CN102149779A - Surface protective film - Google Patents

Surface protective film Download PDF

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Publication number
CN102149779A
CN102149779A CN200980135434XA CN200980135434A CN102149779A CN 102149779 A CN102149779 A CN 102149779A CN 200980135434X A CN200980135434X A CN 200980135434XA CN 200980135434 A CN200980135434 A CN 200980135434A CN 102149779 A CN102149779 A CN 102149779A
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Prior art keywords
surface protection
protection film
polymkeric substance
weight
polymer blocks
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CN200980135434XA
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CN102149779B (en
Inventor
丰岛克典
多田博士
家田泰享
野世溪元
长尾功弘
川村真教
长谷川研二
大久保明彦
中村丈夫
佐野拓哉
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Yinnenshi Materials Co ltd
Sekisui Chemical Co Ltd
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JSR Corp
Sekisui Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C09J125/08—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
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
    • 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]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/1336—Illuminating devices
    • G02F1/133602—Direct backlight
    • G02F1/133606—Direct backlight including a specially adapted diffusing, scattering or light controlling members
    • G02F1/133607—Direct backlight including a specially adapted diffusing, scattering or light controlling members the light controlling member including light directing or refracting elements, e.g. prisms or lenses
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2202/00—Materials and properties
    • G02F2202/28—Adhesive materials or arrangements

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

An adhesive composition characterized by containing a polymer (i), which is a copolymer having a structure represented by the following general formula: [A-B]n (wherein n = 1-3) or a hydrogenated product thereof, and a polymer (ii), which is a copolymer having a structure represented by the following general formula: A-B-A or the following general formula: (A-B)x-Y (wherein x >= 1 and Y represents a residue of a coupling agent) or a hydrogenated product thereof. The adhesive composition is also characterized in that the total aromatic alkenyl compound unit content in the polymers (i) and (ii) is 30-50 wt%, and the weight ratio between the total amount of A and the total amount of B contained in the polymers (i) and (ii) is within the range of from 5:95 to 25:75. In this connection, A represents a polymer block mainly composed of aromatic alkenyl compound units, and B represents a polymer block which is an aromatic alkenyl-conjugated diene random copolymer block having an aromatic alkenyl compound unit content of 10-35 wt%.

Description

Surface protection film
Technical field
The present invention relates to surface protection film.
Background technology
In the past; for the surface of various parts such as the metal sheet after optics, metal sheet, the process application, resin board, sheet glass is protected; widely used is the surface protection film (usually, also being called boundary belt, Masking strip or surface protective plate etc.) that forms at a face superimposed layer adhesive layer of film-shaped matrix material.Particularly, in recent years, used surface protection film at liquid-crystal display on optics.Optics comprises the parts that are concaveconvex shape such as surfaces such as prismatic lens, diffusion barriers.In order this concavo-convexly not to be caused damage; before using, to utilize surface protection film that the surface (particularly concavo-convex outside surface) of these parts is protected; but, therefore need to form the strong adhesive layer of cohesive force owing to when the surperficial coating surface protective membrane of above-mentioned concaveconvex shape, can't obtain big contact area.
But in general, the surface protection film of industrial manufacturing is the coiling body form usually, is rolled into web-like by the film with strip and obtains.For the surface protection film of such coiling body form, knownly the coiling body uncoiling will be needed higher power (expansion power), and its expansion power becomes big easily in time, that is, an urgent demand can easily be carried out uncoiling to coiling body.
In addition, remove, therefore require surface protection film to have separability smoothly, and requirement can not cause by adherend contamination because of the thickener of surface protection film is residual etc. owing to after using, surface protection film will be peeled off.
On the other hand, the starting material as prismatic lens, diffusion barrier etc. adopt acrylic resin and polycarbonate resin isopolarity polymkeric substance mostly.These optical sheets are supplied to optics manufacturers after the coating surface protective membrane, it is transported, the preservation process is medium is exposed in the high temperature sometimes.
Wherein, particularly for the situation that is concaveconvex shape by the adherend surface, exist what is called bonding outer because of time and temperature etc. thereby that cause being increased and then cause the cohesive force rising by the contact area between adherend and the adhesive layer to worsen (the high Jin of adhesion) problem.
Generally speaking, as binding agent, widely used is acrylic adhesive, but the cohesive force of acrylic adhesive rising degree in time is big especially.
Based on this, particularly for the surface protection film that is applied to optical sheet, main use is the rubber-like binding agent in the adhesive layer that constitutes surface protection film, and is not acrylic adhesive.Thus, can avoid cohesive force to increase in time, thereby seek that surface protection film is successfully peeled off from lens section (prism) surface of optical sheet etc.
; because the rubber-like binding agent is generally the solution coat type; therefore; problems such as environmental pollution when not only having solvent seasoning and energy dissipation also must be carried out the demoulding to the back side of alkene base material layer commonly used (surface of the opposite side of one side of adhesive layer being arranged with lamination) simultaneously and be handled.In addition, if hot-melt type adhesive, though can make preceding problem in above-mentioned be eliminated or reduce, but still can't avoid the demoulding at the back side is handled.
At the problem of improving uncoiling; for example proposed in the patent documentation 1 the base material layer surface irradiation electron beam of the stack membrane that forms by base material layer and adhesive layer lamination or the method that gamma-rays is made surface protection film; wherein, described base material layer is made by the organopolysiloxane and the polyolefin resin that have two keys at the intramolecularly more than 1.
In addition; the surface protection film that obtains by following method has been proposed: utilize coetrusion will contain the top layer of polyolefin resin and contain the adhesive layer lamination film forming of thermoplastic elastomer in the patent documentation 2; then, form release layer by coating method at the back side on top layer.
In addition; following surface protection film has been proposed: use with the styrenic elastomerics to replace the adhesive layer of natural rubber in the patent documentation 3 as principal constituent; the surface protection film that this adhesive layer and alkene base material layer is carried out coextrusion and form; friction treatment has been passed through at the back side of the base material layer of this surface protection film, has excellent uncoiling.
On the other hand, at suppressing the problem that bonding worsens, for example, in patent documentation 4, carried out following trial: be mixed in the base material layer by the polymine that importing is had senior alkyl, and make it be exuded to the adhesive layer surface, to guarantee suppressing the bonding deterioration simultaneously with respect to by the initial stage cohesive force of adherend.
But, for the prismatic lens that is fitted with surface protection film, in being installed to goods before, be that unit is stacked and preserves with tens of usually.
At this moment, under the load effect of the prismatic lens above being arranged on, may the concavo-convex top of the prismatic lens below being arranged on be damaged, and then cause the optical quality deterioration.Can think; this is caused by following reason: under the load effect; above-mentioned concavo-convex top can be trapped in the adhesive layer of surface protection film, even arrives the body material of surface protection film, and this has exceeded adhesive layer for the dispersion of above-mentioned load, the limit of alleviation effects.In order to address this problem, considered the method for abundant increase adhesive layer thickness.But the thickness that increases adhesive layer is disadvantageous aspect manufacturing cost not only, and can cause the be absorbed in degree of depth of lens section (prism) in adhesive layer to increase the hidden danger that exists cohesive force rising degree in time to increase.
Based on this reason, proposed to use the styrenic elastomerics to replace natural rubber to be used for the example of surface protection film.The surface protection film of the adhesive layer more than the thick 10 μ m that a kind of employing is principal constituent with the styrenic elastomerics for example, is disclosed in the patent documentation 5.According to record wherein, this surface protection film can satisfy simultaneously to by the sufficient defencive function of adherend and suitable bonding characteristic.
The prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 2-252783 communique
Patent documentation 2: TOHKEMY 2003-41216 communique
Patent documentation 3: Japanese kokai publication hei 07-62311 communique
Patent documentation 4: Japanese kokai publication hei 09-188857 communique
Patent documentation 5: TOHKEMY 2000-80336 communique
Summary of the invention
The problem that invention will solve
But, in above-mentioned prior art, still have following problems.
For the surface protection film of patent documentation 1 or 3, only to handle and can't fully reduce expansion power by the back side, the uncoiling of coiling body is also insufficient, may cause operability to descend.
By the demoulding facture of patent documentation 2,, can guarantee that also derivation property (Kuri goes out fully even when the back side of body material is uneven surface), but exist releasing agent to be transferred to adhesive layer, hidden danger to being descended by the cohesiveness of adherend.
With regard to disclosed surface protection film in the patent documentation 4; at the environment of thermal extremes (for example; the torrid zone region, region, subtropics) in when preserving; the amount that is exuded to surperficial polymine is different with the situation of preserving in common environment, probably can't give play to sufficient bonding and worsen the inhibition effect.
In addition; with regard to disclosed surface protection film in the patent documentation 5; viewpoint from the concavo-convex top shape of protection prism portion; under the state of harshness; for example, particularly this surface protection film is being fitted on the prism facets of prismatic lens, and with the surface of the opposite side of this prism facets side (promptly; the outer surface of surface protection film) presses under the situation of so-called flake prominences such as (fish eye), still have further room for improvement.
Therefore; the object of the present invention is to provide a kind of surface protection film, it can make the defective that exists in the above-mentioned prior art be eliminated, and can guarantee suitable initial stage cohesive force; have excellent extensibility simultaneously, it is residual to prevent after being peeled off by adherend thickener to take place.
In addition, another object of the present invention is to provide a kind of prismatic lens surface protection film, it can guarantee suitable initial stage cohesive force, and the bonding deterioration is suppressed.
In addition; another object of the present invention is to provide a kind of surface protection film; it is under the state of harshness; for example; particularly this surface protection film is being fitted on the prism facets of prismatic lens; and pressing under the situation of prominences such as so-called flake with the surface (that is, the outer surface of surface protection film) of the opposite side of this prism facets side, still can be protected the concavo-convex top shape of prism portion.
The method of dealing with problems
The inventor etc. are through further investigation; found that: be used for adhesive layer by the specific segmented copolymer that will have aromatic series alkenyl polymer blocks and aromatic series alkenyl-conjugated diene copolymer block; can guarantee suitable initial stage cohesive force, can obtain the extensibility excellence and can prevent from after being peeled off, to take place the residual surface protection film of thickener simultaneously by adherend.And finished the present invention through further research.
Adhesive composition of the present invention contains polymkeric substance (i) and polymkeric substance (ii), wherein,
Polymkeric substance (i): contain following polymer blocks A and following polymer blocks B, and have multipolymer (I) or its hydrogenation products of structure shown in general formula [A-B] n (in the formula, A representation polymer block A, B representation polymer B block, n represents integer 1～3),
Polymkeric substance is (ii): contain following polymer blocks A and following polymer blocks B, and have general formula A-B-A (implication of symbol is the same in the formula) or general formula (A-B) x-Y (in the formula, x represents the integer more than 2, Y represents the coupling agent residue, the implication of other symbol is the same) shown in multipolymer (II) or its hydrogenation products of structure
Above-mentioned polymkeric substance (i) and the above-mentioned polymkeric substance unitary total containing ratio of aromatic series alkenyl compound (St (A+B)) in (ii) is 30～50 weight %,
(the A: B) and the weight ratio (A: B) respectively in 5: 95～25: 75 scope of the total amount of the total amount of above-mentioned polymkeric substance contained polymer blocks A in (ii) and polymer blocks B of the weight ratio of the total amount of the total amount of contained polymer blocks A and polymer blocks B in the above-mentioned polymkeric substance (i).
Wherein,
Polymer blocks A: have successive aromatic series alkenyl compound unit and based on the polymer blocks of aromatic series alkenyl compound unit,
Polymer blocks B: randomly contain conjugated diene unit and aromatic series alkenyl compound unit, and the unitary containing ratio of aromatic series alkenyl compound (St (b)) is aromatic series alkenyl-conjugated diene copolymer block of 10～35 weight %.
The adhesive layer that surface protection film of the present invention has base material layer and formed by the adhesive composition of the invention described above.
The adhesive composition of the application of the invention can make surface protection film of the present invention have excellent extensibility, and can prevent in that thickener takes place after adherend is peeled off is residual.
Preferably in above-mentioned surface protection film; above-mentioned base material layer is the polyolefin substrate material layer; also contain tackifier in the above-mentioned adhesive composition; and; when-50 ℃～80 ℃ dynamic viscoelastics to above-mentioned adhesive layer were measured, the temperature when gained tan δ reaches maximum was-10 ℃～20 ℃.
Thus, can make above-mentioned surface protection film obtain the even more ideal balance of extensibility and initial stage cohesive force.
Preferably in above-mentioned surface protection film; above-mentioned base material layer is the polyolefin substrate material layer; also contain tackifier and styrenic block strengthening agent in the above-mentioned adhesive composition; and; with respect to the weight of above-mentioned adhesive layer, the shared ratio (aromatic series alkenyl compound unit containing ratio) of aromatic series alkenyl compound unit weight that above-mentioned polymkeric substance (i), above-mentioned polymkeric substance (ii) reach in the styrenic block strengthening agent is 20～50 weight %.
Thus, can more effectively suppress cohesive force rapid rising (Ang Jin in time).
Preferably in above-mentioned surface protection film, above-mentioned adhesive layer is 4.5 * 10 at 70 ℃ storage modulus G ' 5Pa～6.0 * 10 5Pa.
Thus, can more effectively suppress cohesive force rapid rising in time.
Preferably under the situation on the prism facets surface that above-mentioned surface protection film is used to protect prismatic lens, be fitted in this surface protection film on the above-mentioned prism facets and load 0.3N/cm in 70 ℃ atmosphere 2Load in the time of 24 hours, the prism vertex angle of above-mentioned prism facets in binding agent be absorbed in the degree of depth account for adhesive layer thickness more than 1% and be lower than 40%.
Thus, can guarantee suitable cohesive force, suppress prism effectively simultaneously and sustain damage.
Preferably under the situation of the prism facets that above-mentioned surface protection film is used to protect prismatic lens; this surface protection film is fitted on the above-mentioned prism facets and with the surface pressure of the opposite side of this prism facets side on during the prominence of diameter 400 μ m, high 12 μ m, the prism vertex angle of above-mentioned prism facets in above-mentioned adhesive layer be absorbed in the degree of depth account for above-mentioned adhesive layer thickness more than 1% and be lower than 100%.
Thus, can guarantee suitable cohesive force, suppress prism effectively simultaneously and sustain damage.
Preferably under the situation of the prism facets that above-mentioned surface protection film is used to protect prismatic lens, the surface roughness Ra of the outer surface of base material layer is that the center line average (ripple モ チ one Off mean height さ) of 0.7～2.0 μ m, percent ripple profile roughness is that 3 μ m average headway (ripple モ チ one Off Ping Jun Long さ) above and the percent ripple profile is that 350 μ m are above and below the 600 μ m.
Thus; can guarantee suitable cohesive force; simultaneously under the state of harshness; for example; particularly on the prism facets that this surface protection film is fitted in prismatic lens and with the surface of the opposite side of this prism facets side (promptly; the outer surface of surface protection film) presses under the situation of prominences such as so-called flake, still can be protected the concavo-convex top shape of prism portion.
Preferably above-mentioned surface protection film is used to protect the surface of diffusion barrier.
The effect of invention
Surface protection film of the present invention has excellent extensibility, and it is residual to prevent after being peeled off by adherend thickener to take place.
In addition, the surface protection film of one of embodiments of the present invention can be guaranteed suitable initial stage cohesive force, and the bonding deterioration is inhibited.
In addition; the surface protection film of one of embodiments of the present invention is under the state of harshness; for example; particularly on the prism facets that this surface protection film is fitted in prismatic lens and with the surface of the opposite side of this prism facets side (promptly; the outer surface of surface protection film) presses under the situation of prominences such as so-called flake, still can be protected the concavo-convex top shape of prism portion.
Description of drawings
Fig. 1 is a mode chart, shows the ripple of the outer surface of base material layer.
Fig. 2 is the stereographic map of prismatic lens, and this prismatic lens has used the surface protection film of one of embodiments of the present invention.
The surface protection film that Fig. 3 shows one of embodiments of the present invention is fitted on the prismatic lens and the structure that obtains.
Nomenclature
1 prismatic lens
2
3 lens sections (prism)
The top of 3a lens section (prism vertex angle)
4 the 1st surface protection films
5 base material layers
6 adhesive layers
7 the 2nd surface protection films
Embodiment
The definition of the symbol in＜this specification sheets 〉
Under the situation that does not have special record, the symbol "～" that is used to represent numerical range that uses in this specification sheets represents to comprise in this numerical range two end value.
In this manual, " containing ratio " of the described polymer repeat unit that in technical terms " the unitary containing ratio of aromatic series alkenyl compound " etc., uses, weight ratio when expression is scaled its monomer of originating with repeating unit, promptly, the monomeric weight that above-mentioned repeating unit is originated shared ratio (weight %) in being used to form the whole monomeric gross weight of above-mentioned polymkeric substance, the just content of aromatic series alkenyl compound [alkenyl aromatic compound content] in the polymkeric substance.Wherein, " be used to form the whole monomeric gross weight of above-mentioned polymkeric substance " and be approximately the weight of above-mentioned polymkeric substance.In addition, similarly, " containing ratio " of the described polymer blocks repeating unit among the present invention, weight ratio when expression is scaled its monomer of originating with repeating unit, that is the above-mentioned repeating unit monomeric weight of originating shared ratio (weight %) in being used to form the whole monomeric gross weight of above-mentioned polymer blocks.Wherein, " be used to form the whole monomeric gross weight of above-mentioned polymer blocks " and be approximately the weight of above-mentioned polymer blocks.
In this manual, described " containing ratio of ethylene linkage " representative be: adopt ultra-red absorption spectrometry, by infrared spectroscopy (Morero ' s method) calculate 1,2-ethylene linkage and 3, total containing ratio of 4-ethylene linkage.
＜adhesive composition 〉
Contain following polymkeric substance (i) and following polymkeric substance in the adhesive composition of the present invention (ii).
In this manual, " polymkeric substance (i) " comprises following polymer blocks A and following polymer blocks B, and have general formula [A-B] n (in the formula, A representation polymer block A, B representation polymer B block, n represents integer 1～3) shown in multipolymer (I) or its hydrogenation products of structure.
In this manual, " polymkeric substance (ii) " is to comprise following polymer blocks A and following polymer blocks B, and have general formula A-B-A (the symbol implication in the formula is the same) or general formula (A-B) x-Y (in the formula, x represents the integer more than 2, Y represents the coupling agent residue, and the implication of other symbol is the same) shown in multipolymer (II) or its hydrogenation products of structure.
Need to prove, in this manual, also will contain above-mentioned polymkeric substance (i) sometimes and above-mentioned polymkeric substance composition (ii) abbreviates " copolymer compositions " as.
In adhesive composition of the present invention, above-mentioned polymkeric substance (i) and the above-mentioned polymkeric substance unitary total containing ratio of aromatic series alkenyl compound in (ii) is 30～50 weight %,
The weight ratio of the total amount of the total amount of the weight ratio of the total amount of the total amount of contained polymer blocks A and polymer blocks B and above-mentioned polymkeric substance contained polymer blocks A in (ii) and polymer blocks B is respectively in 5: 95～25: 75 scope in the above-mentioned polymkeric substance (i).
In this manual, " polymer blocks A " has a successive aromatic series alkenyl compound unit, and based on the polymer blocks of aromatic series alkenyl compound unit.
In this manual, " polymer blocks B " is that randomly to contain conjugated diene unit and aromatic series alkenyl compound unit and the unitary containing ratio of aromatic series alkenyl compound (St (b)) be aromatic series alkenyl-conjugated diene copolymer block of 10～35 weight %.
＜polymer blocks A 〉
As mentioned above, " polymer blocks A " has a successive aromatic series alkenyl compound unit, and based on the polymer blocks of aromatic series alkenyl compound unit.
Described " aromatic series alkenyl compound unit " is meant the repeating unit that comes from the aromatic series alkenyl compound.As " aromatic series alkenyl compound ", for example can enumerate: vinylbenzene, t-butyl styrene, alpha-methyl styrene, p-methylstyrene, ethyl styrene, Vinylstyrene, 1,1-diphenylethlene, vinyl naphthalene, vinyl anthracene, N, the N-diethyl is to amino-ethyl vinylbenzene and vinyl pyridine etc.Wherein, be easy to the viewpoint obtained from industrial from raw material, " aromatic series alkenyl compound unit " is preferably styrene units.
" polymer blocks A " must have with aromatic series alkenyl compound unit is the structure of main repeating unit.Particularly, the aromatic series alkenyl compound unit containing ratio among the polymer blocks A is more than the 80 weight %.By aromatic series alkenyl compound unit containing ratio is increased to more than the 80 weight %, the thermoplasticity of adhesive composition is improved, and the advantage of utilizing again of easier realization adhesive composition is arranged.As content can be in the scope that is lower than 20 weight % the repeating unit except that aromatic series alkenyl compound unit, can enumerate come from can with the repeating unit of the compound of aromatic series alkenyl compound copolymerization, for example come from conjugated diene compound or come from the repeating unit of (methyl) acrylic compound.Wherein preferred 1,3-butadiene, isoprene are because they and aromatic series alkenyl compound have high copolymerization.
＜polymer blocks B 〉
As mentioned above, " polymer blocks B " randomly contains conjugated diene unit and the unitary aromatic series alkenyl of aromatic series alkenyl compound-conjugated diene copolymer block, wherein, the unitary containing ratio of aromatic series alkenyl compound (St (b)) is 10～35 weight %.
Constitute described " the conjugated diene compound unit " of " polymer blocks B ", be meant the repeating unit that comes from conjugated diene compound.As " conjugated diene compound ", for example can enumerate: 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-divinyl, 1,3-pentadiene, 2-methyl isophthalic acid, 3-octadiene, 1,3-hexadiene, 1,3-cyclohexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, myrcene and chloroprene etc.Wherein, be easy to the reason obtained from industrial based on polymerisation reactivity height, raw material, " conjugated diene compound unit " is preferably at least a kind of repeating unit that is selected from 1,3-butadiene unit and the isoprene unit.
" polymer blocks B " must have with the conjugated diene compound unit is the structure of main repeating unit.In order to bring into play effect of the present invention, preferred conjugated diene compound unit containing ratio is in the scope of 65～90 weight %.
In addition, in order to obtain effect of the present invention, must make aromatic series alkenyl compound unit containing ratio (St (b)) in " polymer blocks B " in the scope of 10～35 weight %, preferably in the scope of 13～33 weight %, more preferably in the scope of 16～30 weight %.When aromatic series alkenyl compound unit containing ratio is lower than 10 weight %, may cause extensibility variation (heavy ㄑ), operability bad.On the other hand, when aromatic series alkenyl compound unit containing ratio surpasses 35 weight %, may cause the flexibility variation of adhesive composition, can't guarantee sufficient cohesive force, and cohesive force be important for surface protection film fully.
Need to prove, in the scope of not destroying effect of the present invention, also can contain other repeating unit except that conjugated diene compound unit and aromatic series alkenyl compound unit in " polymer blocks B ".
In addition, in order to obtain effect of the present invention, the ethylene linkage containing ratio in " polymer blocks B " is preferably in 50～90% scope, more preferably in 60～80% scope.In addition, make the ethylene linkage containing ratio, following advantage is arranged: can constitute the adhesive composition that viscosity (tuck) and cohesive force have excellent balance more than 50%.
＜multipolymer (I) 〉
" multipolymer (I) " contains following polymer blocks A and following polymer blocks B, and has the multipolymer of structure shown in general formula [A-B] n (in the formula, A representation polymer block A, B representation polymer B block, n represents integer 1～3).
Represent integer 1～3 as can be known by " n ",, can enumerate for example A-B, A-B-A-B and the represented structure of A-B-A-B-A-B as " structure shown in formula [A-B] n ".In these segmented copolymers, A and B repeating unit separately can be the same or different.
In order to have given play to the effect of polymer blocks B effectively, in structure shown in [A-B] n, preferred terminal polymer blocks B accounts in whole multipolymer more than the 2 weight %.Need to prove, even the end of copolymer segment (I) has-structure of A, so long as containing ratio proportion in whole multipolymer (I) of terminal polymer blocks A is lower than under the situation of 2 weight %, also can have given play to end and be the identical effect of multipolymer of polymer blocks B.That is, can think that in fact said structure is the terminal structure of polymer blocks B that is.
N is necessary for integer 1～3.By making n in this scope, can obtain the favorable industrial productivity.Need to prove that in order to reach the purpose that improves the cohesive force and the strength of materials, n more preferably 1～2, especially is preferably 1.That is,, especially be preferably segmented copolymer with structure shown in the general formula A-B as " multipolymer " with structure shown in general formula [A-B] n.
The unitary containing ratio of aromatic series alkenyl compound is preferably in the scope of 30～50 weight, more preferably in the scope of 33～45 weight % in multipolymer (I) or its hydrogenation products (polymkeric substance (i)).Have suitable confining force concurrently and to by the tracing ability of adherend concave-convex surface and adhesive composition by making the unitary containing ratio of aromatic series alkenyl compound in this scope, can constituting with excellent extensibility.
Molecular weight for polymkeric substance (i) does not have particular restriction, and preferably its weight-average molecular weight is 30,000～500,000, and more preferably 80,000～300,000, be preferably 100,000～200,000 especially.By making weight-average molecular weight in 30,000～500,000 scope, can realize polymkeric substance (i) and comprise polymkeric substance (i) and the copolymer compositions of multipolymer (II) or its hydrogenation products (polymkeric substance (ii)) carries out industrial production easily.Weight-average molecular weight is lower than at 30,000 o'clock, polymkeric substance is being carried out in desolventizing, the exsiccant step, may cause polymkeric substance adhering on producing apparatus etc., and then causes the industrial production of polymkeric substance (i) difficulty that becomes.On the other hand, weight-average molecular weight can cause its hot melt property, the solvability variation in solvent, thereby may make the difficulty that become by the processing of adherend 500,000 when above.
In order to obtain excellent thermotolerance and weathering resistance, the hydrogenation products of preferred copolymer (I) is for being hydrogenated to the resulting hydrogenation products of saturated bond by hydrogenation with unsaturated link(age), and the two keys that wherein derive from conjugate diene monomer are more than 80%, preferred position is more than 90%, more preferably more than 95%.
Need to prove that the implication of the ratio of the hydrogenation in this specification sheets (hydrogenation rate) is as follows: use the tetracol phenixin as solvent, by under the 270MHz 1The hydrogenation rate that the H-NMR spectrogram calculates.
Polymkeric substance (i) can use (a kind) separately, also can will be used in combination more than 2 kinds.
＜multipolymer (II) 〉
" multipolymer (II) " contains following polymer blocks A and following polymer blocks B, and have general formula A-B-A (implication of symbol is the same in the formula) or general formula (A-B) x-Y (in the formula, x represents the integer more than 2, and Y represents the coupling agent residue, and the implication of other symbol is the same.) shown in the multipolymer of structure.
By above-mentioned general formula as can be known, whole molecular end of multipolymer (II) have polymer blocks A.
Preferred terminal polymer blocks A accounts for more than the 2 weight % in whole multipolymer (II).This is in order to have given play to the effect of polymer blocks A effectively.Need to prove, even the end of copolymer segment (II) has-structure of B, so long as containing ratio proportion in whole multipolymer (II) of terminal polymer blocks B is lower than 2 weight %, also can have given play to end and be the identical effect of multipolymer of polymer blocks A.That is, can think that in fact said structure is the terminal structure of polymer blocks A that is.
In other words, having the multipolymer of structure shown in general formula (A-B) x-Y (in the formula, x represents the integer more than 2, and Y represents the coupling agent residue, and the implication of other symbol is the same) has by Y multipolymer (I) is coupled at the structure that obtains together.Therefore, from the viewpoint of industry since when multipolymer (II) be under the situation of (A-B) x-Y, can utilize identical reactor to synthesize the mixture of (I), (II), so preferred copolymer (II) is a structure shown in general formula (A-B) x-Y.X is 3 when above, and this multipolymer is so-called star polymer.Consider and when making this multipolymer, to suppress the generation of side reaction and the rerum natura of this multipolymer is controlled that preferred x is 2～4.
In addition, based on the identical reason of polymkeric substance (i), for multipolymer (II) or its hydrogenation products (polymkeric substance is (ii)), the also preferred unitary containing ratio of its aromatic series alkenyl compound in the scope of 30～50 weight %, 33～45 weight % more preferably.
In order to obtain excellent thermotolerance and weathering resistance, preferred polymers is (ii) for being hydrogenated to the resulting hydrogenation products of saturated bond by hydrogenation with unsaturated link(age), and the two keys that wherein derive from conjugate diene monomer be more than 80%, be preferably more than 90%, more preferably more than 95%.
There is no particular restriction for polymkeric substance molecular weight (ii), preferably its weight-average molecular weight is 50,000～500,000, more preferably 50,000～300,000.By making weight-average molecular weight in 50,000～500,000 scope, can realize that polymkeric substance (ii) and comprise polymkeric substance (i) and polymkeric substance copolymer compositions (ii) carries out industrial production easily.Weight-average molecular weight was carried out polymkeric substance in desolventizing, the exsiccant step less than 30,000 o'clock, may cause polymkeric substance adhering on producing apparatus etc., and then caused the industrial production of multipolymer (II) or its hydrogenation products difficulty that becomes.On the other hand, weight-average molecular weight can cause its hot melt property, the solvability variation in solvent 500,000 when above, may make the difficulty that become by the processing of adherend.
Polymkeric substance (ii) can use (a kind) separately, also can will be used in combination more than 2 kinds.
＜copolymer compositions 〉
As mentioned above, adhesive composition of the present invention is to contain to comprise polymkeric substance (i) and the polymkeric substance copolymer compositions (ii) adhesive composition as its constituent.In this copolymer compositions, polymkeric substance (i) and polymkeric substance weight ratio (ii) must be in 90: 10～10: 90 scopes.Contain the above polymkeric substance (i) of 10 weight parts in polymkeric substance (i) and polymkeric substance total amount 100 weight parts (ii) by making, can give play to following ideal effect: can effectively prevent adhesive layer from broken away from (Ga り on the floating I) by the adherend surface thus the unfavorable condition (floating (floating I)) that causes film to be peeled off.On the other hand, contain the above polymkeric substance of 10 weight parts in polymkeric substance (i) and polymkeric substance total amount 100 weight parts (ii) (ii) by making, can give play to following ideal effect: with film from by the adherend sur-face peeling time, can effectively prevent from polluted by the unfavorable condition on adherend surface (thickener is residual) by the adherend surface because of glue residue.
For prevent more effectively adhesive layer float or thickener residual, preferably make polymkeric substance (i) and polymkeric substance weight ratio (ii) in 50: 50～15: 85 scope.
In order to have given play to effect of the present invention, the weight ratio of total amount that must make the total amount of above-mentioned polymkeric substance (i) and above-mentioned polymkeric substance contained polymer blocks A in (ii) and polymer blocks B is in 5: 95～25: 75 scope.In addition, by containing the polymer blocks A more than 5 weight parts in total amount 100 weight parts that make polymer blocks A and polymer blocks B, can give play to following ideal effect: can give suitable confining force for formed adhesive layer.On the other hand; by containing the polymer blocks B more than 75 weight parts in total amount 100 weight parts that make polymer blocks A and polymer blocks B; can give play to following ideal effect: formed adhesive layer is for being demonstrated good tracing ability by the concavo-convex of adherend surface, thereby can protect effectively by the adherend surface.The weight ratio of total amount that preferably makes the total amount of polymer blocks A and polymer blocks B is in 5: 95～25: 75 scope, more preferably in 7: 93～23: 77 scope, especially preferably in 10: 90～21: 79 scope.
＜surface protection film 〉
The adhesive layer that surface protection film of the present invention has base material layer and formed by the adhesive composition of the present invention of above-mentioned explanation.
Preferred above-mentioned adhesive layer is stacked on the side surface of above-mentioned base material layer.
＜base material layer 〉
As above-mentioned base material layer, be preferably the polyolefin substrate material layer.
As this " polyolefine ", for example can enumerate: new LDPE (film grade), medium-density polyethylene, high density polyethylene(HDPE), linear low density polyethylene, ethene-alpha-olefin copolymer, ethylene-ethyl acrylate copolymer, vinyl-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, the positive butyl ester multipolymer of ethylene-acrylic acid, and polypropylene (homopolymer, random copolymers, segmented copolymer) etc.
These polyolefine can use separately, also can will be used in combination more than 2 kinds.In addition, " polyolefine " can be to have substituent polyolefine, can also be added with polyolefine resin in addition.In addition, can be added with the end material of the polyolefin substrate material layer that in the manufacturing processed of surface protection film, produces or the end material of surface protection film.
Base material layer can be an individual layer, also can be to have to form the different layers of multilayered structure more than 2 kinds.
Can suitably adjust the thickness of base material layer according to purposes of surface protection film etc.Usually be preferably set to the thickness about 10～100 μ m.
With regard to the outer surface of this base material layer (promptly, the surface of an opposite side with the adhesive layer side), preferably its surface roughness Ra is that the center line average of 0.7～2.0 μ m, percent ripple profile roughness is that 3 μ m average headway above and the percent ripple profile is that 350 μ m are above and below the 600 μ m.
Thus; even when the surface protection film with present embodiment is fitted in the surface of prismatic lens and carries out the lamination preservation; also be difficult for the lens section (prism) of prismatic lens is caused damage, therefore be fit to the purposes that surface protection film with present embodiment is used to protect the prism facets of prismatic lens.
Particularly; can think: the surfaceness at the back side by making this base material layer, the center line average of percent ripple profile roughness, and the average headway of percent ripple profile in above-mentioned specified range; even when the prismatic lens that multi-disc is fitted with surface protection film carries out the lamination preservation; there is the small foreign matter of sneaking into; also can make this small sneak into the trough place that foreign matter enters into external waviness; therefore; compare with the situation of surface smoothing, can reduce the stress on the lens section that concentrates on prismatic lens.
Need to prove that described " surface roughness Ra " in this specification sheets is by JIS B0601:2001 regulation " arithmetical mean height ".The center line average W of percent ripple profile roughness is the mean value of the Wj in the mode chart (Fig. 2) of the ripple that shows the polyolefin substrate material surface, and the average headway AW of percent ripple profile is the mean value of Awj, and they are obtained by following formula respectively.
[mathematical expression 1]
The average headway AW of percent ripple profile
AW = 1 n Σ i = 1 n AW i
The average headway W of percent ripple profile
W = 1 m Σ j = 1 m W j
Described " average headway of percent ripple profile " in this specification sheets reaches " center line average of percent ripple profile roughness " and reaches " center line average of the profilograph factor " by JIS B0601:2001 regulation " mean length of the profilograph factor " respectively.
＜adhesive layer 〉
Above-mentioned adhesive layer is formed by adhesive composition of the present invention.In this adhesive composition, except above-mentioned polymkeric substance (i) and above-mentioned polymkeric substance (ii), can also contain tackifier, styrenic block strengthening agent, tenderizer, oxidation inhibitor, photostabilizer, UV light absorber, weighting agent, pigment, bonding as required and suitably and worsen and prevent known additives such as agent, olefine kind resin, silicone based polymkeric substance, propylene liquid acid copolymer, phosphate compounds.
As the tackifier that use among the present invention, can use for example rosin based resins such as petroleum resinoids such as aliphatic category multipolymer, aromatic series analog copolymer, aliphatic/aromatic analog copolymer, alicyclic analog copolymer, coumarone-indene resinoid, terpenoid resin, terpene phenolic resinoid, polymerized rosin, (alkyl) phenolic resin, xylene resin or their hydride etc. can be used to the tackifier of binding agent usually, there is no particular restriction.More preferably using softening temperature is 90～140 ℃ tackifier.These tackifier can use separately, also can will be used in combination more than 2 kinds.Wherein, in order to improve separability and weathering resistance etc., more preferably use the tackifier of hydrogenation class.In addition, also can use the commercially available tackifier of the blend that forms with olefin resin.
Described tackifier among the present invention are meant, the soft chain segment that obtains behind hydrogenation with conjugated diene in the aromatic series alkenyl segmented copolymer or this conjugated diene, are that rubber layer is compatible, and the additive that can be controlled cohesive force.
Wherein, described " compatible " refers to following state: compare with the tan δ peak temperature of copolymer compositions, demonstrate different tan δ peak temperatures by tackifier being coupled to the title complex that obtains in the copolymer compositions.Need to prove that described " tan δ peak temperature " in this specification sheets is meant the temperature when tan δ reaches maximum.
The styrenic block strengthening agent can be used for suppressing the bonding deterioration of adhesive layer.
With regard to the styrenic block strengthening agent that uses among the present invention, as the monomer whose unit, for example can enumerate: vinylbenzene and alpha-methyl styrene, p-methylstyrene, to chloro-styrene, 1-chloro-4-methyl-benzene, t-butyl styrene, to styrene compounds such as ethyl styrene, Vinylstyrenes.These styrenic block strengthening agents may be used alone, or two or more kinds may be used in combination.That is to say that the styrenic block strengthening agent can be obtained through polymerization by above-mentioned monomer.For for the multipolymer that monomer forms more than 2 kinds, can be segmented copolymer, also can be random copolymers.Wherein, the styrenic block strengthening agent is preferably the polymkeric substance with softening temperature above about 100 ℃, more preferably has the softening temperature more than 150 ℃.Particularly, the styrenic block strengthening agent of the commodity that preferably use Eastman Chemical company to make " ENDEX155 " (155 ℃ of softening temperatures) by name, " ENDEX160 " (160 ℃ of softening temperatures) etc.
Tenderizer is effective for improving cohesive force usually.As tenderizer, can use for example low-molecular-weight diolefinic polymer, polyisobutene, hydrogenated polyisoprene, hydrogenated butadiene polymer, paraffinic process oil, naphthalene generic operation oil, aromatic series generic operation oil, Viscotrol C, Yatall MA, natural oil, liquid polyisobutene resin, polybutene or their hydride etc. can be used to the tenderizer of binding agent usually, there is no particular restriction.These tenderizers can use separately, also can will be used in combination more than 2 kinds.
As oxidation inhibitor, there is no particular restriction, for example can enumerate: phenols (single phenols, bisphenols, polymer phenols), sulphur class, normally used oxidation inhibitor such as Phosphorus.
As photostabilizer, can enumerate hindered amine compound.
As UV light absorber, there is no particular restriction, for example can enumerate: salicylic acid, benzophenone, benzotriazole category, cyanoacrylate etc.
As weighting agent, for example can enumerate: lime carbonate, magnesiumcarbonate, silicon-dioxide, zinc oxide, titanium oxide etc.
Deterioration prevents agent as bonding, the chain alkyl grafts, soybean oil modified alkyd that can enumerate fatty amide, polymine are (for example, Arakawa Chemical Industries, Ltd. makes, commodity " ARAKYD 251 " by name etc.), tall oil modified Synolac (for example, Arakawa Chemical Industries, Ltd. makes, commodity " ARAKYD 6300 " by name etc.) etc.
Above-mentioned additive can use separately, also can will be used in combination more than 2 kinds.
Thickness for adhesive layer there is no particular restriction, for example is generally about 0.5～50 μ m, is preferably 1～40 μ m, 2～30 μ m more preferably.
In one of preferred implementation of surface protection film of the present invention,
Above-mentioned base material layer is the polyolefin substrate material layer,
Also contain tackifier in the above-mentioned adhesive composition,
And when-50 ℃～80 ℃ dynamic viscoelastics to above-mentioned adhesive layer were measured, the temperature when gained tan δ reaches maximum was-10 ℃～20 ℃.
Wherein, as tackifier, can use the above-mentioned material of enumerating etc.
With regard to the consumption of tackifier, be preferably and prevent that surface protection film from the residual amount of thickener taking place when being peeled off by adherend.For example; under situation about using with surface protection film as prismatic lens; with respect to the rubber resin composition [above-mentioned polymkeric substance (i) and above-mentioned polymkeric substance (ii) (below; also they are referred to as aromatic series alkenyl segmented copolymer)] 100 weight parts; the cooperation ratio of tackifier is preferably 5～50 weight parts, more preferably 10～40 weight parts.
When-50 ℃～80 ℃ dynamic viscoelastics to adhesive layer were measured, the peak temperature of gained tan δ was preferably-10 ℃～20 ℃ scope.For this tan δ peak temperature, can pass through the rubber resin composition in the adhesive layer, for example, cooperation ratio of the unitary containing ratio scope of aromatic series alkenyl compound in the random block of aromatic series alkenyl segmented copolymer, tackifier etc. is adjusted, perhaps under the situation of softening temperature etc. employed tackifier are selected considering, thus tan δ peak temperature is adjusted to ideal range.
Here, tan δ is meant, in-50 ℃～80 ℃ mensuration temperature range, under the following conditions the loss tangent (=out-of-phase modulus/storage modulus) in the dynamic viscoelastic spectrum of measuring.
Visco-elasticity spectrometer: trade(brand)name " DVA-200 " (manufacturing of IT instrumentation Heat ﹠ Control Pty Ltd.)
The sample size of adhesive layer: thick about 1.5mm * 5mm * 10mm
Set heat-up rate: 6 ℃/minute
Measure frequency: 10Hz
Mode determination: shear
Tan δ peak temperature by making said determination in conjunction with the effect of tackifier, can make the cohesive force of adhesive layer be improved in this scope.Thus, even at the back side of the base material layer that adhesive layer is bonded in surface protection film and make under the situation of coiling body, also can easily surface protection film be peeled off from the back side of base material layer.That is, can be successfully with the coiling body uncoiling.And, even be applied to the surface have concavo-convex by the situation of adherend under, also can realize its concavo-convex following, and then realize effectively by the surface protection of adherend.
In another preferred implementation of surface protection film of the present invention,
Above-mentioned base material layer is the polyolefin substrate material layer,
Also contain tackifier and styrenic block strengthening agent in the above-mentioned adhesive composition, and above-mentioned polymkeric substance (i), above-mentioned polymkeric substance (ii) reach, and the unitary weight of aromatic series alkenyl compound shared ratio (the unitary containing ratio of aromatic series alkenyl compound) in adhesive layer weight is 20～50 weight % in the styrenic block strengthening agent.When this ratio is lower than 20 weight %, may cause cohesive force sharply to rise in time easily, when this ratio surpasses 50 weight %, can't obtain high cohesive force sometimes.
Wherein, as tackifier, can use the above-mentioned material of enumerating etc.
With regard to the consumption of tackifier, be preferably and prevent that surface protection film from the residual amount of thickener taking place when being peeled off by adherend.For example, with respect to rubber resin composition (aromatic series alkenyl segmented copolymer) 100 weight parts, the content of tackifier is preferably about 5 weight parts～50 weight parts, more preferably about 10 weight parts～40 weight parts.
In addition,,, can use the above-mentioned material of enumerating etc. here as the styrenic block strengthening agent.
For example,, preferably cooperate about 40 weight parts following styrenic block strengthening agent with respect to aromatic series alkenyl segmented copolymer 100 weight parts, more preferably cooperate about 30 weight parts below.In addition, need only use level greater than 0 weight part, but preferably cooperate more than 1 weight part.
By using the styrenic block strengthening agent, can realize with the styrene copolymer block in mutually compatible of vinylbenzene (St), the cohesive force of adhesive layer is improved.Thus, the agglutinating surface protection film easily can be peeled off from the polyolefin substrate material layer back side, thereby successfully coiling body be carried out uncoiling.In addition, can prevent to realize peeling off with less power in that thickener is taken place when being peeled off by adherend surface protection film is residual.
In surface protection film of the present invention, the storage modulus G ' of above-mentioned adhesive layer under 70 ℃ is preferably 4.5 * 10 5Pa～6.0 * 10 5Pa.
By making storage modulus G ' is 4.5 * 10 5More than the Pa,, also can worsen and be suppressed unfavorable bonding even under hot environment; On the other hand, be 6.0 * 10 by making storage modulus G ' 5Below the Pa, can obtain suitable cohesive force.
For the storage modulus G ' to binding agent adjusts; can adjust the unitary containing ratio of aromatic series alkenyl compound of adhesive layer in the surface protection film of the present invention, the cohesive force that makes above-mentioned aromatic series alkenyl segmented copolymer is in the suitable scope.Can adjust described containing ratio by following method: use to have suitable containing of aromatic series alkenyl monomer composition of the proportional aromatic series alkenyl segmented copolymer that derives from; And/or, in adhesive layer, add the styrenic block strengthening agent.The styrenic block strengthening agent is the additive that carries out reinforcement mutually in order to the island of the formed island structure of aromatic series alkenyl segmented copolymer, has and the compatible character in territory that is formed by aromatic series alkenyl segmented copolymer.
With regard to the usage quantity of this styrenic block strengthening agent, with respect to aromatic series alkenyl segmented copolymer 100 weight parts, be preferably below 40 weight parts, more preferably below 30 weight parts.If this usage quantity is too much, also there is the hidden danger of mobile variation when carrying out extrusion molding simultaneously in cohesive force deficiency then.Lower limit for this usage quantity does not have particular restriction, as mentioned above, in the time need not adjusting the unitary containing ratio of aromatic series alkenyl compound, then need not add the styrenic block strengthening agent, but preferably add more than 1 weight part.
In another preferred implementation of surface protection film of the present invention, it is used to protect the prism facets surface of prismatic lens, wherein, this surface protection film of on described prism facets, fitting, and in 70 ℃ atmosphere load 0.3N/cm 2Load in the time of 24 hours, the prism vertex angle of above-mentioned prism facets in binding agent be absorbed in the degree of depth account for adhesive layer thickness more than 1% and be lower than 40%.
The described degree of depth that is absorbed in can be measured by following method.
Utilize the pressing rubber rollers of 2kg, under the environment of 23 ℃ of room temperatures and relative humidity 50%, the speed of dividing with 300mm/ fits in surface protection film to be measured on the surface of prismatic lens respectively.As prismatic lens, use the prismatic lens of prismatical width between centers 50 μ m, high 25 μ m.Then, be fitted with the prismatic lens of surface protection film with polycarbonate plate (thick 2mm) clamping, and apply 0.3N/cm 2Pressure, in 70 ℃ environment, leaving standstill 24 hours under this state.Then, with the peel angles of 180 degree surface protection film is peeled off, and utilized laser microscope that the adhesive layer surface is observed, lens section (prism) drift angle of measuring prismatic lens is absorbed in the degree of depth in adhesive layer.
By make this be absorbed in the degree of depth account for adhesive layer thickness more than 1% and be lower than 40%, can bonding rerum naturas such as cohesive force not caused under the dysgenic situation, worsen for the bonding in high temperature (for example 70 ℃) environment and suppressed.
For example, can be by the storage modulus G ' of above-mentioned adhesive layer under 70 ℃ be controlled in the above-mentioned preferable range, realize making this be absorbed in the degree of depth account for adhesive layer thickness more than 1% and be lower than 40%.
In another preferred implementation of surface protection film of the present invention; it is used to protect the prism facets surface of prismatic lens; wherein; this surface protection film of applying on described prism facets; and with the surface pressure of the opposite side of this prism facets side on during the prominence of diameter 400 μ m, high 12 μ m, the prism vertex angle of above-mentioned prism facets in above-mentioned adhesive layer be absorbed in the degree of depth account for above-mentioned adhesive layer thickness more than 1% and be lower than 100%.
Wherein, the optimum condition that presses described prominence is: in 50 ℃ atmosphere, with 0.8N/cm 2Power exerted pressure 24 hours.
In addition, even that the diameter of above-mentioned prominence is 400 μ m is following, highly be the situations below the 12 μ m, for the above-mentioned upper limit that is absorbed in the degree of depth, is predicted as too and is lower than 100% of adhesive layer thickness.
Therefore; with surface protection film of the present invention be fitted on the prismatic lens, another surface protection film of fitting on level and smooth sheet surface; and incite somebody to action when for example tens of prismatic lens laminations are preserved; even have FE on the surface protection film on level and smooth sheet surface, sneak into prominences such as foreign matter; because the unitary containing ratio of aromatic series alkenyl compound of binding agent is set to appropriate amount in the adhesive layer of surface protection film; therefore; can make the adhesive layer hardening, thereby suppress lens section excessively being absorbed in the adhesive layer of surface protection film of prismatic lens effectively.So, the lens section surface (prism facets) of prismatic lens is difficult for producing damage.
Mainly by the unitary containing ratio of aromatic series alkenyl compound in the aromatic series alkenyl segmented copolymer is controlled in 30～50 weight % scopes, realize making above-mentioned be absorbed in the degree of depth account for adhesive layer thickness more than 1% and be lower than 100%.When this containing ratio was lower than 30 weight %, the cohesive force of binding agent was low, therefore, possibly can't be suppressed the be absorbed in degree of depth of prism lens in adhesive layer.On the contrary, when this containing ratio surpassed 50 weight %, the cohesive force of binding agent was too high, therefore, may cause the prism lens to be difficult for being absorbed in to adhesive layer, and it is low that cohesive force became, and can't use as protective membrane.
Use the lens section of the prismatic lens of surface protection film of the present invention to have the prism shape that constitutes by triangular prism in fact.In this specification sheets, the face that will have the lens section of such prism shape is called prism facets.More specifically, as shown in Figure 2, prismatic lens 1 has following structure: the integrated lens section 3 that many rhizoma sparganic columns are arranged on a side surface of smooth sheet 2.Lens section 3 has the triangular prism shape in fact.And, closely be set up in parallel a plurality of lens sections 3 with connecting, each crest line of triangular prism is parallel to each other.The outside surface of the lens section 3 of this prism shape is protected by surface protection film of the present invention.
For example, shown in the sectional view of Fig. 3, on the part that is provided with lens section 3 of prismatic lens 1, be fitted with the 1st surface protection film 4 (surface protection film of the present invention).The 1st surface protection film 4 has base material layer 5, be arranged at the adhesive layer 6 on the side surface of base material layer 5, and fits from an above-mentioned side that is provided with a plurality of lens sections 3 of adhesive layer 6 sides and prismatic lens 1.Therefore, when fitting, surface protection film of the present invention contacts with a plurality of top 3a of the lens section 3 of rhizoma sparganic column.In addition, the shape of cross section of the lens section 3 of this triangular prism is a trilateral, but the side that this trilateral is preferably to be fixed on the sheet is two equilateral triangles on base.
On the other hand, on prismatic lens 1 and the tabular surface opposite side of a side that is provided with lens section 3, the 2nd surface protection film 7 of can fitting as required.There is flake (FE) on this surface protection film 7, when sneaking into prominences such as foreign matter, may becomes the ruined reason in top of lens section.
Need to prove that the described side in the prism shape of triangular prism is meant 3 sides of extending along its length of triangular prism.
For the ideal prismatic lens that uses surface protection film of the present invention; in fact; in a plurality of prisms of triangular prism; the distance of adjacent prisms, be that prismatical spacing is preferably about 10～1000 μ m; 10～500 μ m more preferably, but use surface protection film of the present invention not limited by this by adherend.
＜manufacture method 〉
Adhesive composition of the present invention prepares by following method: for example, come synthetic copolymer (I) and multipolymer (II) by block polymerization respectively, and with them with extra fine quality than mixing, then, carry out hydrogenation as required, obtain multipolymer (I) or its hydrogenation products, reach the mixture of multipolymer (II) or its hydrogenation products, and utilize method mixing commonly used to want the additive that cooperates as required, make adhesive composition of the present invention thus.
As hydrogenation catalyst, can use the compound of any metal in containing element periodictable Ib, IVb, Vb, VIb, VIIb, the VIII family metal.For example, can enumerate the compound that comprises Ti, V, Co, Ni, Zr, Ru, Rh, Pd, Hf, Re, Pt atom, more specifically, can enumerate: the metallocene compounds of Ti, Zr, Hf, Co, Ni, Rh, Ru etc., load has the loading type heterogeneous catalyst of metals such as pd, Ni, Pt, Rh, Ru on carriers such as carbon, silicon-dioxide, aluminum oxide, diatomite, alkaline gac.
Wherein, as the object lesson of metallocene compounds, can enumerate: have that 2 cyclopentadiene rings (Cp ring) or Cp ring hydrogen are replaced by alkyl and Kaminsky (Kaminski) catalyzer of the ligand that obtains, ansa type (ansa) metallocene catalyst, non-bridging semi metallocene catalyst, bridging semi-metallocene catalyst etc.
Specifically can enumerate: Japanese kokai publication hei 1-275605 communique, Japanese kokai publication hei 5-271326 communique, Japanese kokai publication hei 5-271325 communique, Japanese kokai publication hei 5-222115 communique, Japanese kokai publication hei 11-292924 communique, TOHKEMY 2000-37632 communique, Japanese kokai publication sho 59-133203 communique, Japanese kokai publication sho 63-5401 communique, Japanese kokai publication sho 62-218403 communique, Japanese kokai publication hei 7-90017 communique, Japanese Patent Publication 43-19960 communique, the catalyzer of putting down in writing in the Japanese Patent Publication 47-40473 communique.Above-mentioned various catalyzer can use a kind separately, also can will be used in combination more than 2 kinds.
Other manufacture method as adhesive composition of the present invention, have the situation of structure shown in above-mentioned general formula (A-B) x-Y (implication of symbol is the same in the formula) for multipolymer (II), adhesive composition of the present invention also can be made by following method (coupling method).Because coupling method can one pot of synthetic copolymer (I) or its hydrogenation products (polymkeric substance (i)) and multipolymer (II) or its hydrogenation products (polymkeric substance (ii)), therefore its manufacturing process is simple, cheap for manufacturing cost, and can come controlling polymers (i) and polymkeric substance ratio (ii) by the kind and the amount of coupling agent, consider from these aspects, preferably adopt coupling method.
Coupling method possesses following step:
The 1st step: the step of synthesizing multipolymer by block polymerization with [A-B] structure;
The 2nd step: utilize coupling agent Y-Z x(wherein, on behalf of coupling agent residue, " Z ", " Y " represent leavings group, " X " to represent the integer more than 2.) make above-mentioned part generation coupling with multipolymer of [A-B] structure, come synthetic have { [A-B] xThe step of the multipolymer of-Y} structure;
When desire obtains hydrogenation products, also possess
The 3rd step: by to above-mentioned multipolymer with [A-B] structure and above-mentionedly have { [A-B] xThe multipolymer of-Y} structure carries out hydrogenation, obtains to comprise the step of the copolymer compositions that passes through hydrogenant multipolymer (I) and multipolymer (II) respectively.
As " coupling agent ", for example can enumerate: halogenide such as dimethyl dichlorosilane (DMCS), dimethyldichlorosilane(DMCS), METHYL TRICHLORO SILANE, butyl trichlorosilane, tetrachloro silicane, ethylene dibromide, tin tetrachloride, butyl tin trichloride, germanium tetrachloride, two (Trichloromonosilane base) ethane; Epoxy compoundss such as epoxidised soybean oil; Carbonyl compound such as diethylene adipate, dimethyl adipate, dimethyl terephthalate (DMT), diethyl terephthalate; The polyvinyl compound of Vinylstyrene etc.; Polyisocyanates; Or the like.Wherein, industry is obtained and reactive high reason based on being easy to, preferable methyl dichlorosilane, dimethyldichlorosilane(DMCS), METHYL TRICHLORO SILANE, tetrachloro silicane.
Surface protection film of the present invention can be by following method manufacturing: for example, making body material sheet (base material layer) afterwards by extrusion molding, with the fused solution of above-mentioned adhesive composition or be dissolved with the solution coat of above-mentioned adhesive composition or sparge method on the body material sheet; Body material sheet that will obtain by blow moulding and the bonding sheet method of fitting maybe; Or utilization possesses the method for the T pattern of multilayer manifold with body material raw material and above-mentioned adhesive composition coextrusion.Wherein, preferably come out to make the method for surface protection film of the present invention by co-extrusion, this is because this method can access the multilayer tablet that is formed by base material layer and adhesive layer driving fit.The solution that it is pointed out that the fused solution of adhesive composition of the present invention or be dissolved with adhesive composition of the present invention also belongs to the category of adhesive composition of the present invention.
＜use
Surface protection film of the present invention has concavo-convex by adherend applicable to optical sheet, prismatic lens and diffusion barrier etc., but is not limited thereto, and for example can also be applied to the surface protection to the sheet of surface smoothing.
As constituting as by the material of the sheet of adherend, there is no particular determination, can enumerate resin, for example acrylic resin, polycarbonate etc. with light transmission.
Embodiment
Below, in conjunction with the embodiments surface protection film of the present invention is specifically described, but the present invention is not limited to following embodiment.
(synthesis example of copolymer compositions)
Polymer blocks A
Through adding hexanaphthene 500 mass parts, vinylbenzene 20 mass parts and tetrahydrofuran (THF) 5 mass parts through the dehydration degassing in the reaction vessel of nitrogen replacement, and begin temperature in polymerization and add n-Butyl Lithium 0.13 mass parts down for 40 ℃, polymerization heats up.
Polymer blocks B
After the polymerisation conversion of polymer A reaches 100% substantially, reaction solution is cooled to 15 ℃, then, add 1,3-butadiene 70 mass parts and vinylbenzene 10 mass parts, proceed the polymerization that heats up.
After polymerisation conversion reaches 100% substantially, add dimethyl dichlorosilane (DMCS) 0.06 mass parts, to carry out linked reaction as coupling agent.After linked reaction finishes,, carry out on one side placing in 10 minutes on one side with the pressure feed hydrogen of 0.4MPa (gauge pressure).The vinyl containing ratio of the polymkeric substance that part is taken out is 64%, weight-average molecular weight is about 110,000, the coupling rate is 60%.
Then, in reaction vessel, add diethyl aluminum chloride 0.03 mass parts and bicyclic pentadiene chlorination chaff oxygen base titanium 0.06 mass parts, stir.Under supply with pressing 80 ℃ of 0.7MPa (gauge pressure), temperature of reaction, hydrogen begins hydrogenation reaction, in the moment that the absorption of hydrogen finishes, make reaction soln be back to normal temperature, normal pressure, and from reaction vessel, discharge, thus, obtain the copolymer compositions (synthesis example 1 of table 1) that (ii) constitutes by polymkeric substance (i) and polymkeric substance.
Below, obtained the copolymer compositions (synthesis example 2～24 of table 1) that needs by same operation.The character of these copolymer compositions is as shown in table 1.
Need to prove that " St (A+B) " in the table 1, " St (B) ", " St (A) " reach " St (b) " and represent the numerical value that has as giving a definition respectively.In following definitions, described " all polymkeric substance " representation polymer (i) and polymkeric substance are (ii) all.
" St (A+B) " representative is the unitary containing ratio of aromatic series alkenyl compound in whole polymkeric substance, is the numerical value of representing with following formula.It is pointed out that this " St (A+B) " equals following " St (B) " and following " St (A) " sum.
Formula:
St (A+B)=(all unitary weight of aromatic series alkenyl compound in the polymkeric substance)/(all weight of the whole monomeric units in the polymkeric substance) * 100 (weight %)
The numerical value that " St (B) " representative is represented with following formula.
Formula:
St (B)=(all unitary weight of aromatic series alkenyl compound among the polymer blocks B)/(all weight of the whole monomeric units in the polymkeric substance) * 100 (weight %)
The numerical value that " St (A) " representative is represented with following formula.
Formula:
St (A)=(all unitary weight of aromatic series alkenyl compound among the polymer blocks A)/(all weight of the whole monomeric units in the polymkeric substance) * 100 (weight %)
" St (b) " representative unitary containing ratio of aromatic series alkenyl compound in polymer blocks B is the numerical value of representing with following formula.
Formula:
St (b)=(all unitary weight of aromatic series alkenyl compound among the polymer blocks B)/(all weight of the whole monomeric units among the polymer blocks B) * 100 (weight %)
In addition, the weight ratio of the total amount of the total amount of " A: B " the representation polymer block A in the table 1 and polymer blocks B.
In addition, in the table 1 " (i): (ii) " representation polymer (i) and polymkeric substance weight ratio (ii).
In addition, the containing ratio of conjugated diene unit in " conjugated diolefine containing ratio " the representation polymer B block in the table 1.
In addition, the containing ratio of ethylene linkage in " ethylene linkage containing ratio " the representation polymer B block in the table 1.
Figure BDA0000049723290000241
(embodiment 1～8, comparative example 1～7)
In each copolymer compositions (table 2) 100 weight part that utilizes above-mentioned each synthetic method to obtain, mix, obtain each adhesive composition as Alcon P100 (Arakawa Chemical Industries, Ltd.'s manufacturing) 30 weight parts of tackifier, as Irganox 1010 (manufacturing of Ciba Specialty Chemicals company) 1 weight part of oxidation inhibitor.Its composed as follows stating shown in the table 2.
Use polypropylene (J715M that Prime Polymer company makes) as body material; utilize T pattern method that body material and each adhesive composition are carried out the coextrusion shaping; thus, obtained being formed with adhesive layer by the base material layer of thick 34 μ m and thick 6 μ m through laminated integratedization and the embodiment 1～8 and the surface protection film of comparative example 1～7 and be wound on coiling body on the refill of 3 inches of internal diameters.
(evaluation)
Each surface protection film at utilizing aforesaid method to obtain has carried out the evaluation of following project.Its result is as shown in table 3.
(1) film-forming properties
The outward appearance of film forming each surface protection film is estimated to passing through above-mentioned coextrusion by visual inspection, and the situation note of no problem is done " zero " in appearance.
(2) initial stage cohesive force
Each surface protection film is fitted on the lens face with concavo-convex prismatic lens, and makes these surface protection films coat the lens face of described prismatic lens.As prismatic lens, sheet materials that prepared to make, prism pitch 50 μ m, high 25 μ m by the acrylic resin of thick 130 μ m.As laminating condition, in the environment of 23 ℃ of room temperatures and relative humidity 50%, use the pressing rubber rollers of 2kg to fit respectively with the speed that 300mm/ divides, and under this state, placed 30 minutes, then, the speed of dividing based on JIS Z0237 standard, with 300mm/ is measured the degree of 180 in 25mm width stripping strength.The direction of delaminate of this moment is prismatical crest line direction.With the stripping strength measured thus as the initial stage cohesive force.
(3) through the time cohesive force
In the environment of 23 ℃ of room temperatures and relative humidity 50%, the speed that the pressing rubber rollers of using 2kg is respectively divided with 300mm/ is fitted in each surface protection film on the surface that is used for the prismatic lens that (2) initial stage cohesive force estimates.Then, use polycarbonate plate (thick 2mm) clamping to be fitted with the prismatic lens of surface protection film, apply 6.0 * 10 -3The pressure of MPa, and in the environment of 60 ℃ and relative humidity 90%, placing 48 hours under this state.It is taken out in the room temperature, places after 30 minutes, the speed of dividing based on JIS Z0237 standard, with 300mm/ is measured the degree of 180 in 25mm width stripping strength.
With the stripping strength measured thus as through the time cohesive force, by following formula calculate through the time cohesive force with respect to the velocity of variation (bonding deterioration rate) of initial stage cohesive force.
Velocity of variation (bonding deterioration rate)=(through the time cohesive force/initial stage cohesive force) * 100
(4) expansion power
Coiling body to the 50mm width of each surface protection film of embodiment and comparative example carries out uncoiling, except changing uncoiling speed, based on JIS Z0237 standard, the uncoiling velocity determination that divides with 15m/ uncoiling power, and with this as expansion power.
Figure BDA0000049723290000271
[table 3]
Figure BDA0000049723290000281
＜criterion 〉
Cohesive force (initial stage)
Zero (very): more than the 0.1N/25mm
* (bad): be lower than 0.1N/25mm
Cohesive force (velocity of variation)
◎ (excellent): be lower than 200%
Zero (very): more than 200% and below 500%
* (bad): surpass 500%
Expansion power
◎ (excellent): be lower than 2.0N/50mm
More than zero (very): the 2.0N/50mm and below the 3.5N/50mm
* (bad): surpass 3.5N/50mm
(embodiment 9)
In copolymer compositions 100 weight parts of synthesis example 4, mix AlconP100 (Arakawa Chemical Industries, Ltd.'s manufacturing) 18 weight parts as tackifier, as Irganox1010 (manufacturing of Ciba Specialty Chemicals company) 1 weight part of oxidation inhibitor, as Tinuvin 326 (manufacturing of Ciba Specialty Chemicals company) 0.5 weight part of UV light absorber, and carry out mixingly, obtained adhesive composition thus.
Use polypropylene (Prime Polymer company makes J715M) as body material; utilize T pattern method that body material and adhesive composition are carried out the coextrusion shaping; thus, obtained being formed with coiling body on surface protection film that the adhesive layer by the base material layer of thick 34 μ m and thick 6 μ m obtains through laminated integratedization and the refill that is wound on 3 inches of internal diameters.
(embodiment 10,11,13, comparative example 8～10)
Ground as shown in table 4 hybrid adhesive composition, and obtained the coiling body of surface protection film according to the method identical with embodiment 9.
(embodiment 12)
In copolymer compositions 100 weight parts of synthesis example 7, mix the Clearon P125 (Network リ ア ロ Application P125) (Yasuhara Chemical company manufacturing) of 40 weight parts as tackifier; except using the adhesive composition obtain thus, obtained the coiling body of surface protection film according to the method identical with embodiment 9.
(evaluation)
Each surface protection film at utilizing aforesaid method to obtain has carried out the evaluation of following project.
Its result is as shown in table 5.
(1) tan δ peak temperature
(IT instrumentation Heat ﹠ Control Pty Ltd. makes to utilize dynamic viscoelastic spectrometry device, product type: DVA-200), with the frequency of 10Hz, 6 ℃/minute heat-up rate, in-50 ℃～80 ℃ scope, measured the visco-elasticity spectrogram of adhesive layer, and the temperature (tan δ peak temperature) when obtaining tan δ and reaching maximum.
(2) initial stage cohesive force
Each surface protection film of embodiment and comparative example is fitted on the lens face with concavo-convex prismatic lens, and makes these surface protection films coat the lens face of described prismatic lens.As prismatic lens, sheet materials that prepared to make, prism pitch 50 μ m, high 30 μ m by the acrylic resin of thick 130 μ m.As laminating condition, in the environment of 23 ℃ of room temperatures and relative humidity 50%, use the pressing rubber rollers of 2kg to fit respectively with the speed that 300mm/ divides, and under this state, placed 30 minutes, then, the speed of dividing based on the JISZ0237 standard, with 300mm/ is measured the degree of 180 in 25mm width stripping strength.The direction of delaminate of this moment is prismatical crest line direction.With the stripping strength measured thus as the initial stage cohesive force.
(3) expansion power
The wide coiling body of 50mm to each surface protection film of embodiment and comparative example carries out uncoiling, except changing uncoiling speed, based on JIS Z0237 standard, the uncoiling velocity determination that divides with 20m/ high speed uncoiling power, and with this as expansion power.
[table 4]
Figure BDA0000049723290000301
[table 5]
Figure BDA0000049723290000302
＜criterion 〉
The initial stage cohesive force
Zero (very): more than the 0.1N/25mm
* (bad): be lower than 0.1N/25mm
Expansion power
◎ (excellent): below the 2.5N/50mm
Zero (very): below the 3.5N/50mm
* (bad): surpass 3.5N/50mm
(embodiment 14)
Adhesive layer:
In copolymer compositions 100 weight parts of synthesis example 4, mix AlconP100 (Arakawa Chemical Industries, Ltd.'s manufacturing) 50 weight parts as tackifier, as ENDEX155 (manufacturing of Eastman Chemical company) 10 weight parts of styrenic block strengthening agent, as Irganox1010 (manufacturing of Ciba Specialty Chemicals company) 1 weight part of oxidation inhibitor, and carry out mixingly, obtained adhesive composition thus.
Base material layer:
Utilize T pattern method that body material (Prime Polymer company makes J715M) and the above-mentioned adhesive composition of being made by polypropylene that obtains carried out coextrusion; and will by the binding agent of the polypropylene matrix material layer of thick 34 μ m and thick 6 μ m through laminated integratedization and the surface protection bonding sheet be wound on the refill of 3 inches of internal diameters, thereby obtained coiling body.
(embodiment 15～19, comparative example 11～14)
Hybrid adhesive composition shown in following table 6, and obtained the coiling body of surface protection film according to the method identical with embodiment 14.
Need to prove that " St/ adhesive layer (the weight %) " in the table 6 represents the unitary gross weight of whole aromatic series alkenyl compounds in copolymer compositions and the styrenic block strengthening agent shared ratio (the unitary containing ratio of aromatic series alkenyl compound) in the weight of binding agent.In addition, " St/ adhesive layer (TF) (weight %) " represents the unitary gross weight of the whole aromatic series alkenyls shared ratio in the gross weight of copolymer compositions and styrenic block strengthening agent in copolymer compositions and the styrenic block strengthening agent.
(evaluation)
Each surface protection film at utilizing aforesaid method to obtain has carried out the evaluation of following project.Its result is as shown in table 7.
(1) tan δ peak temperature
(IT instrumentation Heat ﹠ Control Pty Ltd. makes to utilize dynamic viscoelastic spectrometry device, product type: DVA-200), with the frequency of 10Hz, 6 ℃/minute heat-up rate, in-50 ℃～80 ℃ scope, measured the visco-elasticity spectrogram of adhesive layer, and the temperature when obtaining tan δ and reaching maximum.
(2) initial stage cohesive force
Each surface protection film of embodiment and comparative example is fitted on the lens face with concavo-convex prismatic lens, and makes these surface protection films coat the lens face of described prismatic lens.As prismatic lens, sheet materials that prepared to make, prism pitch 50 μ m, high 30 μ m by the acrylic resin of thick 130 μ m.As laminating condition, in the environment of 23 ℃ of room temperatures and relative humidity 50%, use the pressing rubber rollers of 2kg to fit respectively with the speed that 300mm/ divides, and under this state, placed 30 minutes, then, the speed of dividing based on the JISZ0237 standard, with 300mm/ is measured the degree of 180 in 25mm width stripping strength.The direction of delaminate of this moment is prismatical crest line direction.With the stripping strength measured thus as the initial stage cohesive force.
(3) through the time cohesive force
In the environment of 23 ℃ of room temperatures and relative humidity 50%, the speed that the pressing rubber rollers of using 2kg is respectively divided with 300mm/ is fitted in each surface protection film on the surface that is used for the prismatic lens that (2) initial stage cohesive force estimates.Then, use polycarbonate plate (thick 2mm) clamping to be fitted with the prismatic lens of surface protection film, apply 6.0 * 10 -3The pressure of MPa, and in the environment of 60 ℃ and relative humidity 90%, placing 48 hours under this state.It is taken out in the room temperature, places after 30 minutes, the speed of dividing based on JIS Z0237 standard, with 300mm/ is measured the degree of 180 in 25mm width stripping strength.
With the stripping strength measured thus as through the time cohesive force, by following formula calculate through the time cohesive force with respect to the velocity of variation (bonding deterioration rate) of initial stage cohesive force.
Velocity of variation (bonding deterioration rate)=(through the time cohesive force/initial stage cohesive force) * 100
(4) expansion power
The wide coiling body of 50mm to each surface protection film of embodiment and comparative example carries out uncoiling, except changing uncoiling speed, based on JIS Z0237 standard, the uncoiling velocity determination that divides with 20m/ high speed uncoiling power, and with this as expansion power.
Figure BDA0000049723290000331
Figure BDA0000049723290000341
＜criterion 〉
Cohesive force (initial stage)
Zero (very): more than the 0.1N/25mm
△ (can): 0.05N/25mm is above and be lower than 0.1N/25mm
* (can not): be lower than 0.05N/25mm
Cohesive force (velocity of variation)
◎ (excellent): be lower than 200%
Zero (very): more than 200% and below 500%
* (bad): surpass 500%
Expansion power
Zero (very): below the 3.5N/50mm
* (bad): surpass 3.5N/50mm
(embodiment 20)
Utilize T pattern method to carry out coextrusion, form the prismatic lens surface protection film (wide 700mm) of base material layer (thick 34 μ m)/adhesive layer (thick 6 μ m), having obtained coiling length is the coiling body of 100m.As the material that is used to form adhesive layer, what use is following material: mix alicyclic bubble point oil Resin A lcon P125 (Arakawa Chemical Industries, Ltd.'s manufacturing) 30 weight parts as 125 ℃ of the softening temperatures of tackifier in copolymer compositions 100 weight parts of synthesis example 13, ENDEX155 (manufacturing of Eastman Chemical company) 20 weight parts as the styrenic block strengthening agent, Irganox 1010 (manufacturing of Ciba Specialty Chemicals company) 1 weight part as oxidation inhibitor, Tinuvin 326 (manufacturing of Ciba Specialty Chemicals company) 0.5 weight part as UV light absorber, it is mixing to utilize twin screw extruder to carry out, and carries out granulation and the material that obtains.As the material that is used to form base material layer, what use is following material: after mixing through part 10 weight parts of pruning with block PP 100 weight parts with in order to the film both ends of adjusting the reeling condition of rolling up when film is shaped, it is mixing to utilize twin screw extruder to carry out, and carry out granulation and the material that obtains, wherein, in above-mentioned film, contain block polypropylene (block PP) 100 weight parts as body material, in addition, as adhesive layer, contain copolymer compositions 100 weight parts as the synthesis example 13 of binding agent, and as 30 parts of the Alcon P125 (Arakawa Chemical Industries, Ltd.'s manufacturing) of tackifier, ENDEX155 (manufacturing of Eastman Chemical company) 20 weight parts as the styrenic block strengthening agent, Irganox1010 (manufacturing of Ciba Specialty Chemicals company) 1 weight part as oxidation inhibitor, Tinuvin 326 (manufacturing of Ciba Specialty Chemicals company) 0.5 weight part as UV light absorber.
(embodiment 21～25)
Shown in following table 8, change the amount of tackifier and the amount of styrenic block strengthening agent (in this specification sheets, also abbreviating St class block strengthening agent as), in addition, obtained the coiling body of prismatic lens with surface protection film according to the method identical with embodiment 20.
Need to prove that " St/ binding agent (the weight %) " in the table 8 represents the unitary gross weight of whole aromatic series alkenyl compounds in copolymer compositions and the styrenic block strengthening agent shared ratio (the unitary containing ratio of aromatic series alkenyl compound) in the weight of binding agent.
(evaluation)
At the project of record in following (1)～(4), the surface protection film of embodiment 20～25 has been carried out evaluation test.The result is as shown in table 9.
(1) initial stage cohesive force
Each surface protection film of embodiment and comparative example is fitted on the lens face with concavo-convex prismatic lens, and makes these surface protection films coat the lens face of described prismatic lens.As prismatic lens, use be sheet materials that make by the acrylic resin of thick 130 μ m, prism pitch 50 μ m, high 30 μ m.As laminating condition, in the environment of 23 ℃ of room temperatures and relative humidity 50%, use the pressing rubber rollers of 2kg to fit respectively with the speed that 300mm/ divides, and under this state, placed 1 hour, then, the speed of dividing based on JIS Z0237 standard, with 300mm/ is measured the degree of 180 in 25mm width stripping strength.With the stripping strength measured thus as the initial stage cohesive force.
(2) through the time cohesive force
In the environment of 23 ℃ of room temperatures and relative humidity 50%, the speed that the pressing rubber rollers of using 2kg is respectively divided with 300mm/ is fitted in each surface protection film of embodiment and comparative example on the surface that is used for the prismatic lens that (1) initial stage cohesive force estimates.Then, use polycarbonate plate (thick 2mm) clamping to be fitted with the prismatic lens of surface protection film, apply 0.3N/cm 2Pressure, and in 70 ℃ environment, placing 24 hours under this state.Then, left standstill 1 hour in the environment of 23 ℃ of room temperatures and relative humidity 50%, the speed of dividing based on JIS Z0237 standard, with 300mm/ is measured the degree of 180 in 25mm width stripping strength then.With the stripping strength measured thus as through the time cohesive force, by following formula calculate through the time cohesive force with respect to the velocity of variation (bonding deterioration rate) of initial stage cohesive force.
Velocity of variation (bonding deterioration rate)=(through the time cohesive force/initial stage cohesive force) * 100
(3) storage modulus G '
(IT instrumentation Heat ﹠ Control Pty Ltd. makes to utilize dynamic viscoelastic spectrometry device, product type: DVA-200), with the frequency of 1Hz, 3 ℃/minute heat-up rate, in-50 ℃～+ 150 ℃ scope, measured the storage modulus of adhesive layer, and obtained the storage modulus G ' under 70 ℃.
(4) amount of being absorbed in
In the environment of 23 ℃ of room temperatures and relative humidity 50%, the speed that the pressing rubber rollers of using 2kg is respectively divided with 300mm/ is fitted in surface protection film on the surface of prismatic lens.As prismatic lens, use be the sheet material of prism pitch 50 μ m, high 30 μ m.Then, use polycarbonate plate (thick 2mm) clamping to be fitted with the prismatic lens of surface protection film, apply 0.3N/cm 2Pressure, and in 70 ℃ environment, leaving standstill 24 hours under this state.Then, with 180 degree peel angle stripper surface protective membranes, and utilize laser microscope that the adhesive layer surface is observed, the lens section of having measured prismatic lens is absorbed in the degree of depth in adhesive layer.
Utilize following calculating formula to obtain the amount of being absorbed in.
The amount of being absorbed in (%)=
(lens section of prismatic lens in adhesive layer be absorbed in the degree of depth)/(adhesive layer thickness: 6 μ m) * 100
Figure BDA0000049723290000381
Figure BDA0000049723290000391
＜criterion 〉
The amount of being absorbed in
Zero (excellent): more than 1% and be lower than 40%
△ (very): more than 40% and be lower than 80%
* (bad): more than 80%
Cohesive force (velocity of variation)
◎ (excellent): be lower than 150%
Zero (very): more than 150% and below 300%
(embodiment 26)
Shown in following table 10, in copolymer compositions 100 weight parts of synthesis example 14, add alicyclic bubble point oil resin, be Alcon P-125 (Arakawa Chemical Industries, Ltd.'s manufacturing) 30 weight parts as tackifier, obtained adhesive composition.
On the other hand; utilize T pattern method that adhesive layer that is formed by above-mentioned adhesive composition and the body material that is formed by the resin combination that comprises (block PP) 75 weight parts of the block polypropylene shown in the table 10 and new LDPE (film grade) (LDPE) 25 weight parts are carried out coextrusion, thereby made the surface protection film that the adhesive layer by the polypropylene matrix material of thick 40 μ m and thick 6 μ m obtains through laminated integratedization.
(embodiment 27～28 and comparative example 15～19)
Except according to the composition and thickness that change adhesive layer shown in the following table 10, made surface protection film according to the method identical, and estimated with embodiment 25.Tackifier have all used Alcon P-125.
Wherein, the film-forming properties of comparative example 18 is bad.
(evaluation)
At these surface protection films, following mensuration and evaluation have been carried out according to following main points.
1) in 50 ℃ atmosphere, with 0.8N/cm 2Power the prominence of diameter 400 μ m, high 12 μ m is pressed on the prismatic lens that is fitted with surface protection film, after 24 hours, the be absorbed in amount of the lens section of prismatic lens in binding agent,
2) initial stage cohesive force (to prism facets) and
3) initial stage cohesive force (to even surface).
In addition, carrying out above-mentioned 1) being absorbed in when estimating of the lens section of prismatic lens, carried out following mensuration and evaluation according to following main points.
4) prism damage,
5) through the time cohesive force (to prism facets)
6) thickener is residual;
In addition, following mensuration and evaluation have been carried out according to following main points.
7) expansion power.
The result is shown in following table 11.
1) amount of being absorbed in
The above-mentioned surface protection film that obtains is fitted on the lens face of prismatic lens, and the adhesive layer surface of this surface protection film is contacted with the lens face of prismatic lens, thereby made test film.As prismatic lens, prepared lens section by acrylic resin constitute, sheet is made of the polyethylene terephthalate of thick 150 μ m and prism pitch is that 50 μ m, height are the prismatic lens (BEF, Sumitomo 3M) of 23 μ m.During applying, (that is, a side) opposite with the binding agent aspect applies 5.9 * 10 from the outside of surface protection film 5The pressure of Pa is fitted with the speed that 2m/ divides.During applying, use following laminating machine, with PRESCALE (ultralow pressure is used) the actual measurement laminate pressure of FUJIFILM Business Supply (strain) company manufacturing.
Laminating machine
Manufacturers: MCK (strain)
Model: MRK-600
Roller: heat-resisting silica gel roller
Roller diameter: φ 80
The gained test film is cut into the size of 3cm * 8cm, has made sample strip.
In addition; in order to prepare to be used for the thrust of evaluation test; utilize freezing-microtome the nylon fiber of diameter 0.2mm to be cut into the length of 11～13 μ m; and gained is cut sheet be fixed on the slide glass; the roller that utilizes 2kg is from the above-mentioned surface protection film that obtains of its top applying; thus, will cut sheet is fixed between slide glass and the surface protection film.Its result utilizes laser microscope that the convex form (that is, thrust) that forms is observed, and has obtained its diameter and height.
The diameter of the convex form that is used to estimate and highly as follows.
Diameter: 400 μ m
Highly: 12 μ m
The above-mentioned slide glass that has the surface protection film with convex form is arranged on the sample strip, and sample strip is contacted with above-mentioned surface protection film with convex form, and on slide glass, place the counterweight (0.8N/cm of 200g 2), in 50 ℃ baking oven, placed 24 hours.After 24 hours, take out sample strip, cut its cross section, utilize scanning electron microscope (SEM) that this cross section is observed, and the lens section of having measured prismatic lens is absorbed in the degree of depth (μ m) in adhesive layer.
Utilize following formula, obtained the amount of being absorbed in (%) by the degree of depth (μ m) that is absorbed in of actual measurement.
The amount of being absorbed in (%)=
(lens section of prismatic lens in adhesive layer be absorbed in the degree of depth)/(adhesive layer thickness: 6 μ m) * 100
2) initial stage cohesive force (to prism facets)
The above-mentioned surface protection film that obtains is fitted on the lens face of above-mentioned prismatic lens, and makes above-mentioned surface protection film coat the lens face of above-mentioned prismatic lens.During applying, with 1) similarly apply 5.9 * 10 from the outside of surface protection film 5The pressure of Pa is fitted with the speed that 2m/ divides, and 23 ℃ ± 2 ℃ indoor the placement 30 minutes.
Then,, divide with 300mm/ respectively and peeling rate that 30m/ divides is measured the degree stripping strength of 180 in the 25mm width (unit is N) along the direction parallel with the prism crest line based on JIS Z0237 standard, and with this as initial stage cohesive force (to prism).
3) initial stage cohesive force (to even surface)
At pressure 5.9 * 10 5Under the condition that Pa and speed 2m/ divide; with 1) similarly the above-mentioned surface protection film that obtains is fitted on the smooth acrylic resin board; and 23 ℃ ± 2 ℃ indoor the placement 30 minutes; then; based on JIS Z0237 standard; under the condition that peeling rate 30m/ divides, the degree stripping strength of 180 in the 25mm width (unit is N) is measured, and with this as initial stage cohesive force (to even surface).
4) evaluation of prism damage
Carrying out 1) test the time, will peel off from prismatic lens from the surface protection film that baking oven takes out, whether visual inspection exists the bright spot that produces because of damage on the lens face of prismatic lens.
In following table 10, with observe than the sample of poly-injury note do *, the sample note of only observing a little damage is made △, will not observe the sample note of damage fully and do zero.
5) through the time cohesive force (to prism facets)
At pressure 5.9 * 10 5Under the condition that Pa and speed 2m/ divide; with 1) similarly the surface protection film that obtains is fitted in be used for 2) surface of the prismatic lens estimated of initial stage cohesive force; and in 60 ℃ ± 2 ℃ atmosphere, placed for 1 week; then, the peeling rate that divides based on JIS Z0237 standard, with 300mm/ is measured the degree of 180 in 25mm width stripping strength.With the stripping strength measured thus as through the time cohesive force, by following formula calculate through the time cohesive force with respect to the velocity of variation (bonding deterioration rate) of initial stage cohesive force (to prism facets, peeling rate 300mm/ branch).
Velocity of variation (bonding deterioration rate)=
(through the time cohesive force/initial stage cohesive force (to prism facets, peeling rate 300mm/ branch)) * 100
6) thickener is residual
Carrying out 5) test the time, when measuring stripping strength, whether the lens face of the prismatic lens of visual inspection after peeling off exists thickener residual.To on lens face, observe the residual situation note of thickener to do *, do not do zero with observing the residual situation note of thickener fully.The result is shown in following table 11.
7) expansion power
Coiling body in the 50mm width of each surface protection film of embodiment and comparative example is carried out uncoiling, except changing uncoiling speed, based on JIS Z0237 standard, the uncoiling velocity determination that divides with 20m/ high speed uncoiling power, and with this as expansion power.
[table 10]
Figure BDA0000049723290000431
＜criterion 〉
The amount of being absorbed in
Zero (very): more than 1% and be lower than 100%
* (bad): be lower than 1% or 100%
Initial stage cohesive force (to prism facets) peeling rate: 300mm/ branch
Zero (very): more than the 0.05N/25mm
* (bad): be lower than 0.05N/25mm
Cohesive force (velocity of variation is to prism facets)
◎ (excellent): be lower than 200%
Zero (very): more than 200% and below 500%
* (bad): surpass 500%
The prism damage is estimated
Zero: naked eyes are not observed damage
*: be observed visually damage
The residual evaluation of thickener
Zero: naked eyes are not observed the residual generation of thickener
*: be observed visually the residual generation of thickener
Expansion power
Zero (very): below the 3.5N/50mm
* (bad): surpass 3.5N/50mm
(embodiment 29)
Utilize T pattern method to carry out coextrusion, form the prismatic lens surface protection film (wide 700mm) of base material layer (thick 34 μ m)/adhesive layer (thick 6 μ m), having obtained coiling length is the coiling body of 100m.
As the material that is used to form adhesive layer, what use is following material: add alicyclic bubble point oil Resin A lcon P125 (Arakawa Chemical Industries, Ltd.'s manufacturing) 30 weight parts as 125 ℃ of the softening temperatures of tackifier in copolymer compositions 100 weight parts of synthesis example 13, ENDEX155 (manufacturing of Eastman Chemical company) 10 weight parts as the styrenic block strengthening agent, Irganox 1010 (manufacturing of Ciba Specialty Chemicals company) 1 weight part as oxidation inhibitor, Tinuvin 326 (manufacturing of Ciba Specialty Chemicals company) 0.5 weight part as UV light absorber, it is mixing to utilize twin screw extruder to carry out, and carries out granulation and the material that obtains.
As the material that is used to form base material layer, what use is following material: with block PP 75 weight parts, new LDPE (film grade) (LDPR) 25 weight parts, after the part 10 weight parts mixing of film both ends through pruning of the reeling condition of rolling up when reaching in order to the shaping of adjustment film, it is mixing to utilize twin screw extruder to carry out, and carry out granulation and the material that obtains, wherein in above-mentioned film, contain block polypropylene (block PP) 100 weight parts as body material, in addition, as adhesive layer, contain copolymer compositions 100 weight parts as the synthesis example 13 of binding agent, and as 30 parts of the Alcon P125 (Arakawa Chemical Industries, Ltd.'s manufacturing) of tackifier, ENDEX155 (manufacturing of Eastman Chemical company) 20 weight parts as the styrenic block strengthening agent, Irganox 1010 (manufacturing of Ciba Specialty Chemicals company) 1 weight part as oxidation inhibitor, Tinuvin 326 (manufacturing of Ciba Specialty Chemicals company) 0.5 weight part as UV light absorber.
Need to prove that " St/ binding agent (the weight %) " in the table 12 represents the unitary gross weight of aromatic series alkenyl compound in copolymer compositions and the styrenic block strengthening agent shared ratio (the unitary containing ratio of aromatic series alkenyl compound) in the weight of binding agent.
(embodiment 30～31, comparative example 20～22)
Except the amount of the polyolefine use level that shown in following table 12, changes base material layer and kind, adhesive layer, copolymer compositions and vinylbenzene containing ratio, tackifier, styrenic block strengthening agent (promptly; St is the block strengthening agent) amount beyond, obtained the coiling body of prismatic lens according to the method identical with surface protection film with embodiment 29.
(evaluation)
At the project of record in following (1)～(6), the surface protection film of embodiment 29～31 and comparative example 20～22 has been carried out evaluation test.The result is as shown in table 13.
(1) surface roughness Ra
Utilize SURFTEST SJ-301 (manufacturing of Mitsutoyo company), under following condition determination, surface roughness Ra is measured.
(condition determination)
Measured length: 7.2mm
λc：0.8mm
λs：2.5μm
Finding speed: 0.5mm/s
In addition, based on JIS B0601:2001 standard, calculate the center line average of percent ripple profile roughness and the average headway of percent ripple profile by the skeleton diagram of measuring at this condition determination (profile).
(2) cohesive force
Each surface protection film of embodiment and comparative example is fitted on the lens face with concavo-convex prismatic lens, and makes these surface protection films coat the lens face of described prismatic lens.As prismatic lens, use be sheet materials that make by the acrylic resin of thick 130 μ m, prism pitch 50 μ m, high 30 μ m.As laminating condition, in the environment of 23 ℃ of room temperatures and relative humidity 50%, use the pressing rubber rollers of 2kg to fit respectively with the speed that 300mm/ divides, and under this state, left standstill 1 hour, then, the speed of dividing based on JIS Z0237 standard, with 300mm/ is measured the degree of 180 in 25mm width stripping strength.With the stripping strength measured thus as cohesive force.
(3) initial stage is launched power
Initial stage is launched the following mensuration of power: the coiling body wide to the 50mm of each surface protection film carries out uncoiling, except changing uncoiling speed, based on JIS Z0237 standard, measured the high speed uncoiling power under the uncoiling speed that 15m/ divides.With the high speed uncoiling masterpiece of measuring thus is the initial stage to launch power.
(4) through the time launch power
Through the time launch the following mensuration of power: the coiling body that the 50mm of each surface protection film is wide is given birth at 40 ℃ ± 2 ℃ indoor slaking (Raising) 1 week; then; except changing uncoiling speed,, measured the high speed uncoiling power under the uncoiling speed that 15m/ divides based on JIS Z0237 standard.With the high speed uncoiling masterpiece of measuring thus be through the time expansion power.In the table, with above-mentioned through the time expansion power be that average evaluation below the 3N/50mm is good for derivation property, note does zero; Will through the time expansion power to surpass the average evaluation of 3N/50mm bad for derivation property, note does *.
(5) the prism damage is estimated
Each surface protection film of embodiment and comparative example is fitted in the lens face with concavo-convex prismatic lens, and makes these surface protection films coat the lens face of prismatic lens, thereby made test film.As prismatic lens, being and being used for the identical sheet material of prismatic lens that (2) cohesive force is estimated of use.During applying, apply 5.9 * 10 from the outside of surface protection film 5The pressure of Pa is fitted with the speed that 2m/ divides.Test film is cut into the size of 3cm * 8cm, has made sample strip.
In addition; utilize freezing-microtome the nylon fiber of diameter 0.2mm to be cut into the length of 8～10 μ m; and gained is cut sheet be fixed on the slide glass; utilize the roller of 2kg that the surface protection film that obtains is fitted on the slide glass; thus; sample strip is fixed between slide glass and the surface protection film, has made the convex form sample of diameter 400 μ m, high 10 μ m.
On the sample strip that coats lens section by surface protection film, above-mentioned convex form sample is set, and this convex form sample and the surface protection film that coats lens section are superimposed, on slide glass, place the counterweight of 140g, in 50 ℃ baking oven, left standstill 24 hours.After 24 hours, take out test film, surface protection film is peeled off from prismatic lens, whether visual inspection exists the bright spot that produces because of damage on the lens face of prismatic lens.In following table 13, the sample note of observing than poly-injury is done * (bad), the sample note of only observing a little damage is made △ (very), the sample note of not observing damage is fully made zero (excellent).
Figure BDA0000049723290000491
(embodiment 32～38, comparative example 23～29)
In copolymer compositions 100 weight parts that utilize above-mentioned synthetic method to obtain, mix, obtained adhesive composition as Alcon P125 (Arakawa Chemical Industries, Ltd.'s manufacturing) 5 weight parts of tackifier, as Irganox 1010 (manufacturing of Ciba Specialty Chemicals company) 1 weight part of oxidation inhibitor.
Use polypropylene (Prime Polymer company makes J715M) as body material; utilize T pattern method that body material and adhesive composition are carried out the coextrusion shaping; thus, obtained being formed with coiling body on surface protection film that the adhesive layer by the base material layer of thick 34 μ m and thick 6 μ m obtains through laminated integratedization and the refill that is wound on 3 inches of internal diameters.
(evaluation)
Each surface protection film at utilizing aforesaid method to obtain has carried out the evaluation of following project.Its result is as shown in Table 15.
(evaluation)
Each surface protection film at utilizing aforesaid method to obtain has carried out the evaluation of following project.Its result is as shown in Table 15.
(1) film-forming properties
Outward appearance for the surface protection film of making by coextrusion has been carried out the naked eyes evaluation, and the situation note of no problem is in appearance done zero.
(2) initial stage cohesive force
Each surface protection film of embodiment and comparative example is fitted in diffusion barrier, and (3M company makes, and on lens face DBEF), and makes these surface protection films coat the lens face of described diffusion barrier.As laminating condition, in the environment of 23 ℃ of room temperatures and relative humidity 50%, use the pressing rubber rollers of 2kg to fit respectively with the speed that 300mm/ divides, and under this state, placed 30 minutes, then, the speed of dividing based on JIS Z0237 standard, with 300mm/ is measured the degree of 180 in 25mm width stripping strength.The direction of delaminate of this moment is the MD direction (machine direction (axially)) of surface protection film.With the stripping strength measured thus as the initial stage cohesive force.
(3) through the time cohesive force
In the environment of 23 ℃ of room temperatures and relative humidity 50%, the speed that the pressing rubber rollers of using 2kg is respectively divided with 300mm/ is fitted in each surface protection film of embodiment and comparative example on the surface that is used for the diffusion barrier that (1) initial stage cohesive force estimates.Then, use polycarbonate plate (thick 2mm) clamping to be fitted with the diffusion barrier of surface protection film, apply 6.0 * 10 -3The pressure of MPa, and in the environment of 60 ℃ and relative humidity 90%, placing 48 hours under this state.It is taken out in the room temperature, places after 30 minutes, the speed of dividing based on the JISZ0237 standard, with 300mm/ is measured the degree of 180 in 25mm width stripping strength.
With the stripping strength measured thus as through the time cohesive force, by following formula calculate through the time cohesive force with respect to the bonding deterioration rate of initial stage cohesive force.
Velocity of variation (bonding deterioration rate)=(through the time cohesive force/initial stage cohesive force) * 100
(4) expansion power
The wide coiling body of 50mm to each surface protection film of embodiment and comparative example carries out uncoiling, except changing uncoiling speed, based on JIS Z0237 standard, the uncoiling velocity determination that divides with 5m/ branch, 15m/ uncoiling power, and with this as expansion power.
[table 14]
Figure BDA0000049723290000521
Figure BDA0000049723290000531
＜criterion 〉
Cohesive force (initial stage)
Zero (very): 0.05N/25mm is above and be lower than 0.35N/25mm
* (bad): be lower than 0.05N/25mm or more than 0.35N/25mm
Cohesive force (velocity of variation)
◎ (excellent): be lower than 200%
Zero (very): more than 200% and below 500%
* (bad): surpass 500%
Expansion power
◎ (excellent): be lower than 2.0N/50mm
More than zero (very): the 2.0N/50mm and below the 3.5N/50mm
* (bad): surpass 3.5N/50mm
Industrial applicibility
Adhesive composition of the present invention is applicable to the adhesive layer of the surface protection films such as prismatic lens, diffusion barrier.
Surface protection film of the present invention is applicable to the surface protection of prismatic lens, diffusion barrier etc.

Claims (9)

1. adhesive composition, it contains polymkeric substance (i) and polymkeric substance (ii), wherein,
Polymkeric substance (i): contain following polymer blocks A and following polymer blocks B, and have multipolymer (I) or its hydrogenation products of structure shown in general formula [A-B] n, in general formula [A-B] n, A representation polymer block A, B representation polymer B block, n represents integer 1～3
Polymkeric substance is (ii): contain following polymer blocks A and following polymer blocks B, and multipolymer (II) or its hydrogenation products with structure shown in general formula A-B-A or general formula (A-B) x-Y, in general formula A-B-A, the implication of symbol A, B is the same, in general formula (A-B) x-Y, x represents the integer more than 1, and Y represents the coupling agent residue, the implication of symbol A, B is the same
Above-mentioned polymkeric substance (i) and the above-mentioned polymkeric substance unitary total containing ratio of aromatic series alkenyl compound (St (A+B)) in (ii) is 30～50 weight %,
(the A: B) and the weight ratio (A: B) respectively in 5: 95～25: 75 scope of the total amount of the total amount of above-mentioned polymkeric substance contained polymer blocks A in (ii) and polymer blocks B of the weight ratio of the total amount of the total amount of contained polymer blocks A and polymer blocks B in the above-mentioned polymkeric substance (i)
Wherein,
Polymer blocks A: have successive aromatic series alkenyl compound unit and based on the polymer blocks of aromatic series alkenyl compound unit,
Polymer blocks B: randomly contain conjugated diene unit and aromatic series alkenyl compound unit, and the unitary containing ratio of aromatic series alkenyl compound (St (b)) is aromatic series alkenyl-conjugated diene copolymer block of 10～35 weight %.
2. surface protection film, the adhesive layer that it has base material layer and is formed by the described adhesive composition of claim 1.
3. the described surface protection film of claim 2, wherein,
Described base material layer is the polyolefin substrate material layer,
Also contain tackifier in the described adhesive composition,
And when-50 ℃～80 ℃ dynamic viscoelastics to described adhesive layer were measured, the temperature when gained tan δ reaches maximum was-10 ℃～20 ℃.
4. the described surface protection film of claim 2, wherein,
Described base material layer is the polyolefin substrate material layer,
Also contain tackifier and styrenic block strengthening agent in the described adhesive composition,
Weight with respect to described adhesive layer, described polymkeric substance (i), described polymkeric substance (ii) reach the shared ratio of aromatic series alkenyl compound unit weight in the styrenic block strengthening agent, and promptly aromatic series alkenyl compound unit containing ratio is 20～50 weight %.
5. each described surface protection film in the claim 2～4, wherein, described adhesive layer is 4.5 * 10 at 70 ℃ storage modulus G ' 5Pa～6.0 * 10 5Pa.
6. the described surface protection film of claim 5, it is used to protect the prism facets surface of prismatic lens, wherein,
Fit on the described prism facets this surface protection film and in 70 ℃ atmosphere load 0.3N/cm 2Load in the time of 24 hours, the prism vertex angle of described prism facets in binding agent be absorbed in the degree of depth account for adhesive layer thickness more than 1% and be lower than 40%.
7. each described surface protection film in the claim 2～6, it is used to protect the prism facets of prismatic lens, wherein,
Fit on the described prism facets this surface protection film and with the surface pressure of the opposite side of this prism facets side on during the prominence of diameter 400 μ m, high 12 μ m, the prism vertex angle of described prism facets in described adhesive layer be absorbed in the degree of depth account for described adhesive layer thickness more than 1% and be lower than 100%.
8. each described surface protection film in the claim 2～6, it is used to protect the prism facets of prismatic lens, wherein,
The surface roughness Ra of the outer surface of base material layer is that the center line average of 0.7～2.0 μ m, percent ripple profile roughness is that 3 μ m average headway above and the percent ripple profile is more than the 350 μ m and below the 600 μ m.
9. each described surface protection film in the claim 2～5, it is used to protect the surface of diffusion barrier.
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TWI382071B (en) 2013-01-11
JPWO2010029773A1 (en) 2012-02-02
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KR101176811B1 (en) 2012-08-24
TW201016812A (en) 2010-05-01

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