CN102471646A - Surface protective film - Google Patents

Surface protective film Download PDF

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Publication number
CN102471646A
CN102471646A CN2010800288254A CN201080028825A CN102471646A CN 102471646 A CN102471646 A CN 102471646A CN 2010800288254 A CN2010800288254 A CN 2010800288254A CN 201080028825 A CN201080028825 A CN 201080028825A CN 102471646 A CN102471646 A CN 102471646A
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CN
China
Prior art keywords
weight
styrenic
adhesive linkage
surface protection
protection film
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Granted
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CN2010800288254A
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Chinese (zh)
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CN102471646B (en
Inventor
大胡田久行
辻村真任
井上则英
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Mitsui Chemical Industry Co Ltd
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Mitsui Chemicals Tohcello Inc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/042—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/06—Polystyrene
    • 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
    • C09J125/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
    • C09J125/02—Homopolymers or copolymers of hydrocarbons
    • C09J125/04—Homopolymers or copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241—Polyolefin, e.g.rubber
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2419/00—Buildings or parts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2551/00—Optical elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C09J2423/006—Presence of polyolefin in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2453/00—Presence of block copolymer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Provided is a surface protective film having excellent heat resistance, rewindability, transparency, adhesion to an adherend having a very uneven surface, and adhesion stability over time. The surface protective film comprises at least two layers, namely a surface layer (A) and an adhesion layer (X). The surface layer (A) is formed from a polyolefin resin and the adhesion layer (X) is formed from a composition comprising 20 to 99.8 wt% of a styrene elastomer having a weight-average molecular weight (Mw) of between 10,000 and 300,000, and 0.2 to 80 wt% of a styrene oligomer having a weight-average molecular weight (Mw) between 200 and 9,000.

Description

Surface protection film
Technical field
The present invention relates to employed surface protection film in optical goods, building materials, trolley part etc.In detail; Relate to adhesion properties, particularly excellent to the ageing stability of the cementability of the big adherend of concave-convex surface and bonding force, in addition, excellent heat resistance; Pollution to adherend etc. is few, and the extractable when drum is extracted out is easy to surface protection film.
Background technology
Surface protection film mainly stick to building materials with or adherends such as the resin used of optical applications, metal products, glasswork on use, performance is in conveying, the keeping of these goods and add the effect that prevents that scratch or foreign matter from sneaking into man-hour.These surface protection films generally by the upper layer that does not have cementability be used for constituting with the bonding adhesive linkage of above-mentioned adherend.Upper layer is formed by vinyl polymers such as polyester, SE such as polyolefine such as Vilaterm or Vestolen PP 7052 or ethylene glycol terephthalates usually.
In recent years, carrying out the exploitation of the so-called optical goods of the parts of use in liquid crystal display, plasma display (PDP) or back projection type screen etc.For the surface protection film that is used to protect these optical goods; Not only expectation prevents that scratch and foreign matter from sneaking into, even and be desirably in the characteristic that the state of having pasted surface protection film can be realized the transparency that the goods inspection is so down and under the condition of high temperature, paste or also show through heat treatment step appropriate bonding force etc.
In addition,, a lot of for example so big parts of concave-convex surface of prism plate are arranged about optical goods, though expectation have the bonding force that also can show appropriateness for these high relief members with along with the time through also showing the protective membrane of stable bonding force.
On the other hand, when in building materials or trolley part purposes, using surface protection film, have and under the state of having pasted surface protection film, carry out hot formed situation, thereby exigent thermotolerance.
In addition, than for the higher surface protection film,, therefore process drum, use when adherend is pasted, peeling this dicing film with the state of the dicing film of having fitted on the adhesive linkage owing to be difficult to from the goods of drum, extract out for bonding force.If adopt such operation, then produce a large amount of wastes, so need a kind of surface protection film that also can easily from reel, extract out even without dicing film.
The surface protection film that is the main body with the Vilaterm composition is disclosed in TOHKEMY 2006-116769 communique.Yet in the method for this communique, though can be suitable for a part of purposes parts, bonding force is low, and the transparency is also not enough in addition, aspect the purposes of adherend, has restriction.
In TOHKEMY 2007-126512 communique, disclose and comprised the surface protection film that contains as the adhesive linkage of the styrenic elastomerics of isobutylene type segmented copolymer and tackifying resin.Yet in the method for this communique, when on the concavo-convex adherend of height, fitting, the ageing stability of bonding force is not enough, and further improvement of expectation.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2006-116769 communique
Patent documentation 2: TOHKEMY 2007-126512 communique
Summary of the invention
Invent problem to be solved
The invention reside in the desired characteristic of surface protection film that is used to protect when the keeping of a kind of conduct at optical goods, building material made or trolley part, conveying, processing, inspection are provided, particularly to the adhesion properties of the big adherend of concave-convex surface, the transparency, thermotolerance with from the excellent surface protection film of the extractable of reel.
Be used to solve the method for problem
Contriver of the present invention has carried out deep research in view of above-mentioned problem, and the result finds, can solve above-mentioned problem through the surface protection film with the upper layer that is made up of certain specific resin combination, thereby accomplish the present invention.
Promptly; The present invention is a kind of surface protection film, and it is characterized in that by at least 2 layers of formation of upper layer (A) and adhesive linkage (X); Upper layer (A) is made up of polyolefin resin; Adhesive linkage (X) is formed by the combinations thing, and said composition comprises the weight-average molecular weight (Mw) of 20～99.8 weight % 10,000～300; Styrenic elastomerics in 000 the scope and the weight-average molecular weight (Mw) of 0.2～80 weight % be 200～9, in 000 the scope and the styrenic oligopolymer of softening temperature in 60～160 ℃ scope (styrenic elastomerics and styrenic oligopolymer add up to 100 weight %.)。
In addition; The present invention is a kind of surface protection film; It is characterized in that; Above-mentioned adhesive linkage (X) is formed by the combinations thing, and said composition contains 0.5～1000 weight part crystalline polyolefin and/or polyolefins elastomerics with respect to compsn 100 weight parts that comprise above-mentioned styrenic elastomerics and styrenic oligopolymer.
In addition, the present invention is a kind of surface protection film, and it is at least 2 layers of multilayer film that obtains from T-die head extrusion molding with above-mentioned upper layer (A) and adhesive linkage (X).
The effect of invention
Surface protection film of the present invention is in adhesion properties, particularly to adhesion properties and ageing stability, the transparency, rewinding power and the excellent heat resistance of the concavo-convex adherend of height, as the protective membrane of optical applications, building materials purposes, trolley part purposes and the utility value on industry is high.
Embodiment
Below, the present invention is elaborated.
Surface protection film of the present invention is by upper layer (A) and adhesive linkage (X) at least 2 layers or as required by at least 3 layers of formation of upper layer (A), substrate layer (B) and adhesive linkage (X).Here, when being made as innermost layer, upper layer (A) is positioned at outermost layer with adhesive linkage (X), and when film was processed drum, upper layer (A) contacted with adhesive linkage (X).
Upper layer (A) is made up of polyolefin resin.
As polyolefin resin, can enumerate known polyolefin resines such as Vestolen PP 7052 and Vilaterm.As Vestolen PP 7052, can enumerate homo-polypropylene, Atactic Polypropelene, block polypropylene, as Vilaterm, can enumerate high-pressure process new LDPE (film grade), straight chain shape new LDPE (film grade), high density polyethylene(HDPE).In these polyolefin resines, from the viewpoint of rewinding property, preferably utilize the high-pressure process new LDPE (film grade), from the transparency, stable on heating viewpoint, preferably utilize homo-polypropylene or block polypropylene.
In the compsn that forms above-mentioned upper layer (A); Without detriment to scope, can also add various additives such as static inhibitor, releasing agent, inhibitor, weather resisting agent, crystallization nucleating agent, other modifier such as polyolefin resin, wax, polyester, polymeric amide, elastomerics as the characteristic of surface protection film of the present invention.
The adhesive linkage of surface protection film of the present invention (X) is formed by the combinations thing; Said composition comprises the weight-average molecular weight (Mw) of 20～99.8 weight % 10; 000～300; Styrenic elastomerics in 000 the scope and the weight-average molecular weight (Mw) of 0.2～80 weight % be 200～9, in 000 the scope and the styrenic oligopolymer of softening temperature in 60～160 ℃ scope (styrenic elastomerics and styrenic oligopolymer add up to 100 weight %.)。
As the styrenic elastomerics, can use to have the known styrenic elastomerics of PS as hard segment.Particularly, can enumerate multipolymer and their hydrogenate (for example second-alkene ethylene-butadiene-styrene multipolymer (SEBS) etc.) or vinylbenzene-iso-butylene-styrene triblock copolymer (SIBS), the vinylbenzene-iso-butylene Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock (SIB) of vinylbenzene such as styrene-butadiene copolymer (SBR), styrene-isoprene-styrene copolymer-(SIS), styrene-butadiene-styrene multipolymer (SBS), styrene-ethylene base isoprene-styrene polymer and diene.Be preferably vinylbenzene-iso-butylene-styrene triblock copolymer (SIBS), vinylbenzene-iso-butylene Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock (SIB).
The weight-average molecular weight that above-mentioned styrenic elastomerics is recorded by GPC (GPC) (following brief note is Mw) is 10,000～300, in 000 the scope, preferably 15,000～250, in 000 the scope, more preferably 20,000～200, in 000 the scope.If Mw is less than 10,000 or greater than 300,000, then the productivity of protective membrane is poor, so not preferred.
As the styrenic oligopolymer that in adhesive linkage (X), uses, be that the weight-average molecular weight (Mw) that recorded by GPC is 200～9, in 000 the scope, and the styrenic oligopolymer of softening temperature in 60～160 ℃ scope that is recorded by JIS K2207.Preferred Mw is 300～7,000 and softening temperature in 70～150 ℃ scope, more preferably Mw is 500～5,000 and softening temperature in 80～140 ℃ scope.
As above-mentioned styrenic oligopolymer, so long as satisfy the just not special restriction of the styrenic oligopolymer of above-mentioned molecular weight and softening temperature, but particularly, be to constitute (being total to) polymkeric substance by at least a fragrant same clan monomers such as vinylbenzene or alpha-methyl styrenes.In detail, can enumerate for example styrene homopolymers, alpha-methyl styrene homopolymer, styrene-multipolymer, styrene monomer-aliphatic category monomer copolymer, alpha-methyl styrene-aliphatic category monomer copolymer, styrene monomer-alpha-methyl styrene-aliphatic category monomer copolymer.
Adhesive linkage in the protective membrane of the present invention (X) by the styrenic oligopolymer of above-mentioned styrenic elastomerics that comprises 20～99.8 weight % and 0.2～80 weight % (styrenic elastomerics and styrenic oligopolymer add up to 100 weight %.) compsn form.Preferably the constituent by the styrenic oligopolymer of styrenic elastomerics that comprises 30～99.5 weight % and 0.5～70 weight % forms; More preferably the constituent by the styrenic oligopolymer of styrenic elastomerics that comprises 50～98 weight % and 2～50 weight % forms, and is more preferably compsn by the styrenic oligopolymer of styrenic elastomerics that comprises 65～95 weight % and 3～15 weight % and forms that (total of styrenic elastomerics and styrenic oligopolymer all is 100 weight % under every kind of situation.)。
In the adhesive linkage in the protective membrane of the present invention (X), with bonding force, through the time bonding force control and rewinding power be controlled to be purpose, also can in above-mentioned compsn, add crystalline polyolefin and/or olefin type elastomer.
As crystalline polyolefin; So long as the known polyolefine of fusing point above 110 ℃ just can use ad lib; But particularly, can enumerate for example alfon, propylene-ethylene copolymers, propylene-ethylene-butene-1 copolymer, 1-butylene homopolymer, 1-butylene-ethylene copolymer, 1-butylene-propylene copolymer, 4-methylpentene-1 homopolymer, 4-methylpentene-1 propylene copolymer, 4-methylpentene-1-1-butylene copolymer, 4-methylpentene-1-propylene-butene-1 copolymer, propylene-butene-1 copolymer, Alathon, ethene-alpha-olefin copolymer, vinyl-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate methyl terpolymer etc.
As olefin type elastomer, be that fusing point is below 110 ℃, preferred fusing point is below 100 ℃, more preferably fusing point is below 80 ℃ or does not observe alpha-olefinic polymer or the multipolymer of multipolymer or ethene and unsaturated carboxylic acid or esters of unsaturated carboxylic acids of the carbonatoms 2～20 of fusing point.Particularly, can enumerate ethylene-propylene copolymer, ethene-butene-1 copolymer, ethene-1-hexene copolymer, ethene-4-methylpentene-1 multipolymer, ethene-1-octene copolymer, alfon, propylene-ethylene copolymers, propylene-ethylene-butene-1 copolymer, 1-butylene homopolymer, 1-butylene-ethylene copolymer, 1-butylene-propylene copolymer, 4-methylpentene-1 homopolymer, 4-methylpentene-1-propylene copolymer, 4-methylpentene-1-1-butylene copolymer, 4-methylpentene-1-propylene-butene-1 copolymer, propylene-butene-1 copolymer, vinyl-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate methyl terpolymer etc.Viewpoint from the ageing stability of bonding force is preferably alfon, propylene-ethylene copolymers, propylene-butene-1 copolymer.Propylene-ethylene-butene-1 copolymer more preferably.
Content when above-mentioned crystalline polyolefin and/or olefin type elastomer are used as a kind of composition of the adhesive linkage (X) of protective membrane of the present invention; With respect to above-mentioned compsn 100 weight parts that comprise styrenic elastomerics and styrenic oligopolymer; It is 0.5～1000 weight part; Be preferably 1～700 weight part, more preferably 5～500 weight parts are more preferably 5～100 weight parts.Through adding crystalline polyolefin and/or olefin type elastomer, can show desired bonding force, can also show the adhesion properties that is suitable for various adherends, so preferred.
Through having added the compsn that comprises styrenic elastomerics and styrenic oligopolymer and the compsn of crystalline polyolefin as required and/or olefin type elastomer, can form the adhesive linkage (X) in the surface protection film of the present invention.In addition, in the present invention,, can also contain various additives such as modifiers such as acid modified polyolefin, polyester, polymeric amide, static inhibitor, crystallization nucleating agent, inhibitor in scope without detriment to characteristic of the present invention.
At least 1 layer substrate layer (B) can also be set between upper layer (A) and adhesive linkage (X) in the present invention.The physical strength and the transparency with controlling diaphragm are purpose, in addition, when the bonding force deficiency of upper layer (A) and adhesive linkage (X), can use polyolefin resin, adhesive resin or caking agent as the middle layer.
As the not special restriction of substrate layer, be crystalline polyolefin such as Vestolen PP 7052 or Vilaterm or polyester, polymeric amide, polyolefins elastomerics etc. more than 100 ℃ but generally can use fusing point.When substrate layer is used as adhesive linkage, can use modified polyolefin or polyolefins elastomerics, styrenic elastomerics, polyester elastomer etc.Among these,, preferably use Vestolen PP 7052 or polyolefin elastomer as the middle layer from the viewpoint of productivity with the transparency.
Above-mentioned compsn and crystalline polyolefin as required and/or olefin type elastomer and modifier as required or the additive that comprises styrenic elastomerics and styrenic oligopolymer; Can through with above-mentioned upper layer (A), as required substrate layer (B) lamination, form surface protection film of the present invention.
About stack surface layer (A) and adhesive linkage (X), the not special restriction of the method for laminated substrate layer (B) as required; But can be set forth in advance by the T-die head be shaped or the resulting surperficial tunic of blow molding on, by extruding the method that lamination, known lay-up method such as extrusion coated carry out lamination; Or, each film is carried out the method for lamination etc. through dry lamination with after substrate layer and the adhesive linkage independence film forming, from productive viewpoint, preferably each composition of upper layer, substrate layer, adhesive linkage is supplied with the coextrusion shaping that the multiwalled forcing machine forms.
As the thickness of the upper layer in the surface protection film of the present invention (A), be 0.1～100 micron (μ m), be preferably 0.3～50 micron (μ m), more preferably 0.5～30 micron (μ m), be more preferably 1～20 micron (μ m).As the thickness of adhesive linkage (X), be 0.1～50 micron (μ m), be preferably 0.3～40 micron (μ m), more preferably 0.5～30 micron (μ m).
As the thickness of surface protection film of the present invention, be 1～300 micron (μ m), be preferably 2～200 microns (μ m), more preferably 3～100 microns (μ m).
Through upper layer (A), adhesive linkage (X) and the substrate layer as required (B) that uses above-mentioned optimal way; Can obtain adhesion properties; Particularly for the excellent bonding force of the concavo-convex adherend performance of height; And the excellent surface protection film of the transparency, particularly can utilize well for building materials purposes, optical applications.
Embodiment
Below, through embodiment the present invention is described in further detail, but the present invention is not limited to these embodiment.
[evaluation assessment]
Bonding force (acrylic panel):
Acrylic panel is cut to wide 50 millimeters (mm), long 125 millimeters (mm), on this test board, uses the rubber rollers of 2kg to paste.Then, measure the peeling force when peeling off (180 degree are peeled off) with 300mm/ minute speed, with the peeling force of per 50 millimeters (mm) width as bonding force (N/50mm).
Bonding force (buckle plate):
On Nissin Steel Co., Ltd. system stainless steel HL precision work #180, paste protective membrane, measure the peeling force when peeling off (180 degree are peeled off) with 300mm/ minute speed, with the peeling force of per 50 millimeters (mm) width as bonding force (N/50mm).
Rewinding power:
Use the drum sample, measure with 300mm/ minute the speed peeling force (N/50mm) when reel draws stripping, as rewinding power.
Melt flow rate (MFR):
With ASTM D1238 is benchmark, measures for 230 ℃ in load 2.16 kilograms of (kg), temperature.
[embodiment 1]
Be used for upper layer, substrate layer and adhesive linkage; In three kinds three layers T-die head forming mill of the Mould Breadth 500 millimeters (mm) of the single screw extrusion machine that has
Figure BDA0000125339670000071
concurrently, supply with following resin combination, obtain the surface protection film of 10 microns of surface layer thicknesses (μ m), thickness of adhibited layer 10 microns (μ m), substrate layer thickness 30 microns (μ m), total thickness 50 microns (μ m).The evaluation result of resulting film is illustrated in the table 1.
Upper layer:
LD-1: high-pressure process new LDPE (film grade)
(density 0.920g/cm 3, MFR (190 ℃) 6g/10 minute)
100 weight %
Substrate layer:
PP-1: homo-polypropylene
(160 ℃ of fusing points, MFR (230 ℃) 7g/10 minute)
90 weight %
EL-1: ethene-butene-1 copolymer
(trade(brand)name: TAFMER, trade name: A-4085S, MFR=3.6g/10 minute, Mitsui Chemicals, Inc's system) 10 weight %
Adhesive linkage:
PEBR: propylene-ethylene-butene-1 copolymer
(13 moles of % of ethylene content, 19 moles of % of 1-butylene content do not observe fusing point, MFR=7g/10 minute) 10 weight %
SIBS: vinylbenzene-iso-butylene-styrene triblock copolymer
(trade(brand)name: SIBSTAR, trade name: 062T, MFR=8.0g/10 minute, Kaneka corporate system) 70 weight %
SL-1: styrene monomer-aliphatic category monomer copolymer
(trade(brand)name: FTR, trade name: FTR6125, Mw=1950,125 ℃ of softening temperatures, Mitsui Chemicals, Inc's system) 10 weight %
PP-2: homo-polypropylene
(trade name: F107BV, fusing point=160 ℃, MFR=7g/10 minute, PrimePolymer corporate system) 10 weight %
[embodiment 2,3 and comparative example 1,2]
Except the resin of various layers being formed the resin composition that is made as table 1 record, obtain surface protection film with embodiment 1 same operation.The evaluation result of resulting film is illustrated in the table 1.
[table 1]
Figure BDA0000125339670000091
* with the total of SL-1+SIBS as 100 weight parts, expression is with respect to this weight part.

Claims (3)

1. surface protection film is characterized in that:
It is by at least 2 layers of formation of upper layer (A) and adhesive linkage (X); Upper layer (A) is made up of polyolefin resin; Adhesive linkage (X) is formed by the combinations thing, and said composition comprises the weight-average molecular weight (Mw) of 20～99.8 weight % 10,000～300; Styrenic elastomerics in 000 the scope and the weight-average molecular weight (Mw) of 0.2～80 weight % be 200～9, the styrenic oligopolymer in 000 the scope.
2. surface protection film is characterized in that:
Adhesive linkage (X) is formed by the combinations thing; Said composition with respect to the weight-average molecular weight that comprises 20～99.8 weight % (Mw) 10; 000～300; Styrenic elastomerics in 000 the scope and the weight-average molecular weight (Mw) of 0.2～80 weight % be 200～9, in 000 the scope and compsn 100 weight parts of the styrenic oligopolymer of softening temperature in 60～160 ℃ scope, contains 0.5～1000 weight part crystalline polyolefin and/or polyolefins elastomerics.
3. like each described surface protection film in the claim 1～2, it is characterized in that:
It is at least 2 layers of multilayer film that obtains from T-die head extrusion molding with upper layer (A) and adhesive linkage (X).
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