WO2012046720A1 - 表面保護フィルム - Google Patents
表面保護フィルム Download PDFInfo
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- WO2012046720A1 WO2012046720A1 PCT/JP2011/072846 JP2011072846W WO2012046720A1 WO 2012046720 A1 WO2012046720 A1 WO 2012046720A1 JP 2011072846 W JP2011072846 W JP 2011072846W WO 2012046720 A1 WO2012046720 A1 WO 2012046720A1
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- adhesive layer
- protective film
- surface protection
- base material
- mass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/241—Polyolefin, e.g.rubber
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2423/00—Presence of polyolefin
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2423/00—Presence of polyolefin
- C09J2423/006—Presence of polyolefin in the substrate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2453/00—Presence of block copolymer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2852—Adhesive compositions
- Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
- Y10T428/2883—Adhesive compositions including addition polymer from unsaturated monomer including addition polymer of diene monomer [e.g., SBR, SIS, etc.]
Definitions
- the present invention relates to a surface protective film, and more particularly to a surface protective film temporarily attached to a metal plate, a glass plate, a synthetic resin plate, or the like.
- Patent Document 1 discloses a block copolymer represented by the general formula ABA (where A is a styrene polymer block, B is a copolymer block of ethylene and butylene) and a tackifying resin.
- ABA styrene polymer block
- B is a copolymer block of ethylene and butylene
- a surface protective film formed by forming a pressure-sensitive adhesive layer comprising a composition containing a resin together with a polyolefin resin substrate by a coextrusion method or the like.
- Patent Document 2 discloses a block copolymer represented by the general formula ABA or AB (wherein A is a styrene polymer block, B is a butadiene polymer block, isoprene). A polymer block or a polymer block obtained by hydrogenating these), an adhesive layer containing a tackifying resin and a PO resin, and a surface protection layered on one side of a base film made of PO. A film is disclosed. Furthermore, Patent Document 3 discloses a composition containing a triblock copolymer comprising one intermediate polymer block derived from a conjugated diene compound and two terminal polymer blocks derived from a vinyl aromatic compound. A surface protective film formed by laminating a pressure-sensitive adhesive layer made of a product on one side of a support is disclosed.
- ABA or AB wherein A is a styrene polymer block, B is a butadiene polymer block, isoprene.
- the adhesive strength is controlled by adjusting the blending amount of the tackifier.
- adhesive strength is controlled by adjusting the diblock amount in a styrene-type polymer block.
- the method of Patent Document 2 has a problem that the adjustment range of the blending amount is too narrow in order to achieve both the adhesive strength and the unwinding property from the roll product.
- the method of patent document 3 can raise adhesive strength by increasing the amount of diblocks, there exists a problem that stickiness will become strong and unwinding from a roll product will become difficult.
- the surface has protrusions like a prism sheet
- the hardness of the adhesive layer is decreased (for example, the contact area is increased) or the loop tack is increased ( It is necessary to strengthen the stickiness).
- the increase in the adhesive strength with respect to the substrate surface having less unevenness than the prism sheet is large, the unwinding property is deteriorated as a result. Therefore, it is necessary to roughen the back surface of the base material layer in order to improve the unwinding property. As a result, it is difficult to make the surface protective film transparent, which is a practical problem.
- An object of the present invention is to provide a surface protective film that can be easily unwound from a rolled product while maintaining sufficient adhesive strength.
- the present invention provides the following surface protective film.
- a substrate layer of a polyolefin, a surface protective film and a pressure-sensitive adhesive layer, hardness (Martens hardness) of the adhesive layer has a 1N / mm 2 or more 2.5 N / mm 2 or less, A surface protective film having a loop tack of 0.02 N / 25 mm or more and 0.1 N / 25 mm or less.
- the pressure-sensitive adhesive layer contains a styrene elastomer containing a vinyl-polyisoprene block, a polyolefin, and a tackifier.
- the surface protective film described above wherein the styrene elastomer has a styrene content of 5% by mass or more and 30% by mass or less.
- the styrenic elastomer has a triblock copolymer content of 80% by mass or more.
- the styrene elastomer has a glass transition temperature of ⁇ 60 ° C. or higher and 20 ° C. or lower.
- the surface protective film as described above, wherein the pressure-sensitive adhesive layer has a thickness of 25 ⁇ m or less.
- the surface protective film according to the above-mentioned surface protective film, wherein the base layer has an external haze of 20% or less.
- the surface protective film described above, wherein the adhesive layer is laminated by a coextrusion method.
- the surface protective film of the present invention while maintaining sufficient adhesion strength to the adherend having a protrusion on the surface, even when the back surface of the base material layer forming the surface protective film is smooth, It is possible to provide a surface protective film that can be easily unwound without excessively bonding the surfaces of the pressure-sensitive adhesive layer and the base material layer more than necessary as a rolled product. Therefore, it is useful when used as a surface protective film for an adherend that is shipped as a roll product and has a projection on the surface such as a prism sheet.
- the surface protective film of the present invention is provided with a substrate layer adhesive layer, the hardness of the adhesive layer (Martens hardness) is in 1N / mm 2 or more 2.5 N / mm 2 or less, the loop tack 0 0.02 N / 25 mm or more and 0.1 N / 25 mm or less.
- the base material layer any sheet or film generally used as a support for a surface protective film can be used without any particular limitation.
- a film formed of a polyolefin-based material is preferable. .
- block copolymer polypropylene (hereinafter sometimes abbreviated as “BPP”) is preferable as the material of the base material layer.
- BPP block copolymer polypropylene
- the base material layer is not limited to a single layer and may be formed of a plurality of layers.
- the total thickness of the base layer composed of a single layer or a plurality of layers is, for example, 20 ⁇ m or more and 100 ⁇ m or less, preferably 30 ⁇ m or more and 80 ⁇ m or less.
- a film having an external haze of 20% or less can be used as the base material layer of the present invention.
- a small external haze means that the surface is smooth and contributes to the transparency of the base material layer and also the surface protective film.
- a transparent film having an external haze of 20% or less is used as a base material layer to obtain a wound product. Can also exhibit excellent unwinding properties.
- the external haze of a base material layer can be measured based on JISK7105, for example.
- Adhesive layer of the present invention the hardness is at 1N / mm 2 or more 2.5 N / mm 2 or less, made of a material loop tack becomes less 0.02 N / 25 mm or more 0.1 N / 25 mm.
- the contact area between the adhesive layer and the uneven adherend is dependent on the hardness of the adhesive layer, and the adhesive strength between the adhesive layer and the adherend depends on the unevenness of the adherend.
- a mixture of an elastomer and a tackifier or polyolefin is particularly preferable.
- a styrene elastomer containing a vinyl-polyisoprene block is particularly preferable.
- the most preferable raw material for the pressure-sensitive adhesive layer of the present invention is a mixture of a styrene elastomer containing a vinyl-polyisoprene block, a polyolefin, and a tackifier.
- the styrenic elastomer containing a vinyl-polyisoprene block blended in the adhesive layer is, for example, a block copolymer represented by the following general formula (1) or general formula (2).
- A is a styrene block
- B is an anhydrous vinyl-polyisoprene block represented by the following general formula (3) or a hydrogenated vinyl-polyisoprene block. is there.
- the styrenic elastomer includes an uncoupled styrene block and an uncoupled hydrogenated or non-hydrogenated vinyl-polyisoprene block.
- the styrene elastomer containing the vinyl-polyisoprene block has a styrene content of 5% by mass to 30% by mass, preferably 10% by mass to 25% by mass.
- a styrene content of 5% by mass to 30% by mass, preferably 10% by mass to 25% by mass.
- the styrene content is less than 5% by mass, since the hardness is low and the adhesive strength is too strong, there is a possibility that an adhesive residue may occur at the time of peeling from the adherend. In particular, an adhesive residue is likely to occur on an adherend having a projection on the surface of a prism sheet or the like. If the styrene content exceeds 30% by mass, the hardness is too high, and the adhesive strength to the adherend is weak and may peel off. In particular, peeling is likely to occur on an adherend having a projection on the surface of a prism sheet or the like.
- the styrene content is the content of the styrene block relative to the total amount of the styrene-based elastomer including the vinyl-polyisoprene block.
- the styrene content is determined, for example, by the following method.
- the block copolymer composition contained in the adhesive layer of the surface protective film is dissolved in a small amount of hexane, and then excess acetone is added to separate the acetone insoluble and soluble components. (Spectrum) measurement is performed, and the integral intensity ratio of the spectrum is calculated.
- the block copolymer represented by the general formula (1) is also referred to as a triblock copolymer
- the content of the triblock copolymer is preferably 80% by mass or more, more preferably 90% by mass based on the styrene elastomer. % Or more.
- the content of the triblock copolymer is less than 80% by mass, the adhesive strength to the adherend may be too strong, and adhesive residue may occur at the time of peeling.
- the adhesive strength with the back surface of a base material layer becomes strong, the unwinding property from a roll product may fall.
- content of a triblock copolymer is calculated
- the block copolymer composition contained in the adhesive layer of the protective film is dissolved in tetrahydrofuran (THF), and GS5000H and G4000H liquid chromatographic columns manufactured by Tosoh Corporation are each provided in two stages, for a total of four stages. They are connected in series, and high performance liquid chromatography is performed using THF as the mobile phase under the conditions of a temperature of 40 ° C. and a flow rate of 1 mL / min.
- the peak area corresponding to the coupling component, that is, the triblock copolymer is determined from the obtained chart. The percentage of this peak area relative to the total peak area is taken as the content of the triblock copolymer.
- the glass transition temperature of the styrene-based elastomer containing the vinyl-polyisoprene block is -60 ° C or higher and 20 ° C or lower.
- the adhesive strength in the normal use temperature region of the surface protective film for example, from ⁇ 20 ° C. to 40 ° C.
- peeling from the adherend In particular, there is a possibility that peeling occurs on an adherend having a projection on the surface of a prism sheet or the like.
- a glass transition temperature is calculated
- the content of the vinyl-polyisoprene block can be determined, for example, by the following method.
- the raw material pellet of the adhesive layer is dissolved in deuterated chloroform, NMR (nuclear magnetic resonance spectrum) measurement is performed, and the integral intensity ratio of the spectrum is calculated.
- the styrene elastomer containing the vinyl-polyisoprene block may or may not be hydrogenated.
- polystyrene resin examples include, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, ethylene- ⁇ olefin copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate.
- examples thereof include a copolymer, an ethylene-methyl methacrylate copolymer, an ethylene-n-butyl acrylate copolymer, and polypropylene (homopolymer, random copolymer, block copolymer). Of these polyolefins, polypropylene is preferred as the material for the adhesive layer.
- Polypropylene has good compatibility with styrene-based elastomers containing an anhydrous or hydrogenated vinyl-polyisoprene block, is excellent in heat resistance, and is less likely to cause contamination of the adherend due to bleeding.
- the blended polyolefin is not limited to one type, and two or more types may be mixed and used.
- a desirable ratio of the polyolefin blended in the adhesive layer is 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the styrene elastomer containing the vinyl-polyisoprene block.
- the blending amount of the polyolefin is less than 1 part by mass, the adhesive strength to the adherend becomes strong and there is a possibility that an adhesive residue may be generated at the time of peeling.
- the blending amount of the polyolefin exceeds 10 parts by mass, the hardness of the pressure-sensitive adhesive layer becomes high. For example, the pressure-sensitive adhesive strength to an adherend having a protrusion may be weakened and peeled off.
- the compounding amount of the tackifier is increased in order to increase the adhesive strength, the unwinding property from the wound product may be lowered.
- a resin that is selectively compatible with a hydrogenated or anhydrous vinyl-polyisoprene block of a styrene elastomer can be preferably used.
- resins include aliphatic hydrocarbon resins, terpene resins, coumarone-indene resins, aromatic hydrocarbon resins, and rosin resins.
- blend additives such as softeners, such as a liquid polymer and paraffin oil, a filler, a pigment, anti-aging agent, a stabilizer, and a ultraviolet absorber, with the adhesion layer.
- a desirable ratio of the tackifier to be mixed in the adhesive layer is 1 part by mass or more and 8 parts by mass or less with respect to 100 parts by mass of the styrene-based elastomer containing the vinyl-polyisoprene block.
- the adhesive strength becomes weak, and for example, the adhesive strength to an adherend having a protrusion may be weakened and peeled off.
- the compounding amount of the tackifier exceeds 8 parts by mass, the adherend may be contaminated by bleed and the cohesive force may be reduced.
- the adhesive strength between the adhesive layer and the smooth base material layer having a low external haze (the back surface of the wound body) is increased, the unwinding property from the wound body product may be reduced.
- hardness (Martens hardness) of the adhesive layer is 1N / mm 2 or more 2.5 N / mm 2 or less. If it is less than 1 N / mm 2 , since the hardness of the adhesive layer is too low, the adhesive strength with the back surface of the base material layer becomes strong, which may reduce the unwinding property of the film from the roll product, which is not preferable. If it exceeds 2.5 N / mm 2 , the hardness of the adhesive layer is too high, and when the adherend has protrusions, it becomes difficult to follow the uneven shape of the adherend, so that sufficient adhesive strength is achieved. It cannot be obtained, and the film may be peeled off from the adherend, which is not preferable.
- the hardness of the adhesive layer can be adjusted by, for example, the hardness of a styrene elastomer and a polyolefin containing a vinyl-polyisoprene block blended in the adhesive layer. Furthermore, if two or more kinds of polyolefins are blended, it can be adjusted by the hardness of each polyolefin.
- the loop tack when the adhesive layer is used as the adherend is 0.02 N / 25 mm or more and 0.1 N / 25 mm or less.
- the adhesive force of the adhesive layer is insufficient, and the film may peel from the adherend.
- the loop tack exceeds 0.1 N / 25 mm, the adhesive strength between the pressure-sensitive adhesive layer and the back surface of the base material layer becomes too strong, and the unwinding property from the roll product may be deteriorated.
- the loop tack of the adhesive layer can be adjusted by, for example, the amount of tackifier added to the adhesive layer.
- the thickness of the adhesive layer is preferably 25 ⁇ m or less. More preferably, they are 1 micrometer or more and 15 micrometers or less.
- the thickness of the adhesive layer does not necessarily have a lower limit, but if the thickness is less than 1 ⁇ m, the tip may be damaged when the adherend has a protrusion.
- the adhesive strength may be reduced, and peeling from the adherend may occur.
- the thickness of the pressure-sensitive adhesive layer exceeds 25 ⁇ m, the pressure-sensitive adhesive strength is increased, and there is a possibility that an adhesive residue may be generated when peeling from the adherend.
- the preferable thickness of the adhesive layer is 1 ⁇ m or more and 15 ⁇ m or less.
- the base material layer and the adhesive layer in the surface protective film of the present invention are preferably laminated by a coextrusion method.
- the base material layer and the adhesive layer can be laminated at a time without using any solvent, and the surface protective film can be formed by a relatively simple production apparatus.
- the manufacturing cost of the surface protective film can be reduced at a low cost by simplifying the manufacturing process.
- the interlayer strength between the surface of the base material layer and the adhesive layer is strong, and the possibility that adhesive residue is generated at the time of peeling from the adherend is reduced.
- the coextrusion method may be a feed block method or a multi-manifold method.
- the surface protective film of the present invention can be used for the purpose of protecting the surface of adherends such as metal plates, glass plates, and synthetic resin plates.
- the apex angle is 80 ° to 100 ° on the surface of these adherends. It can be suitably used for a prism sheet having a protrusion having a substantially triangular cross section with a height of 20 ⁇ m to 80 ⁇ m.
- the hardness of the adhesive layer (Martens hardness) of 1N / mm 2 or more 2.5 N / mm 2 or less, the loop tack 0.02 N / 25 mm or more 0.1 N / 25 mm or less Therefore, when the surface protective film is a rolled product, the surface protective film can be unwound from the rolled product while maintaining sufficient adhesive strength even if the release treatment is not particularly applied to the base material layer. It becomes easy. Thereby, efficiency improvement of the sticking operation
- the surface film is wasted because the base material layer is partially stretched and deformed, or the adhesive layer is partially peeled off. Furthermore, the manufacturing cost of the surface protective film can be suppressed by eliminating the need for a mold release process for securing the unwinding property from the wound product. In addition, since there is no particular need to roughen the back surface of the base material layer, the surface protection film can be made highly transparent.
- this invention is not limited to the above-mentioned embodiment, The change in the range which can achieve the objective of this invention, improvement, etc. are included in this invention.
- the surface protective film provided with the base material layer and the adhesive layer is exemplified, but the present invention is not limited thereto, and for example, another functional layer such as an ultraviolet absorbing layer may be provided.
- the adherend surface can be protected not only from physical contact but also from other factors such as ultraviolet rays.
- specific materials and configurations in the implementation of the present invention may be other materials and configurations as long as the object of the present invention can be achieved.
- Example 1 Styrenic elastomer containing vinyl-polyisoprene block having a styrene content of 20% by mass, a triblock copolymer content of 100% by mass, and a glass transition temperature of ⁇ 15 ° C. (trade name Hibler 7125, manufactured by Kuraray Co., Ltd.) To 100 parts by mass, 5 parts by mass of RPP (manufactured by Nippon Polypro Co., Ltd., trade name Wintech WFW-4) and 5 parts by mass of a tackifier (trade name Imabu P-140, produced by Idemitsu Kosan Co., Ltd.) are mixed as polyolefin.
- RPP manufactured by Nippon Polypro Co., Ltd., trade name Wintech WFW-4
- a tackifier trade name Imabu P-140, produced by Idemitsu Kosan Co., Ltd.
- Example 2 Three types of films were obtained in the same manner as in Example 1 except that the amount of the tackifier in the adhesive layer was 3 parts by mass.
- Example 3 Three types of films were obtained in the same manner as in Example 1 except that the amount of polyolefin blended in the adhesive layer was 7 parts by mass.
- Example 4 Three types of films were obtained in the same manner as in Example 1 except that the thickness of the adhesive layer was 3 ⁇ m.
- Example 2 Three types of films were obtained in the same manner as in Example 1 except that the amount of polyolefin in the adhesive layer was 10 parts by mass and the amount of tackifier was 10 parts by mass.
- loop tack was measured using a device in which an Imada digital force gauge ZP-5N was mounted on an Imada vertical electric measurement stand MV-500NII-L550. Specifically, it is as follows. The adhesive layer of the film cut out to a width of 25 mm and a length of 300 mm is fixed to the digital force gauge crosshead with the adhesive layer on the outside, and the crosshead is lowered to the acrylic plate on the stage until the contact length is 5 mm and held for 3 seconds. After that, the digital force gauge value was corrected to zero, peeled at a pulling speed of 0.3 m / min, and the resistance value (N / 25 mm) at that time was measured.
- FIG. 1 schematically shows the outline of the test.
- the total haze of the film was measured according to JIS K 7105 using a haze meter (HZ-1 manufactured by Suga Test Instruments Co., Ltd.).
- the external haze of the base material layer was determined using the following method. Measure the haze in advance by sandwiching only silicone oil (trade name SH200 manufactured by Toray Dow Corning Silicone Co., Ltd.) between two glass plates (Hz1), and then sandwich the film with the adhesive layer coated with silicone oil. Then, the haze was measured (Hz2), then the haze was measured by sandwiching a film coated on both sides with silicone oil (Hz3), and the external haze (Hz4) of the base material layer was determined from the following formula.
- Hz4 (Hz2-Hz1)-(Hz3-Hz1) The case where the external haze was 20% or less was designated as A, and the case where it exceeded 20% was designated as B.
- the adhesive strength to the sheet does not change, and only the adhesive strength, that is, the unwinding strength with the back surface of the smooth base material layer is increased as compared with the prism sheet.
- Martens hardness of the adhesive layer from Comparative Examples 2 and 3 is in the 1N / 25 mm 2 or more 2.5 N / 25 mm 2 within the following ranges, obtaining a good unwinding property the loop tack greater than 0.1 N / 25 mm I can't understand. In such a case, in order to improve the unwinding property, it is necessary to greatly roughen the back surface of the base material layer, and a protective film having good transparency cannot be obtained, which is a practical problem. From Comparative Example 4, it can be seen that when the Martens hardness exceeds 2.5 N / 25 mm 2 , sufficient adhesive strength cannot be obtained.
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Abstract
Description
例えば、特許文献1には、一般式A-B-Aで表されるブロック共重合体(但し、Aはスチレン系重合体ブロック、Bはエチレンとブチレンとの共重合体ブロック)と粘着付与樹脂を含有する組成物からなる粘着剤層をポリオレフィン系樹脂基材とともに、共押出し法などにより形成してなる表面保護フィルムが開示されている。また、特許文献2には、一般式A-B-AもしくはA-Bで表されるブロック共重合体(但し、これらの式中Aはスチレン系重合体ブロック、Bはブタジエン重合体ブロック、イソプレン重合体ブロックまたはこれらを水素添加して得られる重合体ブロック)と粘着性付与樹脂とPO樹脂とを含有してなる粘着剤層を、POからなる基材フィルムの片面に積層してなる表面保護フィルムが開示されている。さらに、特許文献3には、共役ジエン化合物より誘導された1個の中間重合体ブロックとビニル芳香族化合物から誘導された2個の末端重合体ブロックとからなるトリブロック共重合体を含有する組成物からなる粘着剤層を、支持体の片面に積層してなる表面保護フィルムが開示されている。
このような問題を解決するため、基材の背面に対して、離型剤の塗布やコロナ処理等の離型処理を施すことがある。しかし、離型剤を用いる場合、基材とは強固に接着し、かつ粘着剤層とは接着しない特殊な離型剤が必要であるし、離型剤が粘着剤層に移行した場合には、表面保護フィルムの被着体への粘着力が低下するおそれがある。さらに、複雑な離型剤塗布工程やコロナ処理等の離型処理の実施により、表面保護フィルムの製造コストが増大するおそれがある。
しかしながら、特許文献2の方法では、粘着強度と巻重体製品からの巻き出し性を両立させるためには配合量の調整範囲が狭すぎるという問題がある。また、特許文献3の方法では、ジブロック量を増やすことで粘着強度を上げることができるものの、ベトツキが強くなり巻重体製品からの巻きだしが困難となってしまうという問題がある。
また、プリズムシートのように表面に突起状物を有する場合、この凹凸面に対する粘着強度を上げるためには、粘着層の硬度を下げたり(例えば接触面積を増やす)、ループタックを上げたりする(ベトツキを強くする)必要がある。しかし、これら方法ではプリズムシートより凹凸の少ない基材面に対する粘着強度の上昇が大きいため、結果として巻き出し性が悪化してしまう。そのため巻き出し性を改善するために基材層の背面を粗す必要があり、その結果として表面保護フィルムを透明にすることが難しくなり実用上問題となる。
(1)ポリオレフィン系の基材層と、粘着層とを備えた表面保護フィルムであって、前記粘着層の硬度(マルテンス硬さ)が1N/mm2以上2.5N/mm2以下であり、ループタックが0.02N/25mm以上0.1N/25mm以下であることを特徴とする表面保護フィルム。
(2)上述の表面保護フィルムにおいて、前記粘着層がビニル-ポリイソプレンブロックを含むスチレン系エラストマーと、ポリオレフィンと、粘着付与剤とを含むことを特徴とする表面保護フィルム。
(3)上述の表面保護フィルムにおいて、前記スチレン系エラストマーは、スチレン含有量が5質量%以上30質量%以下であることを特徴とする表面保護フィルム。
(4)上述の表面保護フィルムにおいて、前記スチレン系エラストマーは、トリブロック共重合体の含有量が80質量%以上であることを特徴とする表面保護フィルム。
(5)上述の表面保護フィルムにおいて、前記スチレン系エラストマーは、ガラス転移温度が-60℃以上20℃以下であることを特徴とする表面保護フィルム。
(6)上述の表面保護フィルムにおいて、前記粘着層の厚みが25μm以下であることを特徴とした表面保護フィルム。
(7)上述の表面保護フィルムにおいて、前記基材層の外部ヘイズが20%以下であることを特徴とした表面保護フィルム。
(8)上述の表面保護フィルムにおいて、前記粘着層が共押出法によって積層されることを特徴とした表面保護フィルム。
基材層としては、表面保護フィルムの支持体として一般的に用いられるシートまたはフィルムであれば特に限定なく用いることができ、例えば、ポリオレフィン系などの材料により形成されたフィルムが好ましいものとして挙げられる。
さらに、基材層は単層であるものに限られず複数の層で形成されてもよい。単層または複数層からなる基材層の総厚みとしては、例えば、20μm以上100μm以下、好ましくは、30μm以上80μm以下が好適である。
なお、基材層の外部ヘイズは、例えばJIS K 7105に準拠して測定することができる。
本発明は、粘着層と凹凸のある被着体との接触面積が、粘着層の硬度に依存すること、また粘着層と被着体との粘着強度が被着体の凹凸の大小に依存することに着目し、粘着層の硬度とループタックを上記範囲に調整することで、プリズムシートのような比較的大きな凹凸のある被着体に対して良好に粘着するとともに、基材層の背面のようなプリズムシートよりも比較的に小さな凹凸を持つ被着体に対して容易に剥離する粘着力をもつ粘着層となることを見出したものである。すなわち、本発明の粘着層とすることで、表面保護フィルムに必要とされる十分な粘着強度と表面保護フィルムを巻重体製品とした場合に必要とされる良好な巻き出し性を両立させることができたのである。
このような硬度とループタックを達成しうる原料としては、エラストマーが好ましい。また、エラストマーに粘着付与剤やポリオレフィンを混合して用いることがより好ましい。
エラストマーとしては、ビニル-ポリイソプレンブロックを含むスチレン系エラストマーが特に好ましい。本発明の粘着層用原料として最も好ましいのは、ビニル-ポリイソプレンブロックを含むスチレン系エラストマーと、ポリオレフィンと、粘着付与剤とを混合して用いたものである。
粘着層に配合されるビニル-ポリイソプレンブロックを含むスチレン系エラストマーは、例えば、下記一般式(1)または一般式(2)で表されるブロック共重合体である。
A-B-A (1)
A-B (2)
スチレン含有量は、例えば、次の方法によって求められる。
表面保護フィルムの粘着層中に含まれるブロック共重合体組成物を少量のヘキサンに溶解した後、過剰のアセトンを加えてアセトン不溶分と可溶分に分離し、不溶分についてNMR(核磁気共鳴スペクトル)測定を行い、スペクトルの積分強度比により算出する。
保護フィルムの粘着層中に含まれるブロック共重合体組成物をテトラハイドロフラン(THF)に溶解し、東ソー(株)製GS5000HおよびG4000Hの液体クロマトグラフ用カラムをそれぞれ2段ずつ、計4段を直列につなぎ、移動相にTHFを用いて、温度40℃、流量1mL/minの条件下で高速液体クロマトグラフィを実施する。得られたチャートからカップリング成分、つまり、トリブロック共重合体に対応するピーク面積を求める。このピーク面積の、全体のピーク面積に対する100分率を、トリブロック共重合体の含有量とする。
ガラス転移温度は、例えば、次の方法によって求められる。
保護フィルムの粘着層中に含まれるブロック共重合体組成物を少量のヘキサンに溶解した後、過剰のアセトンを加えてアセトン不溶分と可溶分に分離する。不溶分を示差走査熱量計にて室温から20℃/minの割合で昇温させ、発熱量を測定して吸熱曲線を作成する。吸熱曲線に2本の延長線を引き、延長線間の1/2直線と吸熱曲線の交点からガラス転移温度を求める。
粘着層の原料ペレットを重クロロホルムに溶解し、NMR(核磁気共鳴スペクトル)測定を行い、スペクトルの積分強度比により算出する。
なお、当該ビニル-ポリイソプレンブロックを含むスチレン系エラストマーは水素添加されていてもいなくても構わない。
また、配合されるポリオレフィンは1種に限らず、2種以上を混合して用いても構わない。
また、粘着層には、必要に応じて、液状ポリマーやパラフィンオイルなどの軟化剤、充填剤、顔料、老化防止剤、安定剤、および紫外線吸収剤などの添加剤を配合してもよい。
粘着層の硬度は、例えば粘着層に配合するビニル-ポリイソプレンブロックを含むスチレン系エラストマーとポリオレフィンの硬度により調整可能である。さらに、配合されるポリオレフィンが2種以上であれば、各ポリオレフィンの硬度によっても調整可能である。
それ故、実用上、粘着層の好ましい厚みは、1μm以上15μm以下である。
また、本発明の表面保護フィルムは金属板、ガラス板および合成樹脂板などの被着体の表面を保護する目的で使用できるが、特にこれら被着体の表面に頂角80°から100°まで、高さ20μmから80μmまでの断面略三角形状をしている突起状物を有するプリズムシートに好適に使用することができる。
これにより、被着体表面への表面保護フィルムの貼着作業の効率化を図ることができる。また、基材層が部分的に引き伸ばされて変形したり、粘着層が部分的に剥離されたりして、表面フィルムが無駄になる可能性も低い。さらに、巻重体製品からの巻き出し性を確保するための離型処理を不要とすることで、表面保護フィルムの製造コストを抑えることができる。
また、基材層の背面を大きく粗す必要性が特にないので、表面保護フィルムの高透明化が可能となる。
本実施形態では、基材層と粘着層とを備えた表面保護フィルムを例示したが、これに限らず、例えば、紫外線吸収層などの他の機能層を設けた構成としてもよい。この場合、物理的接触のみならず紫外線などの他の要因からも被着体表面を保護することができる。
その他、本発明の実施における具体的な材料および構成などは、本発明の目的を達成できる範囲で他の材料および構成などとしてもよい。
スチレン含有量が20質量%、トリブロック共重合体の含有量が100質量%、ガラス転移温度が-15℃の、ビニル-ポリイソプレンブロックを含むスチレン系エラストマー(クラレ社製、商品名ハイブラー7125)100質量部に対して、ポリオレフィンとしてRPP(日本ポリプロ社製、商品名ウィンテックWFW-4)5質量部、粘着付与剤(出光興産製、商品名アイマーブP-140)5質量部を混合してなる粘着層と、PO系基材層として、BPP(ポリプロピレンブロックコポリマー)とを2層共押出し法にて、粘着層厚みが11μm、基材層厚みが39μmとなるようフィードブロック法により共押出を行い、表面保護フィルム(以下単に「フィルム」ともいう)を得た。
なお、基材層として用いたBPPには、サンアロマー社製の商品であるPC-684S(MFR 5.0)、PC-480A(MFR 2.0)、EP-310K(MFR 3.4)を用い、それぞれ基材層の異なる3種のフィルムを得た。以下の実施例および比較例も同様である。
粘着層における粘着付与剤の配合量を3質量部とした以外は、実施例1と同様にして3種のフィルムを得た。
粘着層におけるポリオレフィンの配合量を7質量部とした以外は、実施例1と同様にして3種のフィルムを得た。
粘着層の厚みを3μmとした以外は、実施例1と同様にして3種のフィルムを得た。
粘着層における粘着付与剤の配合量を15質量部とした以外は、実施例1と同様にして3種のフィルムを得た。
粘着層におけるポリオレフィンの配合量を10質量部とし、粘着付与剤の配合量を10質量部とした以外は、実施例1と同様にして3種のフィルムを得た。
粘着層におけるポリオレフィンの配合量を15質量部とし、粘着付与剤の配合量を15質量部とした以外は、実施例1と同様にして3種のフィルムを得た。
粘着層におけるポリオレフィンの配合量を20質量部とし、粘着付与剤の配合量を20質量部とした以外は、実施例1と同様にして3種のフィルムを得た。
上述した実施例・比較例の各フィルムについて、以下に示す方法で各種の特性を評価した。結果を表1、表2に示した。
(1)粘着層の硬度(マルテンス硬さ)
ダイナミック超微小硬度計(島津製作所製 DHU-211)を用い試験力を1mN、負荷速度を0.05mN/secとしマルテンス硬さを測定した。
ループタックの測定は、イマダ社製縦型電動計測スタンドMV-500NII-L550にイマダ社製デジタルフォースゲージZP-5Nを装着した装置を用いて行った。具体的には、以下の通りである。
幅25mm、長さ300mmに切り出したフィルムの粘着層を外側にしてデジタルフォースゲージのクロスヘッドに固定し、ステージ上のアクリル板にフィルムが接触長さ5mmとなるまでクロスヘッドを下降させ3秒間保持した後、デジタルフォースゲージの値をゼロ点補正し、引張り速度0.3m/minにて剥離しその時の抵抗値(N/25mm)を測定した。図1に試験の概要を模式的に示す。
線圧0.38MPa、2m/minの条件下で、フィルムを被着体(頂角約90°高さ約30μmの断面三角形状をしたアクリル樹脂製のプリズムシート)に圧着し、23℃にて24時間保存した。その後、引張試験機を用い、引張速度0.3m/min、180℃ピールにて剥離し、その時の抵抗値(N/25mm)を測定した。また、0.05N/25mm以上の場合をA、0.05N/25mm未満の場合をBとして表1に併記した。
基材層の異なる3種のフィルムについて線圧0.38MPa、2m/minの条件下で、フィルムの粘着面と基材層の背面とを圧着し、23℃にて5分間保存した。その後、引張試験機を用い、引張速度0.3m/min、90°ピールにて剥離し、その時の抵抗値(N/25mm)を測定した。また、0.2N/25mm未満の場合をA、0.2N/25mm以上の場合をBとして表1に併記した。
フィルムの全ヘイズは、ヘイズメーター(スガ試験機社製 HZ-1)を用いJIS K 7105に準拠して測定した。基材層の外部ヘイズは、以下の方法を用いて求めた。
予めガラス板2枚の間にシリコーンオイル(東レ・ダウコーニング・シリコーン社製 商品名 SH200)のみを挟んでヘイズを測定しておき(Hz1)、次にシリコーンオイルで粘着層面を塗らしたフィルムを挟んでヘイズを測定し(Hz2)、次にシリコーンオイルで両面を塗らしたフィルムを挟んでヘイズを測定し(Hz3)、以下の式より基材層の外部ヘイズ(Hz4)を求めた。
Hz4=(Hz2-Hz1)-(Hz3-Hz1)
外部ヘイズが20%以下の場合をA、20%を超える場合をBとした。
表1に示す結果から、各実施例のフィルムについては、粘着層の硬度およびループタックが所定の範囲であるので、プリズムシートのような大きな凹凸面に対する十分な粘着強度と、良好な巻き出し性との両立が可能であることが分る。
また、実施例1と比較例1の比較からプリズムシートのような大きな凹凸面に対する粘着強度は粘着層のマルテンス硬度が支配的であり、粘着付与剤の配合量を増やしループタックを上げてもプリズムシートに対する粘着強度は変化せず、プリズムシートに比べ平滑な基材層の背面との粘着強度つまり巻き出し強度のみが上がることがわかる。
比較例2、3から粘着層のマルテンス硬度が1N/25mm2以上2.5N/25mm2以下の範囲内にあっても、ループタックが0.1N/25mmを超えると良好な巻き出し性を得ることができないことがわかる。このような場合、巻き出し性を改善するためには基材層の背面を大きく粗す必要があり、透明性の良好な保護フィルムを得ることができず実用上問題となる。
比較例4から、マルテンス硬度が2.5N/25mm2を超えると十分な粘着強度を得ることができないことがわかる。
Claims (8)
- ポリオレフィン系の基材層と、粘着層とを備えた表面保護フィルムであって、
前記粘着層の硬度(マルテンス硬さ)が1N/mm2以上2.5N/mm2以下であり、ループタックが0.02N/25mm以上0.1N/25mm以下である
ことを特徴とする表面保護フィルム。 - 請求項1に記載の表面保護フィルムにおいて、
前記粘着層が、ビニル-ポリイソプレンブロックを含むスチレン系エラストマーと、ポリオレフィンと、粘着付与剤とを含む
ことを特徴とする表面保護フィルム。 - 請求項2に記載の表面保護フィルムにおいて、
前記スチレン系エラストマーは、スチレン含有量が5質量%以上30質量%以下である
ことを特徴とする表面保護フィルム。 - 請求項2または請求項3に記載の表面保護フィルムにおいて、
前記スチレン系エラストマーは、トリブロック共重合体の含有量が80質量%以上である
ことを特徴とする表面保護フィルム。 - 請求項2から請求項4までのいずれか1項に記載の表面保護フィルムにおいて、
前記スチレン系エラストマーは、ガラス転移温度が-60℃以上20℃以下である
ことを特徴とする表面保護フィルム。 - 請求項1から請求項5までのいずれか1項に記載の表面保護フィルムにおいて、
前記粘着層の厚みが25μm以下である
ことを特徴とした表面保護フィルム。 - 請求項1から請求項6までのいずれか1項に記載の表面保護フィルムにおいて、
前記基材層の外部ヘイズが20%以下である
ことを特徴とした表面保護フィルム。 - 請求項1から請求項7までのいずれか1項に記載の表面保護フィルムにおいて、
前記粘着層が共押出法によって積層される
ことを特徴とした表面保護フィルム。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2011800452380A CN103119114A (zh) | 2010-10-05 | 2011-10-04 | 表面保护膜 |
US13/824,406 US20130177761A1 (en) | 2010-10-05 | 2011-10-04 | Surface protection film |
KR1020137009729A KR20130119428A (ko) | 2010-10-05 | 2011-10-04 | 표면 보호 필름 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010225827A JP2012077244A (ja) | 2010-10-05 | 2010-10-05 | 表面保護フィルム |
JP2010-225827 | 2010-10-05 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012046720A1 true WO2012046720A1 (ja) | 2012-04-12 |
Family
ID=45927716
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/072846 WO2012046720A1 (ja) | 2010-10-05 | 2011-10-04 | 表面保護フィルム |
Country Status (6)
Country | Link |
---|---|
US (1) | US20130177761A1 (ja) |
JP (1) | JP2012077244A (ja) |
KR (1) | KR20130119428A (ja) |
CN (1) | CN103119114A (ja) |
TW (1) | TW201229186A (ja) |
WO (1) | WO2012046720A1 (ja) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5288733B2 (ja) * | 2007-05-31 | 2013-09-11 | 出光ユニテック株式会社 | 表面保護フィルム |
JP6615614B2 (ja) | 2013-11-21 | 2019-12-04 | 株式会社クラレ | 表面保護フィルム |
JP6423634B2 (ja) * | 2014-07-22 | 2018-11-14 | 積水化学工業株式会社 | プリズムシート用表面保護フィルム及び表面保護フィルム付きプリズムシート |
JP6446215B2 (ja) * | 2014-09-17 | 2018-12-26 | 積水化学工業株式会社 | プリズムシート用表面保護フィルム及び表面保護フィルム付きプリズムシート |
KR102323855B1 (ko) | 2014-09-25 | 2021-11-09 | 도레이 필름 카코우 가부시키가이샤 | 조성물 및 적층체 |
JP6434282B2 (ja) * | 2014-11-18 | 2018-12-05 | 株式会社サンエー化研 | 表面保護フィルムの製造方法 |
US10301094B2 (en) * | 2015-08-07 | 2019-05-28 | Aicello Corporation | Product conveyance film |
KR101946322B1 (ko) | 2016-03-03 | 2019-02-11 | 도레이 필름 카코우 가부시키가이샤 | 적층 필름 |
JP2019019334A (ja) * | 2018-10-16 | 2019-02-07 | 積水化学工業株式会社 | プリズムシート用表面保護フィルム及び表面保護フィルム付きプリズムシート |
JP2019070133A (ja) * | 2018-12-03 | 2019-05-09 | 積水化学工業株式会社 | プリズムシート用表面保護フィルム及び表面保護フィルム付きプリズムシート |
CN109868080B (zh) * | 2018-12-21 | 2021-10-22 | 宁波激智科技股份有限公司 | 一种新型高粘保护膜及其制备方法 |
CN111777961B (zh) * | 2020-07-15 | 2022-05-17 | 宁波东旭成新材料科技有限公司 | 一种uv减粘保护膜的制备方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008297430A (ja) * | 2007-05-31 | 2008-12-11 | Idemitsu Unitech Co Ltd | 表面保護フィルム |
JP2010126711A (ja) * | 2008-12-01 | 2010-06-10 | Idemitsu Unitech Co Ltd | 表面保護フィルム |
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JP2007119758A (ja) * | 2005-09-29 | 2007-05-17 | Kokuyo S&T Co Ltd | 貼り付け方法、貼り付け用感圧性接着剤及びその感圧性接着剤の層を有する接着製品 |
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2010
- 2010-10-05 JP JP2010225827A patent/JP2012077244A/ja active Pending
-
2011
- 2011-10-04 KR KR1020137009729A patent/KR20130119428A/ko not_active Application Discontinuation
- 2011-10-04 WO PCT/JP2011/072846 patent/WO2012046720A1/ja active Application Filing
- 2011-10-04 US US13/824,406 patent/US20130177761A1/en not_active Abandoned
- 2011-10-04 CN CN2011800452380A patent/CN103119114A/zh active Pending
- 2011-10-05 TW TW100136138A patent/TW201229186A/zh unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008297430A (ja) * | 2007-05-31 | 2008-12-11 | Idemitsu Unitech Co Ltd | 表面保護フィルム |
JP2010126711A (ja) * | 2008-12-01 | 2010-06-10 | Idemitsu Unitech Co Ltd | 表面保護フィルム |
Also Published As
Publication number | Publication date |
---|---|
US20130177761A1 (en) | 2013-07-11 |
JP2012077244A (ja) | 2012-04-19 |
TW201229186A (en) | 2012-07-16 |
CN103119114A (zh) | 2013-05-22 |
KR20130119428A (ko) | 2013-10-31 |
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