中聚合物會附著於製造設備等，而有 時聚合物⑴之工業生產會變得困難。另一方面，重量平均 分子量若為50萬以上，則對溶劑之溶解性、熱熔融性會 變差而有時加工至黏著體會變得困難。 由共聚物（I)之氫化物可獲得優異之耐熱性及耐候性 之觀點來看’來自共軛雙烯單體之雙鍵為8〇%以上，較佳 為90 /〇以上，更佳為95%以上，而以經氫化而不飽和鍵氫 化成飽和鍵所成之氫化物為佳。 又，本說明書中，氫化之比率（氫化率）係指使用四氣 化碳作為溶劑，從270MHz、】H-NMR光譜所算出之氫化率。 17 201016812 聚合物（i)可為單獨（1種）亦可為2種以上之組合。 <共聚物（11)> 「共聚物（II)」為含下述聚合物嵌段A及下述聚合物 礙段B’且具有通式A_B_A(式中之記號表示與上述相同意 義）或通式（A-B)x-Y(式中，X表示2以上之整數，γ表示偶 合劑殘基’其他之記號表示與上述相同意義)所示構造之共 聚物。 八 由上述通式可明瞭，共聚物（II)其所有的分子末端具 有聚合物嵌段A。 0 末端之聚合物嵌段A占共聚物（II)整體之2重量％以上 為佳。此係為了使聚合物嵌段A之效果確實發揮所為。又， 即使一部分的共聚物（II)的末端具有·Β之構造，但當末端 之聚合物嵌段Β之含有率未滿共聚物（π)整體之2重量％ 時，亦可發揮與末端為聚合物嵌段Α時相同之效果。亦即， 上述構造可視為實質上末端為聚合物嵌段A者。 具有以通式（A-B)x-Y(式中，X表示2以上之整數，γ 表示偶合劑殘基’其他記號係表示與上述相同意義）所示構 〇 造之共聚物，換言之’係具有共聚物（I)以γ偶合而成之構 造。因此，（A-B)x-Y的情況時’因為以相同反應釜可合成 (I)、（II)之混合物’故工業觀點來看以（A-B)x-Y為佳。χ 為3以上的情況時’該共聚物為所謂星形聚合物。從抑制 該共聚物製造時之副反應並控制該共聚物之之物性之觀 點來看，χ較佳為2〜4。 又’共聚物（Π)或其氫化物（聚合物（ii))，基於與聚合 18 201016812 物⑴相同之理由，也是以关巷始达w ,, · t疋以务香族烯基化合物單位含有率為 〜5〇重量之範圍内為佳，更佳為33〜45重量％。 聚合物⑼，由可獲得優異之耐熱性及耐候性之觀點來 看，來自共㈣料體之雙鍵為8Q%以上，較佳為9〇%以 j，更佳為95%以上’而以經氫化Μ飽和鍵氫化成飽和 鍵所成之氫化物為佳。 · 聚合物（ii)之分子量並無特別限制，重量平均分子量較 參 ❹ 佳為5萬〜則，更佳為5萬〜3〇萬。藉由使重量平均分 子量為5萬〜50¾之範圍，可使聚合物⑻之工#生產變得 容易，進而由聚合物⑴與聚合物（ii)所構成之共聚物组成 物之工業生產亦變得容易。重量平均分子量若未滿3萬， 則將聚合物脫溶劑、乾燥之步驟中聚合物會附著於製造設 備等，而有時聚合物（11)或其之氫化物之工業生產會變^ 困難。另-方面，重量平均分子量若| 5〇萬以上則對 溶劑之溶解性、熱熔融性會變差而有時加工至黏著體會變 得困難。 聚合物（ii)可為單獨（1種）亦可為2種 •^工（組合< <共聚物組成物> ， 如上所述’本發明之黏著劑組成物係—種含有由聚人 物⑴與聚合物（ii)所構成之共聚物組成物作為構成成八^ 黏著劑組成物。在此共聚物組成物中，聚Aγ .、 *。物（1)與聚合物 (ii)之重量比必須為90 : 10〜10 : 90之範圍内。茲 1 °錯由使得聚 合物⑴與聚合物（ii)之總量100重量份中，人士 3有10重量份 以上之聚合物⑴，而可發揮有效防止黏著劍 剐增從被貼附物 19 201016812 之表面浮起而膜發生剝離這樣的不良情形（浮起）之良好效 果。另一方面，藉由使得聚合物⑴與聚合物（ii)之總量ι〇〇 重量份中，含有1〇重量份以上之聚合物(ii)，而可發揮有 效防止將膜從被貼附物之表面剝離時黏著 附物之表面而汙染被貼附物之表面這樣的不^^； 之良好效果。 由確實防止黏著劑層之浮起、殘糊此一觀點看， 合物⑴與聚合物（ii)之重量比較佳為5〇 : 50〜15 : 85之範 圍内° ❹ 基於達成本發明效果之觀點，上述聚合物⑴與上述聚 合物（ii)中所含之聚合物嵌段A的總量與聚合物嵌段B的 總量之重量比必須為5 : 95〜25 : 75之範圍内。又，就由 使得聚合物嵌段A與聚合物嵌段B的總量1〇〇重量份中含 有5重量伤以上之聚合物嵌段A，而可發揮賦予所形成之 黏著劑層適度之保持力此一良好效果。另一方面，藉由使 得聚合物嵌段A與聚合物後段B的總量1〇〇重量份中含有 75重量份以上之聚合物嵌段B，而所形成之黏著劑層會展0 現對於被貼附物表面凹凸良好之追隨性，故可發揮可確實 保護被貼附物表面此一良好效果。聚合物嵌段A的總量與 聚合物嵌段B的總量之重量比較佳為5: 95〜25 : 75之範 圍内，更佳為7: 93〜23: 77之範圍内，尤佳為1〇: 9〇〜21 : 79之範圍内。 <表面保護膜> 本發明之表面保護膜係具有基材層與以上所說明之 20 201016812 本發明之黏著劑組成物所構成之黏著劑層。 該黏著劑層較佳係積層於該基材層之另一面之表面 上0 <基材層> 該基材層較佳為聚烯烴基材層。Preferably, the surface protective film is used to protect the kneading surface of the cymbal sheet. 'The outer surface of the base material layer has a surface roughness Ra of 3 to 5 m. The waviness motif) average height and the average length of waviness above 35 〇# m and below 600 am. Thereby, it is possible to ensure an appropriate adhesive force, at the same time, even in a rough uneven state, for example, especially when attached to the kneading surface of the cymbal sheet and pressed on the surface opposite to the kneading surface side (ie, the outer surface of the surface protective film). When the protrusions such as fish eyes are used, the top shape of the concavities and convexities of the crotch portion can be protected. Preferably, the above surface protective film is used to protect the surface of the diffusion film. The surface protective film of the present invention is excellent in developability and is resistant to sticking of the adherend after peeling. Further, the surface protective film of the present invention can ensure an appropriate initial adhesion while suppressing the adhesion at an extremely high temperature (for example, a 〇 〇 environment). Further, the surface of the present invention The protective film protects the unevenness of the crotch even when the rough wheel is not flat, such as 'especially when the edge is slanted, and the surface is pressed, so that the fish can be used as a fisherman's dog. 11 201016812 [Embodiment] < Definition of the symbol of the present invention> The symbol "~" used to indicate the range of the number in the present specification includes the number 値 at both ends thereof unless otherwise specified. In the present specification, the "content ratio" of the repeating unit of the polymer used in the term "aromatic alkenyl compound unit content" means the weight ratio obtained by converting into a single ship from which the repeating unit is derived. That is, the ratio of the weight of the monomer from which the above repeating unit is derived to the weight of the total monomer used to form the above polymer (% by weight), that is, the aromatic alkenyl aromatic compound content of the polymer [alkenyl aromatic compound content] . Here, "the weight of the total total monomer used to form the above polymer" is approximately the weight of the above polymer. In addition, in the present specification, the "content ratio" of the repeating unit of the polymer block means the weight ratio obtained by converting the monomer derived from the repeating unit, that is, the monomer derived from the above repeating unit. The weight of the total monomer used to form the above polymer block (weight / 〇) ° "the weight of the total total monomer used to form the above polymer block" is similar to the above polymer The weight of the block. In the present specification, "the content of the vinyl bond" means the total content of the 1,2-vinyl bond and the 3,4-vinyl bond calculated by the Morello method using infrared absorption spectroscopy. . <Adhesive Composition> The adhesive composition of the present invention contains the following polymer (i) and the following polymer (ii). In the present specification, "polymer (i)" is a polymer block B having the following polymer block A and 12 201016812 and having the formula [AB]n (wherein a represents a polymer segment A) And B represents a copolymer (I) having a structure in which the polymer block b and η represent an integer of 1 to 3) or a hydrogenated product thereof. In the present specification, "polymer (ii)" is a polymer block A having the following polymer block B' and having the formula Α_Β·Α (wherein the symbol indicates the same meaning as above) or a general formula (Α_Β) χ·γ (wherein χ represents an integer of 2 or more, and 残 represents a residue of the coupling agent, and other symbols indicate the same meaning as described above) of the copolymer (11) or a hydride thereof. Further, in the present specification, the composition composed of the polymer (i) and the polymer (Π) may be simply referred to as "copolymer composition". In the adhesive composition of the present invention, the polymer (1) and the polymer (the unit content of the aromatic vinyl group compound of the entire oxime) is 3 〇 to 5 〇 by weight, and the polymer (i) and the polymer described above are contained. The weight ratio of the total amount of the polymer block A contained in (ii) to the total amount of the polymer block B is in the range of 5: 95 to 25: In the present specification, "polymer section A" In the present specification, the "polymer block B" is an aromatic dilute unit of the unit of the aromatic compound. Copolymer block, and the lack of athletes, and the double unit contains (4) (st (_ Dong amount / 〇 polymer block. < polymer block A > 13 201016812 as above, "polymer block A" is an aromatic alkenyl compound unit which is continuous and has a polymer block mainly composed of an aromatic alkenyl compound unit. "Aromatic alkenyl compound unit" means a repeating unit derived from an aromatic dilute compound. The base compound may, for example, be styrene or third. Styrene, methyl styrene, p-methylstyrene, vinyl onion, N, Nd, p-aminoethyl styrene, vinyl, etc. Among them, based on industrially easy to obtain raw materials, The compound unit is preferably a styrene unit. The olefin "polymer block A" must be composed of an aromatic alkenyl compound unit as a main repeating unit. Specifically, the aromatic group-based compound has a unit content of 8 Å. By increasing the unit content of the aromatic dilute compound by more than 5% by weight, there is an advantage that the thermoplasticity of the adhesive composition can be improved, and the recycling of the adhesive composition can be made easier. The repeating unit other than the unit of the aromatic alkenyl compound in the range of 20% by weight of the total amount of the aromatic alkenyl compound in the range of 0% by weight of the yoke yue yue, the compound may be a repeating unit derived from a compound copolymerizable with the aromatic (tetra) group compound, for example, from a conjugated diene compound. The repeating unit of the acrylate compound. 1 (A fluorene repeat unit. Among them, M-butadiene is preferred because of high copolymerizability with the aromatic olefin compound; Pentacene <Polymer Block B> As described above, the "polymer segment B" is a copolymer comprising a unit of aromatic dilute radicals in units of aromatic dilute compound units, and The aromatic conjugated compound unit contains: 201016812 10~35 wt% polymer block. / The so-called "polymer block B" "common double olefin compound unit means 'repeating unit from the common light double dilute compound For example, 1,3-butadiene, isoprene, 2,3-dimethyl-13-butadiene, and 1,3-pentadiene can be cited. , 2_Methyl·octadiene, ··, cyclohexadiene, 4 5- - r, 1 2 soil, —octane dilute, 3 — butyl 3 , octane dilute, myrcene and chloroprene The olefin m 0 τ Φ 0 琊 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中The weight of the species is better. ^Polymer block B" must be prepared in units of co-light diene compounds as the main repeating unit. From the viewpoint of exerting the silk of the present (4), it is preferred to be within the unit of the conjugated diene compound. , in the range of 65 to 90% by weight of the hand, 'the polymer block B from the jujubes', from the point of view of the effect of the invention, the square of the aromatic compound, the right i rate ((b)) must be It is in the range of 10 to 35 weights, and preferably in the range of 13 to 33 in the range of 'better' in the range of ΐ/β. When the unit content ratio of the aromatic dilute compound is less than the full weight %, the spreadability may become heavy and the usability may be deteriorated. On the other hand, if more than 35 tongues 0/α1 ^ # . , . . . ^ 1 0 ', the adhesive composition is poor in flexibility and cannot ensure surface protection. It is also possible to include a conjugated diene compound and a scented scented alkenyl compound unit 15 201016812 in a range in which the film is said to be an important sufficient viscous material. Further, the "polymer block B" is preferably in the range of 50 to 90% from the viewpoint of exhibiting the effects of the present invention, and more preferably in the range of 6 to 80%. Further, by setting the vinyl bond content to 5% by weight or more, there is an advantage that an adhesive composition excellent in tackiness and adhesion balance can be formed. <Copolymer (1)> "Copolymer (I)" is a polymer block A having the following polymer block B and having the following formula [A_B]n (wherein a represents a polymer block) a and B represent a copolymer having a structure in which the polymer block B and n represent an integer of 1 to 3). Since "n" represents an integer of 1 to 3, it is understood that "the structure shown by the formula [A-B]n" is a structure represented by, for example, A-B, A-B-A-B, and A-B-A-B-A-B. In the block copolymers, A and B may be the same or different in repetition, respectively. In the structure represented by [A-B]n, from the viewpoint of the effect of the polymer block b being surely exhibited, the polymer block B at the end is preferably 2 parts by weight or more of the entire copolymer. Further, even if a part of the copolymer (I) has a structure of -A, the content of the polymer block a at the end is less than 2% by weight of the entire copolymer (I). /. At the same time, the same effect as when the terminal is the polymer block b can be exerted. That is, the above configuration can be regarded as a substantially terminal polymer block B. η must be an integer from 1 to 3. By making η within this range, industrial productivity becomes good. Further, from the viewpoint of improving adhesion and material strength, 201016812, η is preferably a copolymer of the structure of 1 to 2, which is a copolymer of the structure shown. Better for you. That is, as an "embedded yttrium copolymer (1) having a structure of the formula [Α-Β] η or a hydride thereof (polymer (1)), an aromatic dilute compound: a bit content ratio It is preferably in the range of 30 to 50% by weight, more preferably η, and % by weight. By setting the unit content of the aromatic alkenyl compound within this range, it is possible to form both a moderate retention force and a surface for the attached object. The adhesive composition having excellent followability and unfoldability is not particularly limited, and the weight average molecular weight is preferably 30,000 to 500,000, more preferably 80,000 to 30,000, and particularly preferably ι. By making the weight average molecular weight in the range of 30,000 to 50,000, the industrial production of the polymer (1) can be facilitated, and the polymer (1) and the copolymer (II) or their hydrides can be easily obtained. Industrial production of the copolymer composition composed of (polymer (ii)) is also easy. If the weight average molecular weight is less than 3, the polymer will be attached to the manufacturing equipment in the step of desolvating the polymer and drying 35. And sometimes industrial production of polymer (1) can become difficult. On the other hand, when the weight average molecular weight is 500,000 or more, the solubility in a solvent and the hot melt property may be deteriorated, which may become difficult to process to an adherend. The hydride of the copolymer (I) can be excellent. From the viewpoint of heat resistance and weather resistance, 'the double bond derived from the conjugated diene monomer is 8 〇% or more, preferably 90 Å or more, more preferably 95% or more, and hydrogenated by hydrogenation without a saturated bond. Further, in the present specification, the hydrogenation ratio (hydrogenation ratio) is a hydrogenation ratio calculated from a 270 MHz, H-NMR spectrum using four vaporized carbon as a solvent. 17 201016812 The polymer (i) may be used singly or in combination of two or more kinds. <Copolymer (11)> "Copolymer (II)" is a polymer block A having the following polymerization and polymerization described below. Obscuring the segment B' and having the general formula A_B_A (the symbol in the formula indicates the same meaning as described above) or the general formula (AB) xY (wherein, X represents an integer of 2 or more, and γ represents a coupling agent residue] A copolymer of the configuration shown in the same meaning as above). It is clear from the above formula that the copolymer (II) has a polymer block A at all molecular terminals thereof. The polymer block A at the end of 0 is preferably 2% by weight or more based on the entire copolymer (II). This is to make the effect of the polymer block A work. Further, even if a part of the copolymer (II) has a structure of a ruthenium, when the content of the polymer block at the end is less than 2% by weight of the entire copolymer (π), the end portion may be The same effect is obtained when the polymer block is used. That is, the above structure can be regarded as a substantially polymer terminal A at the end. A copolymer having a structure represented by the formula (AB) xY (wherein X represents an integer of 2 or more, γ represents a coupling agent residue, and other symbols represent the same meaning as described above), in other words, a copolymer (I) A structure in which γ is coupled. Therefore, in the case of (A-B)x-Y, it is preferable to use (A-B)x-Y because of the fact that the mixture of (I) and (II) can be synthesized in the same reactor. When χ is 3 or more, the copolymer is a so-called star polymer. The ruthenium is preferably from 2 to 4 from the viewpoint of suppressing the side reaction at the time of production of the copolymer and controlling the physical properties of the copolymer. Further, 'copolymer (Π) or its hydride (polymer (ii)), based on the same reason as the polymerization of 18 201016812 (1), is also a unit of the scented alkenyl compound. The content is preferably in the range of 〜5 〇 by weight, more preferably 33 to 45% by weight. The polymer (9) has a double bond derived from the co-(tetra) material of 8 Q% or more, preferably 9 % by j, more preferably 95% or more from the viewpoint of obtaining excellent heat resistance and weather resistance. It is preferred that the hydride is hydrogenated to a saturated bond by a hydrazine hydride saturation bond. The molecular weight of the polymer (ii) is not particularly limited, and the weight average molecular weight is preferably 50,000 to 10,000, more preferably 50,000 to 30,000. By making the weight average molecular weight in the range of 50,000 to 503⁄4, the production of the polymer (8) can be facilitated, and the industrial production of the copolymer composition composed of the polymer (1) and the polymer (ii) is also changed. It's easy. If the weight average molecular weight is less than 30,000, the polymer may be attached to a production facility or the like in the step of desolvating and drying the polymer, and industrial production of the polymer (11) or a hydride thereof may become difficult. On the other hand, when the weight average molecular weight is 50,000 or more, solubility in a solvent and hot melt property may be deteriorated, and processing to an adherend may become difficult. The polymer (ii) may be either one type or one type (combination << copolymer composition>, as described above, the adhesive composition of the present invention contains The copolymer composition composed of the person (1) and the polymer (ii) is a composition of the adhesive composition. In the copolymer composition, poly Aγ, * (1) and polymer (ii) The weight ratio must be in the range of 90:10 to 10:90. In the case of 100 parts by weight of the total amount of the polymer (1) and the polymer (ii), the polymer 3 has 10 parts by weight or more of the polymer (1). Further, it is effective in preventing the adhesion of the scabbard from the surface of the affixed article 19 201016812 and peeling off the film (the floating). On the other hand, by making the polymer (1) and the polymer ( Ii) The total amount of the ι〇〇 part by weight contains 1 part by weight or more of the polymer (ii), and it can effectively prevent the film from sticking to the surface of the attached object and sticking to the surface of the attached object to be contaminated. The surface of the appendage has such a good effect that it does not prevent the floating layer of the adhesive layer from floating. From the viewpoint of the paste, the weight of the compound (1) and the polymer (ii) is preferably 5 〇: 50 to 15: within the range of 85 ° 上述 based on the viewpoint of achieving the effects of the present invention, the above polymer (1) and the above polymer ( The weight ratio of the total amount of the polymer block A contained in the ii) to the total amount of the polymer block B must be in the range of 5:95 to 25:75. Further, the polymer block A is made The polymer block B contains 5 parts by weight or more of the polymer block A in a total amount of 1 part by weight of the polymer block B, and exhibits a good effect of imparting a moderate retention force to the formed adhesive layer. The polymer block B is contained in an amount of 1 part by weight or more based on the total amount of the polymer block A and the polymer post-stage B, and the formed adhesive layer is spread to the surface of the attached object. Good followability, so it can play a good effect to protect the surface of the attached material. The total amount of polymer block A and the total weight of polymer block B is preferably 5: 95~25 : 75 Within the range, more preferably in the range of 7: 93~23: 77, especially good for 1〇: 9〇~21: 79. <Surface Protective Film> The surface protective film of the present invention has a base material layer and an adhesive layer composed of the adhesive composition of the present invention described in the above-mentioned 20 201016812. The adhesive layer is preferably laminated to the base. 0 <substrate layer> on the surface of the other side of the material layer. The base material layer is preferably a polyolefin base material layer.
該「聚烯烴」可舉出例如：低密度聚乙烯、中密度聚 乙烯、高密度聚乙#、直鏈低密度聚乙烯、乙烯烯烴 共聚物、乙烯-丙烯酸乙醋共聚物、乙烯_乙酸乙烯西旨共聚 物、乙烯-丙烯酸甲酿共聚物、乙烯·丙烯酸正丁醋共聚物、 及聚丙烯（均聚物、無規共聚物、嵌段共聚物）等。 該等可單獨或組合2種以上使用。又，「聚稀煙」亦 可為具有取代基之聚烯烴’ 1亦可添加丨聚烯烴以外之樹 脂。進而亦可添加有表面保護臈製造過程中所產生之聚烯 經基材層的端材、表面保護膜之端材。 基材層可為單層亦可為具有組成相異之2種以上之多 層構造之層。 基材層可依表面保護臈之用途等適當調整其之厚 度。通常设定成10〜100“ m左右之厚度較適當。 較佳為，該基材層之外側表面（亦即，與黏著劑層側相 反側之表面）具有0.7〜2.0#m之表面粗度Ra、3#m以上 之波紋度（waviness motif)平均高度、及35〇以m以上且6〇〇 # m以下之波紋度（waviness motif)平均長度。 藉此’即使是在將本態樣之表面保護膜貼附於稜鏡片 之表面加以積層保管時’亦不會於稜鏡片之透鏡部（稜鏡） 21 201016812 產生損傷，故可較佳地適用於保護稜鏡片之稜鏡面。 尤其藉由使得該基材層之背面的表面粗度、波紋度平 均高度及波紋度平均長度成為上述既定範圍，而即使是將 複數片之貼附於表面保護膜之稜鏡片積層並加以保管時 有夾帶進來之微小異物存在的情況，因為夾帶進來之微小 異物會進入表面之波紋的突出部位(谷）中，故與表面為平 滑的情況相比’可減低集中於稜鏡片透鏡部之應力。 又，本說明書中，「表面粗度Ra」係JIS B〇6〇l : 2001 所規定之「算術平均高度」。波紋度平均高度W係表示圖 2之聚烯烴基材層表面的波紋之示意圖中之Wj的平均 値’而波紋度平均長度AW為AWj之平均値，係以下式算 出0Examples of the "polyolefin" include low density polyethylene, medium density polyethylene, high density polyethylene #, linear low density polyethylene, ethylene olefin copolymer, ethylene-ethyl acrylate copolymer, ethylene vinyl acetate. A copolymer, an ethylene-acrylic acid copolymer, an ethylene/n-butyl acrylate copolymer, and a polypropylene (a homopolymer, a random copolymer, a block copolymer). These may be used alone or in combination of two or more. Further, the "poly-smoke" may be a polyolefin having a substituent, and a resin other than a polyolefin may be added. Further, it is also possible to add an end material of a polyolefin-based base material layer and an end material of a surface protective film which are produced in the surface protection process. The base material layer may be a single layer or a layer having a multi-layer structure of two or more different compositions. The thickness of the substrate layer can be appropriately adjusted depending on the use of the surface protection crucible or the like. It is usually set to a thickness of about 10 to 100 μm. Preferably, the outer surface of the base material layer (that is, the surface opposite to the side of the adhesive layer side) has a surface roughness of 0.7 to 2.0 #m. Ra, the average height of the waviness motif above 3#m, and the average length of the waviness motif of 35〇 or more and 6〇〇# m or less. By this, even the surface of the present aspect When the protective film is attached to the surface of the cymbal sheet and stored in layers, it does not cause damage to the lens portion (稜鏡) 21 201016812 of the cymbal sheet, so it can be preferably applied to the surface of the cymbal sheet. The surface roughness, the average waviness height, and the average waviness length of the back surface of the base material layer are within the above-described predetermined ranges, and even if a plurality of sheets are attached to the enamel layer of the surface protective film and stored, they are entrained. In the case where tiny foreign matter is present, since the tiny foreign matter entrained enters into the protruding portion (valley) of the corrugation of the surface, the stress concentrated on the lenticular lens portion can be reduced as compared with the case where the surface is smooth. In the present specification, "surface roughness Ra" is the "arithmetic mean height" specified in JIS B〇6〇l: 2001. The average waviness height W is the average 値' of Wj in the schematic diagram of the corrugations on the surface of the polyolefin base material layer of Fig. 2, and the average waviness length AW is the average 値 of AWj, which is calculated by the following formula:
波紋度平均長度AW 1 n AW* — Σ AW· n is1 波紋度平均高度w 4 m w=丄 ς w ΓΠ j: 1 本說明書中，「波紋度平均長度」及「波紋度平均高 度」係分別為Jis B0601 : 2001所規定之「輪郭曲線要素 之平均長度」及「輪郭曲線要素之平均高度」。 <黏著劑層> 上述黏著劑層係由本發明之黏著劑組成物所構成。該 黏著劑組成物除了上述聚合物⑴與上述聚合物（Η)之 201016812 亦可視需要適當含有增黏劑、苯乙婦系嵌段相補強劑、軟 化劑、，氧化劑、光安定劑、紫外線吸收劑、充填劑、顏 料、黏著充進防止劑、烯烴系樹脂、聚石夕氧系聚合物、液 狀丙稀酸系共聚物、磷酸s旨系化合物等習知之添加劑。 本發明中所用之增黏劑可沒有特別限制&使用例 如.月日肪族系共聚物、芳香族系共聚物、脂肪族-芳香族系 共聚物、脂環式系共聚物等石油系樹脂、香豆嗣·節樹脂 ^nn^ne.lndene)系樹脂、㈣系樹脂、㈣·苯紛系樹 士、聚合松香等松香系樹脂、（烧基）苯紛系樹脂、二甲苯 系樹脂或該等之氫化物等—船 叙黏者劑中所使用者。較佳係 劑之軟化點為9〇〜l4〇t者。該等增黏劑可單獨使 、。用2種以上。又，為了提高剝離性及耐候性等， =额用氯化系之增黏劑。又，亦可使用以與稀煙L 之摻合物型態市售之增黏劑。 聚物ί::中之增黏劑係指可相溶於芳香族烯基嵌段共 I 、輛雙稀系或其氫化所得之軟鍵段（soft Segment) 即橡膠層，且可控制黏著力者。 人 彳’合」係&於共聚物組成物中配合增劑所得 之配合物的tan (5峰值〉'田^ w 度為共聚物，組成物之ta以峰值溫 :相異之値之狀態。又，本說明書中，所謂 度」係指Und為最大時之溫度。 嗶值皿 完進系嵌段相補強剩係用以抑制黏著劑層之黏著 《月中所用之苯乙埽系嵌段相補強劑可舉出：單體 23 201016812 單位例如苯乙烯及α -甲基苯乙烯、對甲基苯乙烯、對氯笨 乙烯、氣甲基苯乙烯、第三丁基苯乙烯、對乙基笨乙烯、 二乙烯基苯等苯乙烯系化合物。該等可單獨或組合2種以 上來使用。亦即，苯乙烯系嵌段相補強劑可藉由將該等單 體加以聚合來獲得。當為2種以上之單體所構成之共聚物 的像況時，可為彼段共聚物’亦可為無規共聚物。其中， 笨乙烯系嵌段相補強劑較佳為具有i 〇〇〇c左右以上之軟化 點者’更佳為150 C以上者。具體而言，可較佳地使用 EastmanChemical公司製之商品名rENDEX155」（軟化點❹ 155。〇、「ENDEX160」（軟化點 16〇t)等。 軟化劑通常來說係有效於黏著力的提升。軟化劑可沒 有特別限制地使用例如··低分子量之雙烯系聚合物、聚異 丁烯（polyisobutylene)、氳化聚異戊二烯、氫化聚丁二烯、 石蠟系加工油（process 〇n)、環烷（naphthene)系加工油芳 香族系加工油、蓖麻油、托爾油、天然油、液體聚異丁烯 樹脂、聚丁烯、或該等之氫化物等—般黏著劑中所使用 者。該等軟化劑可單獨使用亦可併用2種以上。 ® 抗氧化劑並不特別限定，可舉出例如：苯酚系（單苯酚 系、雙酚系、高分子型苯酚系）、硫系、磷系等通常所使用 者。 光安定化劑可舉出阻胺系化合物。 糸外線吸收劑並不特別限定，可舉出例如：水陽酸 系、一苯基酮系 '笨並***系、氰基丙烯酸酯系等。 充填劑可舉出例如：碳酸約、碳酸鎮、二氧化石夕、氧 24 201016812 化鋅、氧化鈦等。 黏著亢進防止劑可Iψ . 長鏈烧基接枯物」 肪酸醢胺、聚乙烯亞胺之 接枝物、大豆油變性醇酸樹脂（例如，荒則工 業公司製之商品名「阿拉士 σ于251」等）、托爾油變性醇酸 樹知（例如，荒川化學工業 6300」等）等。 ”司製之商口口名阿拉吉得 該，添加劑可單獨使用亦可併用2種以上。 黍著劑層之厚度並無特別限制，例如，通常為〇 $〜 “左右，較佳為1〜40心，更佳為2〜3“m。 本發明之表面保護骐之一較佳型態中， 該基材層為聚烯烴基材層， 該黏著劑組成物進一步含有增黏劑，且 該點著劑層於-赃〜8代測定動黏彈性所得之 為最大時之溫度為-1(TC〜20t。 此時’增黏劑可使用以上所例示者等。 ❹ 增黏劑較適當係使用將表面保護職被貼附物剝離 防止殘糊的量。例如，使用作為稜鏡片用之表面保護 2情況時’增黏劑的配合比例較佳為相對於橡膠系樹脂 :[上it聚合物⑴及上述聚合物（ii)(以下有時將該等统 冉為芩香族烯基嵌段共聚物）]ΐθ〇重量份為5〜5〇重 佳為10〜40重量份。 =黏著劑層於_5〇1~8〇。〇測定動黏彈性所得之匕115為 最大時之溫度為-1(rc〜2(TC之範圍為佳。此13115峰值溫度 可藉由調整黏著劑層中之橡膠系樹脂成分例如芳香族^ 25 201016812 基嵌段^聚物之無規嵌段中之芳香族烯基化合物 有率之範圍、增黏劑之配合比例等來將其調整至較佳範 圍，或者藉由考量軟化溫度等來選擇所用之增黏劑以將其 調整至較佳範圍。 、 此處，_係指在_5(rc〜80t之測定溫度範圍時以 下述條件所測得之動黏彈性光譜中之損失正切卜損 性模數/儲藏彈性模數）。 € 黏彈性分析儀：商品名「dva_2qg」⑽計測控制公 司製） 黏著劑層之試樣尺寸· 才厚度 4 1.5mmx5mmxl〇mm 設定昇溫速度：6°C/分鐘 測定頻率頻率：1 〇Hz 測定模式··切斷 藉由使得此種方式所制p + 圍 此 裡乃式所測侍之tan d峰值溫 伴隨增黏劑之作用介& 又風馬此把 亦可k升黏著劑層之凝集力。因 即使在表面保護膜之基材層背面黏著有黏著劑層再做 成為捲繞體的情況時，亦 ^ # 了今易地將表面保護膜從基材層 使用於m古 員暢地將捲繞體回捲。又，即使在 便用於表面具有凹凸之被 可確眚,…" 皮貼附物時，亦可追隨其之凹凸而 r確實地保濩被貼附物之表面。 本發明之表面保護膜之另-較佳態樣中， 該基材層為聚烯烴基材層， 該黏著劑組成物進一步本 相補強劑， 有曾黏劑、及苯乙烯系嵌段 26 201016812 該聚合物（i)、該聚合物（ii)及笨乙烯系嵌段相補強劑 中之芳香族烯基化合物單位重量相對於該黏著劑層之重 量的比例（芳香族烯基化合物單位含有率）為2〇〜5〇重量 %。該比例若少於20重量。/。，則有時經時黏著力會易於亢 進，而若該比例超過50重量％ ’則有時無法獲得較高之= 著力。 此時，增黏劑可使用以上所例示者等。 ❿ 增黏劑較佳係使用將表面保護膜從被貼附物剝離時 可防止殘糊的量。例如，增黏劑相對於橡膠系樹脂成分（芳 香族烯基嵌段共聚物）100重量份含有較佳為5重量份〜5〇 重量份左右，更佳為10重量份〜4〇重量份左右。 又，此時苯乙烯系嵌段相補強劑可使用以上所例示 等。 苯乙烯系嵌段相補強劑例如相對於芳香族烯基嵌段 共聚物100重量份較佳係配合有4〇重量份左右以下更 e 佳為30重量份左右以下。又，只要配合多於〇重量份即 可’較佳為1重量份以上。 藉由使用苯乙烯系嵌段相補強劑，而可相溶於苯乙烯 系共聚物嵌段中之苯乙烯（st)相，並提升黏著劑層之凝集 力。藉此可容易A將所黏著之表面保護膜從聚婦烴基材層 之月面剝離，且可順暢地將捲繞體回捲。並且可防止在將 表面保漠膜從被貼附物剝離時之殘糊而可以較小之力道 來剝離。 本發明之表面保護膜中，上述黏著劑層在7(TC時之儲 27 201016812 藏彈性模數G，鉍杜 為.5x10 pa〜6.〇xl〇5pa。 藉由使得料彈性模數G，4 在高溫環境下，所不希望發生之黏著… ，即使 且另一方而1丄 黏著几進亦可獲得抑制， 面，藉由使得储藏彈性模數G，為 下可獲得適當的黏著力。 马6.0xl0Pa以 之表！整黏著劑之儲藏彈性模數g，，只要將本發明 =面保護膜中之黏著劑層的芳香族稀基化合物單位：Average waviness length AW 1 n AW* — Σ AW· n is1 Waviness average height w 4 mw=丄ς w ΓΠ j: 1 In this manual, “average waviness length” and “average waviness height” are respectively Jis B0601 : The "average length of the elements of the turn curve" and the "average height of the elements of the turn curve" as specified in 2001. <Adhesive Layer> The above adhesive layer is composed of the adhesive composition of the present invention. In addition to the above polymer (1) and the above polymer (Η) 201016812, the adhesive composition may optionally contain a tackifier, a benzoic acid block reinforcing agent, a softener, an oxidizing agent, a light stabilizer, and an ultraviolet absorbing agent. A conventional additive such as a solvent, a filler, a pigment, an adhesion preventing agent, an olefin resin, a polyoxopolymer, a liquid acrylic copolymer, or a phosphoric acid s-based compound. The tackifier used in the present invention is not particularly limited. For example, a petroleum resin such as an aliphatic copolymer, an aromatic copolymer, an aliphatic-aromatic copolymer or an alicyclic copolymer is used. , coumarin, phlegm resin, nn^ne.lndene) resin, (four) resin, (iv) benzene, rosin resin such as rosin, rosin-based resin, xylene-based resin, or xylene-based resin These hydrides, etc. - are used by the ship. Preferably, the softening point of the agent is from 9 〇 to 14 〇t. These tackifiers can be used alone. Use two or more types. Moreover, in order to improve peelability, weather resistance, etc., the chlorinated tackifier is used. Further, a tackifier commercially available as a blend with the lean tobacco L may also be used. The tackifier in the polymer ί:: refers to a soft segment which is soluble in the aromatic alkenyl block, a double-dilute or hydrogenated, or a rubber layer, and can control the adhesion. By. The tantalum of the complex obtained by blending the agent with the additive in the copolymer composition is the copolymer of the complex, and the ta of the composition is the peak temperature: the state of the difference In addition, in this specification, the term "degree" refers to the temperature at which Und is the maximum. The value of the 哔 皿 进 系 块 块 块 块 块 块 块 块 块 块 块 块 块 块 块 块 块 块 块 块 块 块 块 块 块 块 块 块 块 块 块 块 块 块 块 块The reinforcing agent can be exemplified by: monomer 23 201016812 units such as styrene and α-methylstyrene, p-methylstyrene, p-chlorostyrene, gas methyl styrene, t-butyl styrene, p-ethyl A styrene compound such as ethylene or divinylbenzene may be used alone or in combination of two or more. That is, the styrene block phase reinforcing agent can be obtained by polymerizing the monomers. In the case of a copolymer composed of two or more kinds of monomers, the copolymer may be a random copolymer. Among them, the stearic vinyl block reinforcing agent preferably has i 〇〇〇 The softening point of c or more is preferably more than 150 C. Specifically, it can be preferably used. The product name rENDEX155" (softening point 155 155. 〇, "ENDEX160" (softening point 16 〇t) manufactured by Eastman Chemical Co., Ltd.) The softener is generally effective for improving the adhesion. The softener can be used without particular limitation. · Low molecular weight diene polymer, polyisobutylene, deuterated polyisoprene, hydrogenated polybutadiene, paraffinic processing oil (process 〇n), naphthene processing oil Household processing oil, castor oil, Thor oil, natural oil, liquid polyisobutylene resin, polybutene, or such hydrides, etc. - such softeners can be used alone or in combination The antioxidant is not particularly limited, and examples thereof include a phenol type (monophenol type, bisphenol type, or polymer type phenol type), a sulfur type, and a phosphorus type. The antimony-line compound is not particularly limited, and examples thereof include a salicylic acid type, a monophenyl ketone type, a stupid triazole type, a cyanoacrylate type, and the like. For example: carbonic acid , carbonic acid town, dioxide dioxide, oxygen 24 201016812 zinc, titanium oxide, etc. Adhesion preventive agent can be Iψ. Long chain burnt base with fats, fatty acid guanamine, polyethylene imine graft, soybean oil A modified alkyd resin (for example, the product name "Alaska 251" manufactured by Araishi Industries Co., Ltd.), a Tal oil-modified alkyd tree (for example, Arakawa Chemical Industry 6300, etc.), etc. The mouth name is Alajid, and the additives may be used singly or in combination of two or more. The thickness of the enamel layer is not particularly limited, and for example, it is usually 〇$~ "about, preferably 1 to 40 hearts, more preferably. 2~3"m. In one preferred embodiment of the surface protection crucible of the present invention, the substrate layer is a polyolefin substrate layer, the adhesive composition further contains a tackifier, and the dot agent layer is - 赃 ~ 8 generations measured by dynamic viscoelasticity when the maximum temperature is -1 (TC ~ 20t. At this time, the above-mentioned exemplified can be used as the tackifier.增 The tackifier is used to remove the surface protector from the stick. For example, in the case of using the surface protection 2 as a crepe sheet, the blending ratio of the tackifier is preferably relative to the rubber-based resin: [the upper polymer (1) and the above polymer (ii) (hereinafter sometimes the same) The oxime is a scented aromatic alkenyl block copolymer)] ΐ θ 〇 is 5 to 5 parts by weight, preferably 10 to 40 parts by weight. = Adhesive layer is _5〇1~8〇. 〇 动 〇 〇 〇 〇 〇 〇 〇 〇 〇 匕 匕 匕 匕 匕 匕 匕 匕 匕 rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc 201016812 The range of the aromatic alkenyl compound in the random block of the base block polymer, the blending ratio of the tackifier, etc., can be adjusted to a preferred range, or can be selected by considering the softening temperature and the like. The tackifier is adjusted to a preferred range. Here, _ refers to the loss tangent damage in the dynamic viscoelastic spectrum measured under the following conditions in the measurement temperature range of _5 (rc~80t) Modulus/storage elastic modulus). * Viscoelastic analyzer: trade name "dva_2qg" (10) Measurement Control Co., Ltd.) Sample size of adhesive layer · Thickness 4 1.5mmx5mmxl〇mm Setting heating rate: 6°C/min Measurement frequency frequency: 1 〇 Hz measurement mode · · Cut off by using the method of making p + in this way to measure the tan d peak temperature of the service with the effect of the tackifier & Can also increase the agglutination force of the adhesive layer, even on the surface When the adhesive layer is adhered to the back surface of the base layer of the film and then becomes a wound body, it is also easy to use the surface protective film from the base layer to rewind the wound body. Moreover, even if it is used for the surface to have irregularities, ..." when attaching the skin, it is possible to follow the unevenness of the surface to securely protect the surface of the attached object. In another preferred embodiment of the film, the substrate layer is a polyolefin substrate layer, the adhesive composition further comprises a phase reinforcing agent, a pre-adhesive agent, and a styrene block 26 201016812. The ratio of the unit weight of the aromatic alkenyl compound in the polymer (ii) and the stupid vinyl block phase reinforcing agent to the weight of the adhesive layer (unit content ratio of the aromatic alkenyl compound) is 2 〇 5 % by weight. If the ratio is less than 20% by weight, the adhesion may be easily broken over time, and if the ratio exceeds 50% by weight, the higher = sometimes cannot be obtained. The tackifier can be used as exemplified above. ❿ The tackifier is preferably used to surface When the film is peeled off from the adherend, the amount of the paste is prevented. For example, the tackifier is preferably contained in an amount of 5 parts by weight to 5 parts by weight based on 100 parts by weight of the rubber-based resin component (aromatic alkenyl block copolymer). It is more preferably about 10 parts by weight to about 4 parts by weight, and more preferably, the styrene-based block phase reinforcing agent can be used as described above. The styrene-based block phase reinforcing agent is, for example, relative to the aromatic olefin. 100 parts by weight of the base block copolymer is preferably blended in an amount of about 4 parts by weight or less, more preferably about 30 parts by weight or less. Further, it may be preferably 1 part by weight or more as long as it is more than 〇 by weight. By using a styrenic block phase reinforcing agent, it is soluble in the styrene (st) phase in the styrenic copolymer block and enhances the cohesive force of the adhesive layer. Thereby, the adhered surface protective film can be easily peeled off from the moon surface of the polysulfide base material layer, and the wound body can be smoothly rewinded. Further, it is possible to prevent the residue from being peeled off when the surface-preserving film is peeled off from the adherend, and it is possible to peel off with a small force. In the surface protective film of the present invention, the above adhesive layer is at 7 (the storage time of TC 27 201016812, the elastic modulus G, the 铋 Du is .5x10 pa 〜6. 〇xl 〇 5pa. By making the elastic modulus G, 4 In a high-temperature environment, the adhesion that is undesired... can be suppressed even if the other side is adhered to the surface, and by making the storage modulus G, the appropriate adhesion can be obtained. 6.0xl0Pa is the table! The storage elastic modulus g of the whole adhesive, as long as the aromatic dilute compound unit of the adhesive layer in the present invention = face protection film:
C 力成為適當的範圍内即可。該含 ^疑集 來自適•方香族稀基單體單體之成分的含有比例之芳 =稀基嵌段絲物、及/或藉由將苯乙㈣嵌段相補強劑 :黏著劑層來實施。苯乙稀系嵌段相補強劑係用以補 方香族烯基嵌段共聚物所形成之海島構造的島相之 劑’並具有與芳香族稀基嵌段共聚物所構成之區域（d_ 相溶之性質。 °亥苯乙烯系嵌段相補強劑之使用量較佳為相對於芳 香族烯基嵌段共聚⑼100重量份為40重量份以下，更佳❹ 為30重里份以下。若該使用量過多，則黏著力會不足且 擠出成形％流動性有變差之虞。該使用量之下限並無特別 制 S…、/員如上述般調整芳香族稀基化合物單位含有率 時，則不用添加，較佳為丨重量份以上。 本發明之表面保護膜之另一較佳態樣係用於保護稜 鏡片之棱鏡面的表面，而當貼附於該棱鏡面，且在7〇<>c之 環境氣氛下負重〇.3N/cm2之荷重24小時的情況時，黏著 28 201016812 齊至°亥稜鏡面的稜鏡頂角之深度為黏著劑層厚度的 1%以上、未滿4〇%。 «亥滲入深度係以下述方法來測得。 將用來測疋之表面保護膜，在室溫23它及相對濕度 5〇 /°之環境下，分別使用2kg之壓著橡膠輥以300mm/分鐘 之速度貼附於棱鏡片之表面。稜鏡片係使用稜鏡之十心距 離50 # m、鬲度25以m者。之後，以聚碳酸酯板（厚度 ❹將貼附有表面保護膜之稜鏡片加以夾持，並施加〇 3N/cm2 之壓力，再以此狀態靜置於7(rc之環境氣氛下24小時。 之後以剝離角1 80度將表面保護膜剝離並以雷射顯微鏡 硯察黏著劑層表面，再測定稜鏡片之透鏡部（稜鏡）頂角滲 入於黏著劑層之滲入深度。 藉由使得該滲入深度為黏著劑層厚度的1 %以上且未 滿40%，而對黏著力等黏著物性不會造成不良影響且在高 溫（例如701:)環境下時之黏著亢進會受到抑制。 〇 使該渗入深度成為黏著劑層厚度的1%以上且未滿 4〇%係藉由例如將上述黏著劑層在70°C時之儲藏彈性模數 °控制在上述較佳範圍來達成。 本發明之表面保護膜之另一較佳態樣係用於保護稜 鏡片之稜鏡面’而當貼附於該稜鏡面，且於與該棱鏡面側 相反側之表面壓有直徑4〇〇#m、高度12"爪之突起物的 凊況時，黏著劑滲入至該稜鏡面的稜鏡頂角之深度為該黏 著劑層厚度的1%以上、未滿1〇〇% 此時’對上述突起物加壓之條件較佳係在5〇t>c環境下 29 201016812 以〇.8N/cm2之力道進行24小時。 高度為12 a m 限為未滿黏著 又，上述突起物為直徑40〇θηι以下、 以下時，亦同樣地預測到上述滲入深度之上 劑層厚度之1 〇〇〇<。 因此’將本發明之矣, 表面保濩膜貼附於稜鏡片，並於平 滑之一面貼附另一表面体 ^ & s M 呆濩膜，再將例如數十片之稜鏡片 積層再加以保管的情況時 ^ ^ A 做便於千滑之一面之表面保護 ^眼、央帶進來之異物等㈣物時，因為表面保 2膜之黏者㈣中的㈣劑的料族烯基化合物單位含 =係被設定成適當量，因此黏著劑層會變硬而稜鏡片之 透鏡部過度滲入至表面保鳟 、°隻膜之黏者劑層的情況可確實 獲得抑制。因此難以產生棱 、 規片之透鏡部表面（稜鏡面）的 相傷。The C force is within the appropriate range. The content of the aryl group containing the proportion of the constituents of the scented aromatic monomer, and/or by the benzene (tetra) block phase reinforcing agent: the adhesive layer To implement. The styrene-based block phase reinforcing agent is used to replenish the island phase of the island structure formed by the aromatic alkenyl block copolymer and has a region composed of the aromatic dilute block copolymer (d_). The amount of the styrene-based block phase reinforcing agent used is preferably 40 parts by weight or less, more preferably 30 parts by weight or less, based on 100 parts by weight of the aromatic vinyl group block copolymerization (9). When the amount used is too large, the adhesive strength is insufficient and the % fluidity of the extrusion molding is deteriorated. The lower limit of the amount of use is not particularly determined as S..., and when the member adjusts the unit content of the aromatic dilute compound as described above, It is not necessary to add, preferably more than 丨 by weight. Another preferred aspect of the surface protective film of the present invention is for protecting the surface of the prism face of the cymbal, and when attached to the prism face, at 7 〇 <>c The load in the ambient atmosphere is 负.3N/cm2 when the load is 24 hours, the adhesion 28 201016812 is equal to the depth of the dome angle of the 稜鏡 稜鏡 surface is 1% or more of the thickness of the adhesive layer, Full 4〇%. «The depth of penetration is measured by the following method. The surface protective film of the crucible was attached to the surface of the prism sheet at a rate of 300 mm/min using a 2 kg pressing rubber roller at room temperature 23 and a relative humidity of 5 〇/°. The distance between the ten cores of the 稜鏡 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 Then, it was left in this state for 24 hours under the ambient atmosphere of rc. Then, the surface protective film was peeled off at a peeling angle of 180 degrees, and the surface of the adhesive layer was observed by a laser microscope, and then the lens portion of the enamel sheet was measured. The penetration angle of the apex angle into the adhesive layer is such that the penetration depth is 1% or more and less than 40% of the thickness of the adhesive layer, and the adhesive property such as adhesion is not adversely affected and is at a high temperature ( For example, 701:) Adhesion is inhibited in an environment. The penetration depth is 1% or more and less than 4% by weight of the adhesive layer by, for example, storing the above adhesive layer at 70 ° C. The elastic modulus ° is controlled to achieve the above preferred range. Another preferred aspect of the surface protective film is for protecting the top surface of the cymbal sheet and attaching to the surface of the cymbal sheet, and having a diameter of 4 〇〇 #m on the surface opposite to the side of the prism surface. When the height is 12" the protrusion of the claw, the depth of the apex angle of the adhesive penetrating into the surface of the enamel is 1% or more of the thickness of the adhesive layer, less than 1%% at this time. The conditions of pressurization are preferably carried out in a 5〇t>c environment at 29 201016812 for 24 hours at a force of N8 N/cm2. The height is 12 am, the limit is not full, and the protrusions are below 40 〇 θηι in diameter. In the following, it is also predicted that the thickness of the agent layer above the penetration depth is 1 〇〇〇 <. Therefore, the surface of the present invention is attached to the enamel film, and the other surface body is attached to the smooth surface of the smear film, and then, for example, dozens of enamel films are laminated. In the case of storage, ^ ^ A is used to facilitate the surface protection of one side of the surface, the foreign matter brought in by the central zone, etc. (4), because the surface of the film is protected by the film (4) = The amount is set to an appropriate amount, so that the adhesive layer is hardened and the lens portion of the cymbal sheet is excessively infiltrated into the surface of the film, and the film layer of the film is surely suppressed. Therefore, it is difficult to cause a phase damage of the surface of the lens portion (facet) of the ribs and the ribs.
使得上述滲入深度成為黏著劑層厚度之胸上且未 滿顧，主要係藉由使得芳香族稀基嵌段共聚物之芳香 ::基化合物單位含有率為3〇〜5〇重量％來達成。此含有 "、右未滿30重量％ ’則黏著劑之凝集力會降低，因此有時 會無法抑制稜鏡透鏡滲人至黏著劑層之滲人深度。相反 地，若此含有率…〇重量％，則黏著劑之凝集力會過 焉，因而棱鏡透鏡會難以渗入黏著劑I，而造成黏著力過 低而有時會無法用作為保護膜。 本發明之表面保護膜戶斤適用之稜鏡片的透鏡部實質 上係具有三角柱所構成之稜鏡形狀。本說明書中，係將1 有此種棱鏡形狀之透鏡部的面稱為稜鏡面。更具體 30 201016812 如圖2所示，稜鏡片丨後 孜鏡月1係於平坦的片 數根三角柱狀之透鏡部3經—體化所成之:另面=複 係實質上具有三角柱之形冓：：鏡。” 透鐘邮.式並排設置。此稜鏡形狀之 ° 、自係、以本發明之表面保護膜來保護。 3之係：圖3之截面圖所示’稜鏡片1之設有透鏡部The above-mentioned penetration depth is made to be on the chest of the thickness of the adhesive layer, and is mainly achieved by making the aromatic-based base copolymer of the aromatic dilute block copolymer a unit content of 3 〇 to 5 〇 by weight. If the content contains ", the right is less than 30% by weight, the cohesive force of the adhesive is lowered, so that it is sometimes impossible to suppress the penetration depth of the enamel lens to the adhesive layer. On the other hand, if the content ratio is 〇% by weight, the cohesive force of the adhesive may be excessive, so that the prism lens may hardly penetrate into the adhesive I, and the adhesion may be too low to be used as a protective film. The lens portion of the cymbal sheet to which the surface protective film of the present invention is applied has a substantially triangular shape composed of a triangular prism. In the present specification, a surface having a lens portion having such a prism shape is referred to as a kneading surface. More specifically 30 201016812 As shown in Fig. 2, the 丨 丨 孜 孜 月 月 系 系 系 系 系 系 系 系 系 月 月 月 月 月 月 月 月 月 月 月 月 月 月 月 月 月 月 月 月 月 月 月 月 月 月 月 月 月冓:: Mirror. The clock shape is arranged side by side. The shape of the crucible is self-contained and protected by the surface protection film of the present invention. 3: The cross-sectional view of Fig. 3
膜"Vi之/有第1之表面保護媒4(本發明之表面保護 另—表面保護膜4係具有基材層5與設於基材層5 —面之黏著劑層6，並從黏著劑層6側貼附於稜鏡片1 :設有該複數之透鏡部3之側。因此，本發明之表面保護 :係以將三角柱狀之透鏡部3的複數個頂部3A接起來的 式來貼附。X，此三角柱之透鏡部3的橫截面形狀為三 形’而此三角形較佳係、以固定於片體之側面作為底邊之 專腰三角形。 、，另方面，稜鏡片1之與設有透鏡部3之側相反側的 ©平垣面上係依據需要貼附有第2之表面保護膜7。當於該 表面保遵膜7中存在有魚眼（FE)、夹帶進來之異物等突起 物時’則可造成透鏡部頂部之破壞。 所°月—角柱之稜鏡形狀之侧面係指延伸於三角柱 長度方向之3個側面。 本發明之表面保護膜所適用之較佳稜鏡片方面，實質 上二角柱之複數個稜鏡中，相鄰之稜鏡的距離亦即稜鏡的 間隔較佳為10〜1000〆m左右，更佳為1〇〜5〇〇y m，但本 發明之表面保護膜所適用之被貼附物並不限定於此。 31 201016812 <製造方法> 本發明之黏著劑組成物係將例如共聚物⑴及共聚物 (π)分別以嵌段聚合來合成’並將該等以既定質量比摻合 後’依需要進行氫化而獲得共聚物⑴或其氫化物、及共聚 物（I)或其氫化物之混合物，再將視需要所配合之添加劑以 慣用方法加以混合，藉此來製造。 氫化觸媒可使用含元素周期表Ib、IVb、Vb、VIb、The film "Vi/the surface protective medium 4 of the first aspect (the surface protection of the present invention - the surface protective film 4 has the substrate layer 5 and the adhesive layer 6 provided on the surface of the substrate layer 5, and adheres thereto The side of the agent layer 6 is attached to the crotch sheet 1 : the side of the plurality of lens portions 3 is provided. Therefore, the surface protection of the present invention is to attach a plurality of top portions 3A of the triangular columnar lens portion 3 Attached to X, the lens portion 3 of the triangular prism has a three-dimensional cross-sectional shape, and the triangular shape is preferably a waist-shaped triangle which is fixed to the side of the sheet as a bottom side. Further, the cymbal 1 The second surface protection film 7 is attached to the flat surface on the side opposite to the side on which the lens portion 3 is provided. The fish eye (FE) and the foreign matter entrained therein are present in the surface protection film 7. When the protrusions are the same, the damage of the top of the lens portion may be caused. The side of the shape of the corner of the prism is the three sides extending in the longitudinal direction of the triangular prism. The preferred wafer for the surface protection film of the present invention is suitable. In terms of the plurality of ridges of the two corners, the distance between the adjacent ridges is the ridge. The interval is preferably from about 10 to about 1000 μm, more preferably from about 1 to about 5 μm, but the adherend to which the surface protective film of the present invention is applied is not limited thereto. 31 201016812 <Manufacturing Method> The adhesive composition of the present invention is obtained by, for example, copolymerization of the copolymer (1) and the copolymer (π) by block polymerization, and after the blending with the predetermined mass ratio, hydrogenation is carried out as needed to obtain the copolymer (1) or The hydride and the mixture of the copolymer (I) or a hydride thereof are prepared by mixing the additives as needed in a conventional manner. The hydrogenation catalyst can be used in the periodic table Ib, IVb, Vb. , VIb,
Vllb、VIII族金屬中任一者之化合物。可舉出含例如们、 V、C〇、Ni、Zr、Ru、Rh、Pd'Hf、Re、Pu2K$*，© 而更具體而言’可舉出Ti、Zr、Hf、Co、Ni、Rh、RU等 二茂金屬（metallocene)系化合物、於碳、二氧化矽、氧化 鋁、矽藻土、鹽基性活性碳等擔體擔持有Pd、Ni、Pt、Rh、A compound of any of the Vllb and Group VIII metals. For example, V, C〇, Ni, Zr, Ru, Rh, Pd'Hf, Re, Pu2K$*, ©, and more specifically, 'Ti, Zr, Hf, Co, Ni, Metallocene compounds such as Rh and RU, and Pd, Ni, Pt, Rh, and the like are supported on carbon, cerium oxide, alumina, diatomaceous earth, and base-based activated carbon.
Ru等金屬之擔持型不均勻系觸媒。 又’二茂金屬系化合物之具體例可舉出：具有環戊烯 (cyel〇pentadienyl)環（CP環）或CP環上之氫以烧基取代之 配位子兩個之Kaminsky觸媒、咖型二茂金屬觸媒、非 交聯半二茂金屬（half metallc)eene)觸媒、交聯半二茂金屬❹ 具體例可舉出日太直Μ # 0B τ 平曰本專利特開平[275605號公報、日 專利特開平5 - 2 7 1 3 2 6骑八4β 唬a報、日本專利特開平5·27 號公報 '曰本專利特開平5_2221 平Η-292924號公報、日太直4，報曰本專利特開 t報日本專利特開2_-37632號公報、 本專利特開昭59.1332G3號公報、日本 63-5401號公報、日太直 特開日° 曰本專利特開昭62_2184〇3號公報、曰 32 201016812 =專:刚平7侧17號公報、日本專利特公昭u•⑽〇 二報、日本專利特公昭47购3號公報所記载之觸媒。 邊等各種觸媒可僅單獨使用丨種亦可併用2種以上。 ❹ 其他方法方面，當共聚物（„)為具有上述通式 (Α = ·Υ(式中之記號係表示與上述相同意義）所示構造^ it况日守，本發明之黏著劑組成物亦可以下述方法（偶合法） 來製造。偶合法因為可以一個釜來合成共聚物⑴或其口氫化 =(聚合物⑴）與共聚物（„)或其氫化物（聚合物⑴）），故在製 迨乂驟簡I 製造費用低廉，而以偶合劑之種類、量即 可控制聚合物⑴與聚合物（ii)之比率等方面較佳。 偶合法係具備下述步驟： 第1步驟：以嵌段聚合合成具有[A_B]構造之共聚物步 第2步驟：將上述具有[A-B]構造之共聚物的一部分以 偶合劑Y-Zx(其中，「γ」表示偶合劑殘基，「z」表示脫 Q 離基（leavmg group)、「X」表示2以上之整數）來偶合，以 合成具有{ [Α·Β]Χ-Υ }構造之共聚物之步驟， 當欲獲得氫化物的情況時係進而具備以下步驟： 第3步驟：藉由將上述具有[Α_Β]構造之共聚物及上述 具有{ [Α-Β]χ_γ }構造之共聚物加以氫化，來獲得分別經 氫化之共聚物⑴與共聚物（II)所構成之共聚物組成物之步 驟。 「偶合劑」可舉出例如：甲基二氣矽烷、二甲基二氣 石夕烧、甲基三氣矽烷、丁基三氯矽烷、四氣矽烷、二溴乙 33 201016812 烷四氣化錫、丁基三氣化錫、四氣化鍺、雙（三氣石夕基） u等i化物；環氧化大豆油等環氧化合物；己二酸二乙 己酸一曱知、對本二甲酸二甲酯、對苯二甲酸二乙 等羰基化0物、一乙烯基苯等聚乙烯基化合物；聚異氰 θ等其中，基於工業上取得容易且反應性亦高之理 由，較隹為甲基二氣矽烷、二甲基二氣矽燒、甲基三氣矽 烷、四氯矽烷。 本發明之表®保護膜可藉由例如以下方法來製造：以 擠出成形來製造基材片（基材層）後’將上述黏著劑組成物❹ 熔融或溶解而得之液體塗佈或喷霧於基材片之方法、或者 將以吹製法（inflation)所得之基材片與黏著片貼合之方 法、或者使用具備多層manifold之τ模來將基材原料與上 述黏著劑組成物共擠出之方法。其中，因為可獲得基材層 與黏著劑層密合而成之多層片故較佳係藉由共擠出來製 造之方法。又’使本發明之黏著劑組成物熔融或溶解而得 之液體亦包含於本發明之黏著劑組成物。 <適用> Ο 本發明之表面保護膜可較佳地使用於光學板、稜鏡 片、及擴散膜等具有凹凸之被貼附物，但並不限定於此， 且亦可使用於例如表面平滑之片體之表面保護。 而構成作為被貼附物之片體並無特別限定，可舉出具 有透光性之樹脂如丙烯酸系樹脂、聚碳酸酯等。 【實施例】 以下基於實施例詳細說明本發明之表面保護膜，但本 34 201016812 發明並不限定於以下實施例。 (共聚物組成物之合成例）A metal such as Ru is not supported by a catalyst. Further, specific examples of the 'metallocene-based compound' include a Kaminsky catalyst having a ring of a cep〇pentadienyl ring (CP ring) or a hydrogen group on the CP ring which is substituted with a burnt group. Type of metallocene catalyst, non-crosslinked metallocene (eene) catalyst, cross-linked semi-metallocene ❹ Specific examples can be cited as Japanese Tai Chi Μ # 0B τ 平曰本本专开平[275605 Japanese Gazette, Japanese Patent Special Kaiping 5 - 2 7 1 3 2 6 riding eight 4β 唬a newspaper, Japanese Patent Laid-Open No. 5·27 Bulletin '曰本专利专开平 5_2221 平Η-292924号, 日太直4, Japanese Patent Laid-Open No. Hei 2_-37632, Japanese Patent Laid-Open No. 59.1332G3, Japanese Patent No. 63-5401, and Japanese Taikoo Special Open Day 曰 Patent Opened No. 62_2184〇 Publication No. 3, 曰32 201016812 =Special: The catalyst described in the No. 17 of the Gangping 7 side, the Japanese Patent Special Publication No. Sho (10), the second report, and the Japanese Patent No. The various catalysts may be used alone or in combination of two or more. ❹ In other methods, when the copolymer („) is a structure having the above-described general formula (Α = · Υ (the symbol in the formula indicates the same meaning as described above), the adhesive composition of the present invention is also It can be produced by the following method (even method). Even if the copolymer (1) or its hydrogenation = (polymer (1)) and copolymer (") or its hydride (polymer (1))) can be synthesized in one pot, In the production process, the manufacturing cost is low, and the ratio of the polymer (1) to the polymer (ii) can be controlled by the type and amount of the coupling agent. The even legal system has the following steps: Step 1: Synthesis of a copolymer having the structure of [A_B] by block polymerization Step 2: A part of the above copolymer having the structure [AB] is used as a coupling agent Y-Zx (wherein "γ" indicates a coupling agent residue, "z" indicates a delocalization (leavmg group), and "X" indicates an integer of 2 or more) to be coupled to synthesize a structure having { [Α·Β]Χ-Υ }. The step of copolymer, when the hydride is to be obtained, further comprises the following steps: Step 3: by using the above copolymer having the structure of [Α_Β] and the above copolymer having the structure of {[Α-Β]χ_γ } Hydrogenation is carried out to obtain a copolymer composition of the hydrogenated copolymer (1) and the copolymer (II), respectively. Examples of the "coupling agent" include methyl dioxane, dimethyl dichacite, methyl trioxane, butyl trichlorodecane, tetrahexane, and dibromoethane 33 201016812 alkane. , butyl tri-vaporized tin, four gasified bismuth, bis (three gas shi ki) u, etc.; epoxidized soybean oil and other epoxy compounds; adipic acid dihexanoic acid, knowing, dimethyl diformate a carbonylated compound such as an ester or a terephthalic acid such as a vinyl compound such as monovinylbenzene; or a polyisocyanine θ or the like, which is industrially easy and highly reactive, and is preferably a methyl group. Gas decane, dimethyl dioxane, methyl trioxane, tetrachloro decane. The watch® protective film of the present invention can be produced, for example, by a method in which a substrate sheet (base material layer) is produced by extrusion molding, and a liquid coating or spraying is performed by melting or dissolving the above-mentioned adhesive composition ❹. a method of fogging a substrate sheet, or a method of bonding a substrate sheet obtained by a blowing method to an adhesive sheet, or coextruding a substrate material with the above-mentioned adhesive composition using a τ mold having a multilayer manifold Way out. Among them, since a multilayer sheet in which a base material layer and an adhesive layer are adhered together can be obtained, it is preferably a method of production by co-extrusion. Further, a liquid obtained by melting or dissolving the adhesive composition of the present invention is also included in the adhesive composition of the present invention. <Applicable> Ο The surface protective film of the present invention can be preferably used for an adhesive having irregularities such as an optical plate, a crepe sheet, and a diffusion film, but is not limited thereto, and can be used, for example, on a surface. Smooth surface protection of the sheet. The sheet to be attached is not particularly limited, and examples thereof include a resin having a light transmissive property such as an acrylic resin or polycarbonate. [Examples] The surface protective film of the present invention will be described in detail below based on examples, but the invention is not limited to the following examples. (Synthesis Example of Copolymer Composition)
聚合物嵌段A 於經氮取代之反應容器填入經脫氣、脫水之環己烷 5 00質量份、苯乙烯20質量份及四氫呋喃5質量份，再於 聚合起始溫度之40°C添加正丁基鋰0.13質量份，進行昇 溫聚合。The polymer block A is filled in a nitrogen-substituted reaction vessel with 500 parts by weight of degassed and dehydrated cyclohexane, 20 parts by mass of styrene, and 5 parts by mass of tetrahydrofuran, and then added at 40 ° C of the polymerization initiation temperature. 0.13 parts by mass of n-butyllithium was subjected to temperature-raising polymerization.
聚合物嵌段B ϋ 聚合物Α之聚合轉化率達約1 〇〇%之後，將反應液冷 卻至15°C ’接著，加入1，3-丁二烯70質量份及苯乙烯10 質量份再進行昇溫聚合。 聚合轉化率大致達1 〇〇%之後，加入作為偶合劑之甲 基二氯石夕院0.06質量份，進行偶合反應。偶合反應結束 後，一邊以0.4MPa-Gauge之壓力供給氫氣一邊放置1〇分 鐘。一部分取出之聚合物之乙烯基含有率為64%、重量平 均分子量約11萬，偶合率為60%。 之後’於反應容器内加入氯化二乙基銨〇〇3質量份及 bis(cyclopentadienyl)titanium furfuryl chloride 0'.06 質量 份’進行授拌。在氫氣供給壓〇7MPa_Gauge、反應溫度 8 0 C之下開始風化反應，再在氫的吸收結束之時點，使反 應溶液返回常溫、常壓，再從反應容器中取出，藉此獲得 由聚合物（i)與聚合物（ii)所構成之共聚物組成物（表1之合 成例1)。 以下以相同之操作獲得所要之共聚物組成物（表丨之 35 201016812 合成例2〜24)。將該等共聚物組成物之性質表示於表i。 又’表 1 中「St(A+ B)」、「St(b)」、「st(A)」、及 「St(b)」係分別表示以下所定義之數値。該定義中，所謂 「總聚合物」係指聚合物（i)及聚合物（ii)之整體。 「St(A+ B)」為總聚合物之芳香族烯基化合物單位含 有率’並指下式所表示之數値。又，其係#下述「st(b)」 與下述「St(A)」之相等。 式：After the polymer block B ϋ polymer Α has a polymerization conversion rate of about 1% by weight, the reaction liquid is cooled to 15 ° C. Then, 70 parts by mass of 1,3-butadiene and 10 parts by mass of styrene are added. The temperature polymerization is carried out. After the polymerization conversion ratio was approximately 1% by weight, 0.06 parts by mass of methyl chlorite as a coupling agent was added to carry out a coupling reaction. After the completion of the coupling reaction, the hydrogen gas was supplied while being supplied at a pressure of 0.4 MPa-Gauge for 1 Torr. A part of the polymer taken out had a vinyl content of 64%, a weight average molecular weight of about 110,000, and a coupling ratio of 60%. Thereafter, 3 parts by mass of diethylammonium chloride and bis (cyclopentadienyl) titanium furfuryl chloride 0'.06 parts by mass were added to the reaction vessel for mixing. The weathering reaction is started at a hydrogen supply pressure of 7 MPa_Gauge and a reaction temperature of 80 ° C. Then, at the end of the absorption of hydrogen, the reaction solution is returned to normal temperature and normal pressure, and then taken out from the reaction vessel, thereby obtaining a polymer ( i) A copolymer composition composed of the polymer (ii) (Synthesis Example 1 of Table 1). The desired copolymer composition was obtained in the same manner as below (Formula 35 201016812 Synthesis Examples 2 to 24). The properties of the copolymer compositions are shown in Table i. Further, "St (A + B)", "St (b)", "st (A)", and "St (b)" in Table 1 indicate the number defined below. In this definition, the term "total polymer" means the entirety of polymer (i) and polymer (ii). "St (A + B)" is the unit content of the aromatic alkenyl compound of the total polymer' and refers to the number 値 represented by the following formula. Further, the following "st(b)" is equal to the following "St(A)". formula:
St(A+B)=(總聚合物中之芳香族缚基化合物單位重❹ 量)/(總聚合物中之總單量體單位重量)χ100(重量％) 「St(b)」係指下式所表示之數値。 式： 署vr蛐夸人铷φ π货奴烯基化合物單位重 「总此干置菔早仪室量）><100(重量％) )」糸^下式所表示之數値。 式： ❹St (A + B) = (unit weight of aromatic chain compound in total polymer) / (total unit weight in total polymer) χ 100 (% by weight) "St (b)" means The number represented by the following formula. Type: Department vr蛐 铷 铷 φ π 奴 奴 奴 化合物 单位 单位 单位 总 总 总 总 总 总 总 总 总 总 总 总 总 总 总 总 总 总 总 总 总 总 总 总 下 下 下 下 下 下 下 下 下 下 下 下 下 下 下 下 下Type: ❹
St(A) = (總聚合物嵌段a中之 重量）/(總聚合物中> _ 香族烯基化合物單位 「St(b)」為聚入 量）xl〇〇(重篁％) σ物嵌段B之芳香放& β 有率，且係指下式你± $姨埽基化合物單位含 所表不之數値。 式：St(A) = (weight in total polymer block a) / (in total polymer > _ aromatic alkenyl compound unit "St(b)" is the amount of aggregation) xl 〇〇 (% by weight) The arsenic block B has an aromatic release & beta rate, and refers to the following formula: you ± 姨埽 base compound units contain the number of 値. formula:
St(b)=(總聚合私山 0物嵌段B中之芳表# 重量）/(總聚合物嵌取^ 贷族烯基化合物單位 〇/〇) 〜单量體卓位重量)ΧΗ)0(重量 36 201016812 又，表1中，「A : B」係表示聚合物嵌段A的總量 與聚合物故段B的總量之重量比。 又，表1中，「（i) : (ii)」係表示聚合物⑴與聚合物（ii) 之重量比。 又，表1中，「共輛雙烯含有率」係表示聚合物嵌段 B之共輛雙烯單位含有率。 又，表1中，「乙烯基鍵含有率」係表示聚合物嵌段 B之乙烯基鍵之含有率。 201016812 (％)St(b)=(Total Aggregate Private Hill 0 Block B in the aromatic table #重量) / (total polymer embedding ^ credit alkenyl compound unit 〇 / 〇) ~ single body weight weight) ΧΗ) 0 (weight 36 201016812 Further, in Table 1, "A: B" represents the weight ratio of the total amount of the polymer block A to the total amount of the polymer segment B. Further, in Table 1, "(i) : ( Ii)" represents the weight ratio of the polymer (1) to the polymer (ii). In Table 1, "the total diene content rate" means the total diene unit content of the polymer block B. In Table 1, "vinyl bond content rate" means the content ratio of the vinyl bond of the polymer block B. 201016812 (%)
^寸 寸9 寸9 3 寸9 P9SS 3 33 寸9 S 寸9 S 3 3 S 寸9 3 S 001 9L 气寸6 S 6¾ 001 9ς ·卜00 9L 6.S8 9·$ •S 001 02 99 SL •9卜 %.F ο00 寸TS •s (ςοιχ) 一一 ζι 31 ON 03 οζβββ ΟΝβ 03 οζ 00 " οζ: - - οζ: οι ei ιι (％)^inch inch 9 inch 9 3 inch 9 P9SS 3 33 inch 9 S inch 9 S 3 3 S inch 9 3 S 001 9L gas inch 6 S 63⁄4 001 9ς ·Bu 00 9L 6.S8 9·$ •S 001 02 99 SL • 9卜%.F ο00 inch TS •s (ςοιχ) 一一ζι 31 ON 03 οζβββ ΟΝβ 03 οζ 00 " οζ: - - οζ: οι ei ιι (%)
(％) SIS(%) SIS
(％) SIS -/0) (q-s (％) (a+v)ls (-**) g:s (-啉蜊) ffl:v S6 °°6 °°6 °°6 °°6 °°6 °°6 °°6 °°6 S6 °°6 °°6 μ6 °°6 °°6 °°6 °°6 S6 °°6 °°6 °°6 S6 °°6 ee 寸3ττ 02 - £1 9 Ζ,寸 寸寸 s et s π 寸寸 寸一 οε 03 or or οι oe - 6 6 Οϊ 03 οζ: οι ΟΙ oe 03 2 ΟΙ 03 - οι - ΟΝ ο 03 03 03Οί ο寸 ο ο寸 οζ οι 03 ot ο寸 οι ο ο oe οζ 03 03 - - οι oe ο寸 ο寸 ο寸 - 09 6 6寸 oe oe 0寸 03 0寸 03 οι 0寸 ο寸 ςε οε ο寸 oe oe 096寸 09令 0_ 00ιώ 09:0寸 oi寸 09:0 寸 65Ϊ寸 0§寸 096寸 096寸 096寸 096寸 09:0寸 096'寸 09:0 寸 09ώ寸 62寸 09:0寸 ?卜£ 09ώ寸 09d寸 09ώ对 OS异 08:03 06ΌΙ S:-16:6 16:6 06H01 ο00耷 08耷 06ώι 06-1 οδε 06ώι 06άι 0°°耷 s-l 06ώιft -:- 08异 寸 Z ί#^φ 13苳噠<0 61 ί4^φ -5^φ 91冢嗜命 -ί#^<0 寸 l ;^φ -苳噠40 2?噠40 U ί在噠4D 01 i杳噠命 6 !φ^φ^ ίφ 寸5^φ ε f4噠<Β ζ!φ^4α - 201016812 (實施例1〜8、比較例Μ) 於上述之各合$古 告曰a Α 去所得之各共聚物組成物（表2) 100 重董份中配合作為婵I杰， ‘，、、曰黏劑之阿魯空Ρ100(荒川化學工業公 司製）30重量份、 0 ’ 抗氧化劑之 Irganoxl〇l〇(Ciba(%) SIS -/0) (qs (%) (a+v)ls (-**) g:s (- 蜊 蜊) ffl:v S6 °°6 °°6 °°6 °°6 °° 6 °°6 °°6 °°6 S6 °°6 °°6 μ6 °°6 °°6 °°6 °°6 S6 °°6 °°6 °°6 S6 °°6 ee inch 3ττ 02 - £ 1 9 Ζ, inch inch s et s π inch inch inch οε 03 or or οι oe - 6 6 Οϊ 03 οζ: οι ΟΙ oe 03 2 ΟΙ 03 - οι - ΟΝ ο 03 03 03Οί ο inchο ο inchοζ οι 03 ot寸 ο ο ο ο ο ο ο ο ο ο ο : 0 inch oi inch 09:0 inch 65 inch inch 0 § inch 096 inch 096 inch 096 inch 096 inch 09:0 inch 096' inch 09:0 inch 09 inch inch 62 inch 09:0 inch? Bu £ 09 inch inch 09d inch 09 ώ right OS 异 08:03 06ΌΙ S:-16:6 16:6 06H01 ο00耷08耷06ώι 06-1 οδε 06ώι 06άι 0°°耷sl 06ώιft -:- 08 异寸 Z ί#^φ 13苳哒<0 61 ί4^φ -5^φ 91冢命命-ί#^<0 inch l ;^φ -苳哒40 2?哒40 U ί在哒4D 01 i杳哒命6 !φ^φ^ ίφ inch 5^φ ε f4哒<Β ζ!φ^4α - 201016812 (Examples 1 to 8, Comparative Example) Each of the copolymer compositions obtained in the above-mentioned various types of ancient 曰a Α (Table 2) is used as a 重I Jie, ',, 曰 曰 阿 阿 ( ( ( (Arakawa chemistry) 30 parts by weight, 0' antioxidant, Irganoxl〇l〇 (Ciba)
Specialty Chemicals 公 丄l Ί製）1重量份，以獲得各黏著劑組 成物。將其之組成示於下述表2。 吏用聚丙稀（pnme聚合物公司製；715M)a T模法來Specialty Chemicals 公l Ί) 1 part by weight to obtain each adhesive composition. The composition thereof is shown in Table 2 below.吏Use polypropylene (made by pnme polymer company; 715M) a T-mode method
將基材與各黏著査彳έ 士、 ”、成物加以共擠出成形，藉此將3 4 # mThe substrate is co-extruded with each of the adhesives, "," and thus the 3 4 # m
厚度之基材層愈6//ΤΠ TSrV 、 /、以111厚度之黏著劑層積層一體化於基 材、成形出實施例卜8、及比較例卜7之表面保護膜， 獲得捲於内徑3吋之紙芯之捲繞體。 (評價） 針對以上述方式所獲得之各表面保護膜來評價以下 項目。將該等結果示於表3 ^ (1)成膜性 〇 以目視評價經上述方式進行共擠出而製膜出之各表 面保護膜的外觀，外觀上沒有問題者記為「〇」。 (2)初期黏著力 將1各表面保護膜貼附成覆蓋具有凹凸之稜鏡片的透 鏡面#文鏡片係準備由厚度為130//m之丙烯酸樹脂所構 成且棱鏡之間距為5〇从m、高度25 " m者。貼附條件係於 至溫23<t及相對濕度50%之環境下，分別使用2kg之壓著 橡膠報以3〇〇mm/分鐘之速度加以貼附，並於該狀態下放 置30分鐘後’依據JIS Z0237，以300mm/分鐘之速度來 39 201016812 測疋25mm寬< i 8〇度剝離強度。此時之制離方向係定 棱鏡之棱線方向。蔣士卜錄士々^ 將此種方式所測得之剝離強度作為初期 黏著力。 ’ (3)經時黏著力 =室溫23。(：及相對濕度5〇%之環境下，分別使用^ 之壓者橡膠轉α 3G()mm/分鐘之速度將各表面保護膜貼附 於=)之初期黏著力評價中所用之稜鏡片之表面。之後，以 聚城酸s旨板（厚度2mm)挾持貼附有表面保護膜之稜鏡片， 並施加6.0X i…服之壓力，再以該狀態於㈣及相對濕 度90%之環境下放置48小時。將其於室溫中取出，放置 =分鐘後依據jis Ζ0237, α 300mm/分鐘之速度來測定 25ttlm寬之180度剝離強度。 將此種方式所測得之剝離強度作為經時黏著力，由初 率)著力以下述式來算出經時黏著力的變化率（黏著亢進 變化率（黏著亢進率）=(經時黏著力/初期黏著力）χ丨〇〇 (4)展開力 Ο 除了變更回捲速度之外，係針對實施例及比較例之各 $面保護膜之50mm寬之捲繞體，依據JIS ζ〇237以 刀鐘之回捲速度來測^回捲力，並以其作為展開力。 IA2] 黏著劑組成物 共聚物组成物 增黏刺 &氧化劑~The thickness of the substrate layer is 6//ΤΠ TSrV, /, and the thickness of the adhesive layer of 111 is integrated into the substrate, and the surface protective film of Example 8 and Comparative Example 7 is formed, and the roll is obtained in the inner diameter. 3) The winding body of the paper core. (Evaluation) The following items were evaluated for each of the surface protective films obtained in the above manner. The results are shown in Table 3 ^ (1) Film-forming property 〇 The appearance of each surface protective film formed by co-extrusion by the above-described method was visually evaluated, and the appearance was not considered to be "〇". (2) Initial adhesion force Each surface protection film is attached to a lens surface covering the ruthenium having irregularities. The lens is prepared by an acrylic resin having a thickness of 130/m and the distance between the prisms is 5 〇 from m. , height 25 " m. The attachment conditions were attached to a temperature of 23 ° t and a relative humidity of 50%, respectively, using a 2 kg compression rubber to be attached at a speed of 3 mm/min, and placed in this state for 30 minutes. According to JIS Z0237, the peeling strength of 25 mm width < i 8 twist was measured at a speed of 300 mm/min 39 201016812. The direction of the separation at this time is the direction of the ridge of the prism. Jiang Shi Bu Shi Shi 々 ^ The peel strength measured in this way is used as the initial adhesion. (3) Adhesive strength over time = room temperature 23. (: and the relative humidity of 〇5% of the environment, respectively, using the pressure of the rubber of the pressure of α 3G () mm / minute, each surface protective film attached to the initial adhesion evaluation of =) surface. After that, the enamel sheet with the surface protective film attached thereto was held by a poly-city s board (thickness: 2 mm), and a pressure of 6.0×i... was applied, and then placed in an environment of (4) and a relative humidity of 90%. hour. It was taken out at room temperature, and after standing for 1 minute, the 180-degree peel strength of 25 ttlm width was measured in accordance with jis Ζ0237, α 300 mm/min. The peel strength measured in this way is used as the time-dependent adhesive force, and the rate of change of the adhesive force over time is calculated by the following formula (the rate of change in adhesion (adhesion rate) = (time-dependent adhesion / Initial adhesion) χ丨〇〇 (4) Deployment force In addition to changing the rewinding speed, it is a 50 mm wide wound body of each of the $face protection films of the examples and the comparative examples, and a knife according to JIS ζ〇237 The rewinding speed of the clock is used to measure the rewinding force and use it as the developing force. IA2] Adhesive composition Copolymer composition viscous thorn & oxidant~
201016812201016812
[表3][table 3]
成膜性 黏著力 展開力 總合評 價 初期 經時 變化率 (N/25 mm) 判定 (N/25 mm) (%) 判定 (N/50mm) 判定 實施例1 〇 0.18 〇 0.38 211 〇 1.7 ◎ 〇 實施例2 〇 0.16 〇 0.34 213 〇 1.5 ◎ 〇 實施例3 〇 0.18 〇 0.27 150 ◎ 1.2 ◎ ◎ 實施例4 〇 0.12 〇 0.39 325 〇 1.8 ◎ 〇 實施例5 〇 0.14 〇 0.22 157 ◎ 1.4 ◎ ◎ 實施例6 〇 0.15 〇 0.19 127 ◎ 1.2 ◎ ◎ 實施例7 〇 0.14 〇 0.65 464 〇 1.1 ◎ 〇 實施例.3 〇 0.11 〇 0.20 181 ◎ 3.3 〇 〇 比較例1 〇 0.10 〇 0.20 200 〇 5.0 X X 比較例2 〇 0.40 〇 0.63 158 ◎ 4.0 X X 比較例3 X - - - - - - X 比較例4 〇 0.15 〇 0.21 140 ◎ 3.6 X X 比較例5 X - - - - - - - - 比較例6 X - - - - - - - - 比較例7 〇 0.10 〇 0.20 200 〇 5.0 X X 實施例4 合成例4 100 30 1 實施例5 合成例5 100 30 1 實施例6 合成例6 100 30 1 實施例7 合成例7 100 30 1 實施例8 合成例23 100 30 1 比較例1 合成例8 100 30 1 比較例2 合成例9 100 30 1 比較例3 合成例10 100 30 1 比較例4 合成例20 100 30 1 比較例5 合成例21 100 30 1 比較例6 合成例22 100 30 1 比較例7 合成例24 100 30 1 <判定基準> 黏著力（初期） 〇（良）：0.1N/25mm以上 x(不良）：未滿 0.1N/2 5mm 黏著力（變化率） ◎(優）：未滿200% 〇（良）：200%以上且500%以下 41 201016812 x(不良）：超過500% 展開力 ◎(優）：未滿 2.0N/50mm 〇（良）：2.0N/50mm以上且3.5N/50mm以下 x(不良）：超過 _3.5N/50mm (實辑例9) 於合成例4之共聚物組成物1〇〇重量份配合作為增黏 劑之阿魯空P1 〇〇(荒川化學工業公司製）18重量份、作為抗 氧化劑之 Irganoxl〇l〇(Ciba Specialty Chemicals 公司製）1 ❹ 重量份、作為紫外線吸收劑之其努賓326(Ciba Specialty Chemicals公司製）〇.5重量份’並加以混練，藉此獲得黏 著劑組成物。 使用聚丙烯（prime聚合物公司製J715M)以τ模法來將 基材與各黏著劑組成物加以共擠出成形，藉此將34 # m厚 度之基材層與6/zm厚度之黏著劑層積層一體化於基材， 以成形出表面保護膜，獲得捲於内徑3吋之紙芯之捲繞體。 (實施例10、11、1 3、比較例8〜1 0) ❹ 以表4所示方式來配合黏著劑組成物，並以與實施例 9同樣之方法獲得表面保護膜之捲繞體。 (實施例12) 使用於合成例7之共聚物組成物1〇〇重量份配合有作 為增黏劑之庫里阿隆P125(YASUHARA CHEMICAL公司 製）40重量知之黏著劑組成物之外，係以與實施例9相同 之方法獲得表面保護膜之捲繞體。 42 201016812 (評價） 針對以上述方式所獲得之各表面保護膜進行以下項 目之評價。 將該等結果示於表5。 (1) tan 5峰值溫度 藉由動黏彈性光譜測定裝置（IT計測控制公司製，品 號：爾-200)以頻率1〇Ηζ、昇溫迷度代/分鐘且_飢〜8〇 ❹C之fe圍内來測定黏著劑層之黏彈性光譜，並求出—占 為最大時之溫度（tan占峰值溫度）。 (2) 初期黏著力 將實施例及比較例之各表面保護膜貼附成覆蓋具有 凹凸之稜鏡片的透鏡面。稜鏡片係準備由厚度^ 13〇㈣ 之丙烯酸樹脂所構成且稜鏡之間距（心叫為5〇心、高度 3〇#m者。貼附條件係於室溫23$)(：及相對濕度5〇%之環境 下，分別使用2kg之壓著橡膠輥以3〇〇mm/分鐘之速度加 © 乂貼附，並於該狀態下放置3〇分鐘後，依據則， 、〇〇mm/为鐘之速度來測定25mm寬之180度剝離強度。 〜寺之剝離方向係、定為稜鏡之稜線方向。將此種方式所測 得之剝離強度作為初期黏著力。 (3)展開力 除了變更回捲速度之外，係針對實施例及比較例之各 八面保護膜之50mm寬之捲繞體，依據JIS z〇237以汕… 里之回捲速度來測定高速回捲力，並以其作為展開力。 43 201016812 [表4] 黏著劑組成物 共聚物組成物 增黏劑 抗氧化劑 紫外線吸收劑 (重量份） (重量份） (重量份） (重量份） 實施例9 合成例4 100 18 1 0.5 實施例10 合成例4 100 50 1 0.5 實施例11 合成例6 100 30 1 0.5 實施例12 合成例7 100 40 1 0.5 實施例13 合成例4 100 40 1 0.5 比較例8 合成例8 100 8 1 0.5 比較例9 合成例9 100 30 1 0.5 比較例10 合成例 100 50 1 0.5 [表5]Film-forming adhesive force development force evaluation Initial time-dependent change rate (N/25 mm) Judgment (N/25 mm) (%) Judgment (N/50 mm) Judgment Example 1 〇0.18 〇0.38 211 〇1.7 ◎ 〇 Example 2 〇 0.16 〇 0.34 213 〇 1.5 ◎ 〇 Example 3 〇 0.18 〇 0.27 150 ◎ 1.2 ◎ ◎ Example 4 〇 0.12 〇 0.39 325 〇 1.8 ◎ 〇 Example 5 〇 0.14 〇 0.22 157 ◎ 1.4 ◎ ◎ Example 6 〇 0.15 〇 0.19 127 ◎ 1.2 ◎ ◎ Example 7 〇 0.14 〇 0.65 464 〇 1.1 ◎ 〇 Example 3. 〇 0.11 〇 0.20 181 ◎ 3.3 〇〇 Comparative Example 1 〇 0.10 〇 0.20 200 〇 5.0 XX Comparative Example 2 〇 0.40 〇0.63 158 ◎ 4.0 XX Comparative Example 3 X - - - - - - X Comparative Example 4 〇 0.15 〇 0.21 140 ◎ 3.6 XX Comparative Example 5 X - - - - - - - - Comparative Example 6 X - - - - - - - - Comparative Example 7 〇 0.10 〇 0.20 200 〇 5.0 XX Example 4 Synthesis Example 4 100 30 1 Example 5 Synthesis Example 5 100 30 1 Example 6 Synthesis Example 6 100 30 1 Example 7 Synthesis Example 7 100 30 1 Example 8 Synthesis Example 23 100 30 1 Comparative Example 1 Synthesis Example 8 100 30 1 Comparative Example 2 Synthesis Example 9 100 30 1 Comparative Example 3 Synthesis Example 10 100 30 1 Comparative Example 4 Synthesis Example 20 100 30 1 Comparative Example 5 Synthesis Example 21 100 30 1 Comparative Example 6 Synthesis Example 22 100 30 1 Comparative Example 7 Synthesis Example 24 100 30 1 <Criteria for determination> Adhesion (initial) 〇(good): 0.1N/25mm or more x (bad): less than 0.1N/2 5mm Adhesion (change rate) ◎(excellent): less than 200% 〇 (good): 200% or more and 500% or less 41 201016812 x (bad): more than 500% Deployment force ◎ (excellent): less than 2.0N/50mm 〇 (good): 2.0N/50mm or more and 3.5N/50mm The following x (defective): more than _3.5 N / 50 mm (Real Example 9) The copolymer composition of Synthesis Example 4 was blended in an amount of 1 part by weight of Arukong P1 as a tackifier (Arakawa Chemical Industry Co., Ltd. 18 parts by weight, Irganoxl® (manufactured by Ciba Specialty Chemicals Co., Ltd.) as an antioxidant, 1 part by weight, and Nubene 326 (manufactured by Ciba Specialty Chemicals Co., Ltd.) as a UV absorber, 5 parts by weight, and kneaded Thereby, an adhesive composition is obtained. The base material and each of the adhesive compositions were co-extruded by a τ method using polypropylene (J715M, manufactured by Prime Polymer Co., Ltd.), whereby a substrate layer of 34 #m thickness and an adhesive of 6/zm thickness were used. The laminated layer was integrated into the substrate to form a surface protective film, and a wound body wound around a paper core having an inner diameter of 3 Å was obtained. (Examples 10, 11, and 13 and Comparative Examples 8 to 10) 黏 The adhesive composition was blended in the manner shown in Table 4, and a wound body of the surface protective film was obtained in the same manner as in Example 9. (Example 12) The copolymer composition of the synthesis example 7 was used in an amount of 1 part by weight, based on 40 parts by weight of a Curelon P125 (manufactured by YASUHARA CHEMICAL Co., Ltd.) as a tackifier. A wound body of the surface protective film was obtained in the same manner as in Example 9. 42 201016812 (Evaluation) The following items were evaluated for each surface protective film obtained in the above manner. These results are shown in Table 5. (1) The peak temperature of tan 5 is measured by a dynamic viscoelasticity spectrometer (manufactured by IT Measurement and Control Co., Ltd., item number: er-200) with a frequency of 1 〇Ηζ, a temperature increase of the degree of generation / minute and _ hunger ~ 8 〇❹ C fe The viscoelastic spectrum of the adhesive layer was measured and the temperature at which the maximum was taken (tan as the peak temperature) was determined. (2) Initial adhesion Each surface protective film of the examples and the comparative examples was attached to a lens surface covering a ruthenium having irregularities. The enamel film is prepared from an acrylic resin having a thickness of 13 〇 (4) and the distance between the 稜鏡 (the heart is called 5 〇 heart, the height is 3 〇 #m. The attachment condition is at room temperature 23$) (: and relative humidity In an environment of 5〇%, use a 2kg pressure rubber roller to attach it at a speed of 3〇〇mm/min, and place it in this state for 3 minutes, then, 〇〇mm/ The speed of the clock is used to measure the peel strength of 180 degrees at a width of 25 mm. The peeling direction of the temple is determined as the ridgeline direction of the ridge. The peel strength measured by this method is used as the initial adhesion. (3) The expansion force is changed. In addition to the rewinding speed, the high-speed rewinding force is measured in accordance with JIS z〇237 for the winding body of 50 mm width of each of the eight-sided protective films of the examples and the comparative examples, and 43 201016812 [Table 4] Adhesive composition Copolymer composition Tackifier Antioxidant UV absorber (parts by weight) (parts by weight) (parts by weight) (parts by weight) Example 9 Synthesis Example 4 100 18 1 0.5 Example 10 Synthesis Example 4 100 50 1 0.5 Example 11 Synthesis Example 6 100 30 1 0.5 Example 12 Synthesis Example 7 100 40 1 0.5 Example 13 Synthesis Example 4 100 40 1 0.5 Comparative Example 8 Synthesis Example 8 100 8 1 0.5 Comparative Example 9 Synthesis Example 9 100 30 1 0.5 Comparative Example 10 Synthesis Example 100 50 1 0.5 [Table 5]
TanS/峰值溫度 初期黏著力 展開力 總合 評價 CC) (N/25mm) 判定 (N/50mm) 判定 實施例9 -10 0.12 〇 3.2 〇 〇 實施例10 12 0.20 〇 1.0 ◎ ◎ 實施例11 5 0.10 〇 1.5 ◎ ◎ 實施例12 19 0.11 〇 0.8 ◎ ◎ 實施例13 20 0.10 〇 0.7 ◎ ◎ 比較例8 -35 0.20 〇 5.0 X X 比較例9 -22 0.40 〇 4.0 X X 比較例10 25 0.01 X 0.4 ◎ X <判定基準>TanS/peak temperature initial adhesion development force evaluation CC) (N/25mm) Judgment (N/50mm) Judgment Example 9 -10 0.12 〇3.2 〇〇Example 10 12 0.20 〇1.0 ◎ ◎ Example 11 5 0.10 〇 1.5 ◎ ◎ Example 12 19 0.11 〇 0.8 ◎ ◎ Example 13 20 0.10 〇 0.7 ◎ ◎ Comparative Example 8 - 35 0.20 〇 5.0 XX Comparative Example 9 -22 0.40 〇 4.0 XX Comparative Example 10 25 0.01 X 0.4 ◎ X < ;Judgement criteria>
初期黏著力 〇（良）：0.1N/25mm以上 x(不良）：未滿 0.1N/25mm 展開力 ◎(優）：2.5N/50mm 以下 〇（良）：3.5N/50mm以下 x(不良）：超過 3.5N/50mm (實施例14) 44 201016812 黏著劑層： 於合成例4之共聚物組成物1 00重量份中配合作為增 黏劑之阿魯空P100(荒川化學工業公司製）50重量份、作為 苯乙烯系嵌段相補強劑之ENDEX155(Eastman Chemical公 司製）1〇重量份、作為抗氧化劑之Irganoxl010(Ciba Specialty Chemicals公司製）1重量份並加以混練，藉此獲 得黏著劑組成物。 基材層： ❹ 以T模法將聚丙稀所構成之基材（prime聚合物公司製 J71 5M)與上述所得之黏著劑組成物加以共擠出，再將積層 一體化有34 μιη厚度之聚丙烯基材層與6/zm厚度之黏著 劑之表面保護黏著片捲於内徑3吋之紙芯以獲得捲繞體。 (實施例1 5〜1 9、比較例1 1〜1 4) 以下述表6所示之方式配合黏著劑組成物，並以與實 施例14相同之方式來護得表面保護膜之捲繞體。 ❹ 又，表6中之「St/黏著劑層（重量°/〇)」係表示共聚物 組成物及苯乙烯系嵌段相補強劑整體之芳香族烯基化合 物皁位之合計重量相對於黏著劑之重量的比例（芳香族烯 基化合物單位含有率）。又’ 「St/黏著劑層（_TF)(重量％)」 係表不共聚物組成物及苯乙烯系嵌段相補強劑整體之芳 香族稀基單位之合計重量相對於共聚物組成物與笨乙稀 系欲段相補強劑之合計重量的比例。 (評價） 針對上述方式所獲得之各表面保護膜進行以下以下 45 201016812 項目之評價。將該等結果示於表7。 (1) tan <5峰值溫度 藉由動黏彈性光譜測定裝置（IT計測控制公司製，品 號：DVA-200)以頻率1〇Ηζ'昇溫速度/分鐘且_5〇乞〜 C之範圍内來測定黏著劑層之黏彈性光譜，並求出以打占 為'最、大時之溫度（tan (5..峰值溫度）。 (2) 初期黏著力 將實施例及比較例之各表面保護膜貼附成覆蓋具有 凹凸之稜鏡片的透鏡面。稜鏡片係準備由厚度為i3〇#m 之丙烯酸樹脂所構成且稜鏡之間距為5〇/^m、高度3〇"m 者。貼附條件係於室溫23〇c及相對濕度5〇%之環境下，分 別使用2kg之壓著橡膠輥以3〇〇mm/分鐘之速度加以貼 附，並於該狀態下放置1小時後，依據JIS Z0237，以 300mm/分鐘之速度來測定25mm寬之18〇度剝離強度。此 時之1丨離方向係定為稜鏡之棱線方向。將此種方式所測得 之剝離強度作為初期黏著力。 (3) 經時黏著力 於室溫231及相對濕度50%之環境下，分別使用2kg 之磨著橡膠輥以3〇〇mm/分鐘之速度將各表面保護膜貼附 於（2)之初期黏著力評價中所用之稜鏡片之表面。之後，以 聚*厌酸S旨板（厚度2mm)挾持貼附有表面保護膜之棱鏡片， 並施加6.〇xi〇-3MPa之壓力，再以該狀態於6〇。匸及相對濕 度90%之環境下放置48小時。將其於室溫中取出，放置 30刀鐘後依據jig z〇237，以300mm/分鐘之速度來測定 46 201016812 25mm寬之180度剝離強度。 將此種方式所測得之剝離強度作為經時黏著力，由初 期黏著力以下述式來算出經時黏著力的變化率（黏著亢進 率）。 變化率（黏著亢進率）=(經時黏著力/初期黏著力）x 100 (4)展開力 除了變更回捲速度之外，係針對實施例及比較例之各 表面保護膜之50mm寬之捲繞體，依據JIS Z0237以20m/ ® 分鐘之回捲速度來測定回捲力，並以其作為展開力。 [表6]Initial adhesion 〇 (good): 0.1N/25mm or more x (bad): less than 0.1N/25mm Deployment force ◎ (excellent): 2.5N/50mm or less 良 (good): 3.5N/50mm or less x (bad) : more than 3.5 N / 50 mm (Example 14) 44 201016812 Adhesive layer: Arukong P100 (manufactured by Arakawa Chemical Industry Co., Ltd.) as a tackifier was blended in an amount of 100 parts by weight of the copolymer composition of Synthesis Example 4 An adhesive composition was obtained by mixing one part by weight of ENDEX 155 (manufactured by Eastman Chemical Co., Ltd.) as a styrene block phase reinforcing agent, and one part by weight of Irganoxl 010 (manufactured by Ciba Specialty Chemicals Co., Ltd.) as an antioxidant, and kneading. . Substrate layer: 基材 A substrate made of polypropylene (J71 5M manufactured by Prime Polymer Co., Ltd.) was coextruded with the above-obtained adhesive composition by a T-die method, and the laminate was integrated into a thickness of 34 μm. The acryl substrate layer and the 6/zm thick adhesive surface protective adhesive sheet were wound around a paper core having an inner diameter of 3 inches to obtain a wound body. (Examples 1 to 5, Comparative Examples 1 to 1 4) The adhesive composition was blended in the manner shown in Table 6 below, and the wound body of the surface protective film was protected in the same manner as in Example 14. . ❹ In addition, the "St/adhesive layer (weight ° / 〇)" in Table 6 indicates the total weight of the aromatic olefinic compound soap of the copolymer composition and the styrene block phase reinforcing agent as a whole. The ratio of the weight of the agent (aromatic alkenyl compound unit content). Further, 'St/adhesive layer (_TF) (% by weight) is the total weight of the aromatic non-copolymer composition and the aromatic dilute unit of the styrene block-reinforcing agent as a whole, relative to the copolymer composition and stupid The ratio of the total weight of the reinforcing agent of the ethylene phase. (Evaluation) Each of the surface protective films obtained in the above manner was evaluated as follows in the following 45 201016812 item. These results are shown in Table 7. (1) tan <5 peak temperature by dynamic viscoelasticity spectrometer (manufactured by IT Measurement and Control Co., Ltd., article number: DVA-200) at a frequency of 1 〇Ηζ 'temperature increase rate / minute and _ 5 〇乞 ~ C range The viscoelastic spectrum of the adhesive layer was measured internally, and the temperature at which the occupancy was the 'most and large time (tan (5.. peak temperature) was determined. (2) Initial adhesion The surfaces of the examples and comparative examples were determined. The protective film is attached to a lens surface covering the embossed sheet. The enamel sheet is prepared from an acrylic resin having a thickness of i3 〇 #m and the distance between the ridges is 5 〇 / ^ m, and the height is 3 〇 " The attachment conditions were adhered to a room temperature of 23 ° C and a relative humidity of 5% by weight, respectively, using a 2 kg pressure-applying rubber roller at a speed of 3 〇〇 mm / minute, and placed in this state for 1 hour. Then, according to JIS Z0237, the peel strength of 18 mm of 25 mm width was measured at a speed of 300 mm/min. At this time, the direction of the 丨 is determined to be the ridge line direction of the 稜鏡. The peel strength measured in this manner. As the initial adhesion. (3) When the adhesion is at room temperature 231 and relative humidity 50%, use 2kg respectively. Each surface protective film was attached to the surface of the ruthenium used in the initial adhesion evaluation of (2) at a speed of 3 〇〇mm/min. After that, a poly* analytic S plate (thickness: 2 mm) was attached. The prism sheet to which the surface protective film is attached is attached, and a pressure of 6. 〇 xi 〇 -3 MPa is applied, and then placed in an environment of 6 〇 in a state of 〇 and 90% relative humidity for 48 hours. After taking out, place 30 knives and then measure the peel strength of 46 201016812 25mm width according to jig z〇237 at a speed of 300mm/min. The peel strength measured by this method is used as the time-dependent adhesive force. The adhesion rate is calculated by the following formula to calculate the rate of change of adhesion over time (adhesion rate). Rate of change (adhesion rate) = (time-dependent adhesion/initial adhesion) x 100 (4) Expansion force in addition to changing the rewinding speed In addition, for the wound body of 50 mm width of each surface protective film of the examples and the comparative examples, the rewinding force was measured at a rewinding speed of 20 m/min according to JIS Z0237, and was used as a developing force. 6]
黏著劑組成物 St/黏著劑 層(-TF) St/黏著劑 層 共聚物組成物 增黏劑 St系嵌段 補強劑 抗氧化劑 (重量份） (重量 份） (重量份） (重量份） (重量％) (重量％) 實施例14 合成例4 100 50 10 1 36 25 實施例15 合成例6 100 30 0 1 40 31 實施例16 合成例6 100 30 15 1 47 38 實施例17 合成例7 100 30 10 1 45 35 實施例1S 合成例5 100 30 25 1 48 38 實施例19 合成例6 100 20 45 1 59 51 比較例11 合成例12 100 30 5 1 23 18 比較例12 合成例11 100 20 25 1 60 51 比較例13 合成例8 100 30 10 1 18 14 比較例14 合成例11 100 30 0 1 55 38 [表7] tan3 峰 值溫度 黏著力 展開力 總合 評價 初期 經時 變化率 CC) (N/25mm) 判定 (N/25mm) (%) 判定 (N/50mm) 判定 實施例14 12 0.16 〇 0.42 263 〇 0.5 〇 〇 實施例15 5 0.11 〇 0.14 127 ◎ 0.9 〇 ◎ 實施例16 6 0.10 〇 0.12 120 ◎ 0,7 〇 ◎ 47 201016812Adhesive composition St/adhesive layer (-TF) St/adhesive layer copolymer composition tackifier St-block reinforcing agent antioxidant (parts by weight) (parts by weight) (parts by weight) (parts by weight) % by weight) (% by weight) Example 14 Synthesis Example 4 100 50 10 1 36 25 Example 15 Synthesis Example 6 100 30 0 1 40 31 Example 16 Synthesis Example 6 100 30 15 1 47 38 Example 17 Synthesis Example 7 100 30 10 1 45 35 Example 1S Synthesis Example 5 100 30 25 1 48 38 Example 19 Synthesis Example 6 100 20 45 1 59 51 Comparative Example 11 Synthesis Example 12 100 30 5 1 23 18 Comparative Example 12 Synthesis Example 11 100 20 25 1 60 51 Comparative Example 13 Synthesis Example 8 100 30 10 1 18 14 Comparative Example 14 Synthesis Example 11 100 30 0 1 55 38 [Table 7] Tan3 Peak temperature adhesion force development force evaluation Initial time change rate CC) (N /25mm) Judgment (N/25mm) (%) Judgment (N/50mm) Judgment Example 14 12 0.16 〇0.42 263 〇0.5 〇〇Example 15 5 0.11 〇0.14 127 ◎ 0.9 〇◎ Example 16 6 0.10 〇0.12 120 ◎ 0,7 〇◎ 47 201016812
-14 ~Τ~ ~2f 0.12 〇 0.5 417 〇 0.6 〇 〇 0.11 〇 0.15 136 ◎ 0.9 〇 ◎ 0.06 Δ 0.11 183 ◎ 0.5 〇 Δ 0.10 ------ 〇 0.22 220 〇 3.9 X X 0.02 X 0.25 1250 X 0.8 〇 X 0.10 --- 〇 0.2 200 〇 5.0 X X 0.09 Δ 2.40 2667 X 0.3 〇 X 實施例π 實施例18 實施例19 比較例11 比較例12 ΙΪ較例13 比較例14 <判定基準> 黏著力(初期） 〇(良）：0.1N/25mm 以上-14 ~Τ~ ~2f 0.12 〇0.5 417 〇0.6 〇〇0.11 〇0.15 136 ◎ 0.9 〇◎ 0.06 Δ 0.11 183 ◎ 0.5 〇Δ 0.10 ------ 〇0.22 220 〇3.9 XX 0.02 X 0.25 1250 X 0.8 〇X 0.10 --- 〇0.2 200 〇5.0 XX 0.09 Δ 2.40 2667 X 0.3 〇X Example π Example 18 Example 19 Comparative Example 11 Comparative Example 12 ΙΪComparative Example 13 Comparative Example 14 <Criteria for Determination> Adhesion (Initial) 〇 (good): 0.1N/25mm or more
△(可）：〇.〇5N/25mm 以上且未滿 0.1N/25mm χ(τ 可）：未滿 〇 〇5Ν/25ηιιη 黏著力（變化率） © (優）：未滿2〇〇% 〇(良）：200%以上且500%以下 x(不良）：超過500% 展開力 〇（良）：3.5N/5 0mm以下 x(不良）··超過 3.5N/50mm 〇 (實施例20) 以T模法進行共擠出，以成膜出基材層（厚度科#爪)/ 黏著劑層（厚度6ym)之稜鏡片用表面保護膜（寬7〇〇mm)， 而獲得卷長l〇〇m之捲繞體。用以形成黏著劑層之材料係 使用··於合成例13之共聚物組成物1〇〇重量份中配合作 為增黏劑之軟化點i25t：之脂環式飽和石油樹脂阿魯空 P 125(荒川化學工業公司製）3〇重量份、作為苯乙稀系嵌段 48 201016812 相補強劑之ENDEXl 55(Eastman Chemical公司製）20重量 伤、作為抗氧化劑之 Irganoxl010(Ciba Specialty Chemicals 公司製）1重量份、作為紫外線吸收劑之其努賓326(Ciba Specialty Chemicals公司製）0.5重量份，並以雙軸擠出機 加以混練再製成為粒狀者。用以形成基材層之材料係使 用：將100重量份之嵌段PP與膜（當作為基材之嵌段聚丙 稀（嵌段PP)為1 〇〇重量份時，於黏著劑層中含有作為黏著 劑之合成例13之共聚物組成物1 〇 〇重量份、及作為增黏 劑之阿魯空P125(荒川化學工業公司製）30份、作為苯乙烯 系喪段相補強劑之ENDEX155(Eastman Chemical公司 製）20重量份、作為抗氧化劑之Irgan〇xl〇1〇(Ciba Chemicals公司製}1重量份、作為紫外線吸收劑之其努賓 326(Ciba Specialty Chemicals 公司製）0.5 重量份）為 了調整 成形時捲繞於輥之狀態而膜兩端部經修整（trimming)之部 分1 〇重量份加以混合之後，以雙軸擠出機進行混練再製 成粒狀者。 (實施例21〜25) 以下述表8所示方式改變增黏劑的量與笨乙稀系喪段 相補強劑（本說明書中有時會簡寫為st系嵌段補強劑）的 量’除此之外，係以與實施例2〇相同之方式來獲得稜鏡 片用表面保護膜之捲繞體。 又，表8中之「St/黏著劑（重量％)」亦表示共聚物組 成物及苯乙烯系嵌段相補強劑整體之芳香族綿基單位之 合計重量相對於黏著劑之重量的比例（芳香族稀基化合物 49 201016812 單位含有率）β (評價） 針對下述（1)〜(4)所記載之項目來評價實施例2〇〜乃之 表面保護膜。結果示於表9。 (1) 初斯黏著力 將實施例及比較例，之各表面保護韻貼附成覆蓋具有 凹凸之稜鏡片的透鏡面。稜鏡片係準備由厚度為13〇#加 之丙烯酸樹脂所構成且稜鏡之間距為5(^m、高度3〇//m 者。貼附條件係於室溫23C及相對濕度50%之環境下，分© 另J使用2kg之壓著橡膠輥以3〇〇mm/分鐘之速度加以貼 附’並於該狀態下放置30分鐘後，依據JIS Z0237，以 300mm/分鐘之速度來測定25mm寬之ι8〇度剝離強度。此 時之剝離方向係定為稜鏡之稜線方向。將此種方式所測得 之剝離強度作為初期黏著力。 (2) 經時黏著力 於室溫23°C及相對濕度50%之環境下，分別使用2kg 之壓著橡膠輥以300mm/分鐘之速度將實施例及比較例之® 各表面保護膜貼附於（丨）之初期黏著力評價中所用之稜鏡 片之表面。之後’以聚碳酸酯板（厚度2mm)挾持貼附有表 面保"蔓膜之棱鏡片’並施加〇. 3n/cm2之壓力，再以該狀態 於7〇C之環境氣氛下放置24小時。之後，將其於室溫23 C及相對濕度5〇%的環境下靜置1小時後，依據jis z〇237 ’以300mm/分鐘之速度來測定25mm寬之180度剝 離強度。以此種方式所測得之剝離強度作為經時黏著力， 50 201016812 並由初期黏著力以下述式來具出經時黏著力的變化率（黏 著充進率）。 變化率（黏著亢進率）==(經時黏著力/初期黏著力）χ〗〇〇 (3) 儲藏彈性模數G’△ (可): 〇.〇5N/25mm or more and less than 0.1N/25mm χ(τ 可): under 〇〇5Ν/25ηιιη adhesion (rate of change) © (excellent): less than 2〇〇% 〇 (good): 200% or more and 500% or less x (bad): more than 500% Deployment force (good): 3.5N/5 0mm or less x (bad) · more than 3.5N/50mm 实施 (Example 20) The T-die method was co-extruded to form a surface protective film (width: 7 mm) of the base material layer (thickness #haw) / adhesive layer (thickness: 6 μm), and the roll length was obtained.卷绕m winding body. The material for forming the adhesive layer was used in combination with the softening point i25t of the tackifier in the copolymer composition of Synthesis Example 13: the alicyclic saturated petroleum resin Arukong P 125 ( 〇 55 化学 2010 2010 END END END END END END END END END END END END END END END END END END END END END END END END END END END END END END END END END END END END END END END END END END END END END END END END END END END END END END END END END END END END 0.5 parts by weight of Nubbin 326 (manufactured by Ciba Specialty Chemicals Co., Ltd.) as a UV absorber, and kneaded by a twin-screw extruder to obtain pellets. The material for forming the substrate layer is used in the adhesive layer when 100 parts by weight of the block PP and the film (when the block polypropylene (block PP) as the substrate is 1 part by weight) 1 part by weight of the copolymer composition of Synthesis Example 13 as an adhesive, and 30 parts of Arukong P125 (manufactured by Arakawa Chemical Industries Co., Ltd.) as a tackifier, and ENTEX155 as a styrene-based tonic phase reinforcing agent ( 20 parts by weight of Irgan® xl〇1〇 (manufactured by Ciba Chemicals Co., Ltd.) as an antioxidant, and Nubene 326 (manufactured by Ciba Specialty Chemicals Co., Ltd.) as an ultraviolet absorber (0.5 parts by weight) The portion which is wound around the roll at the time of molding and the trimmed portions at both ends of the film are mixed and mixed, and then kneaded by a twin-screw extruder to be granulated. (Examples 21 to 25) The amount of tackifier is changed in the manner shown in Table 8 below, and the amount of the stupid ethylene-based eliminator (sometimes abbreviated as st-block reinforcing agent in the present specification) is Obtain the cymbal in the same manner as in Example 2 The winding body of the surface protective film. The "St/adhesive (% by weight)" in Table 8 also indicates the total weight of the aromatic siloxane unit of the copolymer composition and the styrene block phase reinforcing agent as a whole. The ratio of the weight of the adhesive (aromatic thin compound 49 201016812 unit content ratio) β (evaluation) The surface protective film of Example 2〇 was evaluated for the items described in the following (1) to (4). The results are shown in Table 9. (1) Initial adhesion The surface protection of each of the examples and the comparative examples was attached to a lens surface covering the embossed sheet. The enamel sheet was prepared to have a thickness of 13 〇 # plus acrylic. Resin consisting of 5 (^m, height 3〇//m). The attachment conditions are in the environment of room temperature 23C and relative humidity 50%, and the other J uses 2kg of pressed rubber roller. After attaching at a speed of 3 〇〇mm/min and placing it in this state for 30 minutes, the peel strength of 25 mm wide was measured at a speed of 300 mm/min according to JIS Z0237. It is defined as the direction of the ridge line. The stripping measured in this way Degree as the initial adhesion. (2) The adhesion of the examples and comparative examples was carried out at a rate of 300 mm/min using a 2 kg pressing rubber roller in an environment of room temperature 23 ° C and a relative humidity of 50%. Each surface protective film was attached to the surface of the ruthenium used for the evaluation of the initial adhesion of (丨). Then, a polycarbonate plate (thickness: 2 mm) was attached and attached with a surface-protected prism sheet of a vine film and applied. 3. The pressure of 3 n/cm 2 was placed in this state for 24 hours under an ambient atmosphere of 7 ° C. Thereafter, the mixture was allowed to stand in an environment of room temperature 23 C and a relative humidity of 5 〇% for 1 hour, and then a 180-degree peeling strength of 25 mm width was measured at a speed of 300 mm/min in accordance with jis z〇237 '. The peel strength measured in this manner is used as the adhesive strength over time, 50 201016812, and the rate of change of the adhesive force over time (adhesion charge rate) is determined by the initial adhesive force by the following formula. Rate of change (adhesion rate) == (time-dependent adhesion/initial adhesion) χ〗 〇〇 (3) Storage elastic modulus G’
藉由動黏彈性光譜測定裝置（IT計測控制公司製，品 號.DVA-200)以頻率1 Hz、昇溫速度3°C /分鐘且- 50°C〜+1 50 c之範圍内來測定黏著劑層的儲藏彈性模數，並求出7〇 C時之儲藏彈性模數g，。 (4) 滲入量 在室溫23°C及相對濕度50%之環境下，分別使用2kg 之壓著橡膠輥以300mm/分鐘之速度將表面保護膜貼附於 稜鏡片之表面。稜鏡片係準備稜鏡之間距為5〇#m、高度 者。之後以聚碳酸醋板（厚度2mm)挾持貼附有表面 保護膜之稜鏡片，並施加〇.3N/cm2之壓力，再以該狀態於 ㈣之環境氣氛下靜置24小時。之後，以剝離角18〇度 ❾剝離表面保護膜並以雷射顯微鏡觀察黏著劑層表面，並測 定棱鏡片之透鏡部渗入至黏著劑層之滲入深度。 滲入量係以下述計算式算出。 參入量（％) “=(棱鏡片之透鏡部渗入於黏著劑層之滲入深度）/(黏 著劑層厚度：6 y m)xl〇〇 51 201016812 [表8] 黏著劑組成物 St/黏著劑 層 共聚物組成物 增黏劑 St系嵌段 補強劑 抗氧化劑 紫外線吸收 劑 (重量份） (重量份） (重量份） (重量份） (重量份） (重量％) 實施例20 合成例Π 100 30 20 1 0.5 40 實施例21 合成例13 100 20 15 1 0.5 40 實施例22 合成例13 100 20 20 1 0.5 42 實顯23 合成例13 100 30 10 1 0.5 35 實施例24 合崴例13 100 20 10 1 0.5 38 實施例25 合成例13 100 20 0 1 1 33 [表9] 儲藏彈性模 數G’ 滲入量 黏著力 總合 評價 初期 經時 變化率 (xlO^Pa)~ (%) 判定 (N/25mm) (N/25mm) (%) 判定 實施例20 4.8 30 〇 0.12 0.16 133 ◎ ◎ 實施例21 4.6 35 〇 0.10 0.13 130 ◎ ◎ 實施例22 5.5 36 〇 0.10 0.13 130 ◎ ◎ 實施例23 4.2 53 Δ 0.14 0.28 200 〇 〇 實施例24 4.4 50 Λ 0.13 0.23 177 〇 〇 實施例25 4.0 60 Δ 0.14 0.35 250 〇 〇 <判定基準> 滲入量 〇（優）：1 %以上且未滿40% △(良）：40%以上且未滿80% x(不良）：80%以上 黏著力（變化率） ◎(優）：未滿150% 〇（良）：150%以上且300%以下 (實施例26) 以下述表10所示方式，於合成例14之共聚物組成物 1 00重量份中添加作為增黏劑之脂環式飽和石油樹脂之阿 魯空P-125(荒川化學工業公司製）30重量份，以獲得黏著 52 201016812 劑組成物。 另一方面，以τ模法將由上述黏著劑組成物所構成 黏著劑層與含有表10所示之欲段聚丙烯(嵌段ρρ)75重量 份、低密度聚乙稀（1DPE)25重量份之樹脂組成物所構成之 基材加以共擠出，以製作出卿m厚度之聚丙稀基材與6 以m厚度之黏著劑層經積層一體化所成之表面保護膜。 (實施例27〜28、以及比較例15〜19) ❹ 以下述表10所示方式變更黏著劑層之組成及厚度， 除此之外，係以與實施例25相同方式製作表面保護膜， 並進行評價。增黏劑全部選用阿魯空ρ_125。 又，比較例1 8之成膜性不良。 (評價） 針對該等表面保護臈以下述要領來測定及評價以下 各項： 〇於5〇 C之環境下以0_8N/cm2之力將直徑400" m及 ❹阿度之突起物壓於貼附有表面保護膜之稜鏡片24 小時之棱鏡片之透鏡部滲入至黏著劑之滲入量、 2) 初期黏著力（對稜鏡面）及 3) 初期黏著力（對平坦面）。 進而於進行上述1)稜鏡片的透鏡部滲入相關評價 時，以下述要領來測定及評價以下各項： 4) 稜鏡損傷、 5) 經時黏著力（對稜鏡面） 6) 殘糊 53 201016812 再以下述要領來測定及評價以下各項： 7)展開力。 將結果示於下述表1 1。 1)渗入量 將上述所得之表面保護膜以其之黏著劑層面與稜鏡 片之透鏡面相接的方式加以姑附，以製作試驗片。棱鏡片 係準備透鏡部為丙烯酸樹脂所構成且片體為厚度 j聚對笨二甲酸乙二醇酯所構成而稜鏡的間距為50#m、 高度為23e„^(BEF’住友3M)。貼附時，從表面保護膜〇 之外側（亦即，與黏著劑層面相反之側）施加5.9xl〇5Pa之壓 力再以2m/分鐘之速度進行貼附。貼附係使用以下積層 機，貼附壓力係使用富士膜business (股）公司製之 壓力計（超低壓用）來測定。 積層機 製造商：MCK(株） 型式：MRK-600 輥：耐熱聚矽氧橡膠輥 © 輥徑：0 8 0 將所得之s式驗片裁切成3cmx8cm之大小以作成試樣 片。 又’為了準備評價試驗中所用之突起物，係以冷凍切 片機（cryomicrotome)將直徑ojmm之尼龍繊維切成長度 11〜13"m’並將所得之切斷片固定於載玻片上，並從其上 方以2kg報將上述所得之表面保護膜貼附於載玻月，藉此 54 201016812 將切斷片固定於載玻片與表面保護膜之間。以雷射顯微鏡 觀察其結果所形成之凸形狀（亦即，突起物），求出其之直 徑與高度。 將評價中所使用之凸形狀的直徑及高度表示於下方。 直徑：400 // m 兩度：12 // m 以使試樣片與上述具有凸形狀之表面保護膜相接的 方式將附有上述具有凸形狀之表面保護臈之载玻片置於 於試樣片之上，再於載破片上載置2〇〇g之砝碼 (〇.8N/cm2)。然後放置於5〇t之烘箱24小時。24小時後 取出試樣片，裁切出截面並以掃描型電子顯微鏡（SEM)觀 察截面，並測定稜鏡片的透鏡部滲入至黏著劑層之滲入深 度（μ m)。 由實際測得之滲入深度m)以下述式算出滲入量 (%)。 ^ 稜鏡片的透鏡部滲入至黏著劑層之滲入深度）/(黏 著劑層厚度：6 y m)xl〇〇 2)初期黏著力（對稜鏡面） 將上述所得之表面保護膜以覆蓋上述稜鏡片之透鏡 面的方式加以貼附。貼附時係以與1}相同之方式，從表面 保護膜之外側施加5.9xlQ5pa之壓力mm/分鐘之速 度將其加以貼附，然後再放置於2vc±2t之室内30分鐘。 之後，依據JIS Z0237，於與稜鏡之稜線平行之方向 55 201016812 上以剝離速度300mm/分鐘及3〇m/分鐘分別敎25顏時 之180度剝離強度（單位》N)’以作為初期黏著力（對棱 鏡）0 叼切期黏者力（對平坦面） 將5上述所得之表面保護膜以與i )相同之方式，以壓力 5.9x10 Pa及速度2111/分鐘之條件貼附於平坦之丙稀酸樹 脂板’並且放置於2rc±2〇G之室内3〇分鐘後依據jis Z0237,以剝離速度編分鐘之條件測定25咖寬時之刚 度剝離強度（單位為N)，以作為初期點著力（對平坦面）。 4)稜鏡損傷之評價 進行1)之試驗時，將從烘箱取出之表面保護膜從棱鏡 片剝離，並以目視觀察稜鏡片的透鏡面是否有因損傷而產 生之亮點。 於下述表1 〇中，斜於翁狡Adhesion was measured by a dynamic viscoelasticity spectrometer (manufactured by IT Measurement and Control Co., Ltd., product number. DVA-200) at a frequency of 1 Hz, a temperature increase rate of 3 ° C / min, and -50 ° C to +1 50 c. The storage elastic modulus of the agent layer was determined, and the storage elastic modulus g at 7 ° C was obtained. (4) Infiltration amount The surface protective film was attached to the surface of the cymbal sheet at a rate of 300 mm/min using a 2 kg pressing rubber roller in an environment of room temperature of 23 ° C and a relative humidity of 50%. The distance between the bracts is 5〇#m and the height is the height. Thereafter, the ruthenium sheet to which the surface protective film was attached was held by a polycarbonate plate (thickness: 2 mm), and a pressure of 〇3 N/cm 2 was applied thereto, and then allowed to stand in the ambient atmosphere of (4) for 24 hours. Thereafter, the surface protective film was peeled off at a peeling angle of 18 并 and the surface of the adhesive layer was observed with a laser microscope, and the penetration depth of the lens portion of the prism sheet into the adhesive layer was measured. The amount of infiltration was calculated by the following calculation formula. Inclusion amount (%) "= (the depth of penetration of the lens portion of the prism sheet into the adhesive layer) / (adhesive layer thickness: 6 ym) xl 〇〇 51 201016812 [Table 8] Adhesive composition St/adhesive Layer Copolymer Composition Tackifier St-block Reinforcer Antioxidant UV Absorber (parts by weight) (parts by weight) (parts by weight) (parts by weight) (parts by weight) (% by weight) Example 20 Synthesis Example Π 100 30 20 1 0.5 40 Example 21 Synthesis Example 13 100 20 15 1 0.5 40 Example 22 Synthesis Example 13 100 20 20 1 0.5 42 Real 23 Synthesis Example 13 100 30 10 1 0.5 35 Example 24 Synthesis Example 13 100 20 10 1 0.5 38 Example 25 Synthesis Example 13 100 20 0 1 1 33 [Table 9] Storage elastic modulus G' Infiltration amount Adhesion force evaluation Initial time change rate (xlO^Pa)~ (%) Judgment (N /25mm) (N/25mm) (%) Judgment Example 20 4.8 30 〇0.12 0.16 133 ◎ ◎ Example 21 4.6 35 〇0.10 0.13 130 ◎ ◎ Example 22 5.5 36 〇0.10 0.13 130 ◎ ◎ Example 23 4.2 53 Δ 0.14 0.28 200 〇〇 Example 24 4.4 50 Λ 0.13 0.23 177 〇〇 Example 25 4.0 60 0.14 0.35 250 〇〇<Criteria for determination> Infiltration amount 〇(excellent): 1% or more and less than 40% △(good): 40% or more and less than 80% x (bad): 80% or more adhesion ( ≥ (excellent): less than 150% 〇 (good): 150% or more and 300% or less (Example 26) 100 parts by weight of the copolymer composition of Synthesis Example 14 in the manner shown in Table 10 below 30 parts by weight of Arukong P-125 (manufactured by Arakawa Chemical Industries Co., Ltd.) as an alicyclic saturated petroleum resin as a tackifier to obtain a composition of adhesive 52 201016812. On the other hand, the above-mentioned τ mode method will be used. The adhesive composition comprising the adhesive composition and the substrate comprising the resin composition comprising 75 parts by weight of the polypropylene (block ρρ) shown in Table 10 and 25 parts by weight of low-density polyethylene (1DPE). Coextruded to produce a surface protective film formed by laminating a polypropylene substrate having a thickness of m and a thickness of 6 m. (Examples 27 to 28, and Comparative Examples 15 to 19) The composition and thickness of the adhesive layer were changed in the manner shown in Table 10 below, except that it was the same as in Example 25. The surface protective film was produced and evaluated. All the tackifiers are selected from Arukong ρ_125. Further, the film formation property of Comparative Example 18 was poor. (Evaluation) For the surface protection, the following items were measured and evaluated in the following manner: 压In the environment of 5〇C, the protrusions of diameter 400" m and ❹Adu were pressed by the force of 0_8N/cm2. The surface of the prism sheet with the surface protective film for 24 hours penetrates into the amount of penetration of the adhesive, 2) the initial adhesion (opposite surface) and 3) the initial adhesion (to the flat surface). Further, when performing the above-mentioned evaluation of the lens portion infiltration of the cymbal sheet, the following items were measured and evaluated in the following manner: 4) 稜鏡 damage, 5) aging adhesion (opposite surface) 6) 残糊53 201016812 The following items were measured and evaluated in the following manner: 7) Deployment force. The results are shown in Table 1 below. 1) Infiltration amount The surface protective film obtained above was attached in such a manner that the adhesive layer thereof was in contact with the lens surface of the enamel sheet to prepare a test piece. The prism sheet preparation lens portion is made of an acrylic resin, and the sheet body is made of a thickness j-polyethylene glycol dicarboxylate, and the pitch of the crucible is 50#m and the height is 23e^^ (BEF' Sumitomo 3M). At the time of attachment, a pressure of 5.9 x 1 〇 5 Pa was applied from the outer side of the surface protective film (i.e., the side opposite to the adhesive layer) and attached at a speed of 2 m/min. The attached layer was attached using the following laminator. The pressure is measured using a pressure gauge (ultra-low pressure) manufactured by Fujifilm Business Co., Ltd.. Multilayer machine manufacturer: MCK Co., Ltd. Type: MRK-600 Roll: Heat-resistant polyoxygen rubber roller © Roll diameter: 0 8 0 The obtained s-type test piece was cut into a size of 3 cm x 8 cm to prepare a sample piece. In order to prepare the protrusions used in the evaluation test, the nylon o-diameter of the diameter ojmm was cut into lengths by a cryomicrotome. 11~13"m' and fixing the obtained cut piece to the glass slide, and attaching the above-mentioned surface protective film to the carrier glass from 2 kg above, thereby fixing the cut piece to the glass on the basis of 54 201016812 Between the sheet and the surface protective film. The convex shape (i.e., the protrusion) formed by the result was observed by a micromirror, and the diameter and height thereof were determined. The diameter and height of the convex shape used in the evaluation were shown below. Diameter: 400 // m Two degrees :12 // m The glass slide with the surface protection 具有 having the convex shape is placed on the sample piece in such a manner that the sample piece is in contact with the surface protective film having the convex shape, and then loaded on the sample piece. The fragment was placed on a 2 〇〇g weight (〇.8N/cm2) and then placed in an oven at 5 〇t for 24 hours. After 24 hours, the sample piece was taken out, and the cross section was cut out and scanned by scanning electron microscope (SEM). The cross section was observed, and the penetration depth (μm) of the lens portion of the cymbal sheet into the adhesive layer was measured. The penetration amount (%) was calculated from the actually measured penetration depth m) by the following formula: ^ The lens portion of the cymbal sheet was infiltrated into Adhesion depth of the adhesive layer) / (adhesive layer thickness: 6 ym) xl 〇〇 2) initial adhesion (opposite surface) The surface protective film obtained above is attached in such a manner as to cover the lens surface of the above-mentioned cymbal Attached to the surface protection film in the same way as 1} Apply 5.9xlQ5pa at a pressure of mm/min on the outside and attach it to the chamber at 2vc±2t for 30 minutes. Then, according to JIS Z0237, at a peeling speed in the direction parallel to the ridgeline of the 5555 201016812 300mm/min and 3〇m/min respectively, the 180-degree peel strength (unit: N) of the 25-year-old is used as the initial adhesive force (for the prism). 0 The cut-off adhesive force (for the flat surface) The surface protective film is attached to the flat acrylic resin sheet at a pressure of 5.9×10 Pa and a speed of 2111/min in the same manner as i) and placed in a room of 2 rc ± 2 〇 G for 3 minutes. Jis Z0237, the stiffness peel strength (unit: N) at 25 coffee width was measured under the conditions of the peeling speed, and was used as the initial point (for the flat surface). 4) Evaluation of 稜鏡 damage When the test of 1) was carried out, the surface protective film taken out from the oven was peeled off from the prism sheet, and the lens surface of the enamel sheet was visually observed to have a bright spot due to damage. In Table 1 below, oblique to Weng
，：觀"·、到大量損傷之試樣標記為X 2 ’僅觀察到些微損傷的情況時標記為△符號，完全未 觀察到損傷的情況時標記為〇符號。 5)經時黏著力（對稜鏡面） 將所:寻之表面保護臈以與丨)相同之方式，以…％ 1 〇 Pa及速度2m/分鐘之條件貼 _所M m h i 附於2)之初期黏著力評價 之表面，並放置於6〇t±2t之環境星 期後，依據JIS Z0237，以 .. . 迷度3〇〇mm/分鐘來測定 25mm寬時之180度剝離強 疋 強度作為經時黏著力，並由初期點二種方式所測得之剝離 度__分鐘）以下述式來算/著力（對棱鏡面、剝離速 下述式來异出經時黏著力之變化率（黏 56 201016812 著亢進率）。 變化率（黏著亢進率）=(經時黏著力/初期黏著力（對稜 鏡面、剝離速度300mm/分鐘））χ100 6)殘糊 進行5)之試驗時，於測定剝離強度的同時一併以目視 觀察剝離後之稜鏡片的透鏡面是否有殘糊。對於透鏡面觀 察到殘糊的情況標記為X符號，完全未觀察到的情況時標 記為〇符號。結果示於下述表1 1。 ® 7)展開力 除了變更回捲速度之外，係針對實施例及比較例之各 表面保護膜之50mm寬之捲繞體，依據JIS Z0237以20m/ 分鐘之回捲速度來測定高速回捲力，並以其作為展開力。 [表 10] 黏著劑組成物 基和 _構成 共聚物組成物 增黏劑 嵌段PP 低密度PE (重量份） (重量份） (重量份） (重量份） 實施例26 合成例14 100 30 75 25 實施例27 合成例7 100 30 75 25 實施例28 合成例15 100 30 75 25 比較例15 合成例16 100 30 75 25 比較例16 合成例17 100 30 75 25 比較例17 合成例18 100 30 75 25 比較例18 合成例19 100 30 75 25 比較例19 合成例20 100 30 75 25 57 201016812 【二崦】 總合| 評價 〇 ◎ 0 X X X X X 1 展開力 判定 〇 〇 〇 〇 X 1 無法成膜 X (N/50mm p Γ—H fO 00 d d 00 CO 殘糊 評價 〇 〇 〇 〇 〇 1 〇 稜鏡損 傷評價 〇 〇 〇 〇 X 1 〇 黏著力 對棱鏡面 300mm/分鐘 變化率 判定 〇 ◎ 〇 ◎ ◎ 幽 ◎ 213 00 00 200 ο ro 00 1 5： 經時 (N/25mm) 0.17 0.15 0.16 0.02 0.22 1 0.21 初期 判定 o 〇 〇 X 〇 1 ο (N/25mm) 0.08 0.08 0.08 0.02 0.12 故 0.11 30m/分鐘| 初期 (Ν/25ππη) 0.09 0.10 0.10 0.02 0.14 汝 0.21 對平坦面 30m/分鐘 初期 (N/25mm) 00 nS ON <N 00 — iD CS <5 — 丨滲入 ♦1 (N/25mm) 〇 〇 〇 〇 X X 〇 9 ίο 00 o o CN Os 深度 (/xm) 寸 寸 寸 o |實施例26 實施例27 1實施例28 |比較例15 比較例16 I比較例17 比較例18 比較例19 201016812 <判定基準> 滲入量 〇（良）：1 %以上且未滿1 〇〇〇/〇 χ(不良）：1%未滿、100% 初期黏著力（對棱鏡面）剝離速度：3〇〇mm/分鐘 ◦(良）：0.05N/25mm 以上 x(不良）：未滿 〇.〇5N/25mm 黏著力（變化率、對稜鏡面） ◎(優）：未滿200% 〇（良）：200%以上且5〇〇 %以下 x(不良）：超過500% 稜鏡傷評價 〇：以目視無法確認出損傷 X :以目視可確認出損傷 殘糊評價 〇.以目視無法確認出殘糊的發生 X :以目視可確認出殘糊的發生 展開力 〇（良）：3.5N/50mm以下 x(不良）：超過 3.5N/50mm (實施例29),: Viewing "·, a sample with a large amount of damage is marked as X 2 ' When only a slight damage is observed, it is marked with a △ symbol, and when no damage is observed at all, it is marked with a 〇 symbol. 5) Adhesive strength over time (on the surface) The surface protection is found in the same way as 丨), with the condition of %% 〇Pa and speed 2m/min _Mmhi attached to 2) The surface of the initial adhesion evaluation was placed in an environment of 6 〇t ± 2 t, and the strength of the 180-degree peeling strength at 25 mm width was measured in accordance with JIS Z0237, using a density of 3 〇〇 mm/min. The adhesion force, and the peeling degree measured by the initial two methods __min) is calculated by the following formula (the rate of change of the adhesion force on the prism surface and the peeling speed is the following formula) 56 201016812 The rate of change (adhesion rate) = (adhesive adhesion / initial adhesion (on the surface, peeling speed 300mm / min)) χ 100 6) When the residue is tested in 5), At the same time as the peeling strength, the lens surface of the crepe sheet after peeling was visually observed to have a residual paste. The case where the residual surface is observed on the lens side is marked with an X symbol, and the case where it is not observed at all is marked with a 〇 symbol. The results are shown in Table 1 below. ® 7) The expansion force is a 50 mm wide wound body of each of the surface protective films of the examples and the comparative examples, and the high-speed rewinding force is measured at a rewinding speed of 20 m/min in accordance with JIS Z0237 in addition to the change of the rewinding speed. And use it as a deployment force. [Table 10] Adhesive composition base and _ constituent copolymer composition tackifier block PP Low density PE (parts by weight) (parts by weight) (parts by weight) (parts by weight) Example 26 Synthesis Example 14 100 30 75 25 Example 27 Synthesis Example 7 100 30 75 25 Example 28 Synthesis Example 15 100 30 75 25 Comparative Example 15 Synthesis Example 16 100 30 75 25 Comparative Example 16 Synthesis Example 17 100 30 75 25 Comparative Example 17 Synthesis Example 18 100 30 75 25 Comparative Example 18 Synthesis Example 19 100 30 75 25 Comparative Example 19 Synthesis Example 20 100 30 75 25 57 201016812 [二崦] Total | Evaluation 〇 ◎ 0 XXXXX 1 Deployment force determination 〇〇〇〇 X 1 No film formation X ( N/50mm p Γ—H fO 00 dd 00 CO residual paste evaluation 〇〇〇〇〇1 〇稜鏡 damage evaluation 〇〇〇〇X 1 〇adhesion force determination of prism surface 300mm/min change rate 〇◎ 〇◎ ◎ 幽◎ 213 00 00 200 ο ro 00 1 5: Time (N/25mm) 0.17 0.15 0.16 0.02 0.22 1 0.21 Initial judgment o 〇〇X 〇1 ο (N/25mm) 0.08 0.08 0.08 0.02 0.12 Therefore 0.11 30m/min| Initial (Ν/25ππη) 0.09 0.10 0.10 0 .02 0.14 汝0.21 For the flat surface 30m/min initial (N/25mm) 00 nS ON <N 00 — iD CS <5 — 丨Infiltration ♦1 (N/25mm) 〇〇〇〇XX 〇9 ίο 00 oo CN Os Depth (/xm) inch Example o Example 26 1 Example 28 | Comparative Example 15 Comparative Example 16 I Comparative Example 17 Comparative Example 18 Comparative Example 19 201016812 <Criteria for Judging> ): 1% or more and less than 1 〇〇〇 / 〇χ (defective): 1% is not full, 100% initial adhesion (on the prism surface) Peeling speed: 3 〇〇 mm / min ◦ (good): 0.05N /25mm or more x (bad): Not full 〇. 〇 5N/25mm Adhesion (change rate, 稜鏡 face) ◎ (Excellent): Less than 200% 〇 (good): 200% or more and 5% or less x (Bad): More than 500% Evaluation of the sputum 〇: The damage can not be confirmed by visual inspection. X: The damage can be confirmed by visual inspection. The occurrence of the residual paste cannot be confirmed visually. X: The residue can be confirmed by visual inspection. Occurrence force (good): 3.5N/50mm or less x (bad): more than 3.5N/50mm (Example 29)
點荖劑屉r廩由< 、 土何增（厚度34//IT 黏者幻層（厚度6# m)之稜鏡片用表面保 並獲得卷長10〇m之捲繞體。 、（寬700mm) 59 201016812 用以形成黏著劑層之材料係使用：於合成例13之共聚 物組成物_重量份中添加有作為增黏劑之軟化點12代 的脂環族飽和石油梏m p可魯空pi25(荒川化學工業公司 裝）3〇重量#、作為苯乙締系钱段相#強劑之 ENDEX155(East_ Chemical公司製）1〇重量份、作為抗 氧化劑之 Irgan〇xl010(Ciba Spe咖_ 公司製）ι 重量份、作為紫外線吸收劑之其努f 326(_ ¥灿丫The 荖 屉 屉 廪 廪 廪 廪 土 土 土 土 土 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 700mm) 59 201016812 The material used to form the adhesive layer is: used in the copolymer composition of Synthesis Example 13 to add alicyclic saturated petroleum hydrazine mp ru Pi25 (Arakawa Chemical Industry Co., Ltd.) 3 〇 weight #, ENDEX155 (manufactured by East_Chemical Co., Ltd.) as a benzoic acid-based phase-strength agent, 1 part by weight, Irgan 〇xl010 as an antioxidant (Ciba Spe Coffee _ Company ι) parts by weight, as a UV absorber, its Nu f 326 (_ ¥灿丫
Chemicals公司製）0.5重量份，再以雙轴擠出機加以混練並 製成粒狀者。 _ 用以形成基材層之材料係使用： 將75重量份之嵌段PP、25重量份之低密度聚乙烯 (1DPR)、及為了調整膜成形時捲繞於輥狀態而膜兩端部經 修整之。卩为（當作為基材之嵌段聚丙烯（嵌段pp)為重量 份時，於黏著劑層中含有作為黏著劑之合成例13之共聚物 組成物100重量份、及作為增黏劑之阿魯空Pl25(荒川化學 工業公司製）30份、作為苯乙烯系嵌段相補強劑之 ENDEX155(Eastman Chemical公司製）20重量份、作為抗氧Ο 化劑之 Irgan〇xi010(Ciba Specialty chemicals 公司製μ 重 直份、作為紫外線吸收劑之其努賓326(Ciba Specia][ty Chemicals公司製）0.5重量份）10重量份加以混合後再以雙 軸擠出機加以混練並製成粒狀者。 又，表12中之「St/黏著劑（重量％)」係表示共聚物組 成物及苯乙烯系嵌段相補強劑之芳香族烯基化合物單位的 合計重量相對於黏著劑之重量的比例（芳香族烯基化合物 60 201016812 單位含有率）。 (實施例30〜31、比較例2〇〜22) 以下述表12所示方式改變基材層之聚烯烴配合量及種 類、黏著劑層、共聚物組成物及苯乙烯含有率、增黏劑的 量、苯乙烯系嵌段相補強劑（亦即，st系嵌段補強劑）的量， 除此之外，係以與實施例29相同之方式獲得稜鏡片用表面 保護臈之捲繞體。 (評價） ❹ 針對下述（1)〜（6)所記載之項目來對實施例29〜31、及比 較例20〜22之表面保護膜加以評價及試驗。結果示於表！ 3。 (1) 表面粗度 Ra 係使用（SIJRFTEST Sj_301、Mitsutoyo 公司製）以下述測定條件來加以測定。 (測定條件） 測定長度：7.2mm λ c ： 0.8mm ▲ λ s ： 2.5 β m ❹ 測定速度：0.5mm/秒 又，依據JIS B0601 : 2001，由以該測定條件所測得之 數據圖表來計算波紋度平均高度、及波紋度平均長度。 (2) 黏著力 將各表面保護膜貼附成覆蓋具有凹凸之棱鏡片的透鏡 面。稜鏡片係準備由厚度為n〇"m之丙烯酸樹脂所構成且 稜鏡之間距為50 // m、高度25 # m者。貼附條件係於室溫 23 C及相對濕度50%之環境下，分別使用2kg之壓著橡膠 61 201016812 輥、300mm/刀鐘之速度加以貼附，並於該狀態下靜置1小 時後，依據爪⑽厂—/分鐘之速度來測定以麵 寬之180度剝離強度。此時之剝離方向係^為稜鏡之棱線 方向1此種方式所測得之剝離強度作為初期黏著力。 (3) 初期展開力 初斯展開力方面，除了變更回翁速度之外，係針對各 表面保護膜之50酿寬之捲繞體，依據m ζυ23 7來測定回0.5 parts by weight of Chemicals Co., Ltd., which was kneaded by a twin-screw extruder and granulated. _ The material used to form the substrate layer is: 75 parts by weight of block PP, 25 parts by weight of low density polyethylene (1DPR), and both ends of the film are wound in a roll state in order to adjust the film formation. Trimming. When the block polypropylene (block pp) as a base material is a part by weight, 100 parts by weight of the copolymer composition of Synthesis Example 13 as an adhesive is contained in the adhesive layer, and as a tackifier 30 parts of Arukong Pl25 (manufactured by Arakawa Chemical Industry Co., Ltd.), 20 parts by weight of ENDEX155 (manufactured by Eastman Chemical Co., Ltd.) as a styrene block phase reinforcing agent, and Irgan〇xi010 (Ciba Specialty Chemicals Co., Ltd.) as an antioxidant agent The mixture was mixed with 10 parts by weight of a Nubbin 326 (manufactured by Ciba Specia) (manufactured by Ty Chemicals Co., Ltd.) as a UV absorber, and then kneaded by a twin-screw extruder to obtain a pellet. In addition, "St/adhesive (% by weight)" in Table 12 means the ratio of the total weight of the copolymer composition and the aromatic alkenyl compound unit of the styrene block phase reinforcing agent to the weight of the adhesive ( Aromatic alkenyl compound 60 201016812 Unit content ratio) (Examples 30 to 31, Comparative Examples 2 to 22) The amount and type of polyolefin of the base material layer, the adhesive layer, and copolymerization were changed in the manner shown in Table 12 below. Composition and The amount of the ethylene content, the amount of the tackifier, and the amount of the styrene block-phase reinforcing agent (that is, the st-block reinforcing agent) was obtained in the same manner as in Example 29, except that the film was obtained in the same manner as in Example 29. The surface-protected entangled wound body (evaluation) ❹ The surface protective films of Examples 29 to 31 and Comparative Examples 20 to 22 were evaluated and tested for the items described in the following (1) to (6). (1) The surface roughness Ra was measured using the following measurement conditions (SIJRFTEST Sj_301, manufactured by Mitsutoyo Co., Ltd.) (Measurement conditions) Measurement length: 7.2 mm λ c : 0.8 mm ▲ λ s : 2.5 β m ❹ Measurement speed: 0.5 mm/sec Further, according to JIS B0601: 2001, the average waviness height and the average waviness length are calculated from the data chart measured by the measurement conditions. (2) Adhesion force will be the surface The protective film is attached to a lens surface covering the prism sheet having irregularities. The enamel sheet is prepared from an acrylic resin having a thickness of n〇"m and the distance between the ridges is 50 // m and the height is 25 # m. Conditional at 23 C at room temperature and 50% relative humidity Next, using 2kg of pressing rubber 61 201016812 roller, 300mm / knife speed to attach, and after standing in this state for 1 hour, according to the speed of the claw (10) factory - / minute to determine the width of 180 Degree of peeling strength. At this time, the peeling direction is the ridge line direction 1 of the ridge, and the peel strength measured in this manner is used as the initial adhesion. (3) Initial expansion force In addition to changing the speed of the initial swell, the winding body of 50 widths for each surface protective film is measured according to m ζυ 23 7
Q 捲速度15m/分鐘之高速回播力。並以此方式所測mu 回捲力作為展開力 (4) 經時展開力 經時展開力方面 將各表面保護膜< 50mm t的捲繞體保存於㈣饥 之室内1星期後，除了變更回捲速度之外，係依據ns⑽7 來測定回捲速度15m/分鐘時之高速回捲力。以此種方式所 測得之高速回捲力作為經時展開力。表中，該經時展開力 為3则顏以下的情況時係評價為拉取性良好並標記為〇 符號’為超過3N/5Gmin的情況時係評價為拉取性不良並桿 記為X符號。 τ (5) 棱鏡損傷評價 將實施例及比較例之久矣；付祕μ 乎又各表面保護膜貼附成覆蓋具有凹 凸之稜鏡片的透鏡面以製作試驗片。稜鏡片係使用與⑽ 著力評價中所用者相同纟。貼附時，係從表面保護膜之; 側施加5.9xl05Pa之壓力，再以7 /八姐 再以2m/分鐘之速度加其加以貼 附。將試驗片裁切成3emx8em之大小以作成試樣片。 62 201016812 ’以冷;東切片機將直徑0.2mm之尼龍繊維切成長度 8〜並將切斷片固定於載玻片上，再以2kg輥將所得 表面保D蒦膜貼附於載玻片，藉此將試樣片固定於載玻片 與表面保護膜之間，以作成直徑400 # m、高度1〇"m之凸 形狀試樣。 將上述凸形狀試樣以與覆蓋透鏡部之表面保護膜重疊 的方式設置於以表面保護膜覆蓋透鏡部而成之試 上，再於載玻片上載置140g的砝碼，然後靜置於5〇它的烘 箱24小時。24小時後取出試驗片並將表面保護膜從稜鏡片 剝離，亦目視觀察棱鏡片的透鏡面上是否有因為損傷而產 生之亮點。於下述表13中，對於觀察到大量損傷之試樣 記為x(不Μ符號’而對於觀察到些微損傷的情況標記為: (良）符號，完全未觀察到損傷的情況標記為◦(優）符號。High-speed playback power of Q roll speed of 15m/min. In this way, the mu rewinding force is measured as the deployment force. (4) The windshield of each surface protective film < 50mm t is stored in the (4) hunger room for one week, except for the change. In addition to the rewinding speed, the high-speed rewinding force at a rewinding speed of 15 m/min is determined based on ns(10)7. The high-speed rewinding force measured in this manner is used as the elapsed force over time. In the table, when the time expansion force is 3 or less, it is evaluated as a good pullability, and when the mark 〇 symbol is more than 3N/5Gmin, it is evaluated as a pull-down property and the rod is marked as an X symbol. . τ (5) Prism damage evaluation The examples and comparative examples were subjected to a long period of time; and each surface protective film was attached to cover a lens surface having a concave convex sheet to prepare a test piece. The use of the cymbal is the same as that used in (10) Evaluation. When attaching, apply pressure from the surface protective film; apply pressure of 5.9xl05Pa on the side, and attach it at 7m/min and then add it at 2m/min. The test piece was cut into a size of 3 emx 8 cm to prepare a test piece. 62 201016812 'With cold; East slicer cuts 0.2 mm diameter nylon 繊 into length 8~ and fixes the cut piece on the glass slide, then attaches the obtained surface protection film to the slide with 2kg roller. The sample piece was fixed between the slide glass and the surface protective film to prepare a convex shape sample having a diameter of 400 #m and a height of 1〇"m. The convex shaped sample was placed on the test surface covered with the surface protective film so as to overlap the surface protective film covering the lens portion, and then placed on the slide glass with a weight of 140 g, and then placed at 5 〇 Its oven for 24 hours. After 24 hours, the test piece was taken out and the surface protective film was peeled off from the enamel sheet, and the lens surface of the prism sheet was visually observed to have a bright spot due to damage. In Table 13 below, the sample in which a large amount of damage was observed was recorded as x (no symbol ', and the case where slight damage was observed was marked as: (good) symbol, and the case where no damage was observed at all was marked as ◦ ( Excellent) symbol.
63 201016812 【ει« l·總合 評價 1 1_ 〇 〇 〇 X X X 稜鏡損傷 評價 〇 〇 〇 〇 X X 展開力 經時 i 評價 ί_ 〇 〇 〇 X X X (N/50mm) I^„ rn σ\ cs 00 CN 00 C\ vd 初期 (N/50m m) ί-Η 寸 CN 00 o irJ 卜 寸 in 黏著力| (N/25m m) s o d s o d d <N d> 波紋度 (㈣ CO OO CO 吞 VO On 寸 On 1—( CN m ro m 純： (㈣ ΓΟ <> ro CN — <N 'd CO (N Ό CN 表面粗度Ra (μπι) 卜 o 00 O 卜 o 00 o 00 o 1實施例29 I實施例30 實施例31 比較例20 比較例21 |比較例22 【31 s 1再生原料 (重量％) 〇 ο Ο Ο 〇 〇 LDPE (重量％) κη rsi CN ίΝ ΙΛ) CnJ in fS 1嵌段PP | (重量％) | jn 1 JO in CU 〇, (重量％) 1 1 ΙΛ VO 1 1 1 St/黏著劑 1 I 1 (重量％) | V〇 ro m 00 寸 黏著劑組成物 紫外線 吸收劑 (重量％) d d ο d d ΚΤ) d 1抗氧化劑 | (重量％) 1 r—4 Τ-Η Η Τ-Η 1 St系嵌段 i補強劑 1 (重量％) o Ο ο ο 增黏劑 (重量份） 共聚物組成物 合成例13 合成例1 合成例13 合成例8 合成例8 合成例8 實施例29 實施例30 實施例31 比較例20 比較例21 比較例22 201016812 (實施例32〜38、士私/ , 較例23〜29) 於上述之合成方法张 斤仟之共聚物組成物1 00重量份中 配合作為增黏劑之阿魯Λ 皆二ρ125(^:川化學工業公司製）5重 里伤、作為抗氧彳卜細^ 齊i 之！rganoxl〇i〇(Ciba Specialty Chemicals公司製）ι番县八 量伤’以獲得黏著劑組成物。 基材係使用聚丙嫌h，· 神（Prime聚合物公司製j715M)，並以 丁模法將基材與黏著劑紐 則、，且成物加以共擠出成形，藉此成形出 34 # m厚度之基材岸盥（ ^ 、 θ β m厚度之黏著劑層積層一體化而 成之表面保護膜，以獾 以獲侍捲於内徑3吋之紙芯之捲繞體。 (評價） 價 針對上述方式所得之各表面保護膜進行以下項目之評 該等結果示於表1 5。 (1) 成膜性 以目視評價由共擠出所製膜出之表面保護膜的外觀， 外觀上沒有問題者標記為「〇」。 ❹ (2) 初期黏著力 將實施例及比較例之各表面保護膜以覆蓋擴散膜⑽ 公司製，刪F)之透鏡面的方式加以貼附。貼附條件係於室 溫23。〇及相對濕度50%之環境下，分別❹叫之壓著橡 膠輥以300mm/分鐘之速度加以貼附，並於該狀態下放置3〇 分鐘後’依據JIS Z0237，以300mm/分鐘之速度來測定25mm 寬之180度剝離強度。使時之剝離方向係定為表面保護膜 之MDOnachine direction)方向。以此種方式所測得之剝離強 度作為初期黏著力。 65 201016812 (3) 經時黏著力 於室溫23°C及相對濕度50%之環境下，分別使用2kg 之壓著橡膠輥以300mm/分鐘之速度將實施例及比較例之各 表面保護膜貼附於（1)之初期黏著力評價所用之擴散膜之表 面。之後，以聚碳酸酯板（厚度2mm)挾持貼附有表面保護膜 之稜鏡片，並施加6.0xl(T3MPa之壓力，再以該狀態於60 °C及相對濕度90%之環境下放置48小時。將其於室温中取 出，放置30分鐘後依據JIS Z0237，以300mm/分鐘之速度 來測定25mm寬之1 80度剝離強度 〇 以此種方式所測得之剝離強度作為經時黏著力，再由 初期黏著力以下述式算出經時黏著力之黏著亢進率。 變化率（黏著亢進率）=(經時黏著力/初期黏著力）x 100 (4) 展開力 除了變更回捲速度之外，係針對實施例及比較例之各 表面保護膜之50mm寬之捲繞體，依據JIS Z0237以5m/分 鐘、1 5m/分鐘之回捲速度來測定回捲力，並以其作為展開 力。 ◎ [表 14] 黏著劑組成物 共聚物組成物 增黏劑 抗氧化劑 (重量份） (重量份） (重量份） 實施例32 合成例1 100 5 1 實施例33 合成例2 100 5 1 實施例34 合成例3 100 5 1 實施例35 合成例4 100 5 1 實施例36 合成例5 100 5 1 實施例37 合成例6 100 5 1 實施例38 合成例7 100 5 1 實施例39 合成例23 100 5 1 66 201016812 [表 15]63 201016812 [ει« l·总合评价1 1_ 〇〇〇XXX 稜鏡 Injury evaluation 〇〇〇〇 XX Development time i evaluation ί_ 〇〇〇XXX (N/50mm) I^„ rn σ\ cs 00 CN 00 C\ vd initial (N/50m m) ί-Η inch CN 00 o irJ b inch in adhesion | (N/25m m) sodsodd <N d> waviness ((4) CO OO CO swallow VO On inch On 1 —( CN m ro m pure: ((四) ΓΟ <> ro CN — <N 'd CO (N Ό CN surface roughness Ra (μπι) 卜o 00 O 卜 o 00 o 00 o 1 Example 29 I Example 30 Example 31 Comparative Example 20 Comparative Example 21 | Comparative Example 22 [31 s 1 Recycled raw material (% by weight) 〇ο Ο Ο 〇〇 LDPE (% by weight) κη rsi CN Ν ΙΛ ΙΛ) CnJ in fS 1 block PP | (% by weight) | jn 1 JO in CU 〇, (% by weight) 1 1 ΙΛ VO 1 1 1 St/Adhesive 1 I 1 (% by weight) | V〇ro m 00 inch Adhesive composition UV absorber ( % by weight dd ο dd ΚΤ) d 1 Antioxidant | (% by weight) 1 r—4 Τ-Η Η Τ-Η 1 St block i reinforcing agent 1 (% by weight) o Ο ο ο Tackifier (weight Copolymerization Composition Synthesis Example 13 Synthesis Example 1 Synthesis Example 13 Synthesis Example 8 Synthesis Example 8 Synthesis Example 8 Example 29 Example 30 Example 31 Comparative Example 20 Comparative Example 21 Comparative Example 22 201016812 (Examples 32 to 38, Shihsei/, In the case of the above-mentioned synthesis method, the composition of the copolymer composition of the above-mentioned synthesis method is used as a tackifier, and the arubene bis-125 (manufactured by Chuan Chemical Industry Co., Ltd.) is used as an anti-oxidation.彳 细 ^ ^ ! ! ! ! ! r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r ι ι ι ι ι ι ι ι ι ι ι ι And the base material and the adhesive agent are formed by co-extrusion molding by a Ding method, thereby forming a substrate layer of 34 #m thickness (adhesive layer of thickness of ^, θ β m) A surface protective film which is laminated and integrated to obtain a wound body of a paper core having an inner diameter of 3 inches. (Evaluation) Price The following items were evaluated for each of the surface protective films obtained in the above manner. The results are shown in Table 15. (1) Film-forming property The appearance of the surface protective film formed by the co-extrusion film was visually evaluated, and those having no problem in appearance were marked as "〇". (2) Initial adhesion Each surface protective film of the examples and the comparative examples was attached so as to cover the lens surface of the F-film by the diffusion film (10). The attachment conditions are at room temperature 23. In the environment of 〇 and relative humidity of 50%, the squeezing rubber roller is attached at a speed of 300 mm/min, and placed in this state for 3 〇 minutes, according to JIS Z0237, at a speed of 300 mm/min. A 180 degree peel strength of 25 mm width was measured. The peeling direction of the time is set to the MDOnachine direction of the surface protective film. The peel strength measured in this manner was used as the initial adhesion. 65 201016812 (3) Applying the surface protective film of the examples and the comparative examples at a rate of 300 mm/min using a 2 kg pressing rubber roller under an environment of a room temperature of 23 ° C and a relative humidity of 50%. Attached to the surface of the diffusion film used for the initial adhesion evaluation of (1). Thereafter, the plaque to which the surface protective film was attached was held by a polycarbonate plate (thickness: 2 mm), and 6.0 x 1 (pressure of T3 MPa was applied, and then placed in an environment of 60 ° C and a relative humidity of 90% for 48 hours). It was taken out at room temperature, and after standing for 30 minutes, according to JIS Z0237, the peel strength of 1 mm of 25 mm width was measured at a speed of 300 mm/min. The peel strength measured in this manner was used as the adhesive strength over time. From the initial adhesion, the adhesion rate of the adhesive with time was calculated by the following formula: Rate of change (adhesion rate) = (adhesive strength/initial adhesion) x 100 (4) In addition to changing the rewinding speed, With respect to the 50 mm-wide wound body of each of the surface protective films of the examples and the comparative examples, the rewinding force was measured at a rewinding speed of 5 m/min and 15 m/min in accordance with JIS Z0237, and was used as a developing force. [Table 14] Adhesive composition Copolymer composition Tackifier Antioxidant (parts by weight) (parts by weight) (parts by weight) Example 32 Synthesis Example 1 100 5 1 Example 33 Synthesis Example 2 100 5 1 Example 34 Synthesis Example 3 100 5 1 Example 35 Synthesis Example 4 100 5 1 Example 36 Synthesis Example 5 100 5 1 Example 37 Synthesis Example 6 100 5 1 Example 38 Synthesis Example 7 100 5 1 Example 39 Synthesis Example 23 100 5 1 66 201016812 [Table 15]
成膜性 黏著力 展開力 總合 評價 初期 經時 變化為 15m/分鐘 5m/分鐘 (N/25mm) (N/25mm) (%) 判定 N/50mm N/50mm 判定 實施例32 〇 0.29 0.62 214 〇 1.5 2,6 〇 〇 實施例33 〇 0.31 0.75 242 〇 1.4 2.5 〇 〇 實施例34 〇 0.2 0.29 145 ◎ 1.0 1.6 ◎ 〇 實施例35 〇 0.30 0.70 233 〇 1.4 2.4 〇 〇 實施例36 〇 0.25 0.40 160 ◎ 0.9 1.8 ◎ ◎ 實施例37 〇 0.21 0.35 167 ◎ 1.0 1.7 ◎ ◎ 實施例38 〇 0.14 0,43 307 〇 1.1 1.5 ◎ 〇 實施例39 〇 0.21 0.40 190 ◎ 3.1 3.3 〇 〇 比較例23 〇 0.23 0.30 130 ◎ 4.8 5.1 X X 比較例24 〇 0.22 0.30 136 ◎ 4.3 4.6 X X 比較例25 X - - - - - - X 比較例26 〇 0.15 0.29 193 ◎ 3.7 3.9 X X 比較例27 X - - - - - - - - 比較例28 X - - • - - - - - 比較例29 無法成膜 比較例23 合成例8 100 5 1 比較例24 合成例9 100 5 1 比較例25 合成例10 100 5 1 比較例26 合成例20 100 5 1 比較例27 合成例21 100 5 1 比較例28 合成例22 100 5 1 比較例29 合成例24 100 5 1 <判定基準> 黏著力（初期） 〇（良）：0.05N/25mm 以上且未滿 0.35N/25mm x(不良）：未滿 〇.〇5N/25mm 或 0.35N/25mm 以上 黏著力（變化率） ◎(優）：未滿200% 〇（良）：200%以上且500%以下 x(不良）：超過500% 展開力 ◎(優）：未滿 2.0N/50mm 67 201016812 〇（良）：2.0N/50mm以上且3.5N/50mm以下 x(不良）：超過 3.5N/50mm (產業利用性） 本發明之黏著劑組成物係適用於棱鏡片、擴散膜等之 表面保護膜之黏著劑層。 本發明之表面保護膜係適用於稜鏡片、擴散旗等之表 面保護。 ' 【圖式簡單說明】 圖1 圖2 立體圖。 係表示基材層外側表面的波紋之示意圖。 係使用有本發明之一態様之表面保護膜之棱鏡片Film-forming adhesive force development force evaluation Initial change over time is 15 m / min 5 m / min (N / 25 mm) (N / 25 mm) (%) Determination N / 50 mm N / 50 mm Judgment Example 32 〇 0.29 0.62 214 〇 1.5 2,6 〇〇Example 33 〇0.31 0.75 242 〇1.4 2.5 〇〇Example 34 〇0.2 0.29 145 ◎ 1.0 1.6 ◎ 〇Example 35 〇0.30 0.70 233 〇1.4 2.4 〇〇Example 36 〇0.25 0.40 160 ◎ 0.9 1.8 ◎ ◎ Example 37 〇0.21 0.35 167 ◎ 1.0 1.7 ◎ ◎ Example 38 〇 0.14 0, 43 307 〇 1.1 1.5 ◎ Example 39 〇 0.21 0.40 190 ◎ 3.1 3.3 〇〇 Comparative Example 23 〇 0.23 0.30 130 ◎ 4.8 5.1 XX Comparative Example 24 〇0.22 0.30 136 ◎ 4.3 4.6 XX Comparative Example 25 X - - - - - - X Comparative Example 26 〇 0.15 0.29 193 ◎ 3.7 3.9 XX Comparative Example 27 X - - - - - - - - Comparative Example 28 X - - • - - - - - Comparative Example 29 Film formation was not possible Comparative Example 23 Synthesis Example 8 100 5 1 Comparative Example 24 Synthesis Example 9 100 5 1 Comparative Example 25 Synthesis Example 10 100 5 1 Comparative Example 26 Synthesis Example 20 100 5 1 Comparative Example 27 Synthesis Example 21 100 5 1 Comparative Example 28 Synthesis Example 22 100 5 1 Comparative Example 29 Synthesis Example 24 100 5 1 <Criteria for determination> Adhesion (initial) 〇(good): 0.05 N/25 mm or more and less than 0.35 N/25 mm x (bad): not full.〇 5N/25mm or 0.35N/25mm or more adhesion (change rate) ◎(excellent): less than 200% 〇(good): 200% or more and 500% or less x(bad): more than 500% Deployment force ◎(Excellent) : under 2.0N/50mm 67 201016812 〇 (good): 2.0N/50mm or more and 3.5N/50mm or less x (bad): more than 3.5N/50mm (industrial use) The adhesive composition of the present invention is suitable for An adhesive layer of a surface protective film such as a prism sheet or a diffusion film. The surface protective film of the present invention is suitable for surface protection of enamel sheets, diffusion flags, and the like. ' [Simple diagram of the diagram] Figure 1 Figure 2 Stereogram. It is a schematic diagram showing the corrugation of the outer surface of the substrate layer. A prism sheet using a surface protective film having one of the aspects of the present invention
之—實施形態之表面保The surface protection of the implementation
圖3係於稜鏡片貼附有本發明 祺之構造。 【主要元件符號說明】 1 棱鏡片 2 片 透鏡部（稜鏡） 3A透鏡部之頂部（稜鏡頂角） 4 第1表面保護膜 5 基材層 6黏著劑層 7 第2表面保護膜 68Fig. 3 is a view showing the structure in which the cymbal is attached with the cymbal of the present invention. [Description of main components] 1 prism sheet 2 piece lens part (稜鏡) 3A lens part top (dome angle) 4 1st surface protection film 5 base material layer 6 adhesive layer 7 2nd surface protection film 68
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI500730B (en) * | 2011-12-22 | 2015-09-21 | Sekisui Chemical Co Ltd | Surface protective film |
Families Citing this family (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101176811B1 (en) * | 2008-09-11 | 2012-08-24 | 제이에스알 가부시끼가이샤 | Surface protective film |
| US8324309B2 (en) * | 2010-04-27 | 2012-12-04 | Kraton Polymers Us Llc | High melt flow block copolymers for non-woven adhesives |
| JP5753667B2 (en) * | 2010-06-16 | 2015-07-22 | 積水化学工業株式会社 | Adhesive composition and surface protective film |
| JP5623872B2 (en) * | 2010-11-08 | 2014-11-12 | 積水化学工業株式会社 | Adhesive composition and surface protective adhesive film |
| JP5719151B2 (en) * | 2010-11-19 | 2015-05-13 | 積水化学工業株式会社 | Adhesive composition and surface protective adhesive film |
| JP5879111B2 (en) * | 2011-06-15 | 2016-03-08 | 積水化学工業株式会社 | Surface protection film |
| JP2014169347A (en) * | 2011-07-07 | 2014-09-18 | Sekisui Chem Co Ltd | Adhesive composition and surface protecting adhesive sheet |
| JP2013018907A (en) * | 2011-07-13 | 2013-01-31 | Sekisui Chem Co Ltd | Adhesive composition and surface protecting film |
| JP5814036B2 (en) * | 2011-08-05 | 2015-11-17 | 日東電工株式会社 | Adhesive tape |
| JP5879110B2 (en) * | 2011-12-05 | 2016-03-08 | 積水化学工業株式会社 | Adhesive composition and surface protective film |
| WO2014010707A1 (en) * | 2012-07-13 | 2014-01-16 | 古河電気工業株式会社 | Current collector foil, electrode structure, lithium secondary cell, or electric double-layer capacitor |
| JP6026255B2 (en) * | 2012-12-07 | 2016-11-16 | クレイトン・ポリマーズ・ユー・エス・エル・エル・シー | Adhesive composition for protective film for painted surface and method for preparing the same |
| JP5992312B2 (en) * | 2012-12-07 | 2016-09-14 | クレイトン・ポリマーズ・ユー・エス・エル・エル・シー | Adhesive composition for protective film for painted surface and method for preparing the same |
| JP6069004B2 (en) * | 2013-02-04 | 2017-01-25 | 旭化成株式会社 | Adhesive composition and surface protective film |
| JP6573282B2 (en) * | 2014-04-11 | 2019-09-11 | リンテック株式会社 | Back grinding tape substrate and back grinding tape |
| JP6446215B2 (en) * | 2014-09-17 | 2018-12-26 | 積水化学工業株式会社 | Surface protective film for prism sheet and prism sheet with surface protective film |
| JP6416666B2 (en) * | 2015-03-11 | 2018-10-31 | 積水化学工業株式会社 | Surface protective film and prism sheet with surface protective film |
| JP6507009B2 (en) * | 2015-03-27 | 2019-04-24 | 積水化学工業株式会社 | Pressure sensitive adhesive composition, surface protective film, and prism sheet with surface protective film |
| JP6697981B2 (en) * | 2015-08-27 | 2020-05-27 | 積水化学工業株式会社 | Surface protective film for prism sheet and prism sheet with surface protective film for prism sheet |
| JP6863770B2 (en) * | 2016-02-24 | 2021-04-21 | 積水化学工業株式会社 | How to process adhesive film for half-cut processing and adherend |
| JP6206749B1 (en) | 2016-03-03 | 2017-10-04 | 東レフィルム加工株式会社 | Laminated film |
| JP6628101B2 (en) * | 2016-03-03 | 2020-01-08 | 東レフィルム加工株式会社 | Laminated film |
| JP6808998B2 (en) * | 2016-06-24 | 2021-01-06 | Jsr株式会社 | Adhesive film |
| JP6733358B2 (en) * | 2016-06-24 | 2020-07-29 | Jsr株式会社 | Adhesive composition and adhesive film |
| JP7085551B2 (en) * | 2016-12-29 | 2022-06-16 | スリーエム イノベイティブ プロパティズ カンパニー | Decorative sheet |
| JP7238290B2 (en) * | 2018-08-03 | 2023-03-14 | 東洋紡株式会社 | laminated film. |
| JP2019048981A (en) * | 2018-10-04 | 2019-03-28 | 積水化学工業株式会社 | Surface protective film, and prism sheet with surface protective film |
| JP2019070133A (en) * | 2018-12-03 | 2019-05-09 | 積水化学工業株式会社 | Surface protective film for prism sheet and prism sheet with surface protective film |
| JP2019137867A (en) * | 2019-04-01 | 2019-08-22 | 積水化学工業株式会社 | Adhesive composition, surface protective film, and prism sheet with surface protective film |
| JP2020193348A (en) * | 2020-09-04 | 2020-12-03 | Jsr株式会社 | Composition for adhesive |
| JP7323732B1 (en) * | 2022-03-31 | 2023-08-08 | リンテック株式会社 | Protective film attached Film for improving writing quality |
| WO2023188545A1 (en) * | 2022-03-31 | 2023-10-05 | リンテック株式会社 | Writing feeling improvement film with protection film |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999058604A1 (en) * | 1998-05-13 | 1999-11-18 | Nippon Zeon Co., Ltd. | Poly(aromatic vinyl)/polyisoprene block copolymer composition, process for producing the same, and pressure-sensitive adhesive composition |
| JP2000336323A (en) * | 1999-05-26 | 2000-12-05 | Sekisui Chem Co Ltd | Surface-protection film for metal plate |
| JP4694061B2 (en) | 2001-08-02 | 2011-06-01 | 日東電工株式会社 | Surface protective sheet and manufacturing method thereof |
| BRPI0407627B1 (en) * | 2003-02-21 | 2014-04-15 | Kraton Polymers Res Bv | Adhesive composition for tapes, labels and bandages, tapes, labels and bandages, and their use |
| WO2006075383A1 (en) * | 2005-01-14 | 2006-07-20 | Nichiban Company Limited | Surface-protective sheet |
| CN101189317A (en) * | 2005-06-06 | 2008-05-28 | 积水化学工业株式会社 | Surface protective film |
| CN101243153B (en) * | 2005-09-05 | 2010-10-06 | 日东电工株式会社 | Adhesive composition, adhesive sheet and surface-protecting film |
| CN101466810B (en) * | 2006-04-28 | 2011-04-27 | Jsr株式会社 | Adhesive composition, method for producing the same and adhesive body |
| JP4987361B2 (en) * | 2006-06-19 | 2012-07-25 | 積水化学工業株式会社 | Surface protection film |
| JP5295533B2 (en) * | 2006-10-31 | 2013-09-18 | 日東電工株式会社 | Surface protective film and optical film with surface protective film |
| KR101176811B1 (en) * | 2008-09-11 | 2012-08-24 | 제이에스알 가부시끼가이샤 | Surface protective film |
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Cited By (1)
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| TWI500730B (en) * | 2011-12-22 | 2015-09-21 | Sekisui Chemical Co Ltd | Surface protective film |
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| JP5127903B2 (en) | 2013-01-23 |
| JP2011057992A (en) | 2011-03-24 |
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| CN102149779A (en) | 2011-08-10 |
| JPWO2010029773A1 (en) | 2012-02-02 |
| TWI382071B (en) | 2013-01-11 |
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| KR101176811B1 (en) | 2012-08-24 |
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