CN101909887A - Surface protection film - Google Patents

Surface protection film Download PDF

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Publication number
CN101909887A
CN101909887A CN2008801245032A CN200880124503A CN101909887A CN 101909887 A CN101909887 A CN 101909887A CN 2008801245032 A CN2008801245032 A CN 2008801245032A CN 200880124503 A CN200880124503 A CN 200880124503A CN 101909887 A CN101909887 A CN 101909887A
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CN
China
Prior art keywords
protective film
surface protective
copolymer
based polymer
amorphism
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Pending
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CN2008801245032A
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Chinese (zh)
Inventor
薄井达彦
森谷贵史
小桥一范
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DIC Corp
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Dainippon Ink and Chemicals Co Ltd
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Publication of CN101909887A publication Critical patent/CN101909887A/en
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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
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C09J123/0815—Copolymers of ethene with aliphatic 1-olefins
    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C09J2423/04—Presence of homo or copolymers of ethene

Abstract

The invention relates to a surface protection film which is to be applied to the surfaces of building materials, various resin plates for use in electrical and electronic fields, glass plates, metal plates and so on for the purpose of protecting the adherends from scratching, contamination or the like in storage, transportation, or post-processing. A surface protection film which little stains the surface of an adherend and is excellent in fabricability is provided by using, as the main resin component constituting the pressure-sensitive adhesive layer of the film, a resin blend which comprises an amorphous a-olefin polymer and a linear low-density polyethylene at a specific ratio or which comprises an amorphous a-olefin polymer, a linear low-density polyethylene, and a crystalline ethylene/a-olefin copolymer at a specific ratio.

Description

Surface protective film
Technical field
The present invention relates to a kind of protective film; it sticks on their surface for the surface of protecting in construction material, electrical/electronic field etc. the various resin plates that use, glass plate, metallic plate etc., keeping, carrying, after add and protect man-hour adherend to avoid damage, pollution etc.Relate in particular to after surface protective film is secured at adherend, can not float, peel off, and film is peeled off the surface protective films few to the pollution on adherend surface such as back cull from adherend.
Background technology
As Essential Performance Requirements, but can enumerate for aforementioned various adherend non-involvement folds or air and the paste operation excellence of fitly pasting surface protective film; Have keeping at adherend, conveyance etc. during do not float or the adhesion of the appropriateness peeled off; The variation in time of being processed the adhesion that causes by environmental change in the keeping of adherend or back is little, the surface of peeling off and can not pollute adherend easily after peeling off.
As surface protective film in the past; known by with the film formed by Corvic, polyethylene-based resin, polypropylene-based resin etc. as base material; and be coated with the surface protective film of the adhesive of polyurethane series, acrylic acid series, rubber system etc. at its single face; but these surface protective films have following problem: the film and the tack between the adhesive of base material can be poor, perhaps remain in the surface of adherend in the part of adhesive when adherend is peeled off because the cohesive force of adhesive itself is low.In addition; also there are the following problems etc.: coating adhesive on film and the surface protective film made; owing to need the manufacturing process of base film and at least two operations of painting process of adhesive; therefore the problem that exists production cost to uprise needs to remove a large amount of solvents in the painting process of adhesive and makes carrying capacity of environment uprise.
As the method for improving the problems referred to above, the surface protective film of self adhesive type of the thin layer and the adhesive agent layer of base material being extruded simultaneously, are laminated by the coextrusion layered manner has been proposed.As this type of surface protective film; for example, contain amorphism olefin copolymer, crystallinity olefin copolymer and thermoplastic elastomer (TPE) by use and have the mixture (for example with reference to patent documentation 1) of special properties or by using amorphism olefin copolymer, crystallinity olefin polymer and having mixture that the block copolymer of crystallinity olefin block mixes with specific ratio (for example with reference to patent documentation 2.) as the resin combination that adhesion layer is used, adhesion strength can be provided and peel off excellent in stability, do not have the plural layers of the cull after peeling off.
In addition; the inventor etc. provide adhesiveness and the hear resistance that has both appropriateness; and peel off the back surface protective film few to the pollution on adherend surface; this surface protective film is laminated by substrate layer and adhesion layer; described substrate layer is a main component with the crystallinity acrylic polymer, and the resin that described adhesion layer mixes by special ratios with amorphism alpha-olefin based polymer and crystallinity acrylic polymer is main component (for example with reference to a patent documentation 3).
Yet, when the surface protective film that is provided in aforementioned patent document 1 or 2 is sticked to acrylic board etc., because its initial grab height can become and be difficult to peel off from adherend.In addition, have according to purposes that protective film is peeled off the back is the situation that secondary operations such as printing are implemented on the surface of resin plate etc. to adherend.In the surface protective film that the coextrusion laminate film that provides in by aforementioned patent document 1 or 2 is formed; there are the following problems: adherend after film is peeled off surface is because cull etc. produce the residue of denier, and this becomes in secondary operations as described above and prints bad main cause.In addition, when in adhesion layer, mixing the elastomer of polystyrene, be wound into the roller shape after, extract out when using again, exist adhesion layer and substrate layer to adhere to, so-called adhesion might take place in the problem that is difficult to extract out.
In addition; in the surface protective film that in patent documentation 3, provides; but though do not appear at the pollution of the Visual Confirmation degree on adherend surface after peeling off, can change the character on adherend surface, particularly after peeling off, apply, can bring harmful effect during secondary operations such as printing.
Patent documentation 1: TOHKEMY 2006-188646 communique
Patent documentation 2: TOHKEMY 2006-257247 communique
Patent documentation 3: TOHKEMY 2007-130872 communique
Summary of the invention
The problem that invention will solve
Problem of the present invention is to provide a kind of surface protective film; it has the adhesiveness and the adhesion stability of appropriateness; but peel off the back at the residue of the Visual Confirmation on adherend surface from needless to say; the pollution of trace that can not Visual Confirmation does not have yet; the secondary operations applicability of printing etc. is good; and after being wound into the roller shape, adhesion can not appear when extracting use out again.
The scheme that is used to deal with problems
In order to address the above problem; the inventor etc. have carried out deep research; found that; the resin that the resin of the adhesion layer by being used for surface protective film adopts amorphism alpha-olefin based polymer and straight chain shape low density polyethylene (LDPE) to mix by special ratios; perhaps the resin that mixes by special ratios with amorphism alpha-olefin based polymer, straight chain shape low density polyethylene (LDPE) and crystallinity ethene-alpha-olefin copolymer is as main component; make minimum to the pollution on adherend surface; the secondary operations applicability improves, thereby has finished the present invention.
Promptly; surface protective film provided by the invention is characterized in that, it is the surface protective film that adhesion layer (A) and substrate layer (B) are laminated; wherein, this adhesion layer (A) is 0.880～0.938g/cm with amorphism alpha-olefin based polymer (A1) 5～50 quality % and density 3The hybrid resin of straight chain shape low density polyethylene (LDPE) (A2) 50～95 quality % be main component, be 0.880～0.938g/cm perhaps with amorphism alpha-olefin based polymer (A1) 5～50 quality %, density 3Straight chain shape low density polyethylene (LDPE) (A2) 40～90 quality % and the hybrid resin of crystallinity ethene-alpha-olefin copolymer (A3) 5～50 quality % be main component.In addition, among the present invention, in each layer is that main component is meant with specific resin, the resin combination that uses in this layer (comprise various additives or as required and other resins of usefulness etc. whole) in, contain resin or the hybrid resin stipulated among the present invention more than the 65 quality %.
The effect of invention
After surface protective film of the present invention sticks on various resin plates, glass plate, metallic plate etc.; even place for a long time or be exposed under the hot environment; but the adherend surface after peeling off does not have the cull of Visual Confirmation yet, and residue that can not Visual Confirmation is also few.Therefore, surface protective film of the present invention is suitable for use as the film on the surface of protection various resin plates, glass plate, metallic plate etc., is particularly suitable for protective film and peels off in the purposes of implementing secondary operations such as printing in the back.In addition, surface protective film of the present invention, be wound into the roller shape after, when extract out using again, no adhesion, and anti-adhesive excellence.
In addition; the surface protective film of the present invention that particularly uses ethylene-based polymer and obtain as substrate layer; except that above-mentioned performance; be pasted with at adherend under the state of surface protective film this adherend cut off and add man-hour; find the character of following excellence; be that surface protective film cuts off fully, bad orders such as wire drawing, fluffing can not take place, its application is wide.
The specific embodiment
Below, the present invention is described in detail.Surface protective film of the present invention is the coextrusion laminate film that adhesion layer (A) and substrate layer (B) form by the coextrusion layered manner.
The amorphism alpha-olefin based polymer (A1) that uses in the adhesion layer of surface protective film of the present invention (A) is for containing polymer or the copolymer based on the monomeric unit of the alpha-olefin of carbon number 3～20; this polymer is under-100～200 ℃ measurement range of differential scanning calorimetry (DSC) (DSC); the heat of fusion of crystallization is that above melting peak of 1J/g and crystallization heat are that the above peak crystallization of 1J/g all is not observed; they may be used alone, two or more kinds can also be used.
The alpha-olefin of aforementioned carbon number 3～20 can be any of straight chain shape, chain, for example can enumerate the alpha-olefin of straight chain shapes such as propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-endecatylene, 1-dodecylene, 1-tridecylene, tetradecene, 1-15 carbenes, cetene, 1-heptadecene, 1-vaccenic acid, 1-19 carbenes, 1-eicosylene; 3-methyl-1-butene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-hexene, 2,2, the alpha-olefin of a chain such as 4-trimethyl-1-amylene etc.
In addition, aforementioned amorphism alpha-olefin based polymer (A1), preferably has more than 2 kinds copolymer based on the monomeric unit of these alpha-olefins, from industrial easily acquired, compatibility with straight chain shape low density polyethylene (LDPE) described later (A2) or crystallinity ethene-alpha-olefin copolymer (A3), viewpoints such as coextrusion shaping are set out, more preferably have more than a kind based on the monomeric unit of propylene and the copolymer more than a kind, especially most preferably amorphism propylene-butene-1 copolymer based on the monomeric unit of the alpha-olefin of carbon number 4～20, amorphism propylene-ethylene-butene-1 copolymer.In addition, can have above-mentioned alpha-olefin monomeric unit in addition in the amorphism alpha-olefin based polymer (A1).As this type of monomeric unit, for example can enumerate monomeric unit based on ethene, polyenic compounds, cyclic olefin, vinyl aromatic compounds etc.
Stable on heating viewpoint from the surface protective film that improves gained; containing ratio in aforementioned amorphism propylene-butene-1 copolymer based on the monomeric unit of propylene; if the whole monomeric units with amorphism propylene-butene-1 copolymer are the words of 100 quality %; then be preferably more than the 70 quality %; more preferably more than the 80 quality %, more preferably more than the 90 quality %.
The viewpoint that improves from the hear resistance of the surface protective film of gained; containing ratio in aforementioned amorphism propylene-ethylene-butene-1 copolymer based on the monomeric unit of propylene; if whole monomeric units of amorphism propylene-ethylene-butene-1 copolymer are made as the words of 100 quality %; then be preferably more than the 50 quality %, more preferably more than the 60 quality %.In addition, containing ratio in amorphism propylene-ethylene-butene-1 copolymer based on the monomeric unit of ethene, similarly, when being 100 quality % with whole monomeric units of amorphism propylene-ethylene-butene-1 copolymer, be preferably more than the 10 quality %, more preferably more than the 20 quality %.If in this scope, then aforementioned adhesion layer (B) becomes soft material, even exist under the concavo-convex situation on the adherend surface, owing to adhere to follow this concavo-convex shape, therefore can obtain sufficient adhesion based on the containing ratio of the monomeric unit of ethene.
In addition, the limiting viscosity [η] of aforementioned amorphism alpha-olefin based polymer (A1) is preferably 0.1～10.0dl/g, more preferably 0.7～7.0dl/g.In addition,, be preferably greater than 1 and be below 4, more preferably 2～3 with the molecular weight distribution (Mw/Mn) that the ratio of weight average molecular weight (Mw) and number-average molecular weight (Mn) is represented.The limiting viscosity of relevant amorphism alpha-olefin based polymer (A1); when molecular weight distribution during in this scope; hear resistance, the transparency, adhesiveness improve; even perhaps long-term keeping is pasted with the adherend of surface protective film or is exposed under the hot environment, also can reduce the pollution of transferring to the surperficial adherend that causes of adherend owing to the low molecular weight compositions in the amorphism alpha-olefin based polymer (A1).In addition, because amorphism alpha-olefin based polymer (A1) is an olefin polymer, can like that the increase of the adhesion of intersexuality at any time not occur, pass through and can keep stable adhesion for a long time yet as the situation of using the resin that vinyl-vinyl acetate copolymer uses as adhesion layer because of taking off going bad of resin such as acetate.
Manufacture method as aforementioned amorphism alpha-olefin based polymer (A1), have no particular limits, for example can enumerate, adopt gaseous polymerization, solution polymerization process, slurry polymerization process, mass polymerization etc., carry out the method for polymerization etc. by the metallocene series catalysts.As preferred manufacture method, can enumerate disclosed manufacture method in the TOHKEMY 2002-348417 communique.
The resin that uses in the adhesion layer of surface protective film of the present invention (A); be the resin that aforementioned amorphism alpha-olefine polymers (A1) and straight chain shape low density polyethylene (LDPE) (A2) mix, the resin that perhaps aforementioned amorphism alpha-olefine polymers (A1), straight chain shape low density polyethylene (LDPE) (A2) and crystallinity ethene-alpha-olefin copolymer (A3) mix.By in aforementioned amorphism alpha-olefine polymers (A1), cooperating straight chain shape low density polyethylene (LDPE) (A2), crystallinity ethene-alpha-olefin copolymer (A3), material, purposes that can modulate the surface state that satisfies adherend, adherend etc. requires the adhesion of characteristic, no matter the power of adhesion all can reduce the pollution to the adherend surface after peeling off.
Aforementioned linear shape low density polyethylene (LDPE) (A2) is in 0.880～0.938g/cm for density 3The material of scope, more preferably density is 0.898～0.925g/cm 3Material.In addition, and its melt flow rate (MFR) (according to MFR, JIS K7210:1999, measured value under 190 ℃, 21.18N.) be preferably 0.5～30.0g/10 minute, more preferably 2.0～15.0g/10 minute.If the density of straight chain shape low density polyethylene (LDPE) (A2) and MFR are then good with the compatibility of aforesaid amorphism alpha-olefin based polymer (A1) in above-mentioned scope, improve the film forming of laminate film.
As aforementioned crystallinity ethene-alpha-olefin copolymer (A3); can enumerate ethylene-propylene copolymer, ethene-butene-1 copolymer etc.; becoming from the adjustment of the adhesion of industrial easily acquired and gained surface protective film is easy to viewpoint, is preferably ethene-butene-1 copolymer.As crystallinity ethene-alpha-olefin copolymer (A3), preferred MFR (190 ℃, the following value of measuring of 21.18N.) be that 0.5～30.0g/10 minute, density are 0.870～0.905g/cm 3Polymer, more preferably MFR is that 2.0～15.0g/10 minute, density are 0.880～0.900g/cm 3Copolymer.When the MFR of crystallinity ethene-alpha-olefin copolymer (A3) and density during in above-mentioned scope, good with the compatibility of aforesaid amorphism alpha-olefin based polymer (A1), the film forming of laminate film improves.In addition, from the preventing polluting effect on adherend surface, these resins metalloscene catalyst described later that more preferably low molecular weight compositions is few is.In addition, so-called crystallinity is meant in-100～200 ℃ measurement range of differential scanning calorimetry (DSC) (DSC), and the heat of fusion that can observe crystallization is that above melting peak of 1J/g and crystallization heat are the polymer at any peak of the above peak crystallization of 1J/g.
When the hybrid resin of use amorphism alpha-olefin based polymer (A1) and straight chain shape low density polyethylene (LDPE) (A2) is as main component in adhesion layer (A), it cooperates ratio is amorphism alpha-olefin based polymer (A1) 5～50 quality %, straight chain shape low density polyethylene (LDPE) (A2) 50～95 quality %, more preferably mixes with composition (A1) 5～40 quality %, composition (A2) 60～95 quality %.Can not obtain enough adhesions during the cooperation ratio less than 5 quality % of amorphism alpha-olefin based polymer (A1), become difficult problem because adhesion is crossed the operation that has film by force when surpassing 50 quality %.In addition, by the cooperation ratio of composition (A1) and composition (A2) is adjusted to aforesaid scope,, be easy to adjust to the adhesion about about 0.05～5.0N/25mm according to desired adhesion.
In addition, when using resin that amorphism alpha-olefin based polymer (A1), straight chain shape low density polyethylene (LDPE) (A2) and crystallinity ethene-alpha-olefin copolymer (A3) are mixed as main component in adhesion layer (A), its cooperation ratio is that amorphism alpha-olefin based polymer (A1) 5～50 quality %, density are 0.880～0.938g/cm 3Straight chain shape low density polyethylene (LDPE) (A2) 40～90 quality %, crystallinity ethene-alpha-olefin copolymer (A3) 5～50 quality %, more preferably composition (A1) 5～30 quality %, composition (A2) 40～85 quality %, composition (A3) 10～45 quality %.By the cooperation ratio of composition (A1), composition (A2), composition (A3) is adjusted in the aforesaid scope,, be easy to be adjusted into the adhesion about about 0.1～7.0N/25mm according to desired adhesion.
The resin that uses in the adhesion layer of the present invention (A) is for the resin of aforesaid hybrid resin as main component, in the scope of not damaging effect of the present invention, can be also with other resin.As this moment can and other resin of usefulness, for example can enumerate Noblen, propylene-butene-1 copolymer, propylene-1-butylene-ethylene-dien terpolymer, the 1-chevron, s-B-S copolymer (SBS), styrene-isoprene-styrene copolymer-(SIS), styrene-ethylene-butylene-styrene copolymer (SEBS), styrene-ethylene-propylene-styrene copolymer (SEPS), SB (SB), styrene-isoprene copolymer (SI), styrene-ethylene-butylene copolymer (SEB), SBR styrene butadiene rubbers (SBR), styrene-ethylene-butylene-ethylene copolymer (SEBC), and their hydride etc.
In addition, the modulator approach of the hybrid resin that in adhesion layer of the present invention (A), uses, have no particular limits, but in view of amorphism alpha-olefin based polymer (A1) not easy to operate at normal temperatures, adopt the coextrusion layered manner more easy, therefore, preferably in advance amorphism alpha-olefin based polymer (A1) and straight chain shape low density polyethylene (LDPE) (A2) or other crystalline polymer etc. are dissolved mixingly, make the graininess of easy operating.
In addition, such as described above, in each layer of the present invention with specific resin be main component be meant in this layer the resin combination that uses (comprise various additives or as required and and other resin etc. whole of usefulness) in, contain resin or the hybrid resin stipulated among the above the present invention of 65 quality %, from easier embodiment effect of the present invention aspect, be preferably more than the 75 quality %, especially most preferably be more than the 85 quality %.
The resin that uses in the substrate layer of surface protective film of the present invention (B) is thermoplastic resin; so long as can with adhesion layer (A) coextrusion; then have no particular limits; from with the good aspect of compatibility of aforementioned adhesion layer (A); preferably being main component with the olefin polymer, is main component with ethylene-based polymer (B1) or crystallinity acrylic polymer (B2) especially preferably.
As aforementioned ethylene-based polymer (B1), for example can enumerate low density polyethylene (LDPE), straight chain shape low density polyethylene (LDPE), medium density polyethylene, high density polyethylene (HDPE) etc.They can use separately separately, also can and use.Wherein, from the good aspect of hear resistance, preferably the hybrid resin with straight chain shape low density polyethylene (LDPE), medium density polyethylene or low density polyethylene (LDPE) and high density polyethylene (HDPE) is the ethylene-based polymer of main component.
When stating ethylene-based polymer (B1) before use as substrate layer (B); main purpose of the present invention is except the preventing polluting effect to the adherend surface after peeling off; also being included in adherend is pasted with under the state of surface protective film adherend cut off and adds man-hour; surface protective film can cut off fully, shows the excellent cutting of bad orders such as wire drawing, fluffing do not take place.
In addition, as these ethylene-based polymers (B1), from the aspect of easy extrusion molding, preferably its MFR (190 ℃, the following value of measuring of 21.18N) is 0.5～30.0g/10 minute, and more preferably its MFR is 2.0～15.0g/10 minute.In addition, these ethylene-based polymers (B1), as long as fusing point is 90～135 ℃, even then be shaped etc. and be exposed under the hot environment owing to sticking on drying, heating behind the adherend, the contraction of film is also less, thereby can suppress from adherend float or peel off, the warpage of adherend etc., therefore be preferred, the ethylene-based polymer of 105～130 ℃ of fusing points more preferably.
Adopt surface protective film of the present invention and when being required hear resistance, preferably use crystallinity acrylic polymer (B2) as the resin that uses in the substrate layer (B).As aforementioned crystallinity acrylic polymer (B2), for example can enumerate Noblen, ethylene-propylene copolymer, propylene-butene-1 copolymer, propylene-ethylene-butene-1 copolymer etc.They may be used alone, two or more kinds can also be used.In addition, it is 120～165 ℃ polymer that the MFR of these crystalline polypropylene based polymers (B2) (value that 230 ℃, 21.18N are measured down) is preferably 0.5～30.0g/10 minute, fusing point, and more preferably MFR is that 2.0～15.0g/10 minute, fusing point are 125～162 ℃ polymer.As long as MFR and fusing point be in above-mentioned scope, even then owing to stick on drying behind the adherend, heating shaping etc. and be exposed under the hot environment, the contraction of film is also little, therefore, nothing is floated or is peeled off, and also can not make adherend generation warpage, also can improve the film forming of laminate film.In addition, crystallinity is meant that in-100～200 ℃ measurement range of differential scanning calorimetry (DSC) (DSC) heat of fusion that can observe crystallization is that above melting peak of 1J/g and crystallization heat are the polymer at any peak of the above peak crystallization of 1J/g.
In addition, in the crystallinity acrylic polymer (B2) that in aforementioned substrates layer (B), uses, preferably use metalloscene catalyst and the crystallinity acrylic polymer that obtains (being also referred to as metalloscene catalyst is polypropylene.)。Metalloscene catalyst is that polypropylene is the polypropylene that replaces Z-N (Ziegler-Natta) series catalysts in the past to use the metallocene series catalysts to be polymerized.As this metallocene series catalysts, for example can enumerate metallocene supported catalyst that supports Metallocenic compound on the even mixed catalyst of the metallocene that comprises Metallocenic compound and aikyiaiurnirsoxan beta, the particulate carrier etc.The content of relevant metallocene supported catalyst is disclosed in Japanese kokai publication hei 5-155931 communique, Japanese kokai publication hei 8-104691 communique, Japanese kokai publication hei 8-157515 communique and the Japanese kokai publication hei 8-231621 communique etc.Metalloscene catalyst is a polypropylene, because molecular weight distribution reaches and forms the uniformity height of distribution, the content of low molecular weight compositions is few, therefore, by use metalloscene catalyst in substrate layer of the present invention (B) is polypropylene, is easy to prevent owing to oozing out of low molecular weight compositions causes pollution to the adherend surface.In addition, metalloscene catalyst is a polypropylene, can be Noblen, also can be the copolymer of propylene and other alpha-olefins, as the example of the copolymer of propylene and other alpha-olefins, can enumerate ethylene-propylene copolymer etc.
When using aforementioned crystallinity acrylic polymer (B2), can and use and the identical amorphism alpha-olefin based polymer of describing in detail about aforementioned adhesion layer (A) (B3) of amorphism alpha-olefin based polymer as aforementioned substrates layer (B).By and with amorphism alpha-olefin based polymer (B3), the flexibility of the surface protective film of gained increases, film tracing ability to the adherend surface when pasting improves, and is successfully peeled off when peeling off.In addition, the amorphism alpha-olefin based polymer (B3) that uses this moment can be and the middle identical or different copolymer of amorphism alpha-olefin based polymer (A1) that uses of aforementioned adhesion layer (A).
When in substrate layer (B), cooperating amorphism alpha-olefin based polymer (B3), the cooperation ratio of crystallinity acrylic polymer (B2) and amorphism alpha-olefin based polymer (B3), in quality criteria, preferably (crystallinity acrylic polymer (B2)): the scope of (amorphism alpha-olefin based polymer (B3))=70～95: 30～5, more preferably aforementioned ratio are 80～95: 20～5 scope.As long as the cooperation ratio of crystallinity acrylic polymer (B2) and amorphism alpha-olefin based polymer (B3), then not only can be given the enough flexibilities of the surface protective film of gained in above-mentioned scope and can keep hear resistance.
In addition, by as substrate layer (B) and and with aforementioned ethylene-based polymer (B1) and crystallinity acrylic polymer (B2), thereby can adjust the flexibility of gained surface protective film.And then by and with the ethylene-methyl methacrylate methyl terpolymer (below be called " EMMA ".) wait the flexibility that can also adjust the gained film.As EMMA, preferred MFR (190 ℃, the following value of measuring of 21.18N) is 0.5～30.0g/10 minute EMMA, and more preferably MFR is 2.0～15.0g/10 minute EMMA.Be preferably based among the EMMA methyl methacrylate (below, be called " MMA ".) the containing ratio of monomeric unit be the EMMA of 3～30 quality %, 8～25 quality % more preferably.As long as the content of above-mentioned MFR, MMA then can not only give the gained surface protective film sufficient flexibility in this scope, and improve the film forming of laminate film.
In the substrate layer (B), when in crystallinity acrylic polymer (B2), cooperating amorphism alpha-olefin based polymer (B3) and ethylene-based polymer (B1) and/or EMMA, crystallinity acrylic polymer (B2), amorphism alpha-olefin based polymer (B3), the cooperation ratio of ethylene-based polymer (B1) and/or EMMA, in quality criteria, preferably (crystallinity acrylic polymer (B2)): (amorphism alpha-olefin based polymer (B3)): (ethylene-based polymer (B1) and/or EMMA)=70～95: 4～29: 1～12 scope, more preferably aforementioned ratio is 80～95: 4～19: 1～5 scope.As long as cooperate ratio in this scope, then not only can give the gained surface protective film sufficient flexibility, and can keep hear resistance.
Surface protective film of the present invention as described above, must have adhesion layer (A) and substrate layer (B) two-layer, and then the opposite face that is laminated with the face of adhesion layer (A) in substrate layer (B) can be provided with superficial layer (C).As the resin that uses in the superficial layer (C), have no particular limits, from with the good aspect of compatibility of aforementioned substrates layer (B), preferably be main component with the olefin polymer, especially more preferably use ethylene-based polymer (C1) or crystallinity acrylic polymer (C2).Especially when the main component of aforementioned substrates layer (B) is ethylene-based polymer (B1), be main component more preferably with ethylene-based polymer (C1), when the main component of substrate layer (B) is crystallinity acrylic polymer (B2), be main component more preferably with crystallinity acrylic polymer (C2).
As the applicable ethylene-based polymer (C1) of making the main component of superficial layer (C), can enumerate with as the main component of above-mentioned substrate layer (B) and the identical material of ethylene-based polymer (B1) that uses.In addition, by selecting the main component of ethylene-based polymer (C1) as superficial layer (C), ethylene-based polymer (B1) is identical as the situation of the main component of substrate layer (B) with using, and the surface protective film that finally obtains shows high cuttability.In addition, the ethylene-based polymer (C1) that uses in aforementioned ethylene-based polymer (B1) that uses in the substrate layer (B) and the superficial layer (C) can be identical or different resin.
In the ethylene-based polymer (C1) that uses as the main component of aforementioned surfaces layer (C), if use low density polyethylene (LDPE), then the surface of superficial layer (C) easily modification become pears skin shape.Become pears skin shape by the surface that makes superficial layer (C), even under the situation of the adhesion that designs stronger adhesion layer (A), also can alleviate adhesion.In addition,, can improve the rigidity of gained surface protective film, and the operability of pasting, peeling off etc. becomes good with low density polyethylene (LDPE) and when using high density polyethylene (HDPE).
In addition, using the main component of the hybrid resin of aforementioned ethylene-based polymer (C1) and ethylene-propylene copolymer as aforementioned surfaces layer (C), also can be pears skin shape with the surface modification of superficial layer (C).As aforementioned ethylene-propylene copolymer,, for example can be set forth in the polymerization of the polymerization of carrying out ethene under the existence of Noblen or ethene and propylene and Ethylene-Propylene Block Copolymer of obtaining etc. so long as the resin behind ethene and the copolymerization of propylene gets final product.Wherein, from being easy to make the surface make the aspect of pears skin shape, the containing ratio that preferably comes from the composition of ethene is the Ethylene-Propylene Block Copolymer of 8～20 quality %, and more preferably using the containing ratio of the composition that derives from ethene is the Ethylene-Propylene Block Copolymer of 10～15 quality %.And then from being easy to extrude the aspect consideration of processing, the MFR of ethylene-propylene copolymer (230 ℃, the following value of measuring of 21.18N) is preferably 4～12g/10 minute scope, more preferably 6～10g/10 minute scope.Similarly, from being easy to extrude the aspect consideration of processing, the density of this copolymer is preferably 0.890～0.910g/cm 3Scope, 0.895～0.905g/cm more preferably 3Scope.In addition, even owing to use the main component of aforementioned ethylene-propylene copolymer separately as superficial layer (C), also can be pears skin shape with the surface modification of superficial layer (C), therefore, preferably in view of and substrate layer (B) between the resin kind used compatibility etc. and suitably select to use.
As the applicable crystallinity acrylic polymer (C2) of making the main component of superficial layer (C), can enumerate with as the main component of above-mentioned substrate layer (B) and the identical polymer of crystallinity acrylic polymer (B2) that uses.In addition; crystallinity acrylic polymer (B2) is identical as the situation of the main component of substrate layer (B) with using; by the main component of selective freezing acrylic polymer (C2), make the surface protective film that finally obtains show high-fire resistance as superficial layer (C).
In addition, according to the adhesion level or the desired transparency etc., as the main component of superficial layer (C) and hybrid junctions crystallinity acrylic polymer (C2) and aforementioned ethylene-propylene copolymer, can suitably adjust the degree of pears skin.
The whole film thickness of surface protective film of the present invention is preferably 20～120 μ m.As long as the thickness of whole film is in this scope, then the protectiveness of adherend, adhesiveness and the operability pasting, peel off etc. are good.In addition, the thickness of adhesion layer (A) is preferably 3～30 μ m, more preferably 5～25 μ m.As long as the thickness of adhesion layer (A) is this scope, then the film forming of adhesiveness and laminate film is good.In addition, when aforementioned surfaces layer (C) is set in surface protective film of the present invention, preferred 3～30 μ m of the thickness of superficial layer (C), more preferably 5～20 μ m.When the thickness of superficial layer (C) during in this scope, the film forming of hear resistance and laminate film is good.
Manufacture method as surface protective film of the present invention; so long as the stacked rule of coextrusion has no particular limits; for example can be listed below method: use the extruder more than 2; make the resin fusion of using in each resin bed; by coetrusions such as coextrusion die general laws, feed block (feed block) method with the state of dissolving with it stacked after, adopt inflation method, T pattern tool chill roll method methods such as (T-die-Chill roll method) to be processed into the method for film shape.Under the situation of T pattern tool chill roll method, can be between rubber touch roll or steel band (Steel Belt) etc. and chill roll rolling and cooling dissolve the film that is laminated.
In addition, surface protective film of the present invention can stretch along the single shaft direction at least.As drawing process, can adopt vertical or horizontal uniaxial tension, biaxial stretch-formed, known method such as simultaneously biaxial stretch-formed or tubular process is biaxial stretch-formed one by one.In addition, stretching process can be online (in line), also can be off-line type (off line).As the drawing process of uniaxial tension, can adopt and closely connect roller pulling method or rolling.The stretching ratio of uniaxial tension vertical or horizontal, is preferably 1.1～80 times, more preferably 3～30 times.On the other hand, biaxial stretch-formed stretching ratio, than preferred 1.2～70 times, more preferably vertical 4～6 times, horizontal 5～9 times, area ratio are counted 20～54 times in area.
In addition,, may not only limit to 1 section stretching, also can stretch for multistage as vertical or horizontal stretching process.Especially, consider that during the vertical single shaft roller in biaxial stretch-formed one by one stretched, vertically the vertical single ax of single shaft rolling, drawing etc. stretches, preferred multistage stretched from the aspects such as uniformity of thickness, rerum natura.In addition, closely connect in the roller stretching, can adopt any of planar process, cross method, the cross that closely connects that more preferably can seek the multistage of amplitude contraction minimizing stretches.Under the situation of uniaxial tension, draft temperature all is preferably 80 ℃～160 ℃ in arbitrary drawing process, uses at uniaxial tension under the situation of stenter stretching, and draft temperature is preferably 90～165 ℃.In addition, as preferred draft temperature, respectively do for oneself 110～155 ℃, 120～160 ℃.On the other hand, under biaxial stretch-formed situation, all preferred draft temperature scope identical in arbitrary method with the situation of uniaxial tension.In addition, can before stretching process, set and give hot portion, behind stretching process, set the thermosetting bonding part.At this moment, the temperature of giving hot portion is preferably 60～140 ℃, and the temperature of thermosetting bonding part is preferably 90～160 ℃ scope.
Surface protective film of the present invention; by to stretching, the heat fixation of single shaft direction are sought Stability Analysis of Structuresization at least; thereby oriented crystallineization by the resin of use in substrate layer (B), the superficial layer (C); further improve hear resistance; and the variation in time of adhesion diminishes; therefore be preferred, when especially using the crystallinity acrylic polymer in substrate layer (B) and/or superficial layer (C), this effect is higher.
In addition, in the scope of not damaging effect of the present invention, can suitably add lubricant, anti-blocking agent, ultra-violet absorber, light stabilizer, antistatic agent, antifoggant etc., colouring agent etc., the resin bed of interpolation can add to arbitrarily in the layer according to purpose.As these additives, the various additives that preferably use olefin polymer to use.
Embodiment
Below enumerate embodiment and comparative example, the present invention is specifically described.
(synthesis example 1)
[synthesizing of amorphism alpha-olefin based polymer (amorphism propylene-butene-1 copolymer)]
In the stainless steel aggregation container of the 100L that has agitator, use hydrogen to adjust agent as molecular weight, make propylene and 1-butylene carry out copolymerization continuously, obtain amorphism propylene-butene-1 copolymer as the amorphism alpha-olefine polymers.Particularly, bottom by polymerizer, supply with polymer solvent hexane, propylene, 1-butylene continuously with 100L/ hour, 24.00kg/ hour, 1.81kg/ hour feed speed respectively, and top by polymerizer, extracting reactant mixture continuously out, is 100L to keep the reactant mixture in the polymerizer.In addition, bottom by polymerizer, with 0.005g/ hour, 0.298g/ hour, 2.315g/ hour feed speed, supply with dimetylsilyl (tetramethyl-ring pentadienyl) (the 3-tert-butyl group-5-methyl-2-phenoxy group) titanium chloride, trityl group four (pentafluorophenyl group) borate and triisobutyl aluminium continuously respectively as catalyst component.Under 45 ℃, carry out copolyreaction by making recirculated cooling water in the sleeve pipe that is installed in the polymerizer outside.After in the reactant mixture of extracting out continuously by the top of polymerizer, adding a spot of ethanol, polymerisation being stopped, through demonomerization, water washing with remove the operation of desolvating, obtain amorphism propylene-butene-1 copolymer.Then, with the copolymer of gained 80 ℃ of following drying under reduced pressure 24 hours.The containing ratio of the propylene monomer units in this amorphism propylene-butene-1 copolymer is 94.5 quality %, and the containing ratio of 1-butene monomer units is 5.5 quality %.(each monomeric unit is calculated by the nuclear magnetic resonance device JMN-LA300 that Jeol Ltd. makes.) and the DSC of this copolymer (EXSTAR6000 that Seiko Instruments Inc. makes) in do not observe melting peak, in addition, limiting viscosity [η] is 2.3dl/g, molecular weight distribution (Mw/Mn) is 2.2.(molecular weight distribution is analyzed by the gel permeation chromatograph HLC-8020 that TOSOH Co., Ltd makes.)
(synthesis example 2)
[synthesizing of amorphism alpha-olefin based polymer (amorphism propylene-ethylene-butene-1 copolymer)]
Removable flask reactor to the capacity 2L that has agitator, thermometer, dropping funel and reflux condensing tube reduces pressure, behind the nitrogen replacement, import the 1L dry toluene as polymer solvent.This moment under normal pressure to it respectively with 2 * 10 -6Cm 3/ minute, 4 * 10 -6Cm 3/ minute, 1 * 10 -6Cm 3/ minute feed speed supply with ethene, propylene and 1-butylene continuously, solvent temperature is controlled at 30 ℃.After in polymerization tank, adding 0.75mmol triisobutyl aluminium (below be called TIBA), in polymerization tank, add 0.0015mmol dimetylsilyl (tetramethyl-ring pentadienyl) (the 3-tert-butyl group-5-methyl-2-phenoxy group) titanium chloride.In polymerization tank, add 0.0075mmol trityl group four (pentafluorophenyl group) borate, polymerization 10 minutes after 15 seconds.The result obtains amorphism propylene-1-butylene-ethylene copolymer.The content of the propylene monomer units in this amorphism propylene-ethylene-butene-1 copolymer is 61.5 quality %, and the content of ethylene monomer unit is 21.0 quality %, and the content of 1-butene monomer units is 17.5 quality %.And do not observe melting peak in the DSC of this copolymer, in addition, limiting viscosity [η] is 1.69dl/g, and molecular weight distribution (Mw/Mn) is 2.0.
(preparation example 1)
[preparation of the particle that forms by the composition that contains amorphism alpha-olefin based polymer (1)]
Hybrid junctions crystallinity propylene-butene-1 copolymer (density 0.900g/cm in amorphism propylene-butene-1 copolymer that above-mentioned synthesis example 1 obtains 3(230 ℃ of MFR; 21.18N the value of following mensuration) 10.0g/10 minute; 126 ℃ of maximum melting peaks among the DSC); make amorphism propylene-butene-1 copolymer/crystallinity propylene-butene-1 copolymer=60/40 (mass ratio); the mixed aromatic phosphite ester is that antioxidant (" Irgafos168 " that Ciba Specialty Chemicals company makes) and hindered phenol are each 2000ppm of antioxidant (" Irganox1010 " that Ciba Specialty Chemicals company makes) again; adopt the double screw extruder (PCM30 that IKEGAI makes; 30mm φ screw rod) under 230 ℃, carries out melting mixing; then, obtain containing the particle of the composition (1) of amorphism alpha-olefin based polymer by comminutor (CK2 of Na カ タ ニ machine-building).
(preparation example 2)
[preparation of the particle that forms by the composition that contains amorphism alpha-olefin based polymer (2)]
Except mixing, similarly obtain containing the particle of the composition (2) of amorphism alpha-olefin based polymer with preparation example 1 with amorphism propylene-butene-1 copolymer/crystallinity propylene-butene-1 copolymer=95/5 (mass ratio).
(preparation example 3)
[preparation of the particle that forms by the composition that contains amorphism alpha-olefin based polymer (3)]
Except the amorphism alpha-olefin based polymer that will be in the preparation example 1 uses changes the amorphism propylene-ethylene-butene-1 copolymer that obtains in the synthesis example 2 into, similarly obtain containing the particle of the composition (3) of amorphism alpha-olefin based polymer with preparation example 1.
(preparation example 4)
[preparation of the particle that forms by the composition that contains amorphism alpha-olefin based polymer (4)]
Except mixing, similarly obtain containing the particle of the composition (4) of amorphism alpha-olefin based polymer with preparation example 3 with amorphism propylene-ethylene-butene-1 copolymer/crystallinity propylene-butene-1 copolymer=95/5 (mass ratio).
(preparation example 5)
[preparation of the particle that forms by the composition that contains amorphism alpha-olefin based polymer (5)]
Except mixing straight chain shape low density polyethylene (LDPE) (density 0.935g/cm in the amorphism propylene-butene-1 copolymer that obtains in above-mentioned synthesis example 1 3, MFR (value that 190 ℃, 21.18N are measured down) 3.5g/10 minute), make amorphism propylene-butene-1 copolymer/straight chain shape low density polyethylene (LDPE)=95/5 (mass ratio) in addition, similarly obtain containing the particle of the composition (5) of amorphism alpha-olefin based polymer with preparation example 1.
(embodiment 1)
As the superficial layer resin, use 80 mass parts Noblen (density: 0.900g/cm 3, MFR (value that 230 ℃, 21.18N are measured down): 8.0g/10 minute; Below be called " HOPP ".) and 20 mass parts Ethylene-Propylene Block Copolymer (density: 0.900g/cm 3, MFR (value that 230 ℃, 21.18N are measured down): 8g/10 minute) hybrid resin; Use HOPP as substrate layer with resin; As the adhesion layer resin, use 30 mass parts to contain the composition (1) and the 70 mass parts straight chain shape low density polyethylene (LDPE) (density: 0.902g/cm of the amorphism alpha-olefin based polymer of above-mentioned preparation 3, MFR (190 ℃, the following value of measuring of 21.18N): 3.0g/10 minute; Below be called " LLDPE (1) ".) mixture; Supplying to superficial layer respectively uses in the extruder (bore 40mm) with extruder (bore 50mm) and adhesion layer with extruder (bore 50mm), substrate layer; from the T pattern, extrude under 250 ℃ of extrusion temperatures by coetrusion; so that the thickness of superficial layer is the thickness of 12 μ m, substrate layer is that the thickness of 38 μ m and adhesion layer is 10 μ m; after 40 ℃ water-cooled metal chill roll cooling; be wound into the roller shape, obtain surface protective film.In order to stablize the physical property of gained film, with its slaking 48 hours in 35 ℃ curing chamber.
(embodiment 2)
Except using Ethylene-Propylene Block Copolymer with resin as superficial layer; Replace to resin beyond the mixture of composition (1) that 50 mass parts contain amorphism alpha-olefin based polymer and 50 mass parts LLDPE (1) as adhesion layer, obtain surface protective film similarly to Example 1.
(embodiment 3)
With formation similarly to Example 2; supply to superficial layer extruder (bore 50mm) respectively; substrate layer is used in the extruder (bore 40mm) with extruder (bore 50mm) and adhesion layer; from the T pattern, extrude under 250 ℃ of extrusion temperatures by coetrusion; so that the thickness of superficial layer is 40 μ m; the thickness of substrate layer is that the thickness of 120 μ m and adhesion layer is 40 μ m; after 40 ℃ water-cooled metal chill roll cooling; under 140 ℃, carry out vertical 4 times of stretchings by closely connecing the roller pulling method; under 145 ℃, carry out heat fixation again, obtain the surface protective film that uniaxial tension forms.In order to stablize the physical property of gained film, with its slaking 48 hours under 35 ℃ curing chamber.In addition, the thickness of each layer of the embodiment in the table 13 is the thickness behind the uniaxial tension.
(embodiment 4)
Except replace to the mixture of composition (2) that 40 mass parts contain amorphism alpha-olefin based polymer and 60 mass parts LLDPE (1) with resin as adhesion layer, obtain surface protective film similarly to Example 2.
(embodiment 5)
Except as the adhesion layer resin, use 40 mass parts to contain the composition (4) and the 60 mass parts straight chain shape low density polyethylene (LDPE) (density: 0.920g/cm of amorphism alpha-olefin based polymer 3, MFR (value that 190 ℃, 21.18N are measured down): 4.0g/10 minute; Below be called " LLDPE (2) ".) mixture beyond, obtain surface protective film similarly to Example 2.
(embodiment 6)
Except as the adhesion layer resin, use 20 mass parts to contain beyond the mixture of the composition (5) of amorphism alpha-olefin based polymer and 80 mass parts LLDPE (2), obtain surface protective film similarly to Example 2.
(embodiment 7)
Except using HOPP with resin as superficial layer; Use same HOPP as substrate layer with resin; As the adhesion layer resin; use 10 mass parts to contain the composition (2) of amorphism alpha-olefin based polymer and the hybrid resin of 90 quality thing LLDPE (2); supplying to superficial layer respectively uses in the extruder (bore 40mm) with extruder (bore 50mm) and adhesion layer with extruder (bore 50mm), substrate layer; extruding superficial layer that thickness is 14 μ m, substrate layer, thickness that thickness is 42 μ m by coetrusion under 250 ℃ of extrusion temperatures from the T pattern is beyond the adhesion layer of 14 μ m, obtains surface protective film similarly to Example 1.
(embodiment 8)
Except as the substrate layer resin, using metalloscene catalyst is ethylene-propylene random copolymer (density: 0.900g/cm 3, MFR (value that 230 ℃, 21.18N are measured down): 7.0g/10 minute, the containing ratio of ethylene monomer unit: 3.5 quality %; Below be called " metalloscene catalyst is COPP ".); As the adhesion layer resin; use 50 mass parts to contain the composition (3) of amorphism alpha-olefin based polymer and the mixture of 50 mass parts LLDPE (2); supplying to substrate layer respectively uses in the extruder (bore 40mm) with extruder (bore 50mm) and adhesion layer; extrude from the T pattern under 250 ℃ of extrusion temperatures by coetrusion; so that the thickness of substrate layer is the thickness of 50 μ m and adhesion layer is 10 μ m; after 40 ℃ water-cooled metal chill roll cooling; be wound into the roller shape, obtain surface protective film.In order to stablize the physical property of gained film, with its slaking 48 hours in 35 ℃ curing chamber.
(embodiment 9)
Except as the substrate layer resin, using metalloscene catalyst is COPP; As the adhesion layer resin, use 6.0 mass parts to contain beyond the mixture of the composition (2) of amorphism alpha-olefin based polymer and 94 mass parts LLDPE (2), obtain surface protective film similarly to Example 2.
(embodiment 10)
Except as the substrate layer resin, using metalloscene catalyst is COPP; As the adhesion layer resin, use 6.0 mass parts to contain composition (2), 84 mass parts LLDPE (2) and 10 mass parts ethene-butene-1 copolymer (density: 0.895g/cm of amorphism alpha-olefin based polymer 3, MFR (value that 190 ℃, 21.18N are measured down): 3.0g/10 minute; Below be called " EBR ".) mixture beyond, obtain surface protective film similarly to Example 2.
(embodiment 11)
Except as the substrate layer resin, using metalloscene catalyst is COPP; As the adhesion layer resin, use 30 mass parts to contain beyond the mixture of composition (2), 50 mass parts LLDPE (2) and 20 mass parts EBR of amorphism alpha-olefin based polymer, obtain surface protective film similarly to Example 2.
(embodiment 12)
Except as the substrate layer resin, using metalloscene catalyst is COPP; As the adhesion layer resin, use 20 mass parts to contain beyond the mixture of composition (2), 40 mass parts LLDPE (2) and 40 mass parts EBR of amorphism alpha-olefin based polymer, obtain surface protective film similarly to Example 2.
(embodiment 13)
As the substrate layer resin, use 50 mass parts high density polyethylene (HDPE) (density: 0.960g/cm 3, MFR (value that 190 ℃, 21.18N are measured down): 13g/10 minute; Below be called " HDPE ".) and 50 mass parts low density polyethylene (LDPE) (density: 0.902g/cm 3, MFR (value that 190 ℃, 21.18N are measured down): 4g/10 minute; Below be called " LDPE ".) hybrid resin; As the adhesion layer resin; use 30 mass parts to contain the composition (1) of amorphism alpha-olefin based polymer of above-mentioned preparation and the hybrid resin of 70 mass parts LLDPE (1); supplying to substrate layer respectively uses in the extruder (bore 40mm) with extruder (bore 50mm) and adhesion layer; from the T pattern, extrude under 250 ℃ of extrusion temperatures by coetrusion; so that the thickness of substrate layer is the thickness of 56 μ m, adhesion layer is 14 μ m; after 40 ℃ water-cooled metal chill roll cooling; be wound into the roller shape, obtain surface protective film.In order to stablize the physical property of gained film, with its slaking 48 hours in 35 ℃ curing chamber.
(embodiment 14)
Except as the adhesion layer resin, use 50 mass parts to contain beyond the hybrid resin of the composition (1) of amorphism alpha-olefin based polymer and 50 mass parts LLDPE (1), obtain surface protective film similarly to Example 13.
(embodiment 15)
Except as the adhesion layer resin, use 40 mass parts to contain beyond the hybrid resin of the composition (2) of amorphism alpha-olefin based polymer and 60 mass parts LLDPE (1), make surface protective film similarly to Example 13.
(embodiment 16)
Except as the adhesion layer resin, use 40 mass parts to contain beyond the hybrid resin of the composition (4) of amorphism alpha-olefin based polymer and 60 mass parts LLDPE (1), obtain surface protective film similarly to Example 13.
(embodiment 17)
Except as the adhesion layer resin, use 40 mass parts to contain beyond the hybrid resin of composition (2), 40 mass parts LLDPE (1) and 20 mass parts EBR of amorphism alpha-olefin based polymer, obtain surface protective film similarly to Example 13.
(embodiment 18)
Except as the adhesion layer resin, use 15 mass parts to contain beyond the hybrid resin of the composition (2) of amorphism alpha-olefin based polymer and 85 quality LLDPE (2) parts, obtain surface protective film similarly to Example 13.
(embodiment 19)
As the superficial layer resin, use the hybrid resin of 95 mass parts LDPE and 5 mass parts Ethylene-Propylene Block Copolymer; As the substrate layer resin, use the hybrid resin of 50 mass parts HDPE and 50 mass parts LDPE; As the adhesion layer resin; use 10 mass parts to contain the composition (2) of amorphism alpha-olefin based polymer and the hybrid resin of 90 mass parts LLDPE (2); supplying to superficial layer respectively uses in the extruder (bore 40mm) with extruder (bore 50mm) and adhesion layer with extruder (bore 50mm), substrate layer; from the T pattern, extrude under 250 ℃ of extrusion temperatures by coetrusion; so that the thickness of superficial layer is the thickness of 14 μ m, substrate layer is that the thickness of 42 μ m, adhesion layer is 14 μ m; in addition, obtain surface protective film similarly to Example 13.
(embodiment 20)
Except as the superficial layer resin, use beyond the hybrid resin of 85 mass parts HOPP and 15 mass parts Ethylene-Propylene Block Copolymer, obtain surface protective film similarly to Example 19.
(embodiment 21)
Except as the superficial layer resin, use the hybrid resin of 95 mass parts LLDPE (1) and 5 mass parts Ethylene-Propylene Block Copolymer; As the substrate layer resin, use LLDPE (1) in addition, obtain surface protective film similarly to Example 19.
(embodiment 22)
Except as the superficial layer resin, use the hybrid resin of 95 mass parts LLDPE (2) and 5 mass parts Ethylene-Propylene Block Copolymer; As the substrate layer resin, use LLDPE (2) in addition, obtain surface protective film similarly to Example 19.
(embodiment 23)
Except as the superficial layer resin, use 95 mass parts straight chain shape low density polyethylene (LDPE) (density: 0.940g/cm 3, MFR (value that 190 ℃, 21.18N are measured down): 4.0g/10 minute; Below be called " LLDPE (3) ".) and the hybrid resin of 5 mass parts Ethylene-Propylene Block Copolymer; As the substrate layer resin, use LLDPE (3) in addition, obtain surface protective film similarly to Example 19.
(embodiment 24)
Except using the LDPE with resin, obtain surface protective film similarly to Example 18 as substrate layer.
(embodiment 25)
Except using LDPE with resin as substrate layer; As the adhesion layer resin, use 10 mass parts to contain beyond the hybrid resin of the composition (2) of amorphism alpha-olefin based polymer and 90 mass parts LLDPE (2), obtain surface protective film similarly to Example 13.
(embodiment 26)
Except as the adhesion layer resin, use 20 mass parts to contain beyond the mixture of the composition (5) of amorphism alpha-olefin based polymer and 80 mass parts LLDPE (2), obtain surface protective film similarly to Example 19.
(comparative example 1)
Except as the adhesion layer resin, use 3.16 mass parts to contain beyond the mixture of the composition (2) of amorphism alpha-olefin based polymer and 96.84 mass parts LLDPE (2), obtain the relatively surface protective film of usefulness similarly to Example 2.
(comparative example 2)
Except as the adhesion layer resin, use 30 mass parts to contain beyond the mixture of the composition (1) of amorphism alpha-olefin based polymer and 70 mass parts LLDPE (3), obtain the relatively surface protective film of usefulness similarly to Example 2.
(comparative example 3)
Except as the adhesion layer resin, use 52 mass parts to contain composition (2), 8 mass parts crystallinity propylene-butene-1 copolymer and 40 mass parts styrene-ethylene-propylene-styrene block copolymer (Kuraray Co., " SEPTON2063 " that Ltd. make identical of amorphism alpha-olefin based polymer with the crystallinity propylene-butene-1 copolymer of use in the preparation example 1; Below be called " SEPS ".) mixture beyond, obtain the relatively surface protective film of usefulness similarly to Example 2.
(comparative example 4)
Except as the adhesion layer resin, use 50 mass parts to contain beyond the mixture of the composition (1) of amorphism alpha-olefin based polymer and 50 mass parts HOPP, obtain the relatively surface protective film of usefulness similarly to Example 2.
(comparative example 5)
Except as the adhesion layer resin, use 50 mass parts to contain beyond the mixture of composition (1), 30 mass parts LLDPE (2) and 20 mass parts EBR of amorphism alpha-olefin based polymer, obtain the relatively surface protective film of usefulness similarly to Example 2.
(comparative example 6)
Except as the adhesion layer resin, use 30 mass parts to contain beyond the mixture of composition (2), 20 mass parts LLDPE (2) and 50 mass parts EBR of amorphism alpha-olefin based polymer, obtain the relatively surface protective film of usefulness similarly to Example 2.
(comparative example 7)
Except as the adhesion layer resin, use 3.16 mass parts to contain beyond the hybrid resin of the composition (2) of amorphism alpha-olefin based polymer and 96.84 mass parts LLDPE (2), obtain the relatively surface protective film of usefulness similarly to Example 13.
(comparative example 8)
Except as the adhesion layer resin, use 30 mass parts to contain beyond the hybrid resin of the composition (1) of amorphism alpha-olefin based polymer and 70 mass parts LLDPE (3), obtain the relatively surface protective film of usefulness similarly to Example 13.
(comparative example 9)
Except as the adhesion layer resin; use beyond the hybrid resin of identical crystallinity propylene-butene-1 copolymer of crystallinity propylene-butene-1 copolymer of using in composition (2), 8 mass parts that 52 mass parts contain amorphism alpha-olefin based polymer and the preparation example 1 and 40 mass parts SEPS, obtain the relatively surface protective film of usefulness similarly to Example 13.
(comparative example 10)
Except as the adhesion layer resin, use 50 mass parts to contain beyond the hybrid resin of the composition (1) of amorphism alpha-olefin based polymer and 50 mass parts HOPP, obtain the relatively surface protective film of usefulness similarly to Example 13.
(comparative example 11)
Except as the adhesion layer resin, use 50 mass parts to contain beyond the hybrid resin of composition (1), 30 mass parts LLDPE (2) and 20 mass parts EBR of amorphism alpha-olefin based polymer, obtain the relatively surface protective film of usefulness similarly to Example 13.
Use the above embodiments 1～26 and comparative example 1～11 resulting surface protective film, carried out following mensuration and evaluation.
(1) mensuration of adhesion
In 23 ℃, the thermostatic chamber of 50%RH,, the above-mentioned surface protective film that obtains is sticked on the acrylic board (minute surface ornamenting, " Acrylite " that Mitsubishi Rayon Co., Ltd makes) of thickness 2mm according to the adhesion evaluation method of JIS Z0237:2000.The acrylic board that is pasted with film placed 24 hours in 23 ℃ of thermostatic chambers after, use cupping machine (A﹠amp; D Company, Limited makes), along peeling off on 180 ° of directions, measure initial grab with 300mm/ minute speed.In addition, the acrylic board of having pasted film placed 1 day in 50 ℃ drying machine after, similarly measure adhesion.
(2) adhering evaluation
In order to carry out the mensuration of above-mentioned adhesion, by Visual Confirmation the sticking state of surface protective film and acrylic board when sticking on surface protective film on the acrylic board, according to following benchmark, carry out adhering evaluation.
Zero: keep evenly adhering to the acrylic board surface.
*: fail to keep evenly adhering to, a part is floated.
(3) evaluation of cull
In 23 ℃, the thermostatic chamber of 50%RH,, surface protective film is sticked on whole of acrylic board (minute surface ornamenting, " acrylite " that Mitsubishi Rayon Co., Ltd makes) of vertical 15cm * horizontal 5cm according to the method for JIS Z0237:2000.The acrylic board that is pasted with film placed 3 days in 60 ℃ drying machine after, cooling is 1 hour in 23 ℃ of thermostatic chambers.From cool off the back test film on, with film along 180 ° of direction high speed peel manuallies from, the pollution situation on Visual Confirmation acrylic board surface carries out the evaluation of cull by following benchmark.
Zero: not have on acrylic board surface to blur, the pollution of informal voucher line, foreign matter etc.
*: exist fuzzy, informal voucher line, foreign matter etc. to pollute arbitrarily on acrylic board surface.
(4) mensuration of the wetting tension on acrylic board surface
The test film of film has been peeled off in use in the evaluation of above-mentioned (3), adopt the method according to JIS K6768:1999, has measured the wetting tension on acrylic board surface.
(5) printability after protective film is peeled off (printability) is estimated
With with the mensuration of above-mentioned (4) in the blank value of the wetting tension that obtains (to the surface of the acrylic board before the sticking film; after ethanol washing, drying, adopt the wetting tension that uses the same method and measure: the substituting of printability after the reduction amplitude of the wetting tension of 40mN/m) comparing is peeled off as protective film estimated.In addition, metewand carries out according to following.
Zero: wetting tension is below the 2mN/m with respect to the reduction amplitude of blank.
*: wetting tension exceeds 2mN/m with respect to the reduction amplitude of blank.
(6) evaluation of anti-adhesive
The surface protective film of gained is cut into A4 size (vertical 297mm * horizontal 210mm).Direction (MD direction) mode consistent with the A4 longitudinal direction of extruding during at this moment, by forming thin film cut.After 10 of film overlaies after the cutting, it is held with the plate holder of the vinyl chloride system of A4 size, thickness 3mm up and down, put the counterweight of heavy 5kg, keeping after 14 days in 40 ℃ drier was taken care of 1 hour in 23 ℃, the thermostatic chamber of 50%RH.Then, it is wide that this film is cut into 25mm along the MD direction, uses cupping machine (A﹠amp; D Company, Limited makes), peel off along 180 ° of directions with 300mm/ minute speed, measure stiction force.According to the stiction force of gained, anti-adhesive is estimated by following benchmark.
Zero: the not enough 0.8N/25mm of stiction force.
*: stiction force is more than the 0.8N/25mm.
(7) evaluation of cuttability
In 23 ℃, the thermostatic chamber of 50%RH; adhesion evaluation method according to JIS Z0237:2000; the above-mentioned surface protective film that obtains is sticked on the two sides of acrylic board (minute surface ornamenting, " acrylite " that Mitsubishi Rayon Co., Ltd makes) of thickness 2mm.By the cut-out end face of the film of visualization when cutting off the acrylic board that is pasted with film, cuttability is estimated according to following benchmark with high speed cutter.
Zero: the cut-out end face at film is not observed bad orders such as wire drawing, fluffing, breakage.
△: the cut-out end face at film is observed bad orders such as wire drawing, fluffing, breakage slightly.
*: the cut-out end face at film is observed bad orders such as wire drawing, fluffing, breakage.
The evaluation result of using the layer structure of surface protective film of above-mentioned making and their surface protective film and obtaining is shown in table 1～6.In addition, in embodiment that superficial layer is not set and comparative example with this hurdle as empty hurdle.To the composition that contains amorphism alpha-olefin based polymer that uses in the adhesion layer, be divided into each and become to assign to explain.
[table 1]
Figure BPA00001182124600301
[table 2]
Figure BPA00001182124600311
[table 3]
Figure BPA00001182124600321
[table 4]
Figure BPA00001182124600331
[table 5]
Figure BPA00001182124600341
[table 6]
Figure BPA00001182124600351
By the result of embodiment 1～26 as can be known, surface protective film of the present invention is about 0.1～2.2N/25mm for the adhesion of acrylic board, and it has as surface protective film only from little adhesion that adheres to the wide region of medium adhesion level.In addition, can not float yet, peel off after it is pasted acrylic board etc., have the practical good adhesiveness that as surface protective film.Especially from the acrylic board stripping film pasted the time; pollutions such as fuzzy, striped, foreign matter by Visual Confirmation can not appear; the decline of the wetting tension on the acrylic board surface behind the stripper surface protective film is also minimum; therefore, can be preferred for implementing in the purposes of secondary operations such as printing behind the stripper surface protective film.And then; by using ethylene-based polymer at substrate layer; at the state that is pasted with surface protective film with adherend adherend is cut off and to add man-hour; surface protective film cuts off fully; bad orders such as wire drawing, fluffing can not take place, can obtain to have the surface protective film of excellent cuttability.
Comparative example 1 is that the use level of straight chain shape low density polyethylene (LDPE) is the example of surface protective film of about 97 quality % of the overshoot upper limit 95 quality %.In the surface protective film of this comparative example 1, the initial value of adhesion only has about 0.05N/25mm, has confirmed can be observed just floated by slight impact, peels off etc., and adhesion is insufficient.
Comparative example 2 is that the density of straight chain shape low density polyethylene (LDPE) is overshoot upper limit 0.938g/cm 30.940g/cm 3The example of surface protective film.In the surface protective film of this comparative example 2; the initial value of having confirmed adhesion only has about 0.03N/25mm; can be observed and float at once, peel off after film is pasted etc., if the density of the straight chain shape low density polyethylene (LDPE) of cooperation is too high, then adhesion becomes insufficient.
Comparative example 3 is not use straight chain shape low density polyethylene (LDPE) in the adhesion layer, replace it and use the example of the surface protective film of styrene-ethylene-propylene-styrene block copolymer (SEPS).In the surface protective film of this comparative example 3, confirmed can be observed the generation of cull, the wetting tension on the acrylic board surface behind the stripper surface protective film also reduces greatly, and then stiction force is big, and anti-adhesive is also inferior.
Comparative example 4 is not use straight chain shape low density polyethylene (LDPE) in the adhesion layer, replace it and use the example of the surface protective film of Noblen.In the surface protective film of this comparative example 4, confirmed can be observed the generation of cull, the wetting tension on the acrylic board surface behind the stripper surface protective film also reduces greatly.
Comparative example 5 is that the use level of straight chain shape low density polyethylene (LDPE) is the example of surface protective film of the 37.5 quality % of not enough regulation lower limit 40 quality %.In the surface protective film of this comparative example 5, confirmed to exist the problem that produces cull.
Comparative example 6 is that the use level of ethene-alpha-olefin copolymer (EBR) is the example of surface protective film of about 50.8 quality % of the overshoot upper limit 40 quality %.In the surface protective film of this comparative example 6, confirmed that stiction force is big, anti-adhesive is inferior.
Comparative example 7 is that the ratio that cooperates of amorphism propylene-butene-1 copolymer and the straight chain shape low density polyethylene (LDPE) of adhesion layer is the example less than the surface protective film of about 3 quality % of lower limit 5 quality %.In the surface protective film of this comparative example 7, confirmed that the initial value of adhesion only has about 0.05N/25mm, can observe and just can produce by slight impact to float, peel off etc., adhesion is insufficient.
Comparative example 8 is to use the density of straight chain shape low density polyethylene (LDPE) to be overshoot upper limit 0.938g/cm in the adhesion layer 30.940g/cm 3The example of surface protective film.In the surface protective film of this comparative example 8; the initial value of having confirmed adhesion only has about 0.03N/25mm; can be observed and float at once, peel off after film is pasted etc., if the density of the straight chain shape low density polyethylene (LDPE) of cooperation is too high, then adhesion is insufficient.
Comparative example 9 is not use straight chain shape low density polyethylene (LDPE) in the adhesion layer, replace it and use the example of the surface protective film of styrene-ethylene-propylene-styrene block copolymer (SEPS).In the surface protective film of this comparative example 9, confirmed can be observed the generation of cull, the wetting tension on the acrylic board surface behind the stripper surface protective film also reduces greatly, and then stiction force is big, and anti-adhesive is also inferior.
Comparative example 10 is not use straight chain shape low density polyethylene (LDPE) in the adhesion layer, replace it and use the example of the surface protective film of Noblen.In the surface protective film of this comparative example 10, confirmed to observe the generation of cull, the wetting tension on the acrylic board surface behind the stripper surface protective film also reduces greatly.
Comparative example 11 is that the ratio that cooperates of amorphism propylene-butene-1 copolymer and the straight chain shape low density polyethylene (LDPE) of adhesion layer is the example of surface protective film that exceeds the 50 quality % of the upper limit 40 quality %.In the surface protective film of this comparative example 11, confirmed to exist the problem that produces cull.
Utilizability on the industry
Surface protective film of the present invention has onlyly from little wide region adhesion that adheres to medium adhesion level, and it can not float yet, peel off after sticking on acrylic board etc. Especially from the acrylic board stripping film pasted the time; pollution by visual certifiable fuzzy, striped, foreign matter etc. can not appear; the decline of the wetting tension on the acrylic board surface behind the stripper surface protective film is also minimum; therefore, preferably be applicable in the purposes of the secondary operations such as the after-applied printing of stripper surface protective film.

Claims (6)

1. surface protective film; it is characterized in that; its surface protective film for adhesion layer (A) and substrate layer (B) are laminated, wherein, this adhesion layer (A) is 0.880～0.938g/cm with amorphism alpha-olefin based polymer (A1) 5～50 quality % and density 3The hybrid resin of straight chain shape low density polyethylene (LDPE) (A2) 50～95 quality % be main component, be 0.880～0.938g/cm perhaps with amorphism alpha-olefin based polymer (A1) 5～50 quality %, density 3Straight chain shape low density polyethylene (LDPE) (A2) 40～90 quality % and the hybrid resin of crystallinity ethene-alpha-olefin copolymer (A3) 5～50 quality % be main component.
2. surface protective film according to claim 1, wherein, described substrate layer (B) is a main component with ethylene-based polymer (B1) or crystallinity acrylic polymer (B2).
3. surface protective film according to claim 1 and 2, wherein, described amorphism alpha-olefin based polymer (A1) is amorphism propylene-butene-1 copolymer or amorphism propylene-ethylene-butene-1 copolymer.
4. according to each described surface protective film in the claim 1～3, wherein, described ethene-alpha-olefin copolymer (A3) is ethene-butene-1 copolymer.
5. according to each described surface protective film in the claim 1～4, wherein, the reverse side setting that is laminated with the face of adhesion layer (A) in described substrate layer (B) is the superficial layer (C) of main component with the olefin polymer.
6. according to each described surface protective film in the claim 1～5, it stretches along the single shaft direction at least.
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