WO2010084832A1 - Film protecteur de surface - Google Patents

Film protecteur de surface Download PDF

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Publication number
WO2010084832A1
WO2010084832A1 PCT/JP2010/050463 JP2010050463W WO2010084832A1 WO 2010084832 A1 WO2010084832 A1 WO 2010084832A1 JP 2010050463 W JP2010050463 W JP 2010050463W WO 2010084832 A1 WO2010084832 A1 WO 2010084832A1
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WO
WIPO (PCT)
Prior art keywords
protective film
block
mass
copolymer
surface protective
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Application number
PCT/JP2010/050463
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English (en)
Japanese (ja)
Inventor
一範 小橋
芳隆 佐藤
達彦 薄井
Original Assignee
Dic株式会社
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Priority to JP2010537607A priority Critical patent/JPWO2010084832A1/ja
Publication of WO2010084832A1 publication Critical patent/WO2010084832A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • 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
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/387—Block-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
    • 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
    • B32B2307/70—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
    • B32B2571/00—Protective equipment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/025—Copolymer of an unspecified olefin with a monomer other than an olefin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials

Definitions

  • the present invention is applied to the surface of various optical films, various resin plates, glass plates, metal plates and the like used in the electric / electronic field, building materials, etc., and is stored, transported and post-processed. It is related with the surface protection film which protects a to-be-adhered body from a contamination
  • the present invention relates to a surface protective film that exhibits good tackiness even when the adherend surface is uneven and has good handling properties.
  • the basic required performance for the surface protective film includes excellent adherence workability that can be uniformly applied to the above-mentioned various adherends without involving wrinkles or air, storage of the adherend, transportation, etc.
  • Adhesive strength that does not float or peel between the surfaces of the adherend, environmental changes during storage of the adherend, and changes in the adhesive strength over time due to post-processing are less likely to be easily peeled off and the surface of the adherend after peeling And so on.
  • a film made of polyvinyl chloride resin, polyethylene resin, polypropylene resin, etc. is used as a base material, and one surface thereof is coated with an adhesive such as urethane, acrylic or rubber.
  • an adhesive such as urethane, acrylic or rubber.
  • these surface protective films sometimes have poor adhesion between the base film and the pressure sensitive adhesive, or when peeled from the adherend due to the low cohesive strength of the pressure sensitive adhesive itself. There is a problem that a part of the film remains on the surface of the adherend.
  • the surface protection film produced by applying a pressure-sensitive adhesive to the film requires a minimum of two steps, ie, a film production process and a pressure-sensitive adhesive coating process, which increases the production cost. There is a problem that a large amount of solvent needs to be removed in the pressure-sensitive adhesive coating process, which increases the environmental load.
  • a self-adhesive surface protective film in which a base film layer and an adhesive layer are simultaneously extruded and laminated by a coextrusion lamination method has been proposed.
  • a surface protective film has, for example, an adhesive layer made of a resin composition containing 10 to 50 parts by mass of a polyethylene resin with respect to 100 parts by mass of a hydrogenated product of a styrene-conjugated diene polymer.
  • An adhesive film is provided (see, for example, Patent Document 1).
  • Patent Document 1 has a problem in that the adhesive force with respect to the surface of the adherend may be insufficient.
  • the substrate layer has a practical adhesive force for an adherend having an uneven surface, and is wound up into a roll shape and then used again after being unrolled. It is to provide a surface protective film having good handling properties in which the adhesive layer and the pressure-sensitive adhesive layer are in close contact with each other and so-called blocking does not occur, and the surface of the adherend after peeling is small in glue residue.
  • the present inventors have found that a block copolymer having a styrenic elastomer or a specific crystalline olefin block in the adhesive layer of the surface protective film, and an amorphous ⁇ - Using a resin in which three components, an olefin polymer and a crystalline olefin polymer, are mixed at a specific blending ratio, practical adhesion can be achieved even when the surface of the adherend is uneven.
  • the present inventors have found that a surface protective film having good strength, small adhesive residue on the adherend surface after blocking and peeling, and good handleability can be obtained, and the present invention has been completed.
  • this invention is a surface protection film which has a base material layer (A) and an adhesion layer (B), Comprising:
  • This adhesion layer (B) is random of a styrene-type polymer block, styrene, and a conjugated diene compound.
  • Copolymer (B1-1) having a styrene random copolymer block obtained by hydrogenating the double bond portion of the copolymer, a formula aba, or ab (a is a styrene polymer) A block, and b is a styrene block copolymer (B1-2) represented by a conjugated diene polymer block or an olefin polymer block obtained by hydrogenating double bonds in a conjugated diene polymer) Or a block copolymer (B1-3) comprising a crystalline olefin polymer block obtained by hydrogenation of a conjugated diene polymer block and a conjugated diene polymer block, and an amorphous ⁇
  • a surface protective film comprising as a main component a mixture of 5 to 45% by mass of an olefin polymer (B2) and 5 to 45% by mass of a crystalline olefin polymer (B3).
  • the surface protective film of the present invention is a time-dependent change in adhesive force even if it is exposed to a high-temperature environment after being attached to an optical film, various resin plates, a glass plate, a metal plate, etc. whose surface is uneven. And has excellent heat resistance, such as no lifting or peeling from the adherend, and no warpage of the adherend, and there is no adhesive residue visible on the adherend surface after peeling. Furthermore, after winding in a roll shape, there is no blocking at the time of extending and using again, and it is excellent also in blocking resistance.
  • the surface protective film of the present invention is a multilayer film having at least a base material layer and an adhesive layer.
  • the resin used for the substrate layer (A) of the surface protective film in the present invention is not particularly limited, but it is preferable to use an olefin polymer as a main component, for example, a propylene homopolymer, a propylene-ethylene copolymer, Examples thereof include propylene polymers such as propylene-ethylene-butene-1 copolymer, ethylene polymers such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene. These olefin polymers may be used alone or in combination of two or more.
  • the surface protective film of the present invention is applied to various optical films, resin plates, glass plates, metal plates, etc., and then subjected to post-processing such as drying and heat molding to be exposed to a high temperature environment.
  • post-processing such as drying and heat molding to be exposed to a high temperature environment.
  • crystallinity means having a peak of 0.5 J / g or more in the range of 95 to 250 ° C. in DSC (differential scanning calorimetry).
  • the propylene polymer has a melt flow rate (hereinafter referred to as “230 ° C. MFR”; a value measured at 230 ° C. and 21.18 N in accordance with JIS K7210: 1999) of 0.5 to Those having a melting point of 120 to 165 ° C. at 30.0 g / 10 min are preferred, more preferably those having an MFR of 230 to 120 ° C. of 2.0 to 15.0 g / 10 min and a melting point of 125 to 162 ° C. is there.
  • 230 ° C. MFR melt flow rate
  • the film is less shrunk even if it is exposed to a high temperature environment by drying, heat molding or the like after being attached to the adherend, so that it does not float or peel off. There is no warping, and the film formability of the laminated film is improved.
  • the ethylene polymer has a melt flow rate (hereinafter referred to as “190 ° C. MFR”; a value measured at 190 ° C. and 21.18 N in accordance with JIS K7210: 1999) of 0.5 to It is preferable that it is 30.0 g / 10 min since the extrusion is easy, and more preferable is that the MFR at 190 ° C. is 2.0 to 15.0 g / 10 min. Further, these ethylene polymers preferably have a melting point of 90 to 135 ° C, and more preferably have a melting point of 105 to 130 ° C. If the melting point is within this range, since the film shrinks less even when placed in a high temperature environment by drying, thermoforming, etc. after being attached to the adherend, the adherend is lifted or peeled off. Can be suppressed.
  • 190 ° C. MFR a melt flow rate
  • main component means that, in each layer, the specific resin or mixture thereof has a mass ratio of the specific resin or mixture thereof to 65% by mass or more, preferably 80% by mass. That's it.
  • the pressure-sensitive adhesive layer (B) of the surface protective film of the present invention is a styrenic polymer block in order to balance the conformity to unevenness of the adherend surface with the reduction of adhesive residue after peeling and prevention of blocking.
  • Examples of the conjugated diene compound used as a raw material for the copolymer (B1-1) or the styrene block copolymer (B1-2) include 1,3-butadiene, isoprene, 2,3-dimethyl-1, Examples include 3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene, and the like. From the viewpoint of availability, 1,3-butadiene and isoprene are preferably used.
  • styrene compound forming the styrene polymer block examples include styrene, ⁇ -methyl styrene, P-methyl styrene, t-butyl styrene, divinyl benzene, 1.1-diphenyl styrene, N, N-dimethyl.
  • -P-aminomethylstyrene N, N-diethyl-P-aminoethylstyrene and the like can be mentioned, and styrene is preferably used.
  • the styrene compound in the copolymer is preferably in the range of 5/95 to 60/40.
  • the block copolymer (B1-3) includes a crystalline olefin polymer block (I) obtained by hydrogenating a conjugated diene polymer block and a conjugated diene polymer block (II) (I-II) n1 Or (I-II) n2- (I) (n1, n2 is an integer of 1 or more), wherein at least one terminal of the polymer chain is composed of the crystalline olefin polymer block (I). Preferably there is.
  • Examples of such a block copolymer (B1-3) include those provided in JP-A-3-128957 and JP-A-8-231786. Specifically, a polybutadiene polymer block having a low 1,2-vinyl bond content (for example, 25% or less) and a polymer mainly composed of a conjugated diene compound, which contains 1,2- and 3,4-bonds. A copolymer composed of a polymer block having a high rate (for example, 50% or more) is synthesized, and the polybutadiene portion is made to have a structure similar to polyethylene by hydrogenating the copolymer to form a crystalline polymer block. And the like.
  • the conjugated diene compound used as a raw material for the block copolymer (B1-3) is the same as the conjugated diene compound used for the copolymer (B1-1) or the styrene block copolymer (B1-2). Any of these may be exemplified, and 1,3-butadiene and isoprene are preferably used from the viewpoint of industrial availability.
  • Examples of commercially available products include “Dynalon 1320P” manufactured by JSR Corporation, which is a styrene-butadiene random copolymer hydrogenated product (hereinafter abbreviated as HSBR) as the copolymer (B1-1). Also, as the styrene block copolymer (B1-2), “SIS5200” manufactured by JSR Corporation, which is a styrene-isoprene-styrene block copolymer (hereinafter abbreviated as SIS), a styrene-ethylene-butylene-styrene block.
  • SIS styrene-ethylene-butylene-styrene block
  • Kuraray Stock Co., Ltd. which is a copolymer (hereinafter abbreviated as SEBS) “Dynalon 8600P, Dynalon 8601P” manufactured by JSR Corporation, and a styrene-ethylene-propylene-styrene block copolymer (hereinafter abbreviated as SEPS). “Septon 2063, Septon 2004”, etc.
  • the block copolymer (B1-3) is a block copolymer having a structure of crystalline olefin-ethylene / butylene copolymer-crystalline olefin (hereinafter abbreviated as CEBC) manufactured by JSR Corporation. “Dynalon 6200P” and the like.
  • the amorphous ⁇ -olefin polymer (B2) used for the pressure-sensitive adhesive layer (B) of the surface protective film of the present invention is a polymer containing monomer units based on ⁇ -olefins having 3 to 20 carbon atoms.
  • DSC differential scanning calorimeter
  • the ⁇ -olefin having 3 to 20 carbon atoms may be linear or branched, for example, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1 Nonene-1, decene-1, undecene-1, dodecene-1, tridecene-1, tetradecene-1, pentadecene-1, hexadecene-1, heptadecene-1, octadecene-1, nanodecene-1, eicosene-1, etc.
  • the amorphous ⁇ -olefin polymer (B2) is preferably a polymer containing two or more of these ⁇ -olefins, and includes a monomer unit based on propylene and an ⁇ -olefin having 4 to 20 carbon atoms. A polymer containing one or more monomer units based on it is more preferred.
  • the amorphous ⁇ -olefin polymer (B2) may contain a monomer other than the ⁇ -olefin.
  • monomers include ethylene, polyene compounds, cyclic olefins, vinyl aromatic compounds, and the like.
  • amorphous ⁇ -olefin polymers (B2) amorphous propylene-butene-1 copolymers and amorphous propylene-ethylene-butene-1 copolymers are preferable. These may be used alone or in combination of two or more.
  • the monomer unit based on propylene in the amorphous propylene-butene-1 copolymer is 70% by mass when the total monomer unit of the amorphous propylene-butene-1 copolymer is 100% by mass.
  • the above is preferable, More preferably, it is 80 mass% or more, More preferably, it is 90 mass% or more.
  • the heat resistance is improved.
  • the monomer unit based on propylene in the amorphous propylene-ethylene-butene-1 copolymer is 100% by mass based on the total monomer units of the amorphous propylene-ethylene-butene-1 copolymer. , 50% by mass or more, preferably 60% by mass or more. When the monomer unit based on propylene is within this range, the heat resistance is improved.
  • the monomer unit based on ethylene in the amorphous propylene-ethylene-butene-1 copolymer is preferably 10% by mass or more, more preferably 20% by mass or more. If the monomer unit based on ethylene is in this range, the adhesive layer becomes relatively soft, and even if the adherend surface has irregularities, it adheres in a form that follows the irregularities. Power is obtained.
  • the intrinsic viscosity [ ⁇ ] of the amorphous ⁇ -olefin polymer (B2) is preferably in the range of 0.1 to 10.0 dl / g, more preferably 0.7 to 7.0 dl / g. g.
  • the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably more than 1 and 4 or less, more preferably 2 to 3. .
  • the amorphous ⁇ -olefin polymer (B2) When the intrinsic viscosity and molecular weight distribution of the amorphous ⁇ -olefin polymer (B2) are in this range, the heat resistance, transparency and adhesiveness are improved, and the adherend with the surface protective film attached is stored for a long time. Even when exposed to a high temperature environment, the low molecular weight component in the amorphous ⁇ -olefin polymer (B2) does not migrate to the adherend surface and contaminate the adherend. In addition, since the amorphous ⁇ -olefin polymer (B2) is an olefin polymer, the alteration of the resin such as deacetic acid as in the case of using the ethylene-vinyl acetate copolymer for the adhesive layer is performed. Thus, there is no increase in adhesive strength over time, and stable adhesive strength can be maintained over a long period of time.
  • Examples of the method for producing the amorphous ⁇ -olefin polymer (B2) include a method of polymerizing with a metallocene catalyst using a gas phase polymerization method, a solution polymerization method, a slurry polymerization method, a bulk polymerization method, or the like. Can be mentioned.
  • a more preferable production method includes the production method disclosed in JP-A-2002-348417.
  • Examples of the crystalline olefin polymer (B3) used for the adhesive layer (B) of the surface protective film of the present invention include propylene homopolymer, propylene-ethylene copolymer, propylene-ethylene-butene-1 copolymer, and the like. Examples include propylene-based polymers, low-density polyethylene, medium-density polyethylene, high-density polyethylene, and linear low-density polyethylene.
  • the propylene-based polymer preferably has an MFR of 230 ° C. of 0.5 to 30.0 g / 10 min and a melting point of 120 to 165 ° C., more preferably an MFR of 230 ° C. of 2. Those having a weight of 0 to 15.0 g / 10 min are preferred.
  • the ethylene polymer preferably has an MFR at 190 ° C. of 0.5 to 30.0 g / 10 min because of easy extrusion, and more preferably has an MFR at 190 ° C. of 2. 0 to 15.0 g / 10 min.
  • the pressure-sensitive adhesive layer (B) of the present invention comprises 50 to 85 masses of the copolymer (B1-1), the styrenic block copolymer (B1-2), or the block copolymer (B1-3). %, An amorphous ⁇ -olefin polymer (B2) of 5 to 45% by mass, and a crystalline olefin polymer (B3) of 5 to 45% by mass.
  • the blending ratio of the component (B2) is less than 5% by mass or exceeding 45% by mass, there is a problem that the adherence having an uneven surface has insufficient adhesive force. Moreover, it can adjust to the adhesive force requested
  • the surface protective film of the present invention is composed of at least two layers of the base material layer (A) and the adhesive layer (B) as described above, and further on the base material layer (A) (surface having the adhesive layer).
  • the surface layer (C) may be provided on the opposite surface).
  • the resin used for the surface layer (C) is not particularly limited, but it is preferable to use an olefin polymer from the viewpoint of good affinity with the base material layer (A). Examples include linear low density polyethylene, medium density polyethylene, high density polyethylene, propylene homopolymer, propylene-ethylene copolymer, propylene-butene-1 copolymer, propylene-butene-1-ethylene copolymer, and the like. Among these, low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, and propylene homopolymer are more preferable because the film formability of the laminated film is improved.
  • the resin used for the surface layer (C) may be a mixed resin of the above-mentioned resins and a propylene-ethylene block copolymer as a main component, and the surface of the surface layer may be modified into a satin finish.
  • the surface of the surface layer may be modified into a satin finish.
  • the propylene-ethylene block copolymer is a resin obtained by block polymerization of propylene and ethylene, and any resin can be used as long as the surface of the resin layer becomes satin when used in the surface layer (C). There is no particular limitation.
  • Examples thereof include a propylene-ethylene block copolymer obtained by polymerization of ethylene or ethylene and propylene in the presence of a polypropylene homopolymer.
  • a propylene-ethylene block copolymer having an ethylene-derived component content of 8 to 20% by mass because the surface can be easily made into a satin-like surface.
  • the MFR at 230 ° C. of the mixed resin with the propylene-ethylene block copolymer is preferably 4 to 12 g / 10 minutes from the viewpoint of easy extrusion, and more preferably 6 to 10 g / 10 minutes.
  • the density is preferably 0.890 to 0.910 g / cm 3 , more preferably 0.895 to 0.905 g / cm 3 .
  • the surface protective film of the present invention preferably has a total film thickness of 20 to 120 ⁇ m. If the thickness of the entire film is within this range, the protection of the adherend, the adhesive property that does not cause floating or peeling during storage or transportation of the adherend, and the workability such as sticking / peeling are good. It becomes.
  • the thickness of the adhesive layer (B) is preferably 3 to 30 ⁇ m, more preferably 5 to 25 ⁇ m. When the thickness of the pressure-sensitive adhesive layer (B) is within this range, the pressure-sensitive adhesive properties that do not float or peel off during storage, transportation, etc. of the adherend and the film formability of the laminated film are improved.
  • the thickness of the surface layer (C) is preferably 3 to 30 ⁇ m, more preferably 5 to 20 ⁇ m. When the thickness of the surface layer (C) is within this range, the heat resistance and the film formability of the laminated film are good.
  • the method for producing the surface protective film of the present invention is not particularly limited as long as it is a coextrusion lamination method.
  • the resin used for each resin layer is melted by using two or more extruders, Examples include a method of laminating in a molten state by a coextrusion method such as an extrusion die method or a feed block method, and then processing into a film using a method such as inflation or a T-die / chill roll method.
  • the melt-laminated film may be nipped between a rubber touch roll, a steel belt or the like and the chill roll and cooled.
  • the surface protective film of the present invention may be stretched in at least one axial direction.
  • various methods such as longitudinal or lateral uniaxial stretching, sequential biaxial stretching, simultaneous biaxial stretching, or tubular method biaxial stretching can be employed. Further, the stretching process may be inline or offline.
  • a stretching method for uniaxial stretching a proximity roll stretching method or a rolling method may be used.
  • the stretching ratio of uniaxial stretching is preferably 1.1 to 80 times in the longitudinal or transverse direction, more preferably 3 to 30 times.
  • the stretching ratio of biaxial stretching is preferably 1.2 to 70 times in terms of area ratio, more preferably 4 to 6 times in length, 5 to 9 times in width, and 20 to 54 times in terms of area ratio.
  • the longitudinal or lateral stretching process is not necessarily limited to one-stage stretching, and may be multi-stage stretching.
  • longitudinal uniaxial stretching such as longitudinal uniaxial roll stretching and longitudinal uniaxial rolling stretching in sequential biaxial stretching
  • proximity roll stretching either the flat method or the cross method may be used, but multistage proximity cross stretching that can reduce width shrinkage is more preferable.
  • the stretching temperature is preferably 80 to 160 ° C. in any stretching method in the case of uniaxial stretching, and preferably 90 to 165 ° C. in the case of using tenter stretching with uniaxial stretching. Further, more preferable stretching temperatures are 110 to 155 ° C.
  • the stretching temperature range similar to that in the case of uniaxial stretching is preferable in any method.
  • the temperature of the preheating part is preferably 60 to 140 ° C.
  • the temperature of the heat fixing part is preferably 90 to 160 ° C.
  • the surface protective film of the present invention is further stretched in at least uniaxial direction and structurally stabilized by heat setting, and further by orientation crystallization of the base material layer (A) mainly composed of an olefin polymer.
  • the heat resistance is improved, and the change with time of the adhesive force is small, which is preferable.
  • a tackifier may be added as appropriate as long as the effects of the present invention are not impaired.
  • the tackifier include petroleum-based resins such as aliphatic copolymers, aromatic copolymers, aliphatic / aromatic copolymer systems and alicyclic copolymers, and coumarone-indene resins.
  • Terpene resins, terpene phenol resins, rosin resins such as polymerized rosin, phenol resins, xylene resins or hydrogenated products thereof, which are generally used for adhesives can be used without any particular limitation .
  • These tackifiers may be used alone or in combination of two or more.
  • a lubricant an antiblocking agent, an ultraviolet absorber, a light stabilizer, an antistatic agent, an antifogging agent, and the like may be added as appropriate as long as the effects of the present invention are not impaired.
  • these additives it is preferable to use various additives for olefin polymers.
  • the reaction mixture was continuously withdrawn from the top of the reactor so that the reaction mixture in the polymerization vessel maintained 100 L. Further, from the lower part of the polymerization vessel, dimethylsilyl (tetramethylcyclopentadienyl) (3-t-butyl-5-methyl-2-phenoxy) titanium dichloride is added as a catalyst component at 0.005 g / hour at triphenylmethyl. Tetrakis (pentafluorophenyl) borate was continuously fed at a rate of 0.298 g / hr and triisobutylaluminum was fed at a rate of 2.315 g / hr. The copolymerization reaction was carried out at 45 ° C.
  • Example 1 As the resin for the surface layer, low density polyethylene [density: 0.902 g / cm 3 , MFR (190 ° C., 21.18 N): 4 g / 10 min; hereinafter referred to as “LDPE”. And a propylene-ethylene block copolymer in a mass ratio of 15/85, and a metallocene catalyst-based propylene-ethylene random copolymer [density: 0.900 g / cm 3 as a resin for the base layer] , MFR (230 ° C., 21.18 N): 7.0 g / 10 min, content of ethylene monomer unit: 3.5% by mass; hereinafter referred to as “COPP”.
  • LDPE low density polyethylene
  • HSBR styrene / butadiene random copolymer
  • Alcon P-125 manufactured by Arakawa Chemical Co., Ltd.
  • Example 2 As a resin for the adhesive layer, a composition comprising HSBR, an amorphous ⁇ -olefin polymer composition, and LLDPE, 10 parts by mass of Alcon P-125 per 100 parts by mass of a 65/25/10 mixture by mass ratio. A surface protective film of Example 2 was obtained in the same manner as Example 1 except that it was used.
  • Example 3 As a resin for the adhesive layer, a composition in which 10 parts by mass of Alcon P-125 is blended with 100 parts by mass of an 85/10/5 mixture of HSBR, an amorphous ⁇ -olefin polymer composition, and LLDPE. A surface protective film of Example 3 was obtained in the same manner as Example 1 except that it was used.
  • Example 4 As the adhesive layer resin, a styrene-ethylene / propylene-styrene block copolymer (“Septon 2063” manufactured by Kuraray Co., Ltd .; hereinafter referred to as “SEPS”), an amorphous ⁇ -olefin polymer composition, and LLDPE are used.
  • SEPS styrene-ethylene / propylene-styrene block copolymer
  • an amorphous ⁇ -olefin polymer composition an amorphous ⁇ -olefin polymer composition
  • LLDPE low density polyethylene
  • a surface protective film of Example 4 was obtained in the same manner as in Example 1 except that a composition in which 10 parts by mass of Alcon P-125 was added to 100 parts by mass of a 55/35/10 mixture by mass ratio was obtained.
  • Example 5 As the adhesive layer resin, a composition in which 10 parts by mass of Alcon P-125 is blended with 100 parts by mass of a 65/25/10 mixture of SEPS, an amorphous ⁇ -olefin polymer composition, and LLDPE in a mass ratio. A surface protective film of Example 5 was obtained in the same manner as Example 1 except that it was used.
  • Example 6 As a resin for the adhesive layer, a styrene-isoprene block copolymer (“SIS5200” manufactured by JSR Corporation; hereinafter referred to as “SIS”), an amorphous ⁇ -olefin polymer composition, and LLDPE in a mass ratio of 55 / A surface protective film of Example 6 was obtained in the same manner as in Example 1 except that a composition in which 10 parts by mass of Alcon P-125 was mixed with 100 parts by mass of the 35/10 mixture was used.
  • SIS5200 styrene-isoprene block copolymer manufactured by JSR Corporation
  • Example 7 As a resin for the adhesive layer, a hydrogenated product of styrene-isobutylene block copolymer (“Sibstar 072T” manufactured by Kaneka Corporation; hereinafter referred to as “SIBS”), an amorphous ⁇ -olefin polymer composition, and LLDPE are used.
  • SIBS styrene-isobutylene block copolymer
  • amorphous ⁇ -olefin polymer composition an amorphous ⁇ -olefin polymer composition
  • LLDPE low-diene-ethylene
  • Example 8 As a resin for the adhesive layer, a mass ratio of a styrene-ethylene-butylene-styrene copolymer (manufactured by JSR Corporation; Dynalon 88601P; hereinafter referred to as “SEBS”), an amorphous ⁇ -olefin polymer composition, and LLDPE.
  • SEBS styrene-ethylene-butylene-styrene copolymer
  • SEBS styrene-ethylene-butylene-styrene copolymer
  • amorphous ⁇ -olefin polymer composition amorphous ⁇ -olefin polymer composition
  • LLDPE LLDPE
  • Example 9 As a resin for the adhesive layer, a crystalline olefin-ethylene / butylene copolymer-crystalline olefin block copolymer (manufactured by JSR Corporation; Dynalon 6200P, hereinafter referred to as “CEBC”) and an amorphous ⁇ -olefin polymer.
  • CEBC crystalline olefin-ethylene / butylene copolymer-crystalline olefin block copolymer
  • Example 10 As the resin for the base layer, high density polyethylene [density: 0.96 g / cm 3 , MFR (190 ° C., 21.18 N): 13 g / 10 min; hereinafter referred to as “HDPE”. ] And LDPE were used in the same manner as in Example 1 except that 50/50 was mixed and used to obtain a surface protective film of Example 10.
  • Example 11 A surface protective film of Example 11 was obtained in the same manner as Example 5 except that HDPE / LDPE was mixed and used at a mass ratio of 50/50 as the base layer resin.
  • Example 12 A surface protective film of Example 12 was obtained in the same manner as in Example 6 except that HDPE / LDPE was mixed and used at a mass ratio of 50/50 as the base layer resin.
  • Comparative Example 1 Comparative Example 1 was carried out in the same manner as in Example 1 except that as the adhesive layer resin, a composition in which 10 parts by mass of Alcon P-125 was blended with 100 parts by mass of 85/15 mixture of HSBR and LLDPE was used. A surface protective film was obtained.
  • Comparative Example 2 As a resin for the adhesive layer, a composition comprising HSBR, an amorphous ⁇ -olefin polymer composition, and LLDPE blended with 10 parts by mass of Alcon P-125 with respect to 100 parts by mass of a 40/50/10 mixture by mass ratio. A surface protective film of Comparative Example 2 was obtained in the same manner as Example 1 except that it was used.
  • Comparative Example 3 As a resin for the adhesive layer, a composition in which 10 parts by mass of Alcon P-125 is blended with 100 parts by mass of a 90/3/7 mixture of HSBR, an amorphous ⁇ -olefin polymer composition, and LLDPE in a mass ratio. A surface protective film of Comparative Example 3 was obtained in the same manner as Example 1 except that it was used.
  • Comparative Example 4 Comparative Example 4 was carried out in the same manner as in Example 1 except that a composition in which 10 parts by mass of Alcon P-125 was blended with 100 parts by mass of a mixture of SEPS and LLDPE in a mass ratio of 85/15 was used as the adhesive layer resin. A surface protective film was obtained.
  • the surface protection film of Comparative Example 5 was obtained in the same manner as in Example 1 except that the composition containing 125 parts by mass of 125 was used.
  • the obtained surface protective film was cut out in the size of A4 (length 297 mm x width 210 mm). At this time, the film was cut out so that the extrusion direction (MD direction) during film formation coincided with the A4 vertical direction. After 10 cut out films were stacked, the upper and lower sides were sandwiched between A4 size, 3 mm thick vinyl chloride plates, a weight of 5 kg was placed, stored in a dryer at 40 ° C. for 14 days, then stored at 23 ° C. And stored in a constant temperature room of 50% RH for 1 hour.
  • Blocking force is less than 0.8 N / 25 mm
  • Blocking force is 0.8 N / 25 mm or more
  • Tables 1 to 4 show the layer structures of the surface protective films produced above and the evaluation results obtained using these surface protective films.
  • the surface protective film of the present invention has an appropriate adhesive force to the adherend having an uneven surface shape, and has a practically weak adhesive force as a surface protective film. It was. Moreover, when peeling a film from an acrylic board, it turned out that there is no glue residue which can be visually confirmed on the adherend surface, and contamination
  • Comparative Example 1 is an example of a surface protective film in which the surface layer and the base material layer are the same as Example 1, but a mixture of HSBR and LLDPE of 85/15 is used for the adhesive layer and the component (B2) is not blended. It is. In the surface protective film of Comparative Example 1, it was found that the adhesive strength to the adherend having a surface uneven shape was low.
  • the surface layer and the base material layer are the same as Example 1, and the blending ratio of the component (B3) of the adhesive layer is 10 parts by mass, but the blending ratio of the component (B1-1) is 50% of the lower limit. It is an example of the surface protection film which made the compounding ratio of 40 mass parts less than a mass part and a component (B2) 50 mass parts exceeding 45 mass parts of an upper limit. In the surface protective film of this comparative example 2, it turned out that the adhesive force with respect to the adherend of a surface uneven
  • the surface layer and the base material layer are the same as Example 1, but 90 parts by mass of the component (B) exceeding the upper limit of 85 parts by mass of the component (B1-1) of the adhesive layer. It is an example of the surface protection film which made the compounding ratio 3 mass parts less than 5 mass parts of a minimum. In the surface protective film of Comparative Example 3, it was found that the adhesion to the adherend having an uneven surface was low, the blocking power was large, and the blocking resistance was poor.
  • Comparative Example 4 the surface layer and the base material layer are the same as those in Example 1, but the surface protective film is a mixture of SEPS and LLDPE of 85/15 in the adhesive layer and does not contain component (B2). It is an example. In the surface protective film of Comparative Example 1, it was found that the adhesive strength to the adherend having a surface uneven shape was low.
  • the surface protective film of the present invention is useful as a film for protecting the surface of various resin plates, glass plates, metal plates and the like.
  • it is suitable for prisms having unevenness in the surface shape of the adherend and protective film for diffusion plates.

Abstract

Le film protecteur ci-décrit est utilisé pour protéger les surfaces de différents types de plaques de résine, de verre ou de métal utilisées comme matériaux de construction et en électricité/électronique. Ledit film est collé à la surface de ces plaques pour les protéger contre les rayures et/ou la contamination pendant leur stockage, leur transport et leur traitement consécutif. Le film protecteur comporte spécifiquement une couche adhésive en résine préparée en mélangeant dans un rapport spécifique un élastomère de styrène ou un copolymère séquencé de blocs cristallins spécifiques d'oléfines, un polymère d'α-oléfine amorphe et un polymère d'oléfine cristallin. Ainsi, le film présente une bonne adhérence, même sur un substrat de surface inégale, ainsi qu'une excellente aptitude à la manipulation.
PCT/JP2010/050463 2009-01-21 2010-01-18 Film protecteur de surface WO2010084832A1 (fr)

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WO2011016446A1 (fr) * 2009-08-04 2011-02-10 三井化学東セロ株式会社 Film de protection de surface
JP2011037039A (ja) * 2009-08-06 2011-02-24 Mitsui Chemicals Tohcello Inc 表面保護フィルム
JP2012057131A (ja) * 2010-09-13 2012-03-22 Fujifilm Corp 機能性フィルムの製造方法
JP2012107162A (ja) * 2010-11-19 2012-06-07 Gunze Ltd 表面保護フィルム
JP2013124306A (ja) * 2011-12-15 2013-06-24 Okura Ind Co Ltd 表面保護フィルム
JP2013149015A (ja) * 2012-01-18 2013-08-01 Kyodo Printing Co Ltd Ｉｃカード用積層体、及びｉｃカード用積層体の製造方法
JP2013234321A (ja) * 2012-04-10 2013-11-21 Toyobo Co Ltd 自己粘着性表面保護フィルム
JP2014208475A (ja) * 2013-03-28 2014-11-06 三菱化学株式会社 積層体
JP2014208476A (ja) * 2013-03-29 2014-11-06 三菱化学株式会社 積層体
JP2016196650A (ja) * 2010-12-01 2016-11-24 東洋紡株式会社 粘着剤及び粘着フィルム
WO2021193223A1 (fr) * 2020-03-25 2021-09-30 東レフィルム加工株式会社 Film stratifié et rouleau de film

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JP6323690B2 (ja) * 2013-04-11 2018-05-16 東洋紡株式会社 自己粘着性表面保護フィルム
CN106103089B (zh) * 2014-02-28 2018-10-16 东丽薄膜先端加工股份有限公司 加热工序用表面保护膜

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JP2004002624A (ja) * 2002-04-10 2004-01-08 Nitto Denko Corp 表面保護シート
JP2006028347A (ja) * 2004-07-16 2006-02-02 Sumitomo Chemical Co Ltd 粘着フィルム
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Cited By (14)

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Publication number Priority date Publication date Assignee Title
WO2011016446A1 (fr) * 2009-08-04 2011-02-10 三井化学東セロ株式会社 Film de protection de surface
JP2011037039A (ja) * 2009-08-06 2011-02-24 Mitsui Chemicals Tohcello Inc 表面保護フィルム
JP2012057131A (ja) * 2010-09-13 2012-03-22 Fujifilm Corp 機能性フィルムの製造方法
JP2012107162A (ja) * 2010-11-19 2012-06-07 Gunze Ltd 表面保護フィルム
JP2016196650A (ja) * 2010-12-01 2016-11-24 東洋紡株式会社 粘着剤及び粘着フィルム
JP2013124306A (ja) * 2011-12-15 2013-06-24 Okura Ind Co Ltd 表面保護フィルム
JP2013149015A (ja) * 2012-01-18 2013-08-01 Kyodo Printing Co Ltd Ｉｃカード用積層体、及びｉｃカード用積層体の製造方法
JP2013234321A (ja) * 2012-04-10 2013-11-21 Toyobo Co Ltd 自己粘着性表面保護フィルム
JP2018087332A (ja) * 2012-04-10 2018-06-07 東洋紡株式会社 自己粘着性表面保護フィルム
CN110283545A (zh) * 2012-04-10 2019-09-27 东洋纺株式会社 自粘合性表面保护薄膜
JP2014208475A (ja) * 2013-03-28 2014-11-06 三菱化学株式会社 積層体
JP2014208476A (ja) * 2013-03-29 2014-11-06 三菱化学株式会社 積層体
WO2021193223A1 (fr) * 2020-03-25 2021-09-30 東レフィルム加工株式会社 Film stratifié et rouleau de film
JP6966025B1 (ja) * 2020-03-25 2021-11-10 東レフィルム加工株式会社 積層フィルム及びフィルムロール

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