TWI540044B - Surface protective film - Google Patents

Surface protective film Download PDF

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TWI540044B
TWI540044B TW099131169A TW99131169A TWI540044B TW I540044 B TWI540044 B TW I540044B TW 099131169 A TW099131169 A TW 099131169A TW 99131169 A TW99131169 A TW 99131169A TW I540044 B TWI540044 B TW I540044B
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Taiwan
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protective film
surface protective
layer
propylene
polymer
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TW099131169A
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Chinese (zh)
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TW201127622A (en
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Hisayuki Oogoda
Masanori Tsujimura
Norihide Inoue
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Mitsui Chemicals Inc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/10—Homopolymers or copolymers of propene
    • C09J123/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241—Polyolefin, e.g.rubber
    • C09J7/243—Ethylene or propylene polymers
    • 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]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2419/00—Buildings or parts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2551/00—Optical elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/06—Metallocene or single site catalysts
    • 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
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • C08L2666/06—Homopolymers or copolymers of unsaturated hydrocarbons; Derivatives thereof
    • 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
    • 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
    • C09J2423/10—Presence of homo or copolymers of propene

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Description

表面保護膜Surface protection film

本發明係關於光學製品、建材、汽車零件等所使用的表面保護膜。詳言之，係關於黏著特性，尤其是對於被黏體之黏著性及黏著力的經時安定性優異，又，耐熱性優異，對於被黏體等之污染少，且白點(fish eye)等之外觀優異，不會刮傷被黏體，更且由輥狀捲出時的捲出性容易的表面保護膜。The present invention relates to a surface protective film used for optical products, building materials, automobile parts, and the like. In particular, it is excellent in the adhesion property, especially the adhesion and adhesion of the adherend, and the heat resistance is excellent, and the contamination to the adherend is small, and the fish eye is The surface protective film which is excellent in appearance, does not scratch the adherend, and is easy to roll off when rolled out in a roll shape.

表面保護膜主要被貼附至建材用和光學用途用之樹脂製品、金屬製品、玻璃製品等之被黏體而使用，擔任該等之輸送、保管和加工時防止刮傷或混入異物的角色。該等表面保護膜一般係由無黏著性的表面層和用於與上述被黏體黏著的黏著層所構成。表面層通常由聚乙烯和聚丙烯等之聚烯烴、聚對苯二甲酸乙二酯等之聚酯、聚氯乙烯等之乙烯基聚合體所形成。The surface protective film is mainly used for adhering to a resin body such as a resin product for building materials and optical applications, a metal product, or a glass product, and serves as a role of preventing scratching or foreign matter in the transportation, storage, and processing. The surface protective films are generally composed of a non-adhesive surface layer and an adhesive layer for adhering to the adherend. The surface layer is usually formed of a polyolefin such as polyethylene or polypropylene, a polyester such as polyethylene terephthalate or a vinyl polymer such as polyvinyl chloride.

近年來，已發展液晶螢幕、電漿顯示器(PDP)和背投式螢幕等所用之構件，即所謂光學製品的開發。對於用於保護該等光學製品的表面保護膜，不僅期望不會刮傷和混入異物，且需求以貼附表面保護膜之狀態可檢查製品般的透明性、以及即使以高溫狀態貼附和經過熱處理步驟仍可表現適度黏著力等特性。In recent years, components used for liquid crystal screens, plasma display panels (PDPs), and rear projection screens have been developed, that is, the development of so-called optical products. For the surface protective film for protecting such optical articles, it is desired not only to scratch and mix foreign matter, but also to check the transparency of the article in a state in which the surface protective film is attached, and to attach and heat-treat even at a high temperature. The steps can still exhibit characteristics such as moderate adhesion.

又，對於光學製品，例如偏光板、相位差板、導光板、稜鏡板般要求光學特性的構件有很多，期望即使對於該等構件亦可表現適度黏著力及經時安定之黏著力的保護膜。Further, there are many members requiring optical characteristics such as a polarizing plate, a phase difference plate, a light guide plate, and a seesaw, and it is desired that a protective film which exhibits moderate adhesion and stability with stability over time even for such members. .

另一方面，於該等光學構件使用表面保護膜之情況，剝離表面保護膜時，若糊殘留或表面保護膜存在白點，則有在光學構件產生缺陷之情況，期望無糊殘留和白點的表面保護膜。On the other hand, when the surface protective film is used for the optical members, when the surface protective film is peeled off, if the paste remains or the surface protective film has white spots, there is a case where the optical member is defective, and it is desired that no paste remains and white spots are formed. Surface protection film.

又，黏著力較高的表面保護膜，因為難以由輥狀製品捲出，故以黏著層貼合脫模膜的狀態作成輥狀，並在貼附至被黏體時將此脫模膜剝離使用。若採用此種步驟，則會發生大量的廢棄物，故要求即使無脫模膜亦可由輥中輕易捲出的表面保護膜。Further, since the surface protective film having a high adhesive strength is difficult to be wound up by the roll-shaped product, the release film is bonded to the release film to form a roll, and the release film is peeled off when attached to the adherend. use. If such a step is employed, a large amount of waste will occur, so that a surface protective film which can be easily rolled out from the roll even without a release film is required.

於日本專利特開2006-116769號公報中，揭示以聚乙烯成分作為主體的表面保護膜。但是，根據該公報之方法，雖然對於一部分用途構件可應用，但黏著力低，且透明性亦不充分，被黏體的用途有所限制。A surface protective film mainly composed of a polyethylene component is disclosed in Japanese Laid-Open Patent Publication No. 2006-116769. However, according to the method of the publication, although it is applicable to a part of the use member, the adhesive force is low and the transparency is insufficient, and the use of the adherend is limited.

於日本專利特開2009-83110號公報中，提案由茂金屬觸媒系而得之特定丙烯系無規嵌段共聚合體所構成的表面保護膜。但是，根據該公報之方法，黏著力亦低，期望進一步改良。A surface protective film composed of a specific propylene-based random block copolymer obtained from a metallocene catalyst is proposed in Japanese Laid-Open Patent Publication No. 2009-83110. However, according to the method of the publication, the adhesion is also low, and further improvement is desired.

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

專利文獻1：日本專利特開2006-116769號公報Patent Document 1: Japanese Patent Laid-Open No. 2006-116769

專利文獻2：日本專利特開2000-83110號公報Patent Document 2: Japanese Patent Laid-Open Publication No. 2000-83110

本發明在於提供作為光學製品、建材製品和汽車零件之保管、輸送、加工、檢查時用於保護之表面保護膜所要求之特性，尤其是對於被黏體的黏著特性、透明性、耐熱性優異，且對於被黏體等之污染少，無白點且外觀優異，不會刮傷被黏體，以及由輥中捲出性優異的表面保護膜。The present invention provides the characteristics required for the surface protective film used for protection during storage, transportation, processing, and inspection of optical products, building materials, and automobile parts, and is particularly excellent in adhesion properties, transparency, and heat resistance of the adherend. Moreover, it is less contaminated by adherends, has no white spots, is excellent in appearance, does not scratch the adherend, and has a surface protective film excellent in roll-out property from a roll.

本發明者等人鑑於上述問題致力檢討之結果，發現經由具有某特定樹脂組成物所構成之黏著層的表面保護膜可解決上述問題，因而完成本發明。The inventors of the present invention have found that the above problem can be solved by a surface protective film having an adhesive layer composed of a specific resin composition in view of the above-mentioned problems, and thus completed the present invention.

即，本發明係關於由表面層(A)及黏著層(X)之至少2層所構成的表面保護膜，表面層(A)由聚烯烴樹脂所構成，黏著層(X)係由以使用茂金屬觸媒而得之碳數3以上之α-烯烴作為主成分的低結晶性α-烯烴(共)聚合體(X-1)5~95重量%、及熔點為50~130℃之範圍並使用茂金屬觸媒而得之丙烯(共)聚合體(X-2)95~5重量%((X1)與(X-2)之合計為100重量%)所構成之組成物所形成為其特徵的表面保護膜。That is, the present invention relates to a surface protective film comprising at least two layers of a surface layer (A) and an adhesive layer (X), the surface layer (A) is composed of a polyolefin resin, and the adhesive layer (X) is used. The low crystalline α-olefin (co)polymer (X-1) having a carbon number of 3 or more and having a carbon number of 3 or more as a main component is 5 to 95% by weight, and the melting point is 50 to 130 ° C. A composition of 95 to 5 wt% of the propylene (co)polymer (X-2) obtained by using a metallocene catalyst (100% by weight of (X1) and (X-2) in total) is formed as A surface protective film characterized by it.

又，本發明係關於形成上述黏著層(X)之組成物一部分的α-烯烴(共)聚合體(X-1)為丙烯與碳數2~10之α-烯烴(丙烯除外)的共聚合體為其特徵的表面保護膜。Further, the present invention relates to an α-olefin (co)polymer (X-1) which forms a part of the composition of the above-mentioned adhesive layer (X), which is a copolymer of propylene and an α-olefin having 2 to 10 carbon atoms (excluding propylene). A surface protective film characterized by it.

又，本發明係關於形成上述黏著層(X)之組成物一部分的丙烯(共)聚合體(X-2)為熔點60~120℃之範圍並使用茂金屬觸媒而得之丙烯(共)聚合體為其特徵的表面保護膜。Further, the present invention relates to a propylene (co)polymer (X-2) which forms a part of the composition of the above-mentioned adhesive layer (X), which has a melting point of 60 to 120 ° C and which is obtained by using a metallocene catalyst. A surface protective film characterized by a polymer.

更且，本發明係關於將上述之表面層(A)及黏著層(X)之至少2層由T-字模擠出成形而得之多層膜的表面保護膜。Furthermore, the present invention relates to a surface protective film of a multilayer film obtained by extrusion molding at least two layers of the surface layer (A) and the adhesive layer (X) described above by a T-shaped mold.

本發明之表面保護膜為黏著特性及經時安定性、透明性、回捲力及耐熱性優異，作為光學用途、建材用途、汽車零件用途等之保護膜的產業上利用價值極高。The surface protective film of the present invention is excellent in adhesive properties, stability over time, transparency, rewinding power, and heat resistance, and is extremely valuable for industrial use as a protective film for optical applications, building materials, and automobile parts.

其次詳細說明本發明。Next, the present invention will be described in detail.

本發明之表面保護膜由表面層(A)及黏著層(X)之至少2層，或視需要之表面層(A)、基材層(B)及黏著層(X)之至少3層所構成。此處，以黏著層(X)作為最內層之情況，表面層(A)位於最外層，將膜作成輥狀時表面層(A)與黏著層(X)接觸。The surface protective film of the present invention comprises at least two layers of the surface layer (A) and the adhesive layer (X), or at least three layers of the surface layer (A), the substrate layer (B) and the adhesive layer (X) as needed. Composition. Here, in the case where the adhesive layer (X) is the innermost layer, the surface layer (A) is located at the outermost layer, and when the film is formed into a roll shape, the surface layer (A) is in contact with the adhesive layer (X).

表面層(A)由聚烯烴樹脂所構成。The surface layer (A) is composed of a polyolefin resin.

作為聚烯烴樹脂，可列舉聚丙烯和聚乙烯等公知之聚烯烴樹脂。作為聚丙烯，可列舉均質聚丙烯、無規聚丙烯、嵌段聚丙烯，作為聚乙烯，可列舉高壓法低密度聚乙烯、直鏈狀低密度聚乙烯、高密度聚乙烯。其中，由回捲性之觀點而言，以高壓法低密度聚乙烯為較佳利用，由透明性、耐熱性之觀點而言，以均質聚丙烯和含有丙烯-乙烯共聚合體成分或丙烯-1-丁烯-乙烯共聚合體成分的嵌段聚丙烯為較佳利用。The polyolefin resin is a known polyolefin resin such as polypropylene or polyethylene. Examples of the polypropylene include homogeneous polypropylene, random polypropylene, and block polypropylene. Examples of the polyethylene include high pressure low density polyethylene, linear low density polyethylene, and high density polyethylene. Among them, from the viewpoint of rewindability, high-pressure method low-density polyethylene is preferably used, and from the viewpoint of transparency and heat resistance, homogeneous polypropylene and propylene-ethylene copolymer component or propylene-1 are contained. The block polypropylene of the butene-ethylene copolymer component is preferably used.

於形成上述表面層(A)之組成物中，在不損害作為本發明表面保護膜特性之範圍，亦可添加防靜電劑、脫模劑、抗氧化劑、耐候劑、結晶核劑等之各種添加劑，和其他之聚烯烴樹脂、蠟、聚酯、聚醯胺、彈性體等之樹脂改質劑。In the composition for forming the surface layer (A), various additives such as an antistatic agent, a releasing agent, an antioxidant, a weathering agent, and a crystal nucleating agent may be added without impairing the characteristics of the surface protective film of the present invention. And other resin modifiers for polyolefin resins, waxes, polyesters, polyamides, elastomers, and the like.

本發明之表面保護膜的黏著層(X)，係由使用茂金屬觸媒而得之以碳數3以上之α-烯烴作為主成分的低結晶性α-烯烴(共)聚合體(X-1)5~95重量%、較佳為10~90重量%、更佳為35~75重量%，及熔點為50~130℃之範圍並使用茂金屬觸媒而得之丙烯(共)聚合體(X-2)95~5重量%、較佳為90~10重量%、更佳為65~25重量%((X-1)與(X-2)之合計為100重量%)而成之組成物所形成。The adhesive layer (X) of the surface protective film of the present invention is a low crystalline α-olefin (co)polymer obtained by using a metallocene catalyst and having an α-olefin having 3 or more carbon atoms as a main component (X- 1) propylene (co)polymer obtained by using 5 to 95% by weight, preferably 10 to 90% by weight, more preferably 35 to 75% by weight, and having a melting point of 50 to 130 ° C and using a metallocene catalyst (X-2) 95 to 5% by weight, preferably 90 to 10% by weight, more preferably 65 to 25% by weight (the total of (X-1) and (X-2) is 100% by weight) The composition is formed.

黏著層(X)所使用之使用茂金屬觸媒而得之α-烯烴(共)聚合體(X-1)，以-50℃~200℃範圍之示差掃描熱量計(DSC)測定，係具有結晶熔解熱量為0.5~40J/g波峰之低結晶性的α-烯烴(共)聚合體。較佳為結晶熔解熱量為1~20J/g範圍，更佳為具有1~10J/g波峰的α-烯烴(共)聚合體。α-烯烴(共)聚合體(X-1)係以碳數3以上之α-烯烴作為主成分的共聚合體，例如丙烯單獨聚合體、丙烯‧乙烯共聚合體、丙烯‧乙烯‧1-丁烯共聚合體、1-丁烯單獨聚合體、1-丁烯‧乙烯共聚合體、1-丁烯‧丙烯共聚合體、4-甲基戊烯-1單獨聚合體、4-甲基戊烯-1‧丙烯共聚合體、4-甲基戊烯-1‧1-丁烯共聚合體、4-甲基戊烯-1‧丙烯‧1-丁烯共聚合體、丙烯‧1-丁烯共聚合體，較佳為丙烯‧乙烯‧1-丁烯共聚合體。The α-olefin (co)polymer (X-1) obtained by using the metallocene catalyst used in the adhesive layer (X) is measured by a differential scanning calorimeter (DSC) in the range of -50 ° C to 200 ° C. The crystal-solving heat is a low-crystalline α-olefin (co)polymer having a peak of 0.5 to 40 J/g. Preferably, the heat of crystal melting is in the range of 1 to 20 J/g, more preferably an α-olefin (co)polymer having a peak of 1 to 10 J/g. The α-olefin (co)polymer (X-1) is a copolymer having a carbon number of 3 or more α-olefin as a main component, for example, a propylene individual polymer, a propylene/ethylene copolymer, and a propylene/ethylene ‧1-butene Copolymer, 1-butene single polymer, 1-butene ‧ ethylene copolymer, 1-butene ‧ propylene copolymer, 4-methylpentene-1 alone polymer, 4-methylpentene-1 a propylene copolymer, a 4-methylpentene-1‧1-butene copolymer, a 4-methylpentene-1‧propene ‧1-butene copolymer, and a propylene ‧1-butene copolymer, preferably Propylene ‧ ethylene ‧ 1-butene copolymer

將此種α-烯烴(共)聚合體(X-1)使用於黏著層之一部分，可取得黏著力之加溫經時安定性以及對於被黏體之耐污染性優異的表面保護膜。When such an α-olefin (co)polymer (X-1) is used in a part of the adhesive layer, it is possible to obtain a surface protective film excellent in adhesion stability over time and excellent in stain resistance to the adherend.

α-烯烴(共)聚合體(X-1)於230℃測定之熔融流動速率(MFR)為0.1~100克/10分鐘，較佳為0.5~50克/10分鐘之範圍。The melt flow rate (MFR) of the α-olefin (co)polymer (X-1) measured at 230 ° C is from 0.1 to 100 g/10 min, preferably from 0.5 to 50 g/10 min.

丙烯(共)聚合體(X-2)之熔點為50~130℃之範圍、較佳為55~130℃之範圍、更佳為60~120℃之範圍。丙烯(共)聚合體(X-2)為結晶性之聚合體，係在茂金屬觸媒存在下所製造之丙烯的單獨聚合或丙烯與碳數2~10(丙烯除外)的共聚合體，具體而言可列舉例如丙烯單獨聚合體、丙烯‧乙烯共聚合體、丙烯‧1-丁烯共聚合體、丙烯‧1烯‧1-丁烯共聚合體等。更佳為丙烯‧乙烯共聚合體。The melting point of the propylene (co)polymer (X-2) is in the range of 50 to 130 ° C, preferably in the range of 55 to 130 ° C, more preferably in the range of 60 to 120 ° C. The propylene (co)polymer (X-2) is a crystalline polymer, which is a single polymerization of propylene produced in the presence of a metallocene catalyst or a copolymer of propylene and carbon number 2 to 10 (excluding propylene). Examples thereof include a propylene individual polymer, a propylene/ethylene copolymer, a propylene ‧1-butene copolymer, and a propylene ‧1 ene-1-butene copolymer. More preferably, it is a propylene/ethylene copolymer.

作為茂金屬觸媒，係由環戊二烯、茚、茀、該等之烷基取代體、芳基取代體等之環戊二烯衍生物所構成之對稱、非對稱、交聯、非交聯之配位子，和鈦、鋯、鉿等之過渡金屬所構成之化合物作為主成分，並由鋁烷、硼系化合物等之輔助觸媒所構成的觸媒，更且，半茂金屬等其他各種單一部位觸媒，若可聚合烯烴者則亦可使用。As the metallocene catalyst, it is a symmetric, asymmetric, cross-linked, non-crossing composed of a cyclopentadiene derivative such as cyclopentadiene, anthracene, anthracene, an alkyl substituent or an aryl substituent. a ligand composed of a transition metal such as titanium, zirconium or hafnium as a main component and composed of aluminum A catalyst composed of an auxiliary catalyst such as an alkane or a boron compound, and other various single site catalysts such as a semimetallocene may be used if the olefin is polymerizable.

又，若為可表現以茂金屬觸媒所得之烯烴聚合體特徵之狹窄分子量分佈、狹窄組成分佈的觸媒，則可應用。如此處理所得之低結晶性α-烯烴(共)聚合體(X-1)、丙烯(共)聚合體(X-2)分別視需要可使用其1種以上。因此，分別使用2種以上之情況，比使用1種之情況，其分子量分佈(Mw/Mn)值亦有較廣之情況，其分子量分佈(Mw/Mn)係根據換算聚苯乙烯，其值為1~4之聚合體，其中以1.8~4之聚合體為佳。Further, it is applicable to a catalyst which exhibits a narrow molecular weight distribution and a narrow composition distribution characteristic of an olefin polymer obtained by a metallocene catalyst. The low-crystalline α-olefin (co)polymer (X-1) and the propylene (co)polymer (X-2) obtained in this manner may be used alone or in combination, if necessary. Therefore, when two or more types are used, the molecular weight distribution (Mw/Mn) value is also wider than when one type is used, and the molecular weight distribution (Mw/Mn) is based on the converted polystyrene. It is a polymer of 1 to 4, and a polymer of 1.8 to 4 is preferred.

丙烯(共)聚合體(X-2)於230℃測定之熔融流動速率(MFR)為0.1~100克/10分鐘、較佳為0.5~50克/10分鐘之範圍。The melt flow rate (MFR) of the propylene (co)polymer (X-2) measured at 230 ° C is in the range of 0.1 to 100 g/10 min, preferably 0.5 to 50 g/10 min.

本發明之保護膜中的黏著層(X)中，在控制黏著力、經時黏著力和控制回捲力之目的下，亦可在上述組成物中添加其他結晶性聚烯烴、烯烴系彈性體或苯乙烯系彈性體、黏著賦予劑。In the adhesive layer (X) in the protective film of the present invention, other crystalline polyolefins and olefin-based elastomers may be added to the above composition for the purpose of controlling the adhesion, the adhesion over time, and controlling the rewinding force. Or a styrene-based elastomer or an adhesion-imparting agent.

將上述結晶性聚烯烴、烯烴系彈性體或苯乙烯系彈性體、黏著賦予劑使用作為本發明保護膜之黏著層(X)的一成分時的含量，相對於(X-1)及(X-2)所構成之組成物100重量份，為0.1~100重量份、較佳為0.3~50重量份、更佳為0.5~20重量份。經由添加結晶性聚烯烴、烯烴系彈性體或苯乙烯系彈性體、黏著賦予劑，則可表現所欲的黏著力，又，可表現適於各種被黏體的黏著特性，為佳。The content of the above-mentioned crystalline polyolefin, olefin-based elastomer, styrene-based elastomer, and adhesion-imparting agent as a component of the adhesive layer (X) of the protective film of the present invention is relative to (X-1) and (X). -2) The composition of the composition is 0.1 to 100 parts by weight, preferably 0.3 to 50 parts by weight, more preferably 0.5 to 20 parts by weight. By adding a crystalline polyolefin, an olefin-based elastomer, a styrene-based elastomer, or an adhesion-imparting agent, it is possible to exhibit a desired adhesive force, and it is preferable to exhibit adhesive properties suitable for various adherends.

本發明之表面保護膜中之黏著層(X)，可經由加入上述(X-1)及(X-2)所構成之組成物及視需要之結晶性聚烯烴、烯烴系彈性體或苯乙烯系彈性體、黏著賦予劑的組成物而形成。又，於本發明中，於黏著層(X)中亦可進一步在不損害本發明特性之範圍下，含有酸改質聚烯烴、聚酯、聚醯胺等之樹脂改質劑或防靜電劑、結晶核劑、抗氧化劑等各種添加劑。The adhesive layer (X) in the surface protective film of the present invention may be a composition comprising the above (X-1) and (X-2) and optionally a crystalline polyolefin, an olefin elastomer or styrene. It is formed by the composition of an elastomer and an adhesion-imparting agent. Further, in the present invention, a resin modifier or an antistatic agent containing an acid-modified polyolefin, a polyester, a polyamide or the like may be further added to the adhesive layer (X) without impairing the characteristics of the present invention. Various additives such as crystal nucleating agents and antioxidants.

於本發明中，亦可進一步在表面層(A)與黏著層(X)之間至少設置1層基材層(B)。於以控制薄膜之機械強度和透明性為目的，且在表面層(A)及黏著層(X)之黏著力不足的情況，亦可使用聚烯烴樹脂或黏著性樹脂或黏著劑作為基材層。In the present invention, at least one base material layer (B) may be further provided between the surface layer (A) and the adhesive layer (X). For the purpose of controlling the mechanical strength and transparency of the film, and in the case where the adhesion of the surface layer (A) and the adhesive layer (X) is insufficient, a polyolefin resin or an adhesive resin or an adhesive may be used as the substrate layer. .

作為基材層並無特別限制，一般而言，可使用熔點為100℃以上之聚丙烯或聚乙烯等之結晶性聚烯烴、聚酯、聚醯胺、聚烯烴系彈性體等。將基材層使用作為黏著層之情況，可使用改質聚烯烴或聚烯烴系彈性體、苯乙烯系彈性體、聚酯彈性體等。該等中，由生產性及透明性之方面而言，使用聚丙烯和聚烯烴彈性體作為中間層為佳。The base material layer is not particularly limited, and generally, a crystalline polyolefin such as polypropylene or polyethylene having a melting point of 100 ° C or higher, a polyester, a polyamide or a polyolefin elastomer can be used. When a base material layer is used as an adhesive layer, a modified polyolefin, a polyolefin elastomer, a styrene elastomer, a polyester elastomer, or the like can be used. Among these, in terms of productivity and transparency, it is preferred to use polypropylene and a polyolefin elastomer as the intermediate layer.

上述苯乙烯系彈性體與苯乙烯系低聚所構成之組成物、或者進一步在此組成物中視需要配合結晶性聚烯烴及/或烯烴系彈性體的組成物、以及在此組成物中進一步視需要配合樹脂改質劑或添加劑的組成物，藉由與上述表面層(A)或視需要與基材層(B)積層，則可作成構成本發明表面保護膜的追加層。A composition comprising the styrene-based elastomer and a styrene-based oligomerization, or a composition in which a crystalline polyolefin and/or an olefin-based elastomer is blended as needed in the composition, and a further view in the composition If it is necessary to mix a composition of a resin modifier or an additive with the surface layer (A) or the base layer (B) as needed, an additional layer constituting the surface protective film of the present invention can be obtained.

將表面層(A)與黏著層(X)、視需要之基材層(B)積層的方法並無特別限制，可列舉預先在T-字模成形或吹塑成形所得之表面層膜上，將黏著層(X)或者進一步視需要之基材層(B)以擠出層合、擠出塗敷等公知的積層法予以積層的方法，或將基材層及黏著層獨立作成膜後，將各個膜以乾式層合予以積層的方法等，由生產性方面而言，係以將表面層(A)、視需要之基材層(B)、及黏著層(X)各成分供給至多層擠出機予以成形的共同擠出成形為佳。The method of laminating the surface layer (A), the adhesive layer (X), and the optional base material layer (B) is not particularly limited, and it may be mentioned in advance on a surface layer film obtained by T-shaped molding or blow molding. The adhesive layer (X) or the further desired base layer (B) is laminated by a known lamination method such as extrusion lamination or extrusion coating, or the substrate layer and the adhesive layer are separately formed into a film, and then the substrate layer and the adhesive layer are separately formed into a film. A method of laminating each film by dry lamination, etc., in terms of productivity, supplying the surface layer (A), the optional substrate layer (B), and the adhesive layer (X) to a multi-layer extrusion Co-extrusion forming by forming the machine is preferred.

作為本發明表面保護膜之表面層(A)的厚度，係為0.1~100μm、較佳為0.3~50μm、更佳為0.5~30μm、再佳為1~20μm。作為黏著層(X)之厚度為0.1~50μm、較佳為0.3~40μm、再佳為0.5~30μm。The thickness of the surface layer (A) of the surface protective film of the present invention is 0.1 to 100 μm, preferably 0.3 to 50 μm, more preferably 0.5 to 30 μm, still more preferably 1 to 20 μm. The thickness of the adhesive layer (X) is 0.1 to 50 μm, preferably 0.3 to 40 μm, and more preferably 0.5 to 30 μm.

作為本發明表面保護膜之厚度為1~300μm、較佳為2~200μm、更佳為3~100μm。The thickness of the surface protective film of the present invention is 1 to 300 μm, preferably 2 to 200 μm, more preferably 3 to 100 μm.

藉由使用上述較佳形態之表面層(A)、黏著層(X)及視需要之基材層(B)，可表現黏著特性，特別是對於高凹凸被黏體優異之黏著力，且可取得透明性優異之表面保護膜，特別對於建材用途、光學用途可適當利用。By using the surface layer (A), the adhesive layer (X) and the optional substrate layer (B) of the above preferred embodiment, adhesive properties can be exhibited, particularly for high-adhesive adherends, and A surface protective film having excellent transparency can be suitably used for building materials and optical applications.

[實施例][Examples]

以下根據實施例詳細說明本發明，但本發明不被限定於該等實施例。Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited to the examples.

[評估法][evaluation method] 黏著力(丙烯酸板)：Adhesion (acrylic board):

將丙烯酸板切斷成寬50mm、長度125mm，並對此試驗板使用2公斤之橡膠輥予以貼附。其次，測定以300mm/分鐘之速度剝離(180度剝離)時的剝離力，並將每50mm寬之剝離力定為黏著力(N/50mm)。The acrylic plate was cut into a width of 50 mm and a length of 125 mm, and the test plate was attached with a 2 kg rubber roller. Next, the peeling force at the time of peeling at 180 mm/min (180 degree peeling) was measured, and the peeling force per 50 mm width was set as the adhesive force (N/50 mm).

白點(FE)：White point (FE):

準備A4大小的膜樣品，以目視計數長度0.1mm以上的白點。將換算成每單位面積之FE數定為FE數(個/m2)。A film sample of A4 size was prepared to visually count white spots having a length of 0.1 mm or more. The number of FEs converted per unit area was defined as the number of FEs (pieces/m 2 ).

耐污染性：Pollution resistance:

對寬50mm、長度125mm之黑色丙烯酸板貼附表面保護膜。於50℃保管7日後，剝離薄膜，確認對於黑色丙烯酸板的污染狀態。察見顯著污染之情況定為╳、觀測到少量污染之情況定為△、完全未察見污染者定為○。A surface protective film is attached to a black acrylic plate having a width of 50 mm and a length of 125 mm. After storage at 50 ° C for 7 days, the film was peeled off, and the state of contamination with respect to the black acrylic plate was confirmed. The situation in which significant pollution was observed was determined as ╳, the case where a small amount of pollution was observed was determined as △, and the case where no pollution was observed at all was determined as ○.

熔融流動速率(MFR)Melt flow rate (MFR)

根據ASTM D1238，以荷重2.16公斤、溫度230℃測定。It was measured according to ASTM D1238 at a load of 2.16 kg and a temperature of 230 °C.

[實施例1][Example 1]

對表面層、中間層及黏著層用，係於40mmΦ兼具單軸擠出機之模頭寬500mm的3種3層T-字模成形機中，將下列記載之樹脂以表1記載之組成物予以供給，取得表面層厚度為10μm、黏著層厚度為10μm、中間層厚度為30μm、總厚度為50μm的表面保護膜。所得膜之評估結果示於表1。For the surface layer, the intermediate layer and the adhesive layer, in the three-layer three-layer T-shaped molding machine with a die width of 500 mm and a single-axis extruder of 40 mm Φ , the following description of the resin is shown in Table 1. The material was supplied, and a surface protective film having a surface layer thickness of 10 μm, an adhesive layer thickness of 10 μm, an intermediate layer thickness of 30 μm, and a total thickness of 50 μm was obtained. The evaluation results of the obtained film are shown in Table 1.

表面層：Surface layer: PP-1：嵌段聚丙烯PP-1: block polypropylene (熔點160℃，MFR(230℃)3克/10分鐘)(melting point 160 ° C, MFR (230 ° C) 3 g / 10 minutes) 基材層：Substrate layer:

PP-2：均質聚丙烯PP-2: homogeneous polypropylene

(熔點160℃，MFR(230℃)7克/10分鐘)(melting point 160 ° C, MFR (230 ° C) 7 g / 10 min)

黏著層：Adhesive layer:

PEBR-1：丙烯‧乙烯‧1-丁烯共聚合體PEBR-1: propylene ‧ ethylene ‧ 1-butene copolymer

(乙烯含量10莫耳%，1-丁烯含量17莫耳%，MFR=7克/10分鐘，於-50~200℃之DSC測定中，具有熔解熱量4J/g之波峰)(Ethylene content 10 mol%, 1-butene content 17 mol%, MFR=7 g/10 min, with a melting peak of 4 J/g in DSC measurement at -50 to 200 °C)

PEBR-2：丙烯‧乙烯‧1-丁烯共聚合體PEBR-2: propylene ‧ ethylene ‧ 1-butene copolymer

(於-50~200℃之DSC測定中，無熔解熱量0.5J/g以上之波峰)(In the DSC measurement at -50~200°C, there is no peak of melting heat above 0.5J/g)

MP-1：丙烯‧乙烯共聚合體MP-1: propylene ‧ ethylene copolymer

(以茂金屬觸媒製造。熔點=115℃、MFR=7克/10分鐘、以聚苯乙烯作為基準的分子量分佈(Mw/Mn)=2.2)(Made by metallocene catalyst. Melting point = 115 ° C, MFR = 7 g/10 min, molecular weight distribution based on polystyrene (Mw / Mn) = 2.2)

PP-3：丙烯‧乙烯‧1-丁烯共聚合體PP-3: propylene ‧ ethylene ‧ 1-butene copolymer

(以齊格勒‧那塔觸媒製造。熔點=138℃，於-50~200℃之DSC測定中，具有65J/g之波峰)(Manufactured by Ziegler Natta Catalyst. Melting point = 138 ° C, with a peak of 65 J/g in DSC measurement at -50 to 200 ° C)

[實施例2及比較例1、2、3][Example 2 and Comparative Examples 1, 2, 3]

除了將各種層之樹脂組成作成表1記載之樹脂組成以外，同實施例1處理取得表面保護膜。所得膜之評估結果示於表1。A surface protective film was obtained by the same treatment as in Example 1 except that the resin composition of each layer was made into the resin composition shown in Table 1. The evaluation results of the obtained film are shown in Table 1.

Claims (4)

一種表面保護膜，其係由表面層(A)及黏著層(X)之至少2層所構成的表面保護膜，表面層(A)由聚烯烴樹脂所構成，黏著層(X)係由以使用茂金屬觸媒而得之碳數3以上之α-烯烴作為主成分的低結晶性α-烯烴(共)聚合體(X-1)5~95重量%、及熔點為50~130℃之範圍並使用茂金屬觸媒而得之丙烯(共)聚合體(X-2)95~5重量%((X-1)與(X-2)之合計為100重量%)所構成之組成物所形成。 A surface protective film comprising a surface protective film composed of at least two layers of a surface layer (A) and an adhesive layer (X), wherein the surface layer (A) is composed of a polyolefin resin, and the adhesive layer (X) is composed of a low crystalline α-olefin (co)polymer (X-1) having a carbon number of 3 or more and a α-olefin having a carbon number of 3 or more and 5 to 95% by weight, and a melting point of 50 to 130 ° C a composition comprising 95 to 5 wt% of a propylene (co)polymer (X-2) and a total of 100 wt% of (X-1) and (X-2) obtained by using a metallocene catalyst Formed. 如申請專利範圍第1項之表面保護膜，其中，形成黏著層(X)之組成物一部分的α-烯烴(共)聚合體(X-1)為丙烯與碳數2~10之α-烯烴(丙烯除外)的共聚合體。 The surface protective film of claim 1, wherein the α-olefin (co)polymer (X-1) forming a part of the composition of the adhesive layer (X) is propylene and an α-olefin having 2 to 10 carbon atoms. a copolymer of (except propylene). 如申請專利範圍第1或2項之表面保護膜，其中，形成黏著層(X)之組成物一部分的α-烯烴(共)聚合體(X-2)為熔點60~120℃之範圍並使用茂金屬觸媒而得之丙烯(共)聚合體。 The surface protective film according to claim 1 or 2, wherein the α-olefin (co)polymer (X-2) which forms a part of the composition of the adhesive layer (X) has a melting point of 60 to 120 ° C and is used. A propylene (co)polymer derived from a metallocene catalyst. 如申請專利範圍第1或2項之表面保護膜，其係將表面層(A)及黏著層(X)之至少2層由T-字模擠出成形而得之多層膜。 A surface protective film according to claim 1 or 2, which is obtained by extrusion molding at least two layers of the surface layer (A) and the adhesive layer (X) by a T-shaped mold.
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