WO2011096350A1 - Surface protective film - Google Patents

Surface protective film Download PDF

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Publication number
WO2011096350A1
WO2011096350A1 PCT/JP2011/051865 JP2011051865W WO2011096350A1 WO 2011096350 A1 WO2011096350 A1 WO 2011096350A1 JP 2011051865 W JP2011051865 W JP 2011051865W WO 2011096350 A1 WO2011096350 A1 WO 2011096350A1
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WO
WIPO (PCT)
Prior art keywords
protective film
surface protective
layer
propylene
copolymer
Prior art date
Application number
PCT/JP2011/051865
Other languages
French (fr)
Japanese (ja)
Inventor
井上　則英
久行 大胡田
Original Assignee
三井化学東セロ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 三井化学東セロ株式会社 filed Critical 三井化学東セロ株式会社
Priority to JP2011552761A priority Critical patent/JPWO2011096350A1/en
Publication of WO2011096350A1 publication Critical patent/WO2011096350A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—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
    • B32B27/32—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
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • 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
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/21—Anti-static
    • 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
    • B32B2307/538—Roughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/704—Crystalline
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/712—Weather resistant
    • 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
    • B32B2571/00—Protective equipment
    • 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
    • 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
    • C09J2423/106—Presence of homo or copolymers of propene in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2453/00—Presence of block copolymer

Definitions

  • the present invention relates to a surface protective film used for optical products, building materials, automobile parts and the like. Specifically, it has excellent adhesive properties, transparency, and heat resistance, has little contamination to the adherend, etc., and is easy to unwind when the film is unwound from a roll (hereinafter referred to as “unwinding property”). It is related with the surface protection film excellent in.
  • the surface protective film is used by sticking to adherends such as resin products, metal products, glass products, etc. mainly for building materials and optical applications, and prevents them from being scratched or contaminated during transport, storage or processing. Plays.
  • adherends such as resin products, metal products, glass products, etc. mainly for building materials and optical applications, and prevents them from being scratched or contaminated during transport, storage or processing. Plays.
  • These surface protective films generally comprise a non-adhesive surface layer and an adhesive layer for adhering to the adherend.
  • the surface layer is usually formed from a polyolefin such as polyethylene or polypropylene, a polyester such as polyethylene terephthalate, or a vinyl polymer such as polyvinyl chloride.
  • a surface protection film when used for building materials or automotive parts, it may be thermoformed with the surface protection film attached, and high heat resistance that can be used as a surface protection film is required even at high temperatures. Has been.
  • the surface protective film having a relatively high adhesive strength does not have a sufficient payout property, it is in a roll state in which a release film is bonded to the adhesive layer and wound up, and is applied to an adherend.
  • the release film is peeled off and used.
  • a large amount of release film is generated as waste, so that a surface protective film having sufficient payout property without a release film is required.
  • Patent Document 1 discloses a surface protective film mainly composed of a polyethylene component.
  • the protective film of the same publication can be applied to some application members, but has low adhesive strength and insufficient transparency, and the application of the adherend is limited.
  • Patent Document 2 discloses a protective film composed of a back layer and an adhesive layer obtained using a specific resin composition.
  • the protective film of the same publication does not sufficiently prevent the generation of fish eyes, and particularly when used as a protective film for an optical member or the like, there is a risk of adversely affecting the adherend, and there is a need for improvement.
  • the object of the present invention is to provide properties required as a surface protective film for protecting optical products, building material products and automobile parts during storage, transportation, processing and inspection, in particular, adhesive properties, transparency and heat resistance.
  • Another object of the present invention is to provide a surface protective film excellent in feeding performance.
  • the present invention is 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 propylene-based polymer, and the surface layer has a surface roughness.
  • the present invention relates to a surface protective film having (Ra) in the range of 0.2 to 2.0 ⁇ m.
  • the suitable aspect of this invention is the said surface protective film whose adhesive force with respect to an acryl is 1 N / 50mm or more, Furthermore, adhesive layer (X) is formed from an olefin-type elastomer and / or a styrene-type elastomer. It is the said surface protection film characterized by the above-mentioned.
  • the surface protective film of the present invention is excellent in adhesive properties, transparency, roll-out property from a rolled-up state and heat resistance, and is suitable as a surface protective film for optical use, building material use, and automotive part use.
  • the surface protective film of the present invention comprises at least two layers of a surface layer (A) and an adhesive layer (X).
  • the surface layer (A) is made of a propylene polymer.
  • propylene polymer examples include a propylene homopolymer, and a random or block copolymer of ethylene and / or an ⁇ -olefin having 4 to 20 carbon atoms together with propylene.
  • Examples of the ⁇ -olefin having 4 to 20 carbon atoms used in the random or block copolymer include 1-butene, 4-methylpentene-1, 1-hexene, 1-octene and the like.
  • Examples of such a copolymer include a propylene / ethylene copolymer, a propylene / 1-butene copolymer, and a propylene / ethylene / 1-butene copolymer.
  • the propylene polymer preferably has a melting point of 50 to 170 ° C., more preferably 70 to 170 ° C., more preferably 100 to 165 ° C., and most preferably 130 to 165 ° C. from the viewpoint of improving heat resistance.
  • the melting point is a value measured by a differential scanning calorimeter (DSC) at a temperature rising / falling rate of 10 ° C./min.
  • the propylene polymer preferably has a melt flow rate (hereinafter abbreviated as MFR) measured at 230 ° C. of preferably 0.01 to 500 g / 10 minutes, more preferably 0.1 to 100 g / 10 minutes, and still more preferably. It is in the range of 0.3 to 50 g / 10 minutes.
  • MFR melt flow rate
  • the propylene polymer is not only a solid titanium catalyst mainly composed of a solid titanium compound and an alkylaluminum compound, but also a homopolymerization of propylene in the presence of a metallocene compound, a metallocene catalyst, a geometrically constrained catalyst, etc. Alternatively, it can be obtained by copolymerizing ethylene and / or an ⁇ -olefin having 4 to 20 carbon atoms with propylene.
  • the surface roughness (Ra) of the surface layer (A) made of the propylene polymer is in the range of 0.2 to 2.0 ⁇ m from the viewpoint of transparency and feedability.
  • the surface roughness (Ra) is preferably 0.3 ⁇ m or more, and more preferably 0.4 ⁇ m or more.
  • the surface roughness (Ra) is preferably 1.5 ⁇ m or less, and more preferably 1.2 ⁇ m or less.
  • the surface roughness exceeds 2.0 ⁇ m, sufficient transparency cannot be obtained due to irregular reflection of light rays on the surface.
  • an example of the propylene polymer includes a method using a block copolymer of propylene and ethylene (hereinafter referred to as “propylene / ethylene block copolymer”).
  • the MFR (230 ° C.) of the propylene / ethylene block copolymer is preferably in the range of 3 to 20 g / 10 minutes, more preferably 4 to 15 g / 10 minutes.
  • the intrinsic viscosity ([ ⁇ ]) of the rubber component in the propylene / ethylene copolymer is preferably 2.0 dl / g or more.
  • an antistatic agent for the purpose of imparting antistatic properties and weather resistance to the surface protective film of the present invention, improving transparency and improving the appearance, an antistatic agent, a release agent, an oxidation agent It is also possible to add various additives such as inhibitors, weathering agents, crystal nucleating agents, and other resin modifiers such as other crystalline polyolefins such as polyethylene and polybutene, polyesters, polyamides, and elastomers.
  • the film is kneaded with a single-screw or twin-screw extruder, a feeder ruder, etc.
  • a single-screw or twin-screw extruder a feeder ruder, etc.
  • it may be directly put into a T-die molding machine equipped with an extruder to form the surface layer (A) of the surface protective film of the present invention.
  • any known pressure-sensitive adhesive used as the pressure-sensitive adhesive layer of the surface protective film can be used.
  • an olefin elastomer and / or a styrene elastomer is preferable. More preferably, it is an olefin elastomer or a composition comprising an olefin elastomer and a styrene elastomer.
  • an amorphous elastomer whose melting point is not observed in the range of 0 to 200 ° C. by DSC measurement (measured at a temperature rising / falling rate of 10 ° C./min), or is observed in the range of 0 to 200 ° C.
  • a microcrystalline elastomer in which a peak having a melting heat quantity of a melting point peak of 10 J / g or less is suitable, and more preferably, the amorphous elastomer or a microcrystalline elastomer having a melting heat quantity of a melting point peak of 7 J / g or less. It is.
  • the olefin-based elastomer includes an ⁇ -olefin polymer or copolymer having 2 to 20 carbon atoms, or a copolymer of ethylene and unsaturated carboxylic acid or unsaturated carboxylic acid ester.
  • ethylene / propylene copolymer ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene / 4-methylpentene-1 copolymer, ethylene / 1-octene copolymer , Propylene homopolymer, propylene / ethylene copolymer, propylene / ethylene / 1-butene copolymer, 1-butene homopolymer, 1-butene / ethylene copolymer, 1-butene / propylene copolymer, 4 -Methylpentene-1 homopolymer, 4-methylpentene-1 / propylene copolymer, 4-methylpentene-1 / 1-butene copolymer, 4-methylpentene-1 / propylene / 1-butene copolymer , Propylene / 1-butene copolymer, ethylene / vinyl acetate copolymer, ethylene / methacrylic acid cop
  • propylene homopolymer propylene / ethylene copolymer, propylene / 1-butene copolymer, and propylene / ethylene / 1-butene copolymer are preferable.
  • styrene elastomer a known styrene elastomer having a polystyrene phase as a hard segment can be used. Specifically, styrene / butadiene copolymer (SBR), styrene / isoprene / styrene copolymer (SIS), styrene / butadiene / styrene copolymer (SBS), and hydrides thereof (SEBS, SEPS, etc.) And styrene / isobutylene / styrene triblock copolymer (SIBS) and styrene / isobutylene diblock copolymer (SIB).
  • SIBS styrene / isobutylene / styrene triblock copolymer
  • SIB styrene / isobutylene diblock copolymer
  • SIBS styrene / isobutylene / styrene triblock copolymer
  • SIB styrene / isobutylene diblock copolymer
  • the adhesive layer (X) in the surface protective film of the present invention can be formed by using the olefin elastomer and / or styrene elastomer alone or by blending components having different compositions. Further, in the present invention, for the purpose of controlling the adhesive force, and within a range not impairing the effects of the present invention, polyolefins such as polyethylene and polypropylene, resin modifiers such as acid-modified polyolefin, polyester and polyamide, Various additives such as an inhibitor, a crystal nucleating agent and an antioxidant may be contained.
  • the olefin-based elastomer comprises 0 to 80% by weight and styrene-based elastomer 20 to 100% by weight. It is preferably composed of 0 to 75% by weight of olefin elastomer and 25 to 100% by weight of styrene elastomer, more preferably 5 to 75% by weight of olefin elastomer and 25 to 95% by weight of styrene elastomer.
  • the adhesive layer may contain other components as necessary, but in order to explain the ratio between the olefin-based elastomer and the styrene-based elastomer, the total of only these is displayed as 100% by weight. ing).
  • the adhesive layer (X) in the surface protective film of the present invention can be formed by using the olefin elastomer and / or styrene elastomer alone or by blending components having different compositions.
  • a polyolefin modifier such as polyethylene or polypropylene, an acid-modified polyolefin, a polyester, a polyamide, or a resin modifier, as long as the effect of the present invention is not impaired,
  • Various additives such as an antistatic agent, a crystal nucleating agent and an antioxidant may be contained.
  • the adhesive layer (X) composed of the olefin elastomer and / or styrene elastomer and, if necessary, a resin modifier or an additive is laminated with the surface layer (A), whereby the surface protective film of the present invention. It can be.
  • the adhesive strength of the surface protective film of the present invention to the acrylic plate is an index of the drawability and the adhesive strength to the adherend, and is preferably 1 N / 50 mm or more, more preferably in the range of 3 to 40 N / 50 mm, and more. Preferably, it is in the range of 5 to 30 N / 50 mm.
  • the adhesive strength is less than 1 N / 50 mm, the adherence to the adherend may not be sufficient, and when it exceeds 40 N / 50 mm, the rewinding property may deteriorate, which is not preferable.
  • the unwinding force of the surface protective film of the present invention refers to a peeling force when a roll-shaped film is unrolled, and serves as an index of unwinding property.
  • the unwinding force is 2.5 N / It is preferably 50 mm or less, more preferably in the range of 0.01 to 2.0 N / 50 mm.
  • the method for laminating the surface layer (A) and the adhesive layer (X) is not particularly limited, but known methods such as extrusion lamination and extrusion coating on the surface layer film obtained in advance by T-die molding or inflation molding.
  • At least one intermediate layer is also provided between the surface layer (A) and the adhesive layer (X).
  • middle layer Generally, crystalline polyolefins, such as a polypropylene and polyethylene with melting
  • modified polyolefin, polyolefin elastomer, styrene elastomer, polyester elastomer, or the like is used. Among these, from the viewpoint of productivity and transparency, it is preferable to use polypropylene or polyolefin elastomer as the intermediate layer.
  • the intermediate layer is an adhesive or a film for bonding the surface layer (A) and the pressure-sensitive adhesive layer (X).
  • the material may be configured as an adhesive layer.
  • the thickness of the surface layer (A) in the surface protective film of the present invention is usually 0.05 to 200 ⁇ m, preferably 0.5 to 100 ⁇ m, more preferably 1 to 30 ⁇ m, and still more preferably 1 to 15 ⁇ m.
  • the thickness of the pressure-sensitive adhesive layer (X) is usually 0.05 to 50 ⁇ m, preferably 0.3 to 40 ⁇ m, more preferably 0.5 to 30 ⁇ m.
  • the thickness of the surface protective film of the present invention is usually 0.1 to 500 ⁇ m, preferably 0.5 to 400 ⁇ m, more preferably 3 to 300 ⁇ m, including an intermediate layer which may be provided if necessary.
  • the haze measured at 50 ⁇ m according to JISK7105 is preferably in the range of 20 to 90%, particularly preferably in the range of 30 to 85%.
  • the number of fish eyes (FE number) of the surface protective film of the present invention is preferably 20 or less, more preferably 10 or less, 5 or less, and even more preferably 3 or less.
  • Adhesive strength Acrylic plate is cut into a width of 50 mm and a length of 125 mm under conditions of an air temperature of 23 ° C. ⁇ 2 ° C. and a humidity of 50% ⁇ 10%, a film sample is placed on the surface of the acrylic plate, and a 2 kg rubber roller Is attached to the acrylic plate by pressing the entire sample film with its own weight. Next, the peel force when peeled at a speed of 300 mm / min (180 degree peel) is measured, and the peel force per 50 mm width is defined as the adhesive strength (N / 50 mm).
  • Unwinding force Using a roll-shaped sample, the peeling force (N / 50 mm) when peeling from the roll at a speed of 300 mm / min is measured and defined as the unwinding force.
  • Example 1 The raw materials were respectively supplied to a three-type three-layer T-die molding machine having a die width of 500 mm, which was combined with a 30 mm ⁇ single screw extruder for the surface layer and the adhesive layer and a 40 mm ⁇ single screw extruder for the intermediate layer, and the surface layer thickness was 10 ⁇ m.
  • Example 1 shows the raw material which comprises the surface layer of an Example and a comparative example, an intermediate
  • Example 2 to 4 Comparative Examples 1 to 3
  • a surface protective film was obtained in the same manner as in Example 1 except that the resin compositions of the various layers were changed to the resin compositions shown in Table 1.
  • Table 1 shows the evaluation results of the obtained film.
  • the unwinding force is 0.1 to 1.6 N / 50 mm, and it can be seen that it has an excellent feeding property. This is because the surface roughness (Ra) is an appropriate roughness of 0.47 to 0.81 ⁇ m while having sufficient adhesive strength.
  • the haze is 60 to 70%, and the haze has excellent transparency as a surface protective film when it is required to have transparency of 80% or less. I understand.
  • Comparative Examples 1 and 2 the adhesive strength is 7 to 18 N / 50 mm, and sufficient adhesiveness is ensured.
  • the unwinding force is such that peeling does not occur and the feeding property is extremely high. It turns out that it is inferior. This is because in Comparative Examples 1 and 2, the surface roughness (Ra) was as extremely small as 0.25 ⁇ m and 0.05 ⁇ m, respectively, which made peeling difficult.
  • the surface roughness (Ra) is 0.28 ⁇ m
  • the adhesive strength is sufficient
  • the unwinding force is also 0.5 N / 50 mm, that is, the feeding property is good.
  • the surface layer is composed of a composition of h-PP and LDPE (Comparative Example 3)
  • the fish eye number (FE number) is large and is not suitable as a surface protective film.
  • the surface layer is made of a propylene polymer.
  • the surface protective film of the present invention is excellent in adhesive properties, transparency, unwinding property and heat resistance, and has a very high industrial utility value as a protective film for optical use, building material use and automobile part use.

Abstract

Disclosed is a surface protective film which exhibits high adhesion and excellent unwinding characteristics. The surface protective film is characterised in that: the surface protective film comprises at least two layers, which are a surface layer (A) and an adhesive layer (X); the surface layer (A) comprises a propylene polymer and the surface roughness (Ra) of the surface layer is within the range of 0.2-2.0μm; the adhesive strength of the surface protective film with acrylic is 1N/50mm; and the adhesive layer (X) is formed from an olefinic elastomer and/or a styrene elastomer.

Description

表面保護フィルムSurface protection film
　本発明は、光学製品、建材、自動車部品等に使用される表面保護フィルムに関する。詳しくは、粘着特性、透明性、耐熱性に優れ、被着体等への汚染が少なく、さらにフィルムがロール状に巻き取られた状態から繰り出す際の繰り出しの容易性（以下、「繰り出し性」という。）に優れた表面保護フィルムに関する。 The present invention relates to a surface protective film used for optical products, building materials, automobile parts and the like. Specifically, it has excellent adhesive properties, transparency, and heat resistance, has little contamination to the adherend, etc., and is easy to unwind when the film is unwound from a roll (hereinafter referred to as “unwinding property”). It is related with the surface protection film excellent in.
　表面保護フィルムは、主として建材用や光学用途用の樹脂製品、金属製品、ガラス製品等の被着体に貼付して使用し、これらの輸送、保管や加工時の傷付きまたは異物混入を防ぐ役割を果たしている。これらの表面保護フィルムは、一般には粘着性の無い表面層と、前記被着体と粘着させるための粘着層とからなる。表面層は通常、ポリエチレンやポリプロピレンなどのポリオレフィンや、ポリエチレンテレフタレートなどのポリエステル、ポリ塩化ビニルなどのビニル重合体から形成される。 The surface protective film is used by sticking to adherends such as resin products, metal products, glass products, etc. mainly for building materials and optical applications, and prevents them from being scratched or contaminated during transport, storage or processing. Plays. These surface protective films generally comprise a non-adhesive surface layer and an adhesive layer for adhering to the adherend. The surface layer is usually formed from a polyolefin such as polyethylene or polypropylene, a polyester such as polyethylene terephthalate, or a vinyl polymer such as polyvinyl chloride.
　近年、液晶画面、プラズマディスプレイ（ＰＤＰ）やリアプロジェクション画面等に用いる部材、いわゆる光学製品の開発が進んでいる。これら光学製品を保護するための表面保護フィルムに対し、傷付きや異物混入のみならず、表面保護フィルムを貼付した状態で製品検査ができる程度の透明性等の特性が所望されている。 In recent years, development of materials used for liquid crystal screens, plasma displays (PDPs), rear projection screens, etc., so-called optical products, has been progressing. For surface protection films for protecting these optical products, there are demands for characteristics such as transparency so that product inspection can be performed in a state where the surface protection film is applied, as well as scratches and foreign matter contamination.
　また、表面保護フィルムを建材や自動車部品用途に使用した場合、表面保護フィルムを貼付した状態で熱成形される場合があり、高温状態でも表面保護フィルムとしての使用可能な程度の高い耐熱性が要求されている。 In addition, when a surface protection film is used for building materials or automotive parts, it may be thermoformed with the surface protection film attached, and high heat resistance that can be used as a surface protection film is required even at high temperatures. Has been.
　また、比較的粘着力の高い表面保護フィルムでは、十分な繰り出し性を有していないため、粘着層に対し離型フィルムを貼り合わせて巻き取ったロール状態とし、被着体への貼付の際にこの離型フィルムを剥がして使用している。このような手段を採用すると、大量の離型フィルムが廃棄物として発生することから、離型フィルムが無くても十分な繰り出し性を有する表面保護フィルムが求められている。 In addition, since the surface protective film having a relatively high adhesive strength does not have a sufficient payout property, it is in a roll state in which a release film is bonded to the adhesive layer and wound up, and is applied to an adherend. The release film is peeled off and used. When such a means is employed, a large amount of release film is generated as waste, so that a surface protective film having sufficient payout property without a release film is required.
　特許文献１には、ポリエチレン成分を主体とした表面保護フィルムが開示されている。しかしながら、同公報の保護フィルムでは、一部の用途部材に対しては適用可能であるが、粘着力が低く、また透明性も不充分で、被着体の用途には限りがあった。 Patent Document 1 discloses a surface protective film mainly composed of a polyethylene component. However, the protective film of the same publication can be applied to some application members, but has low adhesive strength and insufficient transparency, and the application of the adherend is limited.
　特許文献２には、特定の樹脂組成物を用いて得られる背面層および粘着層からなる保護フィルムが開示されている。しかしながら、同公報の保護フィルムでは、フィッシュアイの発生防止が充分でなく、特に光学部材等の保護フィルムとして使用した場合、被着体へ悪影響を及ぼすおそれもあり、改良が求められている。 Patent Document 2 discloses a protective film composed of a back layer and an adhesive layer obtained using a specific resin composition. However, the protective film of the same publication does not sufficiently prevent the generation of fish eyes, and particularly when used as a protective film for an optical member or the like, there is a risk of adversely affecting the adherend, and there is a need for improvement.
特開２００６－１１６７６９号公報JP 2006-116769 A 特開２００９－２８９３８号公報JP 2009-28938 A
　本発明の課題は、光学製品、建材製品や自動車部品の保管、輸送、加工、検査時に、これらを保護するための表面保護フィルムとして要求される特性、特には、粘着特性、透明性、耐熱性および繰出し性に優れた表面保護フィルムを提供することにある。 The object of the present invention is to provide properties required as a surface protective film for protecting optical products, building material products and automobile parts during storage, transportation, processing and inspection, in particular, adhesive properties, transparency and heat resistance. Another object of the present invention is to provide a surface protective film excellent in feeding performance.
　本発明者らは、上記課題に鑑み、鋭意検討した結果、ある特定の樹脂組成物からなる表面層を有する表面保護フィルムにより上記課題が解決できることを見出し、本発明を完成するに至った。 As a result of intensive studies in view of the above problems, the present inventors have found that the above problems can be solved by a surface protective film having a surface layer made of a specific resin composition, and have completed the present invention.
　すなわち、本発明は、表面層（Ａ）および粘着層（Ｘ）の少なくとも２層からなる表面保護フィルムであり、表面層（Ａ）が、プロピレン系重合体からなり、かつ表面層の表面粗さ（Ｒａ）が０．２～２．０μｍの範囲にある表面保護フィルムに関する。 That is, the present invention is 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 propylene-based polymer, and the surface layer has a surface roughness. The present invention relates to a surface protective film having (Ra) in the range of 0.2 to 2.0 μm.
　さらに本発明の好適な態様は、アクリルに対する粘着力が、１Ｎ／５０ｍｍ以上である上記表面保護フィルムであり、さらには、粘着層（Ｘ）がオレフィン系エラストマーおよび／またはスチレン系エラストマーから形成されることを特徴とする上記表面保護フィルムである。 Furthermore, the suitable aspect of this invention is the said surface protective film whose adhesive force with respect to an acryl is 1 N / 50mm or more, Furthermore, adhesive layer (X) is formed from an olefin-type elastomer and / or a styrene-type elastomer. It is the said surface protection film characterized by the above-mentioned.
　本発明の表面保護フィルムは、粘着特性、透明性、ロール状に巻き取られた状態からの繰り出し性および耐熱性に優れ、光学用途、建材用途、自動車部品用途の表面保護フィルムとして好適である。 The surface protective film of the present invention is excellent in adhesive properties, transparency, roll-out property from a rolled-up state and heat resistance, and is suitable as a surface protective film for optical use, building material use, and automotive part use.
　次に本発明について詳細に説明する。 Next, the present invention will be described in detail.
　本発明の表面保護フィルムは、表面層（Ａ）および粘着層（Ｘ）の少なくとも２層からなる。 The surface protective film of the present invention comprises at least two layers of a surface layer (A) and an adhesive layer (X).
　表面層（Ａ）は、プロピレン系重合体からなる。 The surface layer (A) is made of a propylene polymer.
　プロピレン系重合体としては、例えばプロピレン単独重合体、プロピレンと共にエチレン及び／または炭素数４～２０のα－オレフィンとのランダムまたはブロック共重合体を挙げることができる。 Examples of the propylene polymer include a propylene homopolymer, and a random or block copolymer of ethylene and / or an α-olefin having 4 to 20 carbon atoms together with propylene.
　前記ランダムまたはブロック共重合体に用いられる炭素数４～２０のα－オレフィンとしては、１－ブテン、４－メチルペンテン－１、１－ヘキセン、１－オクテン等を挙げることができる。このような共重合として、プロピレン・エチレン共重合体、プロピレン・１－ブテン共重合体、プロピレン・エチレン・１－ブテン共重合体等を挙げることができる。 Examples of the α-olefin having 4 to 20 carbon atoms used in the random or block copolymer include 1-butene, 4-methylpentene-1, 1-hexene, 1-octene and the like. Examples of such a copolymer include a propylene / ethylene copolymer, a propylene / 1-butene copolymer, and a propylene / ethylene / 1-butene copolymer.
　プロピレン系重合体は、耐熱性の向上の観点から融点が好ましくは５０～１７０℃、より好ましくは７０～１７０℃、さらに好ましくは１００～１６５℃、その中でも１３０～１６５℃が最も好ましい。ここで、融点とは、示差走査熱量計（ＤＳＣ）により、昇温および降温速度１０℃／ｍｉｎにて測定した値である。 The propylene polymer preferably has a melting point of 50 to 170 ° C., more preferably 70 to 170 ° C., more preferably 100 to 165 ° C., and most preferably 130 to 165 ° C. from the viewpoint of improving heat resistance. Here, the melting point is a value measured by a differential scanning calorimeter (DSC) at a temperature rising / falling rate of 10 ° C./min.
　また、プロピレン系重合体は、２３０℃で測定したメルトフローレート（以下、ＭＦＲと略記）が好ましくは０．０１～５００ｇ／１０分、より好ましくは０．１～１００ｇ／１０分、さらに好ましくは０．３～５０ｇ／１０分の範囲にある。 The propylene polymer preferably has a melt flow rate (hereinafter abbreviated as MFR) measured at 230 ° C. of preferably 0.01 to 500 g / 10 minutes, more preferably 0.1 to 100 g / 10 minutes, and still more preferably. It is in the range of 0.3 to 50 g / 10 minutes.
　前記プロピレン系重合体は、固体状チタン化合物およびアルキルアルミニウム化合物を主成分とした固体状チタン触媒のみならず、メタロセン化合物を主成分としてメタロセン触媒、幾何拘束触媒等の存在下に、プロピレンの単独重合またはプロピレンと共にエチレン及び／または炭素数４～２０のα－オレフィンとを共重合することによって得られる。 The propylene polymer is not only a solid titanium catalyst mainly composed of a solid titanium compound and an alkylaluminum compound, but also a homopolymerization of propylene in the presence of a metallocene compound, a metallocene catalyst, a geometrically constrained catalyst, etc. Alternatively, it can be obtained by copolymerizing ethylene and / or an α-olefin having 4 to 20 carbon atoms with propylene.
　本発明の表面保護フィルムにおいては、透明性及び繰り出し性の観点から前記プロピレン重合体からなる表面層（Ａ）の表面粗さ（Ｒａ）は０．２～２．０μｍの範囲にある。その中でも表面粗さ（Ｒａ）は、０．３μｍ以上が好ましく、さらには０．４μｍ以上が好ましい。また表面粗さ（Ｒａ）は、１．５μｍ以下が好ましく、さらに１．２μｍ以下が好ましい。前記表面粗さが０．２μｍ未満であると表面層が粘着層から剥離することが困難となり繰り出し性が低下する。一方、前記表面粗さが２．０μｍを越えると表面での光線の乱反射により十分な透明性が得られない。

　上記表面層の表面粗さを形成する方法としては特に制限は無いが、エンボスロールを表面層に転写し、表面粗さを形成する方法や、前記プロピレン系重合体の分子量や組成を変えることにより表面粗さを制御する方法が用いられる。生産性の観点から、好ましくはプロピレン系重合体の分子量や組成を制御する方法が採用される。好適な表面粗さを実現するためにプロピレン系重合体の例として、プロピレンとエチレンとのブロック共重合体（以下、「プロピレン・エチレンブロック共重合体」という。）を用いる方法が挙げられる。プロピレン・エチレンブロック共重合体のＭＦＲ（２３０℃）は好ましくは３～２０ｇ／１０分、より好ましくは４～１５ｇ／１０分の範囲にある。プロピレン・エチレン共重合体におけるゴム成分の極限粘度（［η］）が２．０ｄｌ／ｇ以上であることが好ましい。 In the surface protective film of the present invention, the surface roughness (Ra) of the surface layer (A) made of the propylene polymer is in the range of 0.2 to 2.0 μm from the viewpoint of transparency and feedability. Among them, the surface roughness (Ra) is preferably 0.3 μm or more, and more preferably 0.4 μm or more. The surface roughness (Ra) is preferably 1.5 μm or less, and more preferably 1.2 μm or less. When the surface roughness is less than 0.2 μm, it is difficult for the surface layer to peel from the adhesive layer, and the feeding property is lowered. On the other hand, when the surface roughness exceeds 2.0 μm, sufficient transparency cannot be obtained due to irregular reflection of light rays on the surface.

Although there is no restriction | limiting in particular as a method of forming the surface roughness of the said surface layer, By transferring the embossing roll to a surface layer and forming surface roughness, or changing the molecular weight and composition of the said propylene polymer. A method for controlling the surface roughness is used. From the viewpoint of productivity, a method of controlling the molecular weight and composition of the propylene polymer is preferably employed. In order to achieve a suitable surface roughness, an example of the propylene polymer includes a method using a block copolymer of propylene and ethylene (hereinafter referred to as “propylene / ethylene block copolymer”). The MFR (230 ° C.) of the propylene / ethylene block copolymer is preferably in the range of 3 to 20 g / 10 minutes, more preferably 4 to 15 g / 10 minutes. The intrinsic viscosity ([η]) of the rubber component in the propylene / ethylene copolymer is preferably 2.0 dl / g or more.
　表面層（Ａ）として用いるプロピレン系重合体中には、本発明の表面保護フィルムへの帯電防止性や耐候性付与、透明性向上や外観向上を目的として、帯電防止剤、離型剤、酸化防止剤、耐候剤、結晶核剤などの各種添加剤や、ポリエチレンやポリブテンなどの他の結晶性ポリオレフィン、ポリエステル、ポリアミド、エラストマー等の樹脂改質剤を添加することも可能である。 In the propylene polymer used as the surface layer (A), for the purpose of imparting antistatic properties and weather resistance to the surface protective film of the present invention, improving transparency and improving the appearance, an antistatic agent, a release agent, an oxidation agent It is also possible to add various additives such as inhibitors, weathering agents, crystal nucleating agents, and other resin modifiers such as other crystalline polyolefins such as polyethylene and polybutene, polyesters, polyamides, and elastomers.
　前記プロピレン系重合体に必要に応じて添加剤や改質剤を添加する場合には、例えば添加剤等を添加後、単軸または二軸押出機やフィーダールーダー等により混錬した上で、フィルム状に加工しても良いが、押出機を兼ね備えたＴ－ダイ成形機に直接投入し、本発明の表面保護フィルムの表面層（Ａ）とすることもできる。 When an additive or a modifier is added to the propylene-based polymer as necessary, for example, after the addition of the additive, etc., the film is kneaded with a single-screw or twin-screw extruder, a feeder ruder, etc. However, it may be directly put into a T-die molding machine equipped with an extruder to form the surface layer (A) of the surface protective film of the present invention.
　本発明の表面保護フィルムの粘着層（Ｘ）としては、表面保護フィルムの粘着層として使用されている公知の粘着剤であれば使用することが可能であるが、フィッシュアイの発生による被着体の損傷や、粘着剤の被着体への移行、即ち糊残りの観点から、オレフィン系エラストマーおよび／またはスチレン系エラストマーであることが好ましい。より好ましくは、オレフィン系エラストマー、またはオレフィン系エラストマーとスチレン系エラストマーからなる組成物である。 As the pressure-sensitive adhesive layer (X) of the surface protective film of the present invention, any known pressure-sensitive adhesive used as the pressure-sensitive adhesive layer of the surface protective film can be used. From the viewpoint of damage of the adhesive and the transfer of the adhesive to the adherend, that is, the adhesive residue, an olefin elastomer and / or a styrene elastomer is preferable. More preferably, it is an olefin elastomer or a composition comprising an olefin elastomer and a styrene elastomer.
　オレフィン系エラストマーとしては、ＤＳＣ測定（昇温および降温速度１０℃／ｍｉｎにて測定）による融点が０～２００℃の範囲に観測されない非晶性エラストマー、または０～２００℃の範囲に観測される融点ピークの融解熱量が１０Ｊ／ｇ以下であるピークが観測される微結晶性エラストマーが好適であり、さらに好ましくは前記非晶性エラストマーまたは融点ピークの融解熱量が７Ｊ／ｇ以下の微結晶性エラストマーである。 As the olefin-based elastomer, an amorphous elastomer whose melting point is not observed in the range of 0 to 200 ° C. by DSC measurement (measured at a temperature rising / falling rate of 10 ° C./min), or is observed in the range of 0 to 200 ° C. A microcrystalline elastomer in which a peak having a melting heat quantity of a melting point peak of 10 J / g or less is suitable, and more preferably, the amorphous elastomer or a microcrystalline elastomer having a melting heat quantity of a melting point peak of 7 J / g or less. It is.
　前記オレフィン系エラストマーとしては炭素数２～２０のα－オレフィン重合体または共重合体、ないしはエチレンと不飽和カルボン酸または不飽和カルボン酸エステルとの共重合体がある。具体的には、エチレン・プロピレン共重合体、エチレン・１－ブテン共重合体、エチレン・１－ヘキセン共重合体、エチレン・４－メチルペンテン－１共重合体、エチレン・１－オクテン共重合体、プロピレン単独重合体、プロピレン・エチレン共重合体、プロピレン・エチレン・１－ブテン共重合体、１－ブテン単独重合体、１－ブテン・エチレン共重合体、１－ブテン・プロピレン共重合体、４－メチルペンテン－１単独重合体、４－メチルペンテン－１・プロピレン共重合体、４－メチルペンテン－１・１－ブテン共重合体、４－メチルペンテン－１・プロピレン・１－ブテン共重合体、プロピレン・１－ブテン共重合体、エチレン・酢酸ビニル共重合体、エチレン・メタクリル酸共重合体、エチレン・メタクリル酸メチル共重合体等を挙げることができる。粘着力の経時安定性の点から、好ましくは、プロピレン単独共重合体、プロピレン・エチレン共重合体、プロピレン・１－ブテン共重合体、プロピレン・エチレン・１－ブテン共重合体である。 The olefin-based elastomer includes an α-olefin polymer or copolymer having 2 to 20 carbon atoms, or a copolymer of ethylene and unsaturated carboxylic acid or unsaturated carboxylic acid ester. Specifically, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene / 4-methylpentene-1 copolymer, ethylene / 1-octene copolymer , Propylene homopolymer, propylene / ethylene copolymer, propylene / ethylene / 1-butene copolymer, 1-butene homopolymer, 1-butene / ethylene copolymer, 1-butene / propylene copolymer, 4 -Methylpentene-1 homopolymer, 4-methylpentene-1 / propylene copolymer, 4-methylpentene-1 / 1-butene copolymer, 4-methylpentene-1 / propylene / 1-butene copolymer , Propylene / 1-butene copolymer, ethylene / vinyl acetate copolymer, ethylene / methacrylic acid copolymer, ethylene / methyl methacrylate copolymer, etc. It can be mentioned. From the viewpoint of stability of adhesive strength with time, propylene homopolymer, propylene / ethylene copolymer, propylene / 1-butene copolymer, and propylene / ethylene / 1-butene copolymer are preferable.
　スチレン系エラストマーとしては、ポリスチレン相をハードセグメントとして有する公知のスチレン系エラストマーが使用できる。具体的には、スチレン・ブタジエン共重合体（ＳＢＲ）、スチレン・イソプレン・スチレン共重合体（ＳＩＳ）、スチレン・ブタジエン・スチレン共重合体（ＳＢＳ）、およびこれらの水素化物（ＳＥＢＳ、ＳＥＰＳ等）、スチレン・イソブチレン・スチレントリブロック共重合体（ＳＩＢＳ）、スチレン・イソブチレンジブロック共重合体（ＳＩＢ）を挙げることができる。被着体との粘着性および繰り出し性の観点から、好ましくはスチレン・イソブチレン・スチレントリブロック共重合体（ＳＩＢＳ）、スチレン・イソブチレンジブロック共重合体（ＳＩＢ）を挙げることができる。 As the styrene elastomer, a known styrene elastomer having a polystyrene phase as a hard segment can be used. Specifically, styrene / butadiene copolymer (SBR), styrene / isoprene / styrene copolymer (SIS), styrene / butadiene / styrene copolymer (SBS), and hydrides thereof (SEBS, SEPS, etc.) And styrene / isobutylene / styrene triblock copolymer (SIBS) and styrene / isobutylene diblock copolymer (SIB). From the viewpoint of adhesiveness to the adherend and feeding property, styrene / isobutylene / styrene triblock copolymer (SIBS) and styrene / isobutylene diblock copolymer (SIB) are preferable.
　上記オレフィン系エラストマーおよび／またはスチレン系エラストマーを、単独または各々異なる組成の成分をブレンド使用することで、本発明の表面保護フィルムにおける粘着層（Ｘ）を形成することができる。また、本発明においては、粘着力の制御を目的として、さらには本発明の効果を損なわない範囲で、ポリエチレンやポリプロピレンなどのポリオレフィン、酸変性ポリオレフィン、ポリエステル、ポリアミド等の樹脂改質剤や、帯電防止剤、結晶核剤、酸化防止剤等の各種添加剤を含んでいてもよい。 The adhesive layer (X) in the surface protective film of the present invention can be formed by using the olefin elastomer and / or styrene elastomer alone or by blending components having different compositions. Further, in the present invention, for the purpose of controlling the adhesive force, and within a range not impairing the effects of the present invention, polyolefins such as polyethylene and polypropylene, resin modifiers such as acid-modified polyolefin, polyester and polyamide, Various additives such as an inhibitor, a crystal nucleating agent and an antioxidant may be contained.
　前記オレフィン系エラストマーおよび／またはスチレン系エラストマーを本発明の表面保護フィルムの粘着層（Ｘ）を形成するため使用する場合、オレフィン系エラストマー０～８０重量％およびスチレン系エラストマー２０～１００重量％からなることが好適であり、さらに好ましくはオレフィン系エラストマー０～７５重量％およびスチレン系エラストマー２５～１００重量％、より好ましくは、オレフィン系エラストマー５～７５重量％およびスチレン系エラストマー２５～９５重量％からなる（粘着層には、必要に応じて他の成分が含まれる場合があるが、オレフィン系エラストマーとスチレン系エラストマーとの間の比率を説明するため、これらのみについての合計を１００重量％として表示している）。 When the olefin-based elastomer and / or styrene-based elastomer is used for forming the adhesive layer (X) of the surface protective film of the present invention, the olefin-based elastomer comprises 0 to 80% by weight and styrene-based elastomer 20 to 100% by weight. It is preferably composed of 0 to 75% by weight of olefin elastomer and 25 to 100% by weight of styrene elastomer, more preferably 5 to 75% by weight of olefin elastomer and 25 to 95% by weight of styrene elastomer. (The adhesive layer may contain other components as necessary, but in order to explain the ratio between the olefin-based elastomer and the styrene-based elastomer, the total of only these is displayed as 100% by weight. ing).
　上記オレフィン系エラストマーおよび／またはスチレン系エラストマーを、単独または各々異なる組成の成分をブレンド使用することで、本発明の表面保護フィルムにおける粘着層（Ｘ）を形成することができる。また、粘着層（Ｘ）においては、粘着力の制御を目的として、本発明の効果を損なわない範囲で、ポリエチレンやポリプロピレンなどのポリオレフィン、酸変性ポリオレフィン、ポリエステル、ポリアミド等の樹脂改質剤や、帯電防止剤、結晶核剤、酸化防止剤等の各種添加剤を含んでいてもよい。 The adhesive layer (X) in the surface protective film of the present invention can be formed by using the olefin elastomer and / or styrene elastomer alone or by blending components having different compositions. In the adhesive layer (X), for the purpose of controlling the adhesive force, a polyolefin modifier such as polyethylene or polypropylene, an acid-modified polyolefin, a polyester, a polyamide, or a resin modifier, as long as the effect of the present invention is not impaired, Various additives such as an antistatic agent, a crystal nucleating agent and an antioxidant may be contained.
　上記オレフィン系エラストマーおよび／またはスチレン系エラストマー、および必要に応じて樹脂改質剤または添加剤からなる粘着層（Ｘ）は、前記表面層（Ａ）と積層することにより、本発明の表面保護フィルムとすることができる。 The adhesive layer (X) composed of the olefin elastomer and / or styrene elastomer and, if necessary, a resin modifier or an additive is laminated with the surface layer (A), whereby the surface protective film of the present invention. It can be.
　本発明の表面保護フィルムのアクリル板に対する粘着力は、繰り出し性及び被着体への粘着力の指標となり、１Ｎ／５０ｍｍ以上であることが好ましく、さらに好ましくは３～４０Ｎ／５０ｍｍの範囲、より好ましくは５～３０Ｎ／５０ｍｍの範囲にある。このような範囲の粘着力とすることで、良好な繰り出し性を維持し、様々な被着体への粘着性を発現することができる。粘着力が１Ｎ／５０ｍｍを下回ると、被着体への粘着性が充分でない場合があり、４０Ｎ／５０ｍｍを超えると巻き戻し性が悪化する場合があり、好ましくない。 The adhesive strength of the surface protective film of the present invention to the acrylic plate is an index of the drawability and the adhesive strength to the adherend, and is preferably 1 N / 50 mm or more, more preferably in the range of 3 to 40 N / 50 mm, and more. Preferably, it is in the range of 5 to 30 N / 50 mm. By setting it as the adhesive force of such a range, favorable feeding property can be maintained and adhesiveness to various to-be-adhered bodies can be expressed. When the adhesive strength is less than 1 N / 50 mm, the adherence to the adherend may not be sufficient, and when it exceeds 40 N / 50 mm, the rewinding property may deteriorate, which is not preferable.
　本発明の表面保護フィルムの巻き戻し力とはロール状のフィルムを繰り出す際の剥離力をいい、繰り出し性の指標となるが、繰り出し性を具有させるためには該巻き戻し力は２．５Ｎ／５０ｍｍ以下が好ましく、さらに好ましくは０．０１～２．０Ｎ／５０ｍｍの範囲にある。 The unwinding force of the surface protective film of the present invention refers to a peeling force when a roll-shaped film is unrolled, and serves as an index of unwinding property. In order to provide unwinding property, the unwinding force is 2.5 N / It is preferably 50 mm or less, more preferably in the range of 0.01 to 2.0 N / 50 mm.
　表面層（Ａ）と粘着層（Ｘ）を積層する方法については特に制限は無いが、あらかじめＴ－ダイ成形またはインフレーション成形にて得られた表面層フィルム上に、押出ラミネーション、押出コーティング等の公知の積層法により粘着層を積層する方法や、表面層および粘着層を形成するフィルムを各々を独立してフィルムとして成形した後、各々のフィルムをドライラミネーションにより積層する方法等が挙げられるが、生産効率の観点から、表面層、粘着層の各成分を多層の押出機に供して共押出成形する方法が好ましい。 The method for laminating the surface layer (A) and the adhesive layer (X) is not particularly limited, but known methods such as extrusion lamination and extrusion coating on the surface layer film obtained in advance by T-die molding or inflation molding. The method of laminating the adhesive layer by the laminating method of the above, the method of laminating each film by dry lamination after forming the surface layer and the film forming the adhesive layer independently as a film, etc. From the viewpoint of efficiency, a method in which each component of the surface layer and the adhesive layer is subjected to coextrusion molding by using a multilayer extruder is preferable.
　本発明においては、表面層（Ａ）と粘着層（Ｘ）との間に少なくとも１層の中間層を設けることも行われる。中間層としては特に制限はないが、一般には、融点が１００以上のポリプロピレンやポリエチレンなどの結晶性ポリオレフィンや、ポリエステル、ポリアミド、ポリオレフィン系エラストマーなどが使用できる。中間層を接着層として使用する場合には、変性ポリオレフィンや、ポリオレフィン系エラストマー、スチレン系エラストマー、ポリエステルエラストマーなどが用いられる。これらの中で、生産性および透明性の点から、ポリプロピレンやポリオレフィンエラストマーを中間層として使用するのが好ましい。 In the present invention, at least one intermediate layer is also provided between the surface layer (A) and the adhesive layer (X). Although there is no restriction | limiting in particular as an intermediate | middle layer, Generally, crystalline polyolefins, such as a polypropylene and polyethylene with melting | fusing point of 100 or more, polyester, polyamide, polyolefin-type elastomer, etc. can be used. When the intermediate layer is used as an adhesive layer, modified polyolefin, polyolefin elastomer, styrene elastomer, polyester elastomer, or the like is used. Among these, from the viewpoint of productivity and transparency, it is preferable to use polypropylene or polyolefin elastomer as the intermediate layer.
　また、表面層（Ａ）および粘着層（Ｘ）との接着力が不足する場合には、中間層は接着剤または表面層（Ａ）と粘着層（Ｘ）とを接合させるためのフィルム等の素材を接着層として構成されていてもよい。 When the adhesive force between the surface layer (A) and the pressure-sensitive adhesive layer (X) is insufficient, the intermediate layer is an adhesive or a film for bonding the surface layer (A) and the pressure-sensitive adhesive layer (X). The material may be configured as an adhesive layer.
　本発明の表面保護フィルムにおける表面層（Ａ）の厚みは、通常０．０５～２００μｍ、好ましくは０．５～１００μｍ、より好ましくは１～３０μｍ、さらに好ましくは１～１５μｍである。粘着層（Ｘ）の厚みは、通常０．０５～５０μｍ、好ましくは０．３～４０μｍ、より好ましくは０．５～３０μｍである。 The thickness of the surface layer (A) in the surface protective film of the present invention is usually 0.05 to 200 μm, preferably 0.5 to 100 μm, more preferably 1 to 30 μm, and still more preferably 1 to 15 μm. The thickness of the pressure-sensitive adhesive layer (X) is usually 0.05 to 50 μm, preferably 0.3 to 40 μm, more preferably 0.5 to 30 μm.
　したがって、本発明の表面保護フィルムの厚みは、必要により設けることもある中間層を含め、通常０．１～５００μｍ、好ましくは０．５～４００μｍ、より好ましくは３～３００μｍである。 Therefore, the thickness of the surface protective film of the present invention is usually 0.1 to 500 μm, preferably 0.5 to 400 μm, more preferably 3 to 300 μm, including an intermediate layer which may be provided if necessary.
　本発明の表面保護フィルムの透明性としては、ＪＩＳＫ７１０５に準じて５０μｍで測定したヘイズが２０～９０％の範囲が好ましく、特に好ましくは３０～８５％の範囲にある。また本発明の表面保護フィルムのフィッシュアイ数（ＦＥ数）は、２０個以下が好ましく、さらに好ましくは１０個以下、５個以下、その中でもさらに好ましくは３個以下である。 As the transparency of the surface protective film of the present invention, the haze measured at 50 μm according to JISK7105 is preferably in the range of 20 to 90%, particularly preferably in the range of 30 to 85%. Further, the number of fish eyes (FE number) of the surface protective film of the present invention is preferably 20 or less, more preferably 10 or less, 5 or less, and even more preferably 3 or less.
　以下、本発明を実施例により詳細説明するが、本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
　［評価法］
　表面粗さ（Ｒａ）：本発明の表面保護フィルム（本実施例では全厚さ５０ミクロン（μｍ）に調整した）を気温２３℃±２℃、湿度５０％±１０％の条件の下、２４時間養生し、５０ｍｍ角に切り取ってフィルムサンプルとし、前記フィルムサンプルを非接触表面粗さ計（型番：ＮＴ－２０００ＳＹＳＴＥＭ－Ｖｅｅｃｏ社製）を用いて測定した。 [Evaluation method]
Surface roughness (Ra): The surface protective film of the present invention (in this example, adjusted to a total thickness of 50 microns (μm)) under the conditions of air temperature 23 ° C. ± 2 ° C. and humidity 50% ± 10%, 24 The film was cured for a period of time and cut into 50 mm squares to obtain film samples. The film samples were measured using a non-contact surface roughness meter (model number: NT-2000 SYSTEM-Veeco).
　粘着力：気温２３℃±２℃、湿度５０％±１０％の条件の下、アクリル板を幅５０ｍｍ、長さ１２５ｍｍに切断し、前記アクリル板表面にフィルムサンプルを載置し、２ｋｇのゴムローラーの自重により当該サンプルフィルムの全体を押圧することによりアクリル板に貼り付ける。次いで、３００ｍｍ／分の速度で剥離（１８０度剥離）した時の剥離力を測定し、５０ｍｍ幅あたりの剥離力を粘着力（Ｎ／５０ｍｍ）とする。 Adhesive strength: Acrylic plate is cut into a width of 50 mm and a length of 125 mm under conditions of an air temperature of 23 ° C. ± 2 ° C. and a humidity of 50% ± 10%, a film sample is placed on the surface of the acrylic plate, and a 2 kg rubber roller Is attached to the acrylic plate by pressing the entire sample film with its own weight. Next, the peel force when peeled at a speed of 300 mm / min (180 degree peel) is measured, and the peel force per 50 mm width is defined as the adhesive strength (N / 50 mm).
　巻き戻し力：ロール状サンプルを用い、３００ｍｍ／分の速度でロールから引き剥がす時の剥離力（Ｎ／５０ｍｍ）を測定し、巻き戻し力とする。 Unwinding force: Using a roll-shaped sample, the peeling force (N / 50 mm) when peeling from the roll at a speed of 300 mm / min is measured and defined as the unwinding force.
　フィッシュアイ（ＦＥ）：アヤハエンジニアリング製オフライン異物検査装置を用い、０．１ｍｍ以上のサイズのＦＥをカウントし、単位面積当たりのＦＥ数（個／ｍ2）とした。 Fish eye (FE): Using an off-line foreign matter inspection apparatus manufactured by Ayaha Engineering, FE having a size of 0.1 mm or more was counted to obtain the number of FEs per unit area (pieces / m 2 ).
　ヘイズ：ＪＩＳ　Ｋ７１０５に準拠し、本発明の表面保護フィルム（本実施例では全厚５０μｍ）にて測定した。
[実施例１]
　表面層および粘着層用に３０ｍｍφの単軸押出機および中間層に４０ｍｍφ単軸押出機を兼ね備えたダイ幅５００ｍｍの３種３層Ｔ－ダイ成形機にそれぞれ原材料を供給し、表面層厚み１０μｍ、粘着層厚み１０μ、中間層厚み３０μｍからなる全厚５０μｍの本発明の表面保護フィルムを得た。得られた表面保護フィルムの評価結果を表１に示す。尚、実施例及び比較例の表面層、中間層、粘着層を構成する原材料及び配合量は表１に評価結果とともに示す。
[実施例２～４、比較例１～３]
　各種層の樹脂組成を表１記載の樹脂組成とした以外は、実施例１と同様にして表面保護フィルムを得た。得られたフィルムの評価結果を表１に示す。 Haze: Measured according to JIS K7105 using the surface protective film of the present invention (total thickness of 50 μm in this example).
[Example 1]
The raw materials were respectively supplied to a three-type three-layer T-die molding machine having a die width of 500 mm, which was combined with a 30 mmφ single screw extruder for the surface layer and the adhesive layer and a 40 mmφ single screw extruder for the intermediate layer, and the surface layer thickness was 10 μm. A surface protective film of the present invention having a total thickness of 50 μm comprising an adhesive layer thickness of 10 μm and an intermediate layer thickness of 30 μm was obtained. Table 1 shows the evaluation results of the obtained surface protective film. In addition, the raw material which comprises the surface layer of an Example and a comparative example, an intermediate | middle layer, and an adhesion layer, and compounding quantity are shown in Table 1 with an evaluation result.
[Examples 2 to 4, Comparative Examples 1 to 3]
A surface protective film was obtained in the same manner as in Example 1 except that the resin compositions of the various layers were changed to the resin compositions shown in Table 1. Table 1 shows the evaluation results of the obtained film.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
ｈ－ＰＰ；
　ホモポリプロピレン（融点＝１６０℃、ＭＦＲ＝７ｇ／１０分　プライムポリマー社製）
ｂ－ＰＰ－１；
　　プロピレン・エチレンブロック共重合体（銘柄名：ＰＣ６８４Ａ、融点＝１６０℃、ＭＦＲ＝６ｇ／１０分、サンアロマー社製）

ｂ－ＰＰ－２；
　　プロピレン・エチレンブロック共重合体（銘柄名：ＢＣ３ＨＦ、融点＝１６０℃、ＭＦＲ＝８．５ｇ／１０分、日本ポリプロ社製）

ｂ－ＰＰ－３；
　　プロピレン・エチレンブロック共重合体（融点＝１６０℃、ＭＦＲ＝３ｇ／１０分）

ＬＤＰＥ；
　　低密度ポリエチレン（高圧法低密度ポリエチレン、密度＝０．９１７ｇ／ｃｍ3、ＭＦＲ＝３ｇ／１０分）

ＰＥＢＲ；
　　プロピレン・エチレン・１－ブテン共重合体（０～２００℃に融解熱量４Ｊ／ｇの融点ピークが観測される、ＭＦＲ＝７ｇ／１０分）

ＳＩＢＳ；
　　スチレン・イソブチレン共重合体（スチレン・イソブチレン・スチレントリブロック共重合体、Ｍｗ＝６５，０００、ＪＩＳ－Ａ硬度＝３３）、銘柄名：シブスター０７２Ｔ（カネカ社製）

実施例１～４では粘着力が７～１８Ｎ／５０ｍｍであり、十分な粘着性が確保されている。また、巻き戻し力が０．１～１．６Ｎ／５０ｍｍであり、優れた繰り出し性を有していることがわかる。これは、十分な粘着力を有する一方で表面粗さ（Ｒａ）が０．４７～０．８１μｍという適切な粗さであるためである。 h-PP;
Homopolypropylene (melting point = 160 ° C, MFR = 7 g / 10 min, manufactured by Prime Polymer Co., Ltd.)
b-PP-1;
Propylene / ethylene block copolymer (brand name: PC684A, melting point = 160 ° C., MFR = 6 g / 10 min, manufactured by Sun Allomer)

b-PP-2;
Propylene / ethylene block copolymer (brand name: BC3HF, melting point = 160 ° C., MFR = 8.5 g / 10 min, manufactured by Nippon Polypro Co., Ltd.)

b-PP-3;
Propylene / ethylene block copolymer (melting point = 160 ° C., MFR = 3 g / 10 min)

LDPE;
Low density polyethylene (high pressure method low density polyethylene, density = 0.917 g / cm 3 , MFR = 3 g / 10 min)

PEBR;
Propylene / ethylene / 1-butene copolymer (A melting point peak of 4 J / g of heat of fusion is observed at 0 to 200 ° C., MFR = 7 g / 10 min)

SIBS;
Styrene / isobutylene copolymer (styrene / isobutylene / styrene triblock copolymer, Mw = 65,000, JIS-A hardness = 33), brand name: Shibster 072T (manufactured by Kaneka Corporation)

In Examples 1 to 4, the adhesive strength is 7 to 18 N / 50 mm, and sufficient adhesiveness is ensured. Further, the unwinding force is 0.1 to 1.6 N / 50 mm, and it can be seen that it has an excellent feeding property. This is because the surface roughness (Ra) is an appropriate roughness of 0.47 to 0.81 μm while having sufficient adhesive strength.
　さらに、実施例１～４では、ヘイズが６０～７０％であり、ヘイズが８０％以下の透明性を有することが要求されている場合の表面保護フィルムとして優れた透明性を有していることがわかる。 Furthermore, in Examples 1 to 4, the haze is 60 to 70%, and the haze has excellent transparency as a surface protective film when it is required to have transparency of 80% or less. I understand.
　一方、比較例１、２では粘着力が７～１８Ｎ／５０ｍｍであり、十分な粘着性が確保されているものの、巻き戻し力が比較例１、２では剥離しない程度であり、繰り出し性が極めて劣っていることがわかる。これは比較例１，２では表面粗さ（Ｒａ）が各々０．２５μｍ、０．０５μｍと極めて小さいことから剥離が困難となったためである。 On the other hand, in Comparative Examples 1 and 2, the adhesive strength is 7 to 18 N / 50 mm, and sufficient adhesiveness is ensured. However, in Comparative Examples 1 and 2, the unwinding force is such that peeling does not occur and the feeding property is extremely high. It turns out that it is inferior. This is because in Comparative Examples 1 and 2, the surface roughness (Ra) was as extremely small as 0.25 μm and 0.05 μm, respectively, which made peeling difficult.
　比較例３にいては、表面粗さ（Ｒａ）が０．２８μｍで、十分な粘着力を有しており、巻き戻し力も０．５Ｎ／５０ｍｍ、即ち繰り出し性は良好である。しかしながら、表面層がｈ-ＰＰ及びＬＤＰＥの組成物からなる場合（比較例３）は、フィッシュアイ数（ＦＥ数）が多く、表面保護フィルムとして適していない。 In Comparative Example 3, the surface roughness (Ra) is 0.28 μm, the adhesive strength is sufficient, the unwinding force is also 0.5 N / 50 mm, that is, the feeding property is good. However, when the surface layer is composed of a composition of h-PP and LDPE (Comparative Example 3), the fish eye number (FE number) is large and is not suitable as a surface protective film.
　このように、実施例１～４、及び比較例３から、表面層がプロピレン系重合体からなることが必要である。


Thus, from Examples 1 to 4 and Comparative Example 3, it is necessary that the surface layer is made of a propylene polymer.


　本発明の表面保護フィルムは、粘着特性、透明性、巻き戻し性および耐熱性に優れ、光学用途、建材用途、自動車部品用途との保護フィルムとして産業上の利用価値は極めて高い。 The surface protective film of the present invention is excellent in adhesive properties, transparency, unwinding property and heat resistance, and has a very high industrial utility value as a protective film for optical use, building material use and automobile part use.

Claims (3)

  1. 　表面層（Ａ）および粘着層（Ｘ）の少なくとも２層からなる表面保護フィルムであり、表面層（Ａ）が、プロピレン系重合体からなり、かつ表面層の表面粗さ（Ｒａ）が０．２～２．０μｍの範囲にある表面保護フィルム。 It is 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 propylene-based polymer, and the surface layer has a surface roughness (Ra) of 0. Surface protective film in the range of 2 to 2.0 μm.
  2. 　アクリル板に対する粘着力が１Ｎ／５０ｍｍ以上であることを特徴とする請求項１記載の表面保護フィルム。 The surface protective film according to claim 1, wherein the adhesive strength to the acrylic plate is 1 N / 50 mm or more.
  3. 　粘着層（Ｘ）がオレフィン系エラストマーおよび／またはスチレン系エラストマーから形成されることを特徴とする請求項１記載の表面保護フィルム。 2. The surface protective film according to claim 1, wherein the adhesive layer (X) is formed of an olefin elastomer and / or a styrene elastomer.
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JP2013116626A (en) * 2011-10-31 2013-06-13 Toyobo Co Ltd Polyolefin film
WO2013166294A1 (en) * 2012-05-02 2013-11-07 Tredegar Film Products Corporation Low peel force surface protection film and method of using same
US9203050B2 (en) 2013-05-21 2015-12-01 Samsung Display Co., Ltd. Organic light emitting diode display and method of manufacturing the same
JPWO2015190230A1 (en) * 2014-06-10 2017-04-20 リンテック株式会社 Dicing sheet
JPWO2015178346A1 (en) * 2014-05-23 2017-04-20 リンテック株式会社 Composite sheet for protective film formation
WO2021004340A1 (en) * 2019-07-05 2021-01-14 歌尔股份有限公司 Diaphragm of sound emission device, and sound emission device
US11145838B2 (en) 2013-05-21 2021-10-12 Samsung Display Co., Ltd. Organic light emitting diode display and method of manufacturing the same

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JP2009166305A (en) * 2008-01-15 2009-07-30 Toray Ind Inc Surface protection polyolefin film and its manufacturing method

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JP2008068564A (en) * 2006-09-15 2008-03-27 Dainippon Ink & Chem Inc Surface protecting film
JP2008115212A (en) * 2006-11-01 2008-05-22 Mitsui Chemical Fabro Inc Surface protective film
JP2008265302A (en) * 2007-03-22 2008-11-06 Japan Polypropylene Corp Propylene resin film for surface protection
JP2009166305A (en) * 2008-01-15 2009-07-30 Toray Ind Inc Surface protection polyolefin film and its manufacturing method

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013116626A (en) * 2011-10-31 2013-06-13 Toyobo Co Ltd Polyolefin film
WO2013166294A1 (en) * 2012-05-02 2013-11-07 Tredegar Film Products Corporation Low peel force surface protection film and method of using same
CN104395078A (en) * 2012-05-02 2015-03-04 屈德加薄膜产品股份有限公司 Low peel force surface protection film and method of using same
US9138979B2 (en) 2012-05-02 2015-09-22 Tredegar Film Products Corporation Low peel force surface protection film and method of using same
US9203050B2 (en) 2013-05-21 2015-12-01 Samsung Display Co., Ltd. Organic light emitting diode display and method of manufacturing the same
US9614167B2 (en) 2013-05-21 2017-04-04 Samsung Display Co., Ltd. Organic light emitting diode display and method of manufacturing the same
US10038161B2 (en) 2013-05-21 2018-07-31 Samsung Display Co., Ltd. Organic light emitting diode display and method of manufacturing the same
US11145838B2 (en) 2013-05-21 2021-10-12 Samsung Display Co., Ltd. Organic light emitting diode display and method of manufacturing the same
JPWO2015178346A1 (en) * 2014-05-23 2017-04-20 リンテック株式会社 Composite sheet for protective film formation
JPWO2015190230A1 (en) * 2014-06-10 2017-04-20 リンテック株式会社 Dicing sheet
WO2021004340A1 (en) * 2019-07-05 2021-01-14 歌尔股份有限公司 Diaphragm of sound emission device, and sound emission device

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