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CN103254809A - Surface protection sheet - Google Patents

Surface protection sheet Download PDF

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Publication number
CN103254809A
CN103254809A CN2012100361246A CN201210036124A CN103254809A CN 103254809 A CN103254809 A CN 103254809A CN 2012100361246 A CN2012100361246 A CN 2012100361246A CN 201210036124 A CN201210036124 A CN 201210036124A CN 103254809 A CN103254809 A CN 103254809A
Authority
CN
China
Prior art keywords
layer
surface protective
protective plate
black
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN2012100361246A
Other languages
Chinese (zh)
Inventor
武田公平
生岛伸祐
山户二郎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nitto Denko Corp
Original Assignee
Nitto Denko Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nitto Denko Corp filed Critical Nitto Denko Corp
Priority to CN2012100361246A priority Critical patent/CN103254809A/en
Priority to PCT/JP2013/051371 priority patent/WO2013121848A1/en
Publication of CN103254809A publication Critical patent/CN103254809A/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • C09J7/29—Laminated material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2274/00—Thermoplastic elastomer material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/542—Shear strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/712—Weather resistant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2405/00—Adhesive articles, e.g. adhesive tapes
    • 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
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/16—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer
    • C09J2301/162—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer the carrier being a laminate constituted by plastic layers only
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C09J2423/006—Presence of polyolefin in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2453/00—Presence of block copolymer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention provides a surface protection sheet. The surface protection sheet has a very excellent weatherability, has an extremely-small adhesion difference caused by the change of the temperature, and can effectively prevent the adhesive residual on an adhered boy even during high temperature peeling after attachment. The surface protection sheet is obtained through forming an adhesive layer on one side of a substrate layer, the adhesive layer includes a styrene series resin, the shear storage elastic modulus of the adhesive layer at 0DEG C under 1Hz is below 2.0MPa, and the change rate of the shear storage elastic modulus of the adhesive layer heated to 60DEG C is within 1/100.

Description

Surface protective plate
Technical field
The present invention relates to a kind of surface protective plate.Specifically; the present invention relates to the surface protective plate that can in following purposes etc., use; namely; for example to metal sheet, application member such as metal sheet, aluminum alloy frame, resin board, decorative steel plate, vinylchlorid laminate steel, sheet glass carry, when processing or maintenance etc., be attached to these component surface and protected.
Background technology
As necessary characteristic for surface protective plate, can enumerate following characteristic, that is, and on being attached at by adherend after, do not have floating or peeling off of this surface protective plate, peeling off on bonding coat can not remain in by adherend when removing.Particularly; during before surface protective plate is peeled off at high temperature or carry out under the inferior harsh condition of outdoor exposure when being attached the operation of this surface protective plate by adherend; in necessary above-mentioned characteristic concerning surface protective plate, then require the characteristic of higher level.In addition, need to suppress to be attached to the situation of splitting when being peeled off by the surface protective plate on the adherend.
In the past, in the bonding coat of the surface protective plate that generally uses, use in natural rubber or modified natural rubber, cooperate an amount of tackifier etc. and natural rubber be tackiness agent.This kind surface protective plate does not have special problem with regard to indoor use.But, because natural rubber is that tackiness agent has unsaturated double-bond in its structure, therefore be exposed under the outdoor situation, can cause molecular breakdown because of ultraviolet ray.Thus, be the surface protective plate of tackiness agent when peeling off having used natural rubber, can produce adhesive residue in by the problem in the adherend.Thus, wish to have weathering resistance surface of good screening glass.In addition, also have and to be attached at splintery problem when being peeled off by the surface protective plate on the adherend.
In order to address the above problem, the synthetic rubber such as acrylic adhesive, polyisobutene that proposed when the formation of bonding coat acrylic copolymer is improved not lose fusible degree cross-linked three Dization with isocyanate compound or methylol compound cohesive force is tackiness agent.But, because these tackiness agents are solvent systems, therefore in the safety and sanitation of surface protective plate, aspect existing problems such as the viewpoint of public hazards, economy.
In recent years, in order to improve these problems, require to realize the solvent free of tackiness agent.As its strong approach, the substrate layer of studying the bonding coat that will comprise thermoplastic elastomer and comprising polyolefin-based resins utilizes coextrusion film processed and makes the method (for example with reference to patent documentation 1, patent documentation 2) of surface protective plate.
But, in these surface protective plates, also have the problem of weathering resistance deficiency.
The prior art document
Patent documentation
Patent documentation 1 Japanese kokai publication hei 5-194923 communique (page 2)
Patent documentation 2 Japanese kokai publication sho 61-103975 communiques (page 1)
Summary of the invention
The objective of the invention is to, a kind of surface protective plate is provided, its weathering resistance is very excellent, and the difference of the bounding force that is caused by temperature variation is minimum, even can prevent effectively that also tackiness agent is by the glue trace on the adherend peeling off during at high temperature after the attaching.
Surface protective plate of the present invention is the surface protective plate that is formed with bonding coat in the one side of substrate layer,
This bonding coat comprises phenylethylene resin series,
Shearing storage elastic modulus under the 1Hz of this binder layer is below the 2.0MPa at 0 ℃, and the velocity of variation of this shearing storage elastic modulus is in 1/100 when being heated to 60 ℃.
In preferred embodiment, above-mentioned substrate layer comprises the white color system layer at least and black is 2 layers on layer.
In preferred embodiment, above-mentioned phenylethylene resin series is the hydrogenation thing of the segmented copolymer of vinylbenzene and divinyl.
According to the present invention, following surface protective plate can be provided, its weathering resistance is very excellent, and the difference of the bounding force that is caused by temperature variation is minimum, even can prevent effectively that also tackiness agent is by the glue trace on the adherend peeling off during at high temperature after the attaching.
Embodiment
Surface protective plate of the present invention is formed with bonding coat in the one side of substrate layer.
Substrate layer can contain appropriate arbitrarily resin.Substrate layer preferably contains polyolefin-based resins.Polyolefin-based resins in the substrate layer contain proportional being preferably more than the 60 weight %, more preferably more than the 70 weight %, more preferably more than the 80 weight %, be preferably especially more than the 85 weight %, most preferably be more than the 90 weight %.This kind polyolefin-based resins both can only use a kind, also can use more than 2 kinds.
As polyolefin-based resins contained in the substrate layer, can adopt appropriate arbitrarily polyolefin-based resins, yet from becoming viewpoints such as membrane stability, burning to consider acrylic polymers such as optimization polypropylene; Low Density Polyethylene (LDPE), linear low density polyethylene ethylene-based polymers such as (LLDPE).
The density of the ethylene-based polymer that can contain in the substrate layer is preferably 0.88～0.93g/cm 3, 0.895～0.920g/cm more preferably 3
Substrate layer preferably comprises 2 layers on white color system layer and black system layer at least.Like this, just can form the very outstanding surface protective plate of weathering resistance.
The white color system layer is the layer that demonstrates the tone of white color system, and for example the whiteness by the JIS-L-1015 regulation is preferably more than 60%, more preferably more than 70%, more preferably more than 80%, is preferably more than 85% especially.The white color system layer preferably comprises white pigment.As white pigment, can adopt appropriate arbitrarily white pigment.As this kind white pigment, for example can enumerate titanium oxide.Contain at the white color system layer under the situation of white pigment, it contains proportional resinous principle with respect to formation white color system layer and is preferably 0.1～50 weight %, more preferably 1～30 weight %, more preferably 5～20 weight %.
The resinous principle that forms the white color system layer is preferably polyolefin-based resins, more preferably is selected from least a kind in acrylic polymer and the ethylene-based polymer, more preferably density 0.88～0.93g/cm 3Ethylene-based polymer.As the resinous principle that forms the white color system layer, specifically, can preferably enumerate polypropylene, Low Density Polyethylene (LDPE), linear low density polyethylene (LLDPE).Polyolefin-based resins in the white color system layer contain proportional being preferably more than the 60 weight %, more preferably more than the 70 weight %, more preferably more than the 80 weight %, be preferably especially more than the 85 weight %, most preferably be more than the 90 weight %.This kind polyolefin-based resins both can only use a kind, also can use more than 2 kinds.
The thickness of white color system layer can adopt appropriate arbitrarily thickness according to purpose.This kind thickness is preferably 1～50 μ m, 3～40 μ m more preferably, and more preferably 5～30 μ m are preferably 10～30 μ m especially.
Black system layer is the layer that demonstrates the tone of black system.Black system layer preferably comprises black pigment.As black pigment, can adopt appropriate arbitrarily black pigment.As this kind black pigment, for example can enumerate carbon black.Layer contains under the situation of black pigment in black system, and it contains proportional resinous principle with respect to formation black system layer and is preferably 0.01～10 weight %, more preferably 0.1～5 weight %, more preferably 0.5～3 weight %.
The resinous principle that forms black system layer is preferably polyolefin-based resins, more preferably is selected from least a kind in acrylic polymer and the ethylene-based polymer, more preferably density 0.88～0.93g/cm 3Ethylene-based polymer.As the resinous principle that forms black system layer, specifically, can preferably enumerate polypropylene, Low Density Polyethylene (LDPE), linear low density polyethylene (LLDPE).Polyolefin-based resins in the black system layer contain proportional being preferably more than the 60 weight %, more preferably more than the 70 weight %, more preferably more than the 80 weight %, be preferably especially more than the 85 weight %, most preferably be more than the 90 weight %.This kind polyolefin-based resins both can only use a kind, also can use more than 2 kinds.
The thickness of black system layer can adopt appropriate arbitrarily thickness according to purpose.This kind thickness is preferably 1～100 μ m, 5～70 μ m more preferably, and more preferably 10～60 μ m are preferably 20～50 μ m especially.
In substrate layer, for preventing purposes such as deterioration, also can contain appropriate arbitrarily additive.As this kind additive, for example can enumerate oxidation inhibitor; UV light absorber; Hindered amine is photostabilizers such as photostabilizer; The anti-electrostatic agent interfering; Weighting agents such as calcium oxide, magnesium oxide, silicon-dioxide, zinc oxide, titanium oxide; Pigment; Preventing materials accumulation agent (order ヤ ニ prevents drug); Lubricant; Anti; Whipping agent; Polymine etc.
The thickness of substrate layer can adopt appropriate arbitrarily thickness according to purpose.As this kind thickness, be preferably 20～300 μ m, more preferably 30～250 μ m, more preferably 40～200 μ m.
In the rear side of substrate layer, for giving anti-skid or the easy purpose of cutting property (handycut), also can implement concavo-convex processing.In addition, also can form various functional layers such as printed layers in the rear side of substrate layer.
Bonding coat is the phenylethylene resin series layer, contains phenylethylene resin series.Phenylethylene resin series in the bonding coat contain proportional being preferably more than the 50 weight %, more preferably more than the 60 weight %, more preferably more than the 70 weight %, be preferably especially more than the 80 weight %, most preferably be more than the 90 weight %.This kind phenylethylene resin series both can only use a kind, also can use more than 2 kinds.
As phenylethylene resin series contained in the bonding coat, can adopt appropriate arbitrarily phenylethylene resin series.Among the present invention, as phenylethylene resin series, be preferably the hydrogenation thing of the mixture of A/B/A or A/B/A and A '/B '.Here, A and A ' are the polymeric blocks that is made of styrenic monomers, and B and B ' are the polymeric blocks that is made of conjugated diolefine.
The molecular weight of the polymeric blocks that is made of styrenic monomers is preferably 1000～1000000, and more preferably 2000～100000.The second-order transition temperature of the polymeric blocks that is made of styrenic monomers is preferably more than 20 ℃.
The molecular weight of the polymeric blocks that is made of conjugated diolefine is preferably 1000～1000000, and more preferably 10000～300000.The second-order transition temperature of the polymeric blocks that is made of conjugated diolefine is preferably below-20 ℃.
As styrenic monomers, can adopt the appropriate monomer arbitrarily with vinylbenzene structure.As this kind styrenic monomers, for example can enumerate vinylstyrene, vinyl-dimethyl benzene, ethyl styrene, isopropyl benzene ethene, alpha-methyl styrene etc.Styrenic monomers can only be a kind both, also can be more than 2 kinds.
As conjugated diolefine, can adopt the appropriate monomer arbitrarily with conjugated diolefine structure.As this kind conjugated diolefine, for example can enumerate divinyl, isoprene etc.Conjugated diolefine can only be a kind both, also can be more than 2 kinds.
Among the present invention, phenylethylene resin series is preferably the hydrogenation thing of the segmented copolymer of vinylbenzene and divinyl.
The hydrogenation of phenylethylene resin series is preferably the optionally state of hydrogenation of the polymeric blocks that will be made of conjugated diolefine.The degree of the hydrogenation of the polymeric blocks that is made of conjugated diolefine of phenylethylene resin series generally is preferably more than the 60 weight % with respect to the conjugated diolefine composition, more preferably more than the 80 weight %.Generally under the situation less than 60 weight %, enough tear strengths might can't be embodied with respect to the conjugated diolefine composition in the degree of the hydrogenation of the polymeric blocks that is constituted by conjugated diolefine of phenylethylene resin series.
In the phenylethylene resin series of the present invention, the ratio of A and B is preferably A: B=5: 95～50: the ratio of 50, A ' and B ' is preferably A ': B '=5: 95～50: 50.
Shearing storage elastic modulus under the 1Hz of binder layer is below the 2.0MPa at 0 ℃, is preferably below the 1.5MPa, more preferably 0.5～1.0MPa.If the shearing storage elastic modulus under the 1Hz of binder layer is limited in the above-mentioned scope; just can provide following surface protective plate; namely; weathering resistance is very excellent; the difference of the bounding force that is caused by temperature variation is minimum, even can prevent effectively that also tackiness agent is by the glue trace on the adherend peeling off during at high temperature after the attaching.
The velocity of variation of this shearing storage elastic modulus of the shearing storage elastic modulus under the 1Hz of binder layer when being heated to 60 ℃ from 0 ℃ is in 1/100, is preferably in 1/50, more preferably in 1/30, is preferably in 1/10 especially.If the rate of change limit of the above-mentioned shearing storage elastic modulus in the time of will being heated to 60 ℃ from 0 ℃ is in the above-mentioned scope; just can provide following surface protective plate; namely; weathering resistance is very excellent; the difference of the bounding force that is caused by temperature variation is minimum, even can prevent effectively that also tackiness agent is by the glue trace on the adherend peeling off during at high temperature after the attaching.
In bonding coat, for purposes such as adjusting binding propertys, also can in the scope of not damaging purpose of the present invention, mix other phenylethylene resin series.
When forming bonding coat, for purposes such as control adhesion characteristics, as required, for example can suitably add tenderizer, ethylene series resin, silicone-based polymkeric substance, aqueous acrylic copolymer, tackifier, protective agent, hindered amine is photostabilizer, UV light absorber, polymine, fatty acid amide, phosphoric acid ester, weighting agent or pigment additives such as (for example calcium oxide, magnesium oxide, silicon-dioxide, zinc oxide, titanium oxide etc.).
As tackifier, for example can use petroleum line resin, coumarone-indenes such as aliphatics based copolymer, aromatic series based copolymer, aliphatics aromatic series based copolymer system or ester ring type based copolymer is that resin, terpenic series resin, terpenes phenolic aldehyde are that rosin series resins such as resin, polymerized rosin, (alkyl) phenolic aldehyde are the material that resin, diformazan benzene series resin, their hydride etc. generally use in tackiness agent with being not particularly limited.Tackifier both can only use a kind, also can use more than 2 kinds.In the middle of these tackifier, consider the tackifier that preferred hydrogenation is from aspects such as separability or weathering resistances.And, the material that tackifier also can use conduct and the mixture of olefin resin to sell in market.
The cooperation of tenderizer is effective for improving bounding force.As tenderizer, for example can enumerate softening agent such as treated oils such as low-molecular-weight diene polymer, polyisobutene, hydrogenated polyisoprene, hydrogenated butadiene polymer, naphthene series or aromatic series, dioctyl phthalate (DOP) or Octyl adipate, fragrant family hydrogenated resin, their derivative etc.As this kind derivative, for example can example be illustrated in the material that an end or two ends have OH base or COOH base, specifically, can enumerate hydrogenated butadiene polymer glycol, hydrogenated butadiene polymer single methanol, hydrogenated polyisoprene glycol, hydrogenated polyisoprene single methanol etc.Particularly, from suppressing considered the hydride of diene polymers such as preferred hydrogenated butadiene polymer or hydrogenated polyisoprene or ethylene series tenderizer etc. by the purpose of the fusible raising of adherend.As this kind tenderizer, specifically, can buy the trade(brand)name " Kuraprene LIR-200 " of (strain) Kuraray system etc.These tenderizers both can only use a kind, also can use more than 2 kinds.
The molecular weight of tenderizer can suitably be set at appropriate arbitrarily amount, if yet molecular weight diminishes, then might cause from bonding coat to by the substance transfer of adherend or heavy peeling off etc., on the other hand, if the molecule quantitative change is big, then have the trend of the raising effect that lacks bounding force, so the number-average molecular weight of tenderizer is preferably 5000～100,000, more preferably 10,000～50,000.
Also can be as required to bonding coat surface embodiment such as Corona discharge Treatment, uviolizing processing, flame treating, Cement Composite Treated by Plasma, sputter etching processing etc. with to fusible control or to attach operability etc. be the surface treatment of purpose.
The thickness of bonding coat is as long as suitably be set at appropriate arbitrarily thickness according to desired bounding force etc.The thickness of bonding coat is preferably 1～50 μ m, more preferably 2～40 μ m, more preferably 5～20 μ m.
Phenylethylene resin series before the hydrogenation can utilize arbitrarily appropriate methods to make.As this kind manufacture method, for example in unreactive hydrocarbons solvent (for example hexanaphthene etc.), use s-butyl lithium etc. is carried out the living polymerization of styrenic monomers, add conjugated diolefine then, two block structures of the polymeric blocks of the polymeric blocks that formation is made of styrenic monomers/constituted by conjugated diolefine, if desired, then form three block structures to wherein adding styrenic monomers again.In addition, also can form three block structures, branched block copolymer structure etc. by using the above coupling agent of 2 officials energy.
Method as to the hydrogenation of phenylethylene resin series can adopt appropriate methods arbitrarily.As this kind method, for example can enumerate following method etc., namely, dissolving phenylethylene resin series in unreactive hydrocarbons solvent (for example hexanaphthene etc.), add to use catalyst reduction such as aluminum alkyls cobalt or nickel etc., under the temperature about 25～50 ℃, use 5～40kg/cm 3About hydrogen, under pressure, react about 10～60 minutes.
Surface protective plate of the present invention can utilize arbitrarily appropriate methods to make.Surface protective plate of the present invention for example can utilize the coetrusion film forming to obtain substrate layer and bonding coat by using the formation material that forms above-mentioned substrate layer and the formation material that forms above-mentioned bonding coat.Surface protective plate of the present invention is because substrate layer comprises the white color system layer at least and black is 2 layers on layer; therefore the formation material that forms substrate layer is more than 2 kinds; so; surface protective plate of the present invention can be by the formation material more than 2 kinds that use to form substrate layer and the formation material that forms bonding coat, with substrate layer and bonding coat multilayer utilize the coetrusion film forming to obtain.
Formation as surface protective plate of the present invention is not particularly limited, and can adopt any one formation of " white color system layer/black system layer/bonding coat ", " black system layer/white color system layer/bonding coat ".In addition, as substrate layer, also can be made as the layer more than 3 layers that forms black system layer and white color system layer layer in addition and constitute.Specifically, also can be made as formations such as " transparent resin layers/white color system layer/black system layer/bonding coat ".In addition, the thickness of white color system layer and black system layer both can be identical, also can be different thickness (the white color system layer than the black system thin thickness of layer constitute, the white color system layer is that the thickness of bed thickness constitutes than black).
As coetrusion, can wait to carry out according to blow moulding, the T die head method generally used in the thin film fabrication etc.Can implement above-mentioned surface treatment to substrate layer and bonding coat as required.
For bonding coat, also can be as required, before being used for practical application during, attach barrier film etc. temporarily and protected.And, the face of not setting up bonding coat for substrate layer, be easy to the purposes such as coiling body of uncoiling for formation, for example also can carry out the demoulding and handle or arrange the coating layer that comprises suitable stripper such as silicone-based, chain alkyl system, fluorine system by in substrate layer, adding fatty acid amide or polymine etc.
Embodiment
Below, utilize the present invention of embodiment to be specifically described, yet the present invention is not subjected to any restriction of these embodiment.
[Production Example 1]: the manufacturing of polymkeric substance 1
Vinylbenzene 40g and hexanaphthene 400g are dropped in the autoclave, carry out nitrogen replacement, drop into 0.003 mole the s-butyl lithium in the hexanaphthene of being dissolved in.After 1 hour, additional input divinyl 400g, hexanaphthene 2000g reacted 2 hours at 60 ℃ again 60 ℃ of reactions.After the reaction, drop into vinylbenzene 40g and hexanaphthene 400g again, reacted again 1 hour at 60 ℃.Utilize this reaction, prepare the SBS block polymer.As catalyzer, make acetylacetonate nickel 1.5 mmoles and triethyl aluminum 3 mmoles in hexanaphthene 500ml with 25 ℃ of reactions 10 minutes, it is added in the reaction system of SBS block polymer of above-mentioned gained.Thereafter, to using hydrogen with 30kg/cm in the autoclave 3Pressurization is elevated to 50 ℃ with temperature of reaction, stops hydrogenation after 20 minutes.Like this, just obtain polymkeric substance as shown in table 11.
[Production Example 2]: the manufacturing of polymkeric substance 2
Except changing, obtain polymkeric substance as shown in table 12 in the same manner with Production Example 1 as shown in table 1ly.
[Production Example 3]: the manufacturing of polymkeric substance 3
Except changing, obtain polymkeric substance as shown in table 13 in the same manner with Production Example 1 as shown in table 1ly.
[Production Example 4]: the manufacturing of polymkeric substance 4
Except changing, obtain polymkeric substance as shown in table 14 in the same manner with Production Example 1 as shown in table 1ly.
[embodiment 11
To add in the polyethylene (Japanese polyethylene corporate system, ノ バ テ Star Network LD-LF547) 20 weight % white pigment (corporate system, HCM2035W refine big day) and the white layer of base material form material and add in the polyethylene (Japanese polyethylene corporate system, ノ バ テ Star Network LD-LF547) 2 weight % carbon black (Mitsubishi Chemical's system, carbon black " #45 ") and the black layer of base material form a material use T die head coextrusion (extruder temperature: 200 ℃, die head temperature: the 200 ℃) film forming that is shaped, obtain white black bilayer film (white layer/black layer=30 μ m/30 μ m).
White black layer side of deceiving bilayer film to gained implemented corona treatment; the polymkeric substance 1 that obtains in Production Example 1 in the coating of this treated side and various composition cooperate as shown in table 2ly and be dissolved in the toluene and binder composition (solids component 33 weight %); with 100 ℃ * 5 minutes dryings, produce surface protective plate.
The thickness of the substrate layer of the surface protective plate of gained is 60 μ m, and the thickness of bonding coat is 10 μ m.
[embodiment 2]
Will be to polyethylene (Japanese polyethylene corporate system; ノ バ テ Star Network LD-LF547) adds the white pigment (corporate system of refining big day of 20 weight % in; HCM2035W) and the white layer of base material form material; to polyethylene (Japanese polyethylene corporate system; ノ バ テ Star Network LD-LF547) adds carbon black (Mitsubishi Chemical's system of 2 weight % in; carbon black " #45 ") and the black layer of base material form a material; form material use T die head coextrusion shaping (extruder temperature: 200 ℃ with bonding coat; die head temperature: 200 ℃) film forming; obtain surface protective plate (white layer/black layer/bonding coat=40 μ m/40 μ m/10 μ m); wherein; it is that the polymkeric substance 2 that will obtain in the Production Example 2 and various composition cooperate as shown in table 2ly and be dissolved in the toluene that bonding coat forms material; from the binder composition of gained, remove toluene, the material of gained is mixing and get with 150 ℃ * 20 minutes with kneader.
[embodiment 3]
To add in the polyethylene (Japanese polyethylene corporate system, ノ バ テ Star Network LD-LF547) 20 weight % white pigment (corporate system, HCM2035W refine big day) and the white layer of base material form material and add in the polyethylene (Japanese polyethylene corporate system, ノ バ テ Star Network LD-LF547) 2 weight % carbon black (Mitsubishi Chemical's system, carbon black " #45 ") and the black layer of base material form a material use T die head coextrusion (extruder temperature: 200 ℃, die head temperature: the 200 ℃) film forming that is shaped, obtain white black bilayer film (white layer/black layer=30 μ m/30 μ m).
White black layer side of deceiving bilayer film to gained implemented corona treatment; the polymkeric substance 3 that obtains in Production Example 3 in the coating of this treated side and various composition cooperate as shown in table 2ly and be dissolved in the toluene and binder composition (solids component 33 weight %); with 100 ℃ * 5 minutes dryings, produce surface protective plate.
The thickness of the substrate layer of the surface protective plate of gained is 60 μ m, and the thickness of bonding coat is 10 μ m.
[comparative example 1]
The substrate layer that will be only be made of polyethylene (Japanese polyethylene corporate system, ノ バ テ Star Network LD-LF547) forms material and the substrate layer that only is made of polyethylene (Japanese polyethylene corporate system, ノ バ テ Star Network LD-LF547) forms material use T die head coextrusion shaping (extruder temperature: 200 ℃, die head temperature: 200 ℃) film forming, obtains transparent double-layer film (transparent layer/transparent layer=30 μ m/30 μ m).
One side side to the transparent double-layer film of gained is implemented corona treatment; the polymkeric substance 1 that obtains in Production Example 1 in the coating of this treated side and various composition cooperate as shown in table 2ly and be dissolved in the toluene and binder composition (solids component 33 weight %); with 100 ℃ * 5 minutes dryings, produce surface protective plate.
The thickness of the substrate layer of the surface protective plate of gained is 60 μ m, and the thickness of bonding coat is 10 μ m.
[comparative example 2]
The substrate layer that will be only be made of polyethylene (Japanese polyethylene corporate system, ノ バ テ Star Network LD-LF547) forms material and the substrate layer that only is made of polyethylene (Japanese polyethylene corporate system, ノ バ テ Star Network LD-LF547) forms material use T die head coextrusion shaping (extruder temperature: 200 ℃, die head temperature: 200 ℃) film forming, obtains transparent double-layer film (transparent layer/transparent layer=30 μ m/30 μ m).
One side side to the transparent double-layer film of gained is implemented corona treatment; the polymkeric substance 2 that obtains in Production Example 2 in the coating of this treated side and various composition cooperate as shown in table 2ly and be dissolved in the toluene and binder composition (solids component 33 weight %); with 100 ℃ * 5 minutes dryings, produce surface protective plate.
The thickness of the substrate layer of the surface protective plate of gained is 60 μ m, and the thickness of bonding coat is 10 μ m.
[comparative example 3]
The substrate layer that will be only be made of polyethylene (Japanese polyethylene corporate system, ノ バ テ Star Network LD-LF547) forms material and the substrate layer that only is made of polyethylene (Japanese polyethylene corporate system, ノ バ テ Star Network LD-LF547) forms material use T die head coextrusion shaping (extruder temperature: 200 ℃, die head temperature: 200 ℃) film forming, obtains transparent double-layer film (transparent layer/transparent layer=30 μ m/30 μ m).
One side side to the transparent double-layer film of gained is implemented corona treatment; the polymkeric substance 3 that obtains in Production Example 3 in the coating of this treated side and various composition cooperate as shown in table 2ly and be dissolved in the toluene and binder composition (solids component 33 weight %); with 100 ℃ * 5 minutes dryings, produce surface protective plate.
The thickness of the substrate layer of the surface protective plate of gained is 60 μ m, and the thickness of bonding coat is 10 μ m.
[comparative example 4]
To add in the polyethylene (Japanese polyethylene corporate system, ノ バ テ Star Network LD-LF547) 20 weight % white pigment (corporate system, HCM2035W refine big day) and the white layer of base material form material and add in the polyethylene (Japanese polyethylene corporate system, ノ バ テ Star Network LD-LF547) 2 weight % carbon black (Mitsubishi Chemical's system, carbon black " #45 ") and the black layer of base material form a material use T die head coextrusion (extruder temperature: 200 ℃, die head temperature: the 200 ℃) film forming that is shaped, obtain white black bilayer film (white layer/black layer=30 μ m/30 μ m).
White black layer side of deceiving bilayer film to gained implemented corona treatment; the polymkeric substance 2 that obtains in Production Example 2 in the coating of this treated side and various composition cooperate as shown in table 2ly and be dissolved in the toluene and binder composition (solids component 33 weight %); with 100 ℃ * 5 minutes dryings, produce surface protective plate.
The thickness of the substrate layer of the surface protective plate of gained is 60 μ m, and the thickness of bonding coat is 10 μ m.
[comparative example 5]
To add in the polyethylene (Japanese polyethylene corporate system, ノ バ テ Star Network LD-LF547) 20 weight % white pigment (corporate system, HCM2035W refine big day) and the white layer of base material form material and add in the polyethylene (Japanese polyethylene corporate system, ノ バ テ Star Network LD-LF547) 2 weight % carbon black (Mitsubishi Chemical's system, carbon black " #45 ") and the black layer of base material form a material use T die head coextrusion (extruder temperature: 200 ℃, die head temperature: the 200 ℃) film forming that is shaped, obtain white black bilayer film (white layer/black layer=30 μ m/30 μ m).
White black layer side of deceiving bilayer film to gained implemented corona treatment; the polymkeric substance 1 that obtains in Production Example 1 in the coating of this treated side and various composition cooperate as shown in table 2ly and be dissolved in the toluene and binder composition (solids component 33 weight %); with 100 ℃ * 5 minutes dryings, produce surface protective plate.
The thickness of the substrate layer of the surface protective plate of gained is 60 μ m, and the thickness of bonding coat is 10 μ m.
[comparative example 6]
To add in the polyethylene (Japanese polyethylene corporate system, ノ バ テ Star Network LD-LF547) 20 weight % white pigment (corporate system, HCM2035W refine big day) and the white layer of base material form material and add in the polyethylene (Japanese polyethylene corporate system, ノ バ テ Star Network LD-LF547) 2 weight % carbon black (Mitsubishi Chemical's system, carbon black " #45 ") and the black layer of base material form a material use T die head coextrusion (extruder temperature: 200 ℃, die head temperature: the 200 ℃) film forming that is shaped, obtain white black bilayer film (white layer/black layer=30 μ m/30 μ m).
White black layer side of deceiving bilayer film to gained implemented corona treatment; the polymkeric substance 4 that obtains in Production Example 4 in the coating of this treated side and various composition cooperate as shown in table 2ly and be dissolved in the toluene and binder composition (solids component 33 weight %); with 100 ℃ * 5 minutes dryings, produce surface protective plate.
The thickness of the substrate layer of the surface protective plate of gained is 60 μ m, and the thickness of bonding coat is 10 μ m.
[evaluation test]
(bounding force)
Respectively on polyvinyl chloride panel (Ra=2.6 μ m), melamine plate (Ra=1.6 μ m); under the condition of 0 ℃ and 60 ℃; the surface protective plate that obtains in applying embodiment and the comparative example is placed after 1 hour under 20 ℃, 65%RH, measures 180 ° of bounding forces that draw when shelling.Draw stripping speed to be made as 300mm/ minute.The results are shown in Table 2.
(glue trace)
Respectively on polyvinyl chloride panel (Ra=2.6 μ m), melamine plate (Ra=1.6 μ m); under 60 ℃ condition; the surface protective plate that obtains in applying embodiment and the comparative example; under 20 ℃, 65%RH, place after 1 hour, utilize visual observation to carry out having or not of 180 ° of glue traces when drawing stripping with 300mm/ minute the stripping speed of drawing.The results are shown in Table 2.
(shearing storage elastic modulus)
The shearing storage elastic modulus of 0 ℃ of the bonding coat of surface protective plate and 60 ℃ is when the ARES that uses Rheometric Scientific corporate system gives the shear of frequency of 1Hz, give-60～150 ℃ temperature variation (5 ℃ of heat-up rates/min) measure.The bonding coat that the mensuration sample is made about thick 3mm is measured.The making of bonding coat is to utilize the casting method of organic solvent or pressure sintering to carry out.And, for the mensuration of the shearing storage elastic modulus of bonding coat, can't carry out under the situation of these methods, also can be with the mensuration of obtaining according to the difference of the shearing storage elastic modulus of the shearing storage elastic modulus of surface protective plate and base material such as method.The results are shown in Table 2.
(mensuration of weathering resistance)
The surface protective plate that obtains in embodiment and the comparative example is cut into the rectangle of wide 20mm and produces the evaluation sample.The roller by making 2kg 1 time and after being crimped on this sample on the SUS430BA plate back and forth, dropped in the sunlight carbon arc weather resistance test machine (Suga trier Co., Ltd. product) 1000 hours, then, peel off length to 100mm with 0.3m/ minute the end of draw speed along 180 ° of directions from sample.
According to the above-mentioned result of following benchmark evaluation.The results are shown in Table 2.
Zero: sample is not broken, can peel off very well.
*: because the deterioration of base material makes sample broken on the way, perhaps adhesive residue is in by adherend and with its pollution.
[table 1]
Figure BSA00000671563500131
Can distinguish that according to table 2 surface protective plate weathering resistance of the present invention is very excellent, the difference of the bounding force that is caused by temperature variation is minimum, even can prevent effectively that also tackiness agent is by the glue trace on the adherend peeling off during at high temperature after the attaching.
Utilizability on the industry
Surface protective plate of the present invention can be used for following purposes etc.; namely; for example to metal sheet, application member such as metal sheet, aluminum alloy frame, resin board, decorative steel plate, vinylchlorid laminate steel, sheet glass carry, when processing or maintenance etc., be attached to these component surface and protected.

Claims (3)

1. surface protective plate, its one side at substrate layer is formed with bonding coat,
This bonding coat comprises phenylethylene resin series,
Shearing storage elastic modulus under the 1Hz of this binder layer is below the 2.0MPa at 0 ℃, and the velocity of variation of this shearing storage elastic modulus is in 1/100 when being heated to 60 ℃.
2. surface protective plate according to claim 1, wherein,
Described substrate layer comprises the white color system layer at least and black is these 2 layers on layer.
3. surface protective plate according to claim 1, wherein,
Described phenylethylene resin series is the hydrogenation thing of the segmented copolymer of vinylbenzene and divinyl.
CN2012100361246A 2012-02-15 2012-02-15 Surface protection sheet Pending CN103254809A (en)

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Application publication date: 20130821