CN103254813A - Surface protection sheet - Google Patents
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- CN103254813A CN103254813A CN2012100361392A CN201210036139A CN103254813A CN 103254813 A CN103254813 A CN 103254813A CN 2012100361392 A CN2012100361392 A CN 2012100361392A CN 201210036139 A CN201210036139 A CN 201210036139A CN 103254813 A CN103254813 A CN 103254813A
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- protective plate
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Abstract
The invention provides a surface protection sheet. The surface protection sheet is formed through co-extrusion molding, and has the advantages of excellent weatherability, good uncoiling property, inhibition of the pollution of the surface of an adhered surface, and excellent adhesive strength even the surface protection sheet is stored in the high temperature environment. The invention also provides a making method of the surface protection sheet. The surface protection sheet is formed through the co-extrusion molding of a substrate layer including a polyolefin series resin as a main component, a back processing layer formed on one side of the substrate layer and including a polyethylene series resin as a main component, and an adhesive layer formed on the other side of the substrate layer and including a thermoplastic resin as a main component, wherein the substrate layer includes a black pigment, the back processing layer includes a white pigment, and the back processing layer also includes fatty acid derivatives accounting for 0.05-1.00wt% of the polyethylene series resin.
Description
Technical field
The present invention relates to a kind of surface protective plate.Specifically, the present invention relates to the surface protective plate that a kind of substrate layer, back side processing layer and bonding coat form as one by coextrusion.Surface protective plate of the present invention can be used for being fitted on their surface and purposes of protecting etc. for example when opticses such as parts, polarizing coating, liquid crystal panel, electronic units such as carrying, processing or maintenance metal sheet, coated plate, aluminum alloy frame, resin board, decorative steel plate, vinylchlorid laminate steel, sheet glass etc. etc.
Background technology
Surface protective plate is provided with bonding coat in a side of substrate sheet, is typically provided with the release layer of the separability when guaranteeing sheet material from the roll body uncoiling at opposite side.For such surface protective plate, except claimed performance, as essential function, pay attention to through the time separability, the contaminative after peeling off etc. after preserving.
Be contaminative outbalance under the situations such as optics, electronic unit, coated plate or mirror metal plate by adherend particularly.At present; such by the surface protective plate of the purposes of protecting on the surface of adherend as being fitted in, general known have solution coat by will being dissolved in back side treatment agent in the organic solvent or demoulding drug on substrate sheet and carry out the solvent-borne type surface protective plate that drying forms release layer.But, in recent years, consider from the viewpoint of environment protection, not with an organic solvent and the requirement of the surface protective plate of making just improves constantly.
As one of method of with an organic solvent not making surface protective plate, propose to have a kind of substrate layer that will be constituted by polyolefin-based resins by coetrusion and the bonding coat shaped surface protection that constituted by the thermoplastic bonded resin with bonding film (for example with reference to patent documentation 1).But this surface protection only is made of substrate layer and bonding coat with bonding film, therefore, is making under the situation of roll body, and uncoiling sometimes is poor, can't uncoiling.
Therefore, for the surface protective plate that utilizes coetrusion to obtain (comprising surface protection film, self adhesive tape etc.), up to now, propose to have various demoulding factures.
For example, propose to have by roller or cloth etc. the self adhesive tape (for example with reference to patent documentation 2) that friction treatment obtains is carried out at the back side of substrate layer.But such self adhesive tape is difficult to carry out uniform friction treatment, and therefore, existence can't obtain good release property, can not fully reduce problems such as uncoiling power.In addition, because the cooperation of substrate layer produces uneven sometimes in stripping result.And then, can't remove the resin-oatmeal that produces in when friction fully, this becomes the reason of pollution etc.
Proposition has that a kind of to add fatty acid amide in bonding coat be the surface protective plate (for example with reference to patent documentation 3) of additive.But such surface protective plate need contain fatty acid amide in bonding coat be additive, therefore, easily becomes and pollute the reason that produces.
Proposition has that a kind of to add the ether acid amides in substrate layer be the surface protection film (for example with reference to patent documentation 4) of additive.But; though uncoiling, contaminative after such surface protection film is made are good; but under the situation of taking care of under the high temperature environment such as summer; sometimes the ether acid amides as demoulding composition is that additive is separated out between processing layer and the substrate layer or between bonding coat and the substrate layer in time overleaf, produces to pollute.
Proposition has that a kind of to add fatty acid amide in as the substrate layer in the middle layer of surface protection film be the surface protection film (for example with reference to patent documentation 5) of additive.But, such surface protection film makes fatty acid amide be additive through the time separate out, therefore, do not have effect after existing in manufacturing, even through behind the certain hour, can't show the problem of effect yet.
The trial of the reduction of the bounding force that causes as dividing a word with a hyphen at the end of a line of the stripper that improves relative tackiness agent etc., proposing has a kind of use that the self adhesive tape (for example with reference to patent documentation 6) of polyvinyl polymkeric substance and chain alkyl isocyanic ester is arranged.But, because that chain alkyl is the molecular weight of back side treatment agent is big, therefore, exist stripper to the surface separate out the effect deficiency, almost do not show the problem of stripping result.And then therefore such self adhesive tape back side treatment agent thermal degradation when and generate low molecular compound when extrusion molding, becomes the reason of the pollution of bonding coat etc.
In addition, existing surface protective plate does not fully possess weathering resistance is arranged, use without or high temperature under under the situation of preserving, exist its bounding force through the time increase the problem of the separability variation when being peeled off by adherend.
As mentioned above; in the existing surface protective plate that forms that forms as one by coextrusion; even under hot environment under the situation of keeping, also can't balancedly show excellent weathering resistance, good uncoiling, by the inhibition of the pollution on adherend surface, excellent adhesion strength.
The prior art document
Patent documentation 1: Japanese kokai publication sho 61-103975 communique
Patent documentation 2: Japanese kokai publication hei 2-252777 communique
Patent documentation 3: Japanese kokai publication hei 10-176147 communique
Patent documentation 4: Japanese kokai publication hei 10-309781 communique
Patent documentation 5: Japanese kokai publication hei 9-217046 communique
Patent documentation 6: Japanese kokai publication hei 11-43655 communique
Summary of the invention
The problem that invention will solve
Problem of the present invention is to provide a kind of surface protective plate; it forms as one by coextrusion and forms; wherein; even under the situation of described surface protective plate keeping under hot environment, also can balancedly show excellent weathering resistance, good uncoiling, by the inhibition of the pollution on adherend surface, excellent adhesion strength.In addition, the object of the present invention is to provide a kind of method of making such surface protective plate.
Be used for solving the means of problem
Surface protective plate of the present invention be comprise polyolefin-based resins as the substrate layer of main component, be formed at the comprising polyethylene-based resin as the back side processing layer of main component and be formed at the comprising that thermoplastic resin is shaped by coextrusion as the bonding coat of main component of another side of this substrate layer and integrally formed of one side of this substrate layer
This substrate layer comprises black pigment,
This back side processing layer comprises white pigment,
This back side processing layer comprises the derivative of fatty acid of 0.05～1.00 weight % with respect to this polyethylene-based resin.
In preferred embodiment, described derivative of fatty acid is fatty acid amide.
In preferred embodiment, described fatty acid amide is for being selected from least a in methylene-bis stearylamide, ethylenebisstearamide, N-stearyl-N '-stearylamide.
In preferred embodiment, the density of described polyethylene-based resin is 0.880～0.940g/cm
3
In preferred embodiment, the thickness of described back side processing layer is 1～20 μ m.
A kind of manufacture method of surface protective plate is provided according to other aspects of the invention.The manufacture method of surface protective plate of the present invention has: will comprise polyolefin-based resins as main component and comprise black pigment substrate layer, be formed at this substrate layer one side back side processing layer and be formed at this substrate layer another side comprise thermoplastic resin as the bonding coat of main component; be shaped and integrally formed operation by coextrusion
In the processing layer of the described back side, comprise polyethylene-based resin and comprise the derivative of fatty acid of 0.05～1.00 weight % and comprise white pigment as main component and with respect to this polyethylene-based resin.
In preferred embodiment, described derivative of fatty acid is fatty acid amide.
In preferred embodiment, described fatty acid amide is for being selected from least a in methylene-bis stearylamide, ethylenebisstearamide, N-stearyl-N '-stearylamide.
In preferred embodiment, the density of described polyethylene-based resin is 0.880～0.940g/cm
3
In preferred embodiment, the thickness of above-mentioned back side processing layer is 1～20 μ m.
The invention effect
According to the present invention; a kind of surface protective plate can be provided; it forms as one by coextrusion and forms; wherein; even under the situation of described surface protective plate keeping under hot environment, also can balancedly show excellent weathering resistance, good uncoiling, by the inhibition of the pollution on adherend surface, excellent adhesion strength.In addition, can provide a kind of method of making such surface protective plate.
Embodiment
Surface protective plate of the present invention be comprise polyolefin-based resins as the substrate layer of main component, the one side of this substrate layer formed comprise polyethylene-based resin as the back side processing layer of main component, and be shaped and integrally formed surface protective plate by coextrusion as the bonding coat of main component at the formed thermoplastic resin that comprises of the another side of this substrate layer.
At this, in the present invention, " main component " refers to more than the preferred 50 weight %, more preferably more than the 60 weight %, further more than the preferred 70 weight %, more than the preferred especially 80 weight %, most preferably more than the 90 weight %.
Surface protective plate of the present invention can by coextrusion be shaped laminated substrate layer, back side processing layer, and bonding coat make.Be shaped as coextrusion, can adopt the general appropriate means arbitrarily that is used for the manufacturing of film, sheet material etc.Be shaped as coextrusion, particularly, make the multilayer more than three layers or four layers, for example can use blow moulding, coextrusion T die head method etc.From the cost aspect and the productivity aspect consider, preferably use these coextrusion to be shaped.
Substrate layer, back side processing layer, and bonding coat can be individual layer respectively, also can be multilayer.
Substrate layer comprises polyolefin-based resins as main component.Substrate layer comprises polyolefin-based resins as main component, can have thermotolerance, solvent resistance, pliability thus, can easily be wound into the roller shape.Polyolefin-based resins contained in the substrate layer can only be a kind of, also can be for two or more.
As polyolefin-based resins, for example can enumerate: polyethylene-based resin, the propylene resin that is formed by propylene or propylene composition and ethene composition, ethylene vinyl acetate copolymer etc.
As polyolefin-based resins, particularly, for example can enumerate: high density polyethylene(HDPE) (HDPE), medium-density polyethylene, Low Density Polyethylene (LDPE), straight chain shape Low Density Polyethylene (LLDPE), polypropylene, poly-1-butylene, poly--4-methyl-1-pentene, ethylene propylene copolymer, the ethene butene-1 copolymer, ethene 1-hexene copolymer, the ethene 4 methyl 1 pentene copolymer, ethene 1-octene copolymer, ethylene methyl acrylate copolymer, the ethylene methacrylic acid methyl terpolymer, ethylene vinyl acetate copolymer, ethylene ethyl acrylate copolymer, ethylene-vinyl alcohol copolymer etc.
Under the situation that substrate layer is made of the multilayer more than two-layer, preferably the layer of each adjacency selects to form mutually by dissolving coextrusion firm bonding layer as the resinous principle that constitutes it.
Substrate layer comprises black pigment.Thus, can make the very excellent surface protective plate of weathering resistance.
As black pigment, for example can enumerate carbon black.The proportional resinous principle with respect to the formation substrate layer that contains of the black pigment in the substrate layer is preferably 0.01～10 weight %, more preferably 0.1～5 weight %, more preferably 0.5～3 weight %.Containing of black pigment in the substrate layer is proportional when being lower than 0.01 weight %, might give sufficient weathering resistance to the surface protective plate that obtains.Containing of black pigment in the substrate layer is proportional when surpassing 10 weight %, might be extrudability etc. the plasticity deficiency.
Substrate layer can contain suitable additive arbitrarily.As such additive, for example can enumerate: the pigment beyond various weighting agents, the black pigment, UV light absorber, antioxidant, heat-resisting stabilizing agent, lubricant etc.
The thickness of substrate layer is preferably 20～300 μ m, more preferably 20～250 μ m, more preferably 40～200 μ m.Thickness at substrate layer is lower than under the situation of 20 μ m, might be when peeling off substrate layer damaged or break.Surpass under the situation of 300 μ m at the thickness of substrate layer, hardness that might substrate layer becomes big, fit the back easily generation float etc.
Back side processing layer is formed on the one side of substrate layer, when surface protective plate of the present invention is wound into the roller shape, with the bonding coat butt, during uncoiling, with the uncoiling power of appropriateness, easily peels off from bonding coat, has the effect of keeping good uncoiling.
Back side processing layer comprises polyethylene-based resin as main component.Back side processing layer comprises polyethylene-based resin as main component, can have thermotolerance, solvent resistance, pliability thus, can easily be wound into the roller shape.Polyethylene-based resin contained in the processing layer of the back side can only be a kind of, also can be for two or more.
As polyethylene-based resin, for example can enumerate density is 0.880～0.940g/cm
3Polyethylene-based resin.As such polyethylene-based resin, particularly, for example can enumerate: Low Density Polyethylene (LDPE), straight chain shape Low Density Polyethylene (LLDPE), medium-density polyethylene, high density polyethylene(HDPE) (HDPE), ethylene propylene copolymer, ethene butene-1 copolymer, ethene 1-hexene copolymer, ethene 4 methyl 1 pentene copolymer, ethene 1-octene copolymer, ethylene methyl acrylate copolymer, ethylene methacrylic acid methyl terpolymer etc.In addition, the density (g/cm among the present invention
3) refer to the value measured according to ISO1183.The polyethylene-based resin of such density is used for back side processing layer, even the addition of derivative of fatty acid is a small amount of thus, also can brings into play and peel off effect fully, and then, also can make through the time the surface amount of separating out stabilization, therefore, be difficult to through the time to being polluted by adherend.Density at polyethylene-based resin is lower than 0.880g/cm
3Situation under, the sliding that might cause back side processing layer reduce or the adhesion the when back side of surface protective plate overlapped each other defective.Density at polyethylene-based resin surpasses 0.940g/cm
3Situation under, adding a spot of aliphatic derivatives does not separate out from the teeth outwards, be difficult to show fully stripping result, it is heavy that uncoiling power becomes, on the other hand, the addition that increases aliphatic derivatives when showing the degree of stripping result fully, overleaf in the processing layer residual aliphatic derivatives and through the time carry out the surface and separate out, produce and pollute.
Density as polyethylene-based resin is preferably 0.880～0.923g/cm
3, 0.880～0.915g/cm more preferably
3
In separating out under the degree of effect also processing layer overleaf, the surface that does not reduce derivative of fatty acid adds the polyolefin-based resins beyond the polyethylene-based resin.As the addition of such polyolefin-based resins, be preferably 0～30 weight % with respect to polyethylene-based resin, more preferably 0～20 weight %, more preferably 0～10 weight %.Such polyolefin-based resins can only be a kind of, also can be for two or more.
Back side processing layer comprises white pigment.Thus, can make the very excellent surface protective plate of weathering resistance.
Back side processing layer is preferably the layer of the tone of display white system, and for example the whiteness of stipulating among the JIS-L-1015 is preferably more than 60%, more preferably more than 70%, more preferably more than 80%, is preferably more than 85% especially.
As white pigment, for example can enumerate titanium oxide.The proportional resinous principle with respect to formation back side processing layer that contains of the white pigment in the processing layer of the back side is preferably 5～30 weight %, more preferably 6～25 weight %, more preferably 6～20 weight %.Containing of white pigment in the processing layer of the back side is proportional when being lower than 5 weight %, might hidden power deficiency, and substrate layer and bonding coat are easily because of the ultraviolet ray deterioration.Containing of white pigment in the processing layer of the back side is proportional when surpassing 20 weight %, might be extrudability etc. the plasticity deficiency.
Back side processing layer contains derivative of fatty acid.Derivative of fatty acid in the processing layer of the back side can only be a kind of, also can be for two or more.
Derivative of fatty acid in the processing layer of the back side contain proportional to be 0.05～1.00 weight % with respect to the polyethylene-based resin in the processing layer of the back side, to be preferably 0.10～0.90 weight %, more preferably 0.30～0.80 weight %.Overleaf containing under the proportional situation that is lower than 0.05 weight % with respect to the polyethylene-based resin in the processing layer of the back side of the derivative of fatty acid in the processing layer, might uncoiling power become heavy, can't show stripping result fully.Proportionally surpass under the situation of 1.00 weight % with respect to the polyethylene-based resin in the processing layer of the back side containing of derivative of fatty acid in the processing layer overleaf, when making roll body, might move to bonding coat by the significant quantities of fat acid derivative, generation is to by the pollution of adherend.
As derivative of fatty acid, refer in molecular structure, comprise the compound of derivative of fatty acid structure.
As derivative of fatty acid, for example can enumerate: saturated fatty acid bisamide, unsaturated fatty acids bisamide, fragrant family bisamide, replacement urea, fatty acid metal salt etc.As derivative of fatty acid, particularly, for example can enumerate: methylene-bis stearylamide, ethylenebisstearamide, ethylenebisoleoamide, N, N-two oil base adipamides, N-stearyl-N '-N-stearyl-N '-stearylamide, Zinic stearass etc. such as stearyl urea.
As derivative of fatty acid, be preferably fatty acid amide, more preferably be selected from least a in methylene-bis stearylamide, ethylenebisstearamide, N-stearyl-N '-stearylamide.
The preferred fusing point of derivative of fatty acid is more than 100 ℃.Fusing point is lower than 100 ℃ derivative of fatty acid and might becomes the transfer printing on bonding coat surface and significantly, easily produce bounding force and reduce.
The thickness of back side processing layer is preferably 1～20 μ m, more preferably 2～18 μ m, more preferably 3～15 μ m.Be made as more than the 1 μ m by the thickness with back side processing layer, produce uneven thickness in the time of can being suppressed at coextrusion, even under the environment of heating or pressurization, also can prevent adhesion.The thickness of processing layer surpasses under the situation of 20 μ m overleaf, and total quantitative change of possible derivative of fatty acid is many, and therefore, peeling off that the transfer printing of generation pollution or derivative of fatty acid causes is bad.
Back side processing layer can contain suitable additive arbitrarily.As such additive, for example can enumerate: antioxidant, UV light absorber, anti-aging agent, hindered amine are photostabilizers such as photostabilizer; Static inhibitor, surface lubricant, flow agent, softening agent, low-molecular(weight)polymer, sanitas, stopper, silane coupling agent, inorganic and organic weighting agent (for example calcium oxide, magnesium oxide, silicon-dioxide, zinc oxide, titanium oxide etc.), metal powder, tinting material, pigment, heat-resisting stabilizing agent, preventing materials accumulation agent, lubricant, anti etc.
Bonding coat comprises thermoplastic resin as main component.Thermoplastic resin contained in the bonding coat can only be a kind of, also can be for two or more.
As thermoplastic resin, can adopt suitable arbitrarily thermoplastic resin.As such thermoplastic resin, for example can enumerate: it is resin etc. that ethylene series resin, aromatic series base contain olefin/diene copolymers, phenylethylene resin series, ester.In these thermoplastic resins, for example optimization styrene diene copolymers (comprising block polymer, graftomer, unregulated polymer), their hydride.
As phenylethylene resin series, particularly, for example can enumerate: styrene-butadiene-copolymer (SB), styrene isoprene multipolymer (SI), styrene ethylene-butylene copolymer (SEB), styrene ethylene-propylene copolymer A-B type diblock polymers such as (SEP); The multi-block polymer that styrene butadiene styrene multipolymer (SBS), styrene isoprene styrol copolymer (SIS), the cinnamic multipolymer of styrene ethylene-butylene copolymer (SEBS), styrene ethylene-propylene copolymer vinylbenzene A-B-A type three blocks such as (SEPS) or A-B-A-B type four blocks are above; Styrene butadiene ribber multipolymer polystyrene random copolymerss such as (SBR); The vinylbenzene alkene crystal system block polymer of styrene ethylene-butylene copolymer alkene crystallization A-B-C such as (SEBC) type etc.
As the ethylene series resin, particularly, for example can enumerate: ethylene series binder resins such as the alkene crystal system block polymer of alkene crystalline ethylene-butylene copolymer alkene crystallization C-B-C such as (CEBC) type, ethene-alpha-olefin copolymer, ethylene-propylene-alpha-olefin copolymer, propylene-alpha-olefin copolymers, ethylene vinyl acetate copolymer etc.
Bonding coat can contain suitable additive arbitrarily.As such additive, for example can enumerate: tenderizer, tackifier, as being used for the ethylene series resin of substrate layer and so on, the silicone-based polymkeric substance, aqueous propylene series copolymer, the phosphoric acid ester based compound, protective agent, hindered amine is photostabilizer, UV light absorber, surface lubricant, flow agent, softening agent, low-molecular(weight)polymer, antioxidant, sanitas, stopper, silane coupling agent, inorganic and organic weighting agent (calcium oxide for example, magnesium oxide, silicon-dioxide, zinc oxide, titanium oxide etc.), metal powder, tinting material, pigment, heat-resisting stabilizing agent etc.The cooperation of tenderizer is effective to the raising of bounding force usually.As tenderizer, for example can enumerate:
Low-molecular-weight polyisobutene, polybutene, polyisoprene, polyhutadiene, hydrogenated polyisoprene, hydrogenated butadiene polymer and be that softening agent or phosphoric acid ester are softening agent, aqueous aliphatics through-stone oleo-resinous etc. at their derivative, ethylene-propylene rubber(EPR), Viscotrol C, linseed oil, soybean oil, treated oil, naphthenic oil, a phthalic ester terminal or that two ends have reactive groups such as OH base, COOH base or epoxy group(ing).Tenderizer can only be a kind of, also can be for two or more.
As said derivative, more specifically, for example can enumerate: hydrogenated butadiene polymer glycol, hydrogenated butadiene polymer single methanol, hydrogenated polyisoprene glycol, hydrogenated polyisoprene single methanol.Wherein, from suppressing considered the hydride of diene polymers such as preferred especially hydrogenated butadiene polymer or hydrogenated polyisoprene or ethylene series tenderizer etc. by the purpose of the fusible raising of adherend.
The number-average molecular weight of tenderizer is preferably 5000～100,000, and more preferably 10,000～50,000.When the number-average molecular weight of tenderizer was too small, might become material changeed from bonding coat and moves to by adherend and the heavy reason of peeling off etc., on the other hand, when molecular weight is excessive, the raising effect deficiency of bounding force.
The use level of tenderizer is preferably below the 100 weight % with respect to the matrix polymer of bonding coat, more preferably below the 60 weight %, more preferably below the 40 weight %.
The cooperation of tackifier is effective to the raising of bounding force usually.As tackifier, for example can enumerate: petroleum line resin, coumarone-indenes such as fatty family or fragrant family, aliphatic/aromatic copolymer system or ester ring type system are that resin, terpenic series resin, terpenes phenolic aldehyde are that resin, alkyl phenolic are that resin, rosin series resin, polymerized rosin are resin, diformazan benzene series resin and then their hydride etc.Tackifier can only be a kind of, also can be for two or more.
The reduction of avoiding cohesive force from the limit produces cull problem limit and improves aspect considerations such as bounding force, and the use level of tackifier is preferably below the 80 weight % with respect to the matrix polymer of bonding coat, more preferably below the 40 weight %, more preferably below the 20 weight %.
Be purpose to suppress bonding force rising etc., also can in bonding coat, add polyolefin-based resins.Polyolefin-based resins can the illustration resin same with the resin of the formation that is used for substrate layer.This polyolefin-based resins can only be a kind of, also can be for two or more.The use level of this polyolefin-based resins is preferably below the 50 weight % with respect to the matrix polymer of bonding coat, more preferably below the 30 weight %, more preferably below the 20 weight %.
The thickness of bonding coat is preferably 1～50 μ m, more preferably 2～40 μ m, more preferably 5～20 μ m.Be accommodated in the above-mentioned scope by the thickness with bonding coat, making by coextrusion under the situation of surface protective plate of the present invention, key-course constitutes easily, in addition, can obtain having the surface protective plate of sufficient mechanical.
Also can for example implement Corona discharge Treatment, uviolizing processing, flame treating, Cement Composite Treated by Plasma, sputter etching processing etc. to the surface of bonding coat as required is the surface treatment of purpose with fusible control and applying operation etc.
Also can be as required protect to for during practicality at the temporary transient dividing plate etc. installed on the bonding coat.
The thickness of the integral body of surface protective plate of the present invention is preferably 80～150 μ m, more preferably 90～130 μ m.
Owing to give manual cut and slip resistance to the back side processing layer side of surface protective plate of the present invention, therefore also can implement embossing processing or concavo-convex processing etc.
The manufacture method of surface protective plate of the present invention have with comprise polyolefin-based resins as main component and comprise black pigment substrate layer, be formed at this substrate layer one side back side processing layer and be formed at this substrate layer another side comprise thermoplastic resin as the bonding coat of main component; be shaped and integrally formed operation by coextrusion; wherein; in the processing layer of the described back side, comprise polyethylene-based resin and comprise the derivative of fatty acid of 0.05～1.00 weight % and comprise white pigment as main component and with respect to this polyethylene-based resin.Thus; in the one side of substrate layer, back side processing layer is formed as one, at another side; bonding coat is formed as one, can high-level efficiency and make the surface protective plate of the three-decker multilayer more than four layers of three-decker (or comprise) of the thickness with regulation at an easy rate.
Manufacture method according to surface protective plate of the present invention; can make a kind of surface protective plate; described surface protective plate since back side processing layer and bonding coat under the fusion heated condition, do not join; therefore; there are not generation and the by product thereof of the by product that the thermal degradation when of back side treatment agent causes to move to bonding coat; show excellent uncoiling, suppress the pollution on bonding coat surface, the bond strength excellence.
Embodiment
Below, specifically describe the present invention by embodiment, but the present invention is not subjected to any restriction of these embodiment.
(mensuration of density)
Density (the g/cm of each resin
3) be the value of measuring according to ISO1183.
(mensuration of uncoiling power (uncoiling))
Based on JIS-Z0237 (2000); (Shimadzu Seisakusho Ltd.'s system Autograph) is measured roller product (roller width: 20mm, the length: A-stage 50m) and in the low speed uncoiling power (N/20mm) of 50 ℃ of states after preserving seven days down of surface protective plate respectively to use INSTRON type tensile testing machine.In addition, mensuration is under the environment of 23 ℃ * 50%RH, and with draw speed 300mm/min, the angle of uncoiling sheet and roll surface becomes vertical mode and carries out uncoiling and measure.In addition, the metewand of uncoiling is as described below.
Zero: uncoiling power is lower than the situation of 1.5N.
△: uncoiling power is that 1.5N is above and be lower than 2.5N, but to the unencumbered situation of purposes of the present invention.
*: uncoiling power is the above situation of 2.5N.
(evaluation of contaminative)
In the roller product of surface protective plate (roller width: 20mm, length: initial stage 50m) and be fitted in stainless steel plate (day golden steel, SUS304BA) after preserving seven days down at 50 ℃ and go up and make assess sample respectively.Then, preserve above-mentioned assess sample down after one day at 50 ℃, under 23 ℃ above-mentioned surface protective plate is peeled off from stainless steel plate, the visual detection evaluation has or not generation to be derived from the pollution of tackiness agent at stainless steel plate.Metewand is as described below.
Zero: the situation to the generation of polluting unconfirmed.
△: only confirm the generation of pollution, but to the unencumbered situation of purposes of the present invention.
*: the situation that confirms the generation of pollution.
(evaluation of measuring of bounding force (the residual binding property of binding property))
Descend preservation after seven days in the early stage or at 50 ℃ the roller product of surface protective plate; be fitted on the stainless steel plate (SUS304BA); with INSTRON type tensile testing machine (Shimadzu Seisakusho Ltd.'s system, Autograph); based on JIS Z0237 (2000), the power (N/20mm) when becoming 180 ° with draw speed 300mm/min mensuration peel angle is as bounding force.In addition, will be with value that (50 ℃ * handle the bounding force/initial stage bounding force after seven days) * 100 (%) try to achieve as residual binding property (%).And then, estimate binding property according to above-mentioned residual fusible value.Fusible metewand is as described below.
Zero: residual binding property is the situation more than 70%.
*: residual binding property is lower than the situation of 70% (might float and peel off).
(mensuration of weathering resistance)
The rectangle that the surface protective plate that obtains in embodiment and the comparative example is cut into width 20mm is made the evaluation sample.The roller of 2kg is made a round trip and after carrying out crimping at the SUS430BA plate in this sample, put in the weather-proof machine of sunlight carbon arc (Suga trier Co., Ltd. goods) 1000 hours, then, peel off length to 100mm with 0.3m/ minute draw speed in 180 ° of directions from an end of sample.
With following benchmark evaluation The above results.
Zero: sample is not shredded, and can peel off well by the utmost point.
*: because the deterioration of base material, sample is on the way shredded, or adhesive residue pollutes in by adherend.
(coextrusion shaping condition)
In embodiment and comparative example, the temperature condition that dissolves according to following is shaped by blow moulding.
Back side processing layer: 180 ℃
Substrate layer: 180 ℃
Binder layer: 180 ℃
Coextrusion temperature: 180 ℃
[embodiment 1]
Use is with respect to density 0.897 (g/cm
3) polyethylene (Dow Chemical's system, Affinity PF1140) contain the white pigment (big day refine corporate system, HCM 2035W) of 20 weight %, the back side processing layer that the ethylenebisstearamide (Japan changes into corporate system, Slipax E) of 0.5 weight % forms forms material (thickness 5 μ m), with respect to density 0.922 (g/cm
3) polyethylene (eastern Cao's corporate system, Petrothene 180) contain the substrate layer that the carbon black (Mitsubishi Chemical's system, carbon black " #45 ") of 1 weight % forms and form material (thickness 100 μ m); the binder layer that is made of styrene ethylene butylene styrene segmented copolymer (Asahi Chemical Industry's corporate system, TuftecH1221) forms material (thickness 10 μ m); by utilizing the co-extrusion modling of blow moulding, obtain the surface protective plate (thickness 115 μ m) of three-decker.Show the result in table 1.
[embodiment 2]
Use is with respect to density 0.918 (g/cm
3) polyethylene (eastern Cao's corporate system, Petrothene213) contain the white pigment (big day refine corporate system, HCM2035W) of 20 weight %, the back side processing layer that the ethylenebisstearamide (Japan changes into corporate system, SlipaxE) of 0.2 weight % forms forms material (thickness 10 μ m), with respect to density 0.922 (g/cm
3) polyethylene (eastern Cao's corporate system, Petrothene180) contain the substrate layer that the carbon black (Mitsubishi Chemical's system, carbon black " #45 ") of 1 weight % forms and form material (thickness 100 μ m); the binder layer that is made of styrene ethylene butylene styrene segmented copolymer (Asahi Chemical Industry's corporate system, TuftecH1221) forms material (thickness 10 μ m); by utilizing the co-extrusion modling of blow moulding, obtain the surface protective plate (thickness 120 μ m) of three-decker.Show the result in table 1.
[embodiment 3]
Use is with respect to density 0.922 (g/cm
3) polyethylene (eastern Cao's corporate system, Petrothene180) contain the white pigment (corporate system of refining big day of 20 weight %, HCM2035W), the back side processing layer that forms of the ethylenebisstearamide (Japan changes into corporate system, SlipaxE) of 0.4 weight % forms material (thickness 7 μ m), with respect to density 0.922 (g/cm
3) polyethylene (eastern Cao's corporate system, Petrothene180) contain the substrate layer that the carbon black (Mitsubishi Chemical's system, carbon black " #45 ") of 1 weight % forms and form material (thickness 100 μ m); by styrene ethylene butylene styrene segmented copolymer [Asahi Chemical Industry's corporate system; TuftecH1221) binder layer that constitutes forms material (thickness 10 μ m); by utilizing the co-extrusion modling of blow moulding, obtain the surface protective plate (thickness 117 μ m) of three-decker.Show the result in table 1.
[embodiment 4]
Use is with respect to density 0.922 (g/cm
3) polyethylene (eastern Cao's corporate system, Petrothene180) contain the white pigment (big day refine corporate system, HCM2035W) of 20 weight %, the back side processing layer that the ethylenebisstearamide (Japan changes into corporate system, SlipaxE) of 0.5 weight % forms forms material (thickness 5 μ m), with respect to density 0.922 (g/cm
3) polyethylene (eastern Cao's corporate system, Petrothene180) contain the substrate layer that the carbon black (Mitsubishi Chemical's system, carbon black " #45 ") of 1 weight % forms and form material (thickness 100 μ m); by styrene ethylene butylene styrene segmented copolymer (Asahi Chemical Industry's corporate system, TuftecH1221)) binder layer that constitutes forms material (thickness 10 μ m); by utilizing the co-extrusion modling of blow moulding, obtain the surface protective plate (thickness 115 μ m) of three-decker.Show the result in table 1.
[embodiment 5]
Use is with respect to density 0.918 (g/cm
3) polyethylene (eastern Cao's corporate system, Petrothene213) contain the white pigment (big day refine corporate system, HCM2035W) of 20 weight %, the back side processing layer that the methylene-bis stearylamide (Japan changes into corporate system, BisamideLA) of 0.5 weight % forms forms material (thickness 5 μ m), with respect to density 0.922 (g/cm
3) polyethylene (eastern Cao's corporate system, Petrothene180) contain the substrate layer that the carbon black (Mitsubishi Chemical's system, carbon black " #45 ") of 1 weight % forms and form material (thickness 100 μ m); the binder layer that is made of styrene ethylene butylene styrene segmented copolymer (Asahi Chemical Industry's corporate system, TuftecH1221) forms material (thickness 10 μ m); by utilizing the co-extrusion modling of blow moulding, obtain the surface protective plate (thickness 115 μ m) of three-decker.Show the result in table 1.
[embodiment 6]
Use is with respect to density 0.932 (g/cm
3) polyethylene (eastern Cao's corporate system, Petrothene219) contain the white pigment (big day refine corporate system, HCM2035W) of 20 weight %, the back side processing layer that N-stearyl-N '-stearyl urea (Japan changes into corporate system, Ha Network リ one Application SS) of 0.2 weight % forms forms material (thickness 8 μ m), with respect to density 0.922 (g/cm
3) polyethylene (eastern Cao's corporate system, Petrothene180) contain the substrate layer that the carbon black (Mitsubishi Chemical's system, carbon black " #45 ") of 1 weight % forms and form material (thickness 100 μ m); the binder layer that is made of styrene ethylene butylene styrene segmented copolymer (Asahi Chemical Industry's corporate system, TuftecH1221) forms material (thickness 10 μ m); by utilizing the co-extrusion modling of blow moulding, obtain the surface protective plate (thickness 118 μ m) of three-decker.Show the result in table 1.
[embodiment 7]
Use is with respect to density 0.951 (g/cm
3) polyethylene (eastern Cao's corporate system, Nipolon Hard1200) contain the white pigment (big day refine corporate system, HCM2035W) of 20 weight %, the back side processing layer that the ethylenebisstearamide (Japan changes into corporate system, SlipaxE) of 0.5 weight % forms forms material (thickness 5 μ m), with respect to density 0.922 (g/cm
3) polyethylene (eastern Cao's corporate system, Petrothene180) contain the substrate layer that the carbon black (Mitsubishi Chemical's system, carbon black " #45 ") of 1 weight % forms and form material (thickness 100 μ m); the binder layer that is made of styrene ethylene butylene styrene segmented copolymer (Asahi Chemical Industry's corporate system, TuftecH1221) forms material (thickness 10 μ m); by utilizing the co-extrusion modling of blow moulding, obtain the surface protective plate (thickness 115 μ m) of three-decker.Show the result in table 1.
[embodiment 8]
Use is with respect to density 0.918 (g/cm
3) polyethylene (eastern Cao's corporate system, Petrothene213) contain the white pigment (big day refine corporate system, HCM2035W) of 20 weight %, the back side processing layer that the ethylenebisstearamide (Japan changes into corporate system, SlipaxE) of 0.3 weight % forms forms material (thickness 60 μ m), with respect to density 0.922 (g/cm
3) polyethylene (eastern Cao's corporate system, Petrothene180) contain the substrate layer that the carbon black (Mitsubishi Chemical's system, carbon black " #45 ") of 1 weight % forms and form material (thickness 40 μ m); the binder layer that is made of styrene ethylene butylene styrene segmented copolymer (Asahi Chemical Industry's corporate system, TuftecH1221) forms material (thickness 10 μ m); by utilizing the co-extrusion modling of blow moulding, obtain the surface protective plate (thickness 110 μ m) of three-decker.Show the result in table 1.
[embodiment 9]
Use is with respect to density 0.948 (g/cm
3) polyethylene (eastern Cao's corporate system, Nipolon Hard) contain the white pigment (big day refine corporate system, HCM2035W) of 20 weight %, the back side processing layer that N-stearyl-N '-stearyl urea (Japan changes into corporate system, Ha Network リ one Application SS) of 0.1 weight % forms forms material (thickness 15 μ m), with respect to density 0.922 (g/cm
3) polyethylene (eastern Cao's corporate system, Petrothene180) contain the substrate layer that the carbon black (Mitsubishi Chemical's system, carbon black " #45 ") of 1 weight % forms and form material (thickness 100 μ m); the binder layer that is made of styrene ethylene butylene styrene segmented copolymer (Asahi Chemical Industry's corporate system, TuftecH1221) forms material (thickness 10 μ m); by utilizing the co-extrusion modling of blow moulding, obtain the surface protective plate (thickness 125 μ m) of three-decker.Show the result in table 1.
[comparative example 1]
Use is with respect to density 0.897 (g/cm
3) polyethylene (Dow Chemical's system, AffinityPF 1140) contain the back side processing layer that the white pigment (big day refine corporate system, HCM2035W) of 20 weight % forms and form material (thickness 10 μ m), with respect to density 0.922 (g/cm
3) polyethylene (eastern Cao's corporate system, Petrothene180) contain the substrate layer that the carbon black (Mitsubishi Chemical's system, carbon black " #45 ") of 1 weight % forms and form material (thickness 100 μ m); the binder layer that is made of styrene ethylene butylene styrene segmented copolymer (Asahi Chemical Industry's corporate system, TuftecH1221) forms material (thickness 10 μ m); by utilizing the co-extrusion modling of blow moulding, obtain the surface protective plate (thickness 120 μ m) of three-decker.Show the result in table 1.
[comparative example 2]
Use is with respect to density 0.922 (g/cm
3) polyethylene (eastern Cao's corporate system, Petrothene180) contain the white pigment (big day refine corporate system, HCM2035W) of 20 weight %, the back side processing layer that the ethylenebisstearamide (Japan changes into corporate system, SlipaxE) of 4.8 weight % forms forms material (thickness 7 μ m), with respect to density 0.922 (g/cm
3) polyethylene (eastern Cao's corporate system, Petrothene180) contain the carbon black of 1 weight % (" substrate layer that #45 ") forms form material (thickness 100 μ m) for Mitsubishi Chemical's system, carbon black; the binder layer that is made of styrene ethylene butylene styrene segmented copolymer (Asahi Chemical Industry's corporate system, TuftecH1221) forms material (thickness 10 μ m); by utilizing the co-extrusion modling of blow moulding, obtain the surface protective plate (thickness 117 μ m) of three-decker.Show the result in table 1.
[comparative example 3]
Use is with respect to density 0.922 (g/cm
3) polyethylene (eastern Cao's corporate system, Petrothene180) contain the white pigment (big day refine corporate system, HCM2035W) of 20 weight %, the back side processing layer that the ethylenebisstearamide (Japan changes into corporate system, SlipaxE) of 0.5 weight % forms forms material (thickness 100 μ m); the binder layer that is made of styrene ethylene butylene styrene segmented copolymer (Asahi Chemical Industry's corporate system, TuftecH1221) forms material (thickness 10 μ m); by utilizing the co-extrusion modling of blow moulding, obtain the surface protective plate (thickness 110 μ m) of double-layer structure.Show the result in table 1.
[comparative example 4]
Use is with respect to density 0.922 (g/cm
3) polyethylene (eastern Cao's corporate system; Petrothene180) contain the white pigment (corporate system of refining big day of 20 weight %; HCM2035W) back side processing layer that forms forms material (thickness 100 μ m); by styrene ethylene butylene styrene segmented copolymer (Asahi Chemical Industry's corporate system; TuftecH1221) and ethylenebisstearamide (Japan changes into corporate system; SlipaxE) binder layer of (polyethylene that forms in the material with respect to back side processing layer is 0.3 weight %) formation forms material (thickness 10 μ m); by utilizing the co-extrusion modling of blow moulding, obtain the surface protective plate (thickness 110 μ m) of double-layer structure.Show the result in table 1.
[comparative example 5]
In embodiment 1, do not form to back side processing layer and add white pigment in the material and in substrate layer formation material, add carbon black, in addition, carry out similarly to Example 1, obtain surface protective plate.Show the result in table 1.
Judged by table 1; surface protective plate of the present invention is a kind ofly to be shaped and integrally formed surface protective plate by coextrusion; even under the situation of under hot environment, taking care of; also can balancedly show excellent weathering resistance, good uncoiling, by the inhibition of the pollution on adherend surface, excellent adhesion strength.
Utilizability on the industry
Surface protective plate of the present invention can be used for being fitted on their surface and purposes of protecting etc. for example when opticses such as parts, polarizing coating, liquid crystal panel, electronic units such as carrying, processing or maintenance metal sheet, coated plate, aluminum alloy frame, resin board, decorative steel plate, vinylchlorid laminate steel, sheet glass etc. etc.
Claims (10)
1. surface protective plate; its be comprise polyolefin-based resins as the substrate layer of main component, be formed at the comprising polyethylene-based resin as the back side processing layer of main component and be formed at the comprising that thermoplastic resin is shaped by coextrusion as the bonding coat of main component of another side of this substrate layer and integrally formed of one side of this substrate layer
This substrate layer comprises black pigment,
This back side processing layer comprises white pigment,
This back side processing layer comprises the derivative of fatty acid of 0.05～1.00 weight % with respect to this polyethylene-based resin.
2. surface protective plate according to claim 1, wherein,
Described derivative of fatty acid is fatty acid amide.
3. surface protective plate according to claim 2, wherein,
Described fatty acid amide is for being selected from least a in methylene-bis stearylamide, ethylenebisstearamide, N-stearyl-N '-stearylamide.
4. surface protective plate according to claim 1, wherein,
The density of described polyethylene-based resin is 0.880～0.940g/cm
3
5. surface protective plate according to claim 1, wherein,
The thickness of described back side processing layer is 1～20 μ m.
6. the manufacture method of a surface protective plate, it has:
To comprise polyolefin-based resins as main component and comprise black pigment substrate layer, be formed at this substrate layer one side back side processing layer and be formed at this substrate layer another side comprise thermoplastic resin as the bonding coat of main component, be shaped and integrally formed operation by coextrusion
In the processing layer of the described back side, comprise polyethylene-based resin and comprise the derivative of fatty acid of 0.05～1.00 weight % and comprise white pigment as main component and with respect to this polyethylene-based resin.
7. the manufacture method of surface protective plate according to claim 6, wherein,
Described derivative of fatty acid is fatty acid amide.
8. the manufacture method of surface protective plate according to claim 7, wherein,
Described fatty acid amide is for being selected from least a in methylene-bis stearylamide, ethylenebisstearamide, N-stearyl-N '-stearylamide.
9. the manufacture method of surface protective plate according to claim 6, wherein,
The density of described polyethylene-based resin is 0.880～0.940g/cm
3
10. the manufacture method of surface protective plate according to claim 6, wherein,
The thickness of described back side processing layer is 1～20 μ m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100361392A CN103254813A (en) | 2012-02-15 | 2012-02-15 | Surface protection sheet |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100361392A CN103254813A (en) | 2012-02-15 | 2012-02-15 | Surface protection sheet |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107820505A (en) * | 2015-06-30 | 2018-03-20 | 陶氏环球技术有限责任公司 | Polymer formulation with stain resistance |
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|---|---|---|---|---|
| JPH06271821A (en) * | 1993-03-23 | 1994-09-27 | Lintec Corp | Removable type tacky protecting tape |
| CN1470887A (en) * | 2002-07-08 | 2004-01-28 | �ն��繤��ʽ���� | Surface protective film for optical film |
| JP2006219520A (en) * | 2005-02-08 | 2006-08-24 | Nitto Denko Corp | Surface-protecting sheet and its manufacturing method |
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2012
- 2012-02-15 CN CN2012100361392A patent/CN103254813A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06271821A (en) * | 1993-03-23 | 1994-09-27 | Lintec Corp | Removable type tacky protecting tape |
| CN1470887A (en) * | 2002-07-08 | 2004-01-28 | �ն��繤��ʽ���� | Surface protective film for optical film |
| JP2006219520A (en) * | 2005-02-08 | 2006-08-24 | Nitto Denko Corp | Surface-protecting sheet and its manufacturing method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107820505A (en) * | 2015-06-30 | 2018-03-20 | 陶氏环球技术有限责任公司 | Polymer formulation with stain resistance |
| CN107820505B (en) * | 2015-06-30 | 2021-05-04 | 陶氏环球技术有限责任公司 | Polymer formulations with stain resistance |
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Application publication date: 20130821 |