CN103709947A - Surface protective sheet - Google Patents
Surface protective sheet Download PDFInfo
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- CN103709947A CN103709947A CN201210369682.4A CN201210369682A CN103709947A CN 103709947 A CN103709947 A CN 103709947A CN 201210369682 A CN201210369682 A CN 201210369682A CN 103709947 A CN103709947 A CN 103709947A
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Abstract
The invention provides a surface protective sheet which comprises a substrate layer and an adhesive layer and which exhibits sufficiently and moderately high adhesive force in high-speed peeling even with respect to an adherend having a rough surface and further exhibits sufficiently and moderately high adhesive force even in high-speed peeling at a low temperature. The surface protective sheet provided by the invention comprises the substrate layer and the adhesive layer. An adhesive force of the surface protective sheet with respect to a hairline-processed SUS plate at a temperature of 23 DEG C is 1.0 N/20mm or more and the adhesive force of the surface protective sheet with respect to a hairline-processed SUS plate at a temperature of 5 DEG C is 1.5 N/20mm or more, each adhesive force being determined in 180-degree peeling at a tensile rate of 10 m/min.
Description
Technical field
The present invention relates to a kind of surface protective plate.Specifically, the present invention relates to a kind of surface protective plate that comprises substrate layer and bonding coat.Surface protective plate of the present invention, when the 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, pvdc layer laminated steel, sheet glass etc., can be used for sticking on purposes of protecting on these surface etc.Surface protective plate of the present invention particularly as effects on surface carry out the processing of hair line SUS hairline plate surface protective plate of great use.
Background technology
Surface protective plate is provided with bonding coat in a side of substrate layer conventionally.The method of the surface protective plate that comprises such substrate layer and bonding coat as manufacture, proposes to have a kind of method (for example,, with reference to patent documentation 1) that is shaped substrate layer and bonding coat are formed as one by coextrusion.
But existing surface protective plate is enough not high to the bonding force by under the sticking state of adherend.Therefore, when having pasted being processed by adherend of existing surface protective plate etc., the problem that exists the part of this surface protective plate to peel off.The high adhesive sheet of bonding force when particularly for example even the low speed of about 0.3m/min is peeled off, the not high problem of bonding force while existing the high speed of 10m/min left and right to peel off.Being reduced in of bonding force when such high speed is peeled off used synthetic rubber be on the surface protective plate of tackiness agent significantly.On the other hand, even the bonding force while peeling off for low speed or for the bonding force of peeling off at a high speed, all because be difficult to peel off when too high, so these bonding force appropriateness are sought high level.
In addition, existing surface protective plate has following problem: the cementability to uneven surface is low, in the situation that for example stick on the SUS hairline plate that effects on surface has carried out the processing of hair line, peels off in man-hour etc. or breaks etc. adding, and can not show sufficient cementability.
And; bonding force when existing surface protective plate high speed is at low temperatures peeled off is poor, has following problem: for example, and under the low temperature environment of 5 ℃ of left and right; stick on by the surface protective plate of adherend and peel off or break etc. in generations such as adding man-hour, can not show sufficient cementability.
Prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication sho 61-103975 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 comprises substrate layer and bonding coat, even if be asperities for surface by adherend, the bonding force while peeling off is at a high speed also abundant and moderately high; and, even if peeling off, the high speed under low temperature also can show abundant and high bonding force moderately.For solving the means of problem
Surface protective plate of the present invention comprises substrate layer and bonding coat, wherein,
To the bonding force at 23 ℃ of SUS hairline plate, as draw speed, be that the lower 180 ° of bonding forces while peeling off of 10m/min are more than 1.0N/20mm,
To the bonding force at 5 ℃ of SUS hairline plate, as draw speed, be that the lower 180 ° of bonding forces while peeling off of 10m/min are more than 1.5N/20mm.
Surface protective plate of the present invention, it comprises substrate layer and bonding coat, wherein,
This bonding coat comprises styrene series thermoplastic elastomer and tackifier,
The styrene content of this styrene series thermoplastic elastomer is 5 % by weight～13 % by weight,
The softening temperature of these tackifier is 90 ℃～120 ℃.
Preferred embodiment, in surface protective plate of the present invention, described substrate layer and described bonding coat are shaped to form as one by coextrusion and form.
Preferred embodiment, in surface protective plate of the present invention, described substrate layer comprises polyolefin-based resins as principal constituent.
Invention effect
According to the present invention, a kind of surface protective plate can be provided, it comprises substrate layer and bonding coat; even if be asperities for surface by adherend; bonding force while peeling off is at a high speed also abundant and moderately high, and, even if peeling off, the high speed under low temperature also can show fully and the high bonding force of appropriateness.
Accompanying drawing explanation
Fig. 1 is the sectional view that schematically shows a configuration example of surface protective plate of the present invention.
Nomenclature
100 surface protective plates
10 bonding coats
20 substrate layers
21 white color system layers
22 black system layers
Embodiment
Surface protective plate of the present invention comprises substrate layer and bonding coat.Surface protective plate of the present invention also can comprise the layer of suitable arbitrarily other in the scope of not damaging effect of the present invention.
The thickness of substrate layer is preferably 20 μ m～300 μ m, 30 μ m～250 μ m more preferably, and more preferably 40 μ m～200 μ m, are particularly preferably 45 μ m～150 μ m, most preferably are 50 μ m～100 μ m.By the thickness of substrate layer is adjusted in above-mentioned scope; not cracky or fracture of substrate layer while peeling off after surface protective plate of the present invention is pasted by adherend; in addition; the toughness that can suppress substrate layer becomes large; therefore, surface protective plate of the present invention is sticked on be difficult for after on adherend producing and float etc.
The thickness of bonding coat is preferably 1 μ m～50 μ m, 2 μ m～40 μ m more preferably, and more preferably 3 μ m～30 μ m, are particularly preferably 4 μ m～20 μ m, most preferably are 5 μ m～10 μ m.By the thickness of bonding coat is adjusted in above-mentioned scope, when utilizing coextrusion to be shaped manufacture surface protective plate of the present invention, easy key-course forms, and in addition, can obtain having the surface protective plate of sufficient physical strength.
The thickness of surface protective plate integral body of the present invention is preferably 30 μ m～150 μ m, 35 μ m～140 μ m more preferably, and more preferably 40 μ m～130 μ m, are particularly preferably 45 μ m～120 μ m, most preferably are 50 μ m～110 μ m.By the total thickness of surface protective plate of the present invention is adjusted in above-mentioned scope, can obtain treatability excellent and there is the surface protective plate of sufficient physical strength.
Surface protective plate preferred substrates layer of the present invention and bonding coat are shaped to form as one by coextrusion and form.As coextrusion, be shaped, can adopt the suitable coextrusion arbitrarily of the manufacture that is generally used for film, sheet material etc. to be shaped.As coextrusion, be shaped, such as adopting blow moulding, coextrusion T-modulus method etc.From the aspect of cost aspect or productivity, consider, preferably these coextrusion are shaped.
What surface protective plate effects on surface of the present invention was asperities is excellent by the bonding force of adherend.As such surface, be asperities by adherend, can enumerate have surface roughness Ra be 0.210 μ m～0.310 μ m asperities by adherend.Like this by adherend, as the surface protective plate of the present invention surface protective plate that particularly effects on surface has carried out the SUS hairline plate of hair line processing, can show excellent effect.What in this specification sheets, be called " SUS hairline plate " is the SUS plate that the processing of hair line has been carried out on surface, and it has the asperities that surface roughness Ra is 0.210 μ m～0.310 μ m.In addition, in the present invention, surface roughness Ra is used contact surfaceness meter (SJ400: the ITUTOYO of M Co., Ltd. system), measure having carried out ridge orientation SUS plate, hair line and the right angle orientation of hair line processing and (take condition determination: JIS-B-0601:(2001) as benchmark is measured.Specifically, under contact pilotage radius 2 μ m, cutoff (cut off) 0.8mm, measured length 4mm, measure) time value.
Surface protective plate of the present invention is the lower 180 ° of bonding forces while peeling off of 10m/min to the bonding force at 23 ℃ of SUS hairline plate as draw speed; more than being preferably 1.0N/20mm; 1N/20mm～5N/20mm more preferably; more preferably 1N/20mm～4N/20mm, is particularly preferably 1N/20mm～3N/20mm.If be that the lower 180 ° of bonding forces while peeling off of 10m/min are contained in above-mentioned scope using the bonding force at 23 ℃ of SUS hairline plate as draw speed, when surface protective plate of the present invention high speed is at room temperature peeled off, can show abundant and high bonding force moderately.In addition, for the measuring method to the various bonding forces of SUS hairline plate, after narrate.
Surface protective plate of the present invention is more than the lower 180 ° of bonding forces while peeling off of 10m/min are preferably 1.5N/20mm to the bonding force at 5 ℃ of SUS hairline plate as draw speed; 1.5N/20mm～5N/20mm more preferably; more preferably 1.5N/20mm～4N/20mm, is particularly preferably 1.5N/20mm～3.5N/20mm.If be that the lower 180 ° of bonding forces while peeling off of 10m/min are contained in above-mentioned scope using the bonding force at 5 ℃ of SUS hairline plate as draw speed, when surface protective plate of the present invention high speed is at low temperatures peeled off, can show abundant and high bonding force moderately.In addition, for the measuring method to the various bonding forces of SUS hairline plate, after narrate.
Surface protective plate of the present invention is the lower 180 ° of bonding forces while peeling off of 10m/min to the bonding force at 10 ℃ of SUS hairline plate as draw speed; more than being preferably 1.5N/20mm; 1.5N/20mm～5N/20mm more preferably; more preferably 1.5N/20mm～4N/20mm, is particularly preferably 1.5N/20mm～3.5N/20mm.If the bonding force under 180 ° when draw speed is 10m/min of the bonding force at 10 ℃ of SUS hairline plate is contained in above-mentioned scope, surface protective plate of the present invention high speed at low temperatures can show abundant and high bonding force moderately in peeling off.In addition, for the measuring method to the various bonding forces of SUS hairline plate, after narrate.
Substrate layer preferably comprises polyolefin-based resins as principal constituent.By substrate layer, comprise polyolefin-based resins as principal constituent, can there is thermotolerance, solvent resistance, flexible, can easily form the form of roller winding article.Polyolefin-based resins contained in substrate layer can be only a kind of, also can be for two or more.Substrate layer can be individual layer, can be also multilayer.
At this, in the present invention, so-called " principal constituent ", more than being preferably 50 % by weight, more preferably more than 60 % by weight, more preferably more than 70 % by weight, more than being particularly preferably 80 % by weight, more than most preferably being 90 % by weight.
As polyolefin-based resins, such as enumerating: polyethylene-based resin, the propylene resin being 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/propene copolymer, Ethylene/1-butene multipolymer, ethene/1-hexene copolymer, ethene/4 methyl 1 pentene copolymer, ethene/1-octene copolymer, ethylene/methyl acrylate copolymer, ethylene/methacrylic acid methyl terpolymer, ethylene/vinyl acetate copolymer, ethylene/ethyl acrylate multipolymer, ethylene/vinyl alcohol copolymer etc.
In the situation that substrate layer consists of the multilayer more than two-layer, the layer of each adjacency preferably selection can reciprocally form firmly bonding material as their resinous principle of formation by dissolving coextrusion.
Substrate layer also can comprise white color system layer.By substrate layer, comprise white color system layer and can make the surface protective plate having excellent weather resistance.
Substrate layer also can comprise black system layer.By substrate layer, comprise black system layer and can make the surface protective plate having excellent weather resistance.
Substrate layer preferably at least comprises that white color system layer and black are that layer is two-layer.By substrate layer, at least comprise white color system layer and black system layer two-layer, can make the surface protective plate that weathering resistance is very excellent.
In the situation that substrate layer at least comprises 2 layers, white color system layer and black system layer; surface protective plate of the present invention stacked is configured to such as " white color system layer/black system layer/bonding coat ", " black is layer/white color system layer/bonding coat " etc.; only otherwise damage effect of the present invention, can take suitable arbitrarily stacked formation.Fig. 1 is the sectional view of a configuration example of situation that schematically shows surface protective plate 100 of the present invention and have the stacked formation of " white color system layer 21/ black system layer 22/ bonding coat 10 ".White color system layer 21 and black system layer 22 become substrate layer 20.
White color system layer is the layer of the tone of display white system, and the whiteness of for example stipulating in JIS-L-1015 is preferably more than 60%, more preferably more than 70%, more preferably more than 80%, is particularly preferably more than 85%.White color system layer preferably comprises white pigment.As white pigment, can adopt suitable arbitrarily white pigment.As such white pigment, for example, can enumerate titanium oxide.In the situation that white color system layer contains white pigment, it is 0.1 % by weight～50 % by weight containing the proportional preferred resinous principle with respect to forming white color system layer, more preferably 1 % by weight～40 % by weight, more preferably 2 % by weight～30 % by weight.By by with respect to form white color system layer resinous principle white pigment containing proportional being contained in above-mentioned scope, can make the surface protective plate having excellent weather resistance, the plasticity such as extrudability is also excellent.
The resinous principle that forms white color system layer is preferably polyolefin-based resins, more preferably acrylic polymer, ethylene-based polymer.As the resinous principle that forms white color system layer, particularly, can preferably enumerate: homo-polypropylene, block polypropylene, Atactic Polypropelene, high density polyethylene(HDPE) (HDPE), medium-density polyethylene, Low Density Polyethylene (LDPE), straight chain shape Low Density Polyethylene (LLDPE).White color system layer preferably comprises polyethylene-based resin as principal constituent.Density as this polyethylene-based resin, is preferably 0.880g/cm
3～0.940g/cm
3, 0.880g/cm more preferably
3～0.923g/cm
3, 0.880g/cm more preferably
3～0.915g/cm
3.By white color system layer, comprise polyethylene-based resin as principal constituent, substrate layer can have thermotolerance, solvent resistance, flexible, surface protective plate of the present invention easily can be formed to the form of roller winding article.In the situation that white color system layer comprises polyethylene-based resin as principal constituent, this polyethylene-based resin preferably comprises Low Density Polyethylene.By above-mentioned polyethylene-based resin, comprise Low Density Polyethylene, substrate layer can fully have thermotolerance, solvent resistance, flexible, surface protective plate of the present invention easily can be formed to the form of roller winding article.
Polyolefin-based resins in white color system layer containing proportional be preferably 60 % by weight more than, more preferably more than 70 % by weight, more preferably more than 80 % by weight, more than being particularly preferably 85 % by weight, more than most preferably being 90 % by weight.Such polyolefin-based resins can only be used a kind of, also can use two or more.
The thickness of white color system layer can adopt suitable arbitrarily thickness according to object.Such thickness is preferably 2 μ m～100 μ m, 3 μ m～80 μ m more preferably, and more preferably 4 μ m～60 μ m, are particularly preferably 5 μ m～50 μ m.
Black system layer is for showing the layer of the tone of black system.Black system layer preferably comprises black pigment.As black pigment, can adopt suitable arbitrarily black pigment.As such black pigment, for example, can enumerate carbon black.In the situation that black system layer contains black pigment, it is 0.01 % by weight～10 % by weight containing the proportional preferred resinous principle with respect to forming black system layer, more preferably 0.1 % by weight～5 % by weight, more preferably 0.5 % by weight～3 % by weight.By by with respect to form black system layer resinous principle black pigment containing proportional being contained in above-mentioned scope, can make the surface protective plate having excellent weather resistance, the plasticity such as extrudability is also excellent.
The resinous principle that forms black system layer is preferably polyolefin-based resins, more preferably acrylic polymer, ethylene-based polymer.As the resinous principle that forms black system layer, particularly, can preferably enumerate: homo-polypropylene, block polypropylene, Atactic Polypropelene, high density polyethylene(HDPE) (HDPE), medium-density polyethylene, Low Density Polyethylene (LDPE), straight chain shape Low Density Polyethylene (LLDPE).Black system layer preferably comprises polyethylene-based resin as principal constituent.Density as this polyethylene-based resin, is preferably 0.880g/cm
3～0.940g/cm
3, 0.880g/cm more preferably
3～0.923g/cm
3, 0.880g/cm more preferably
3～0.915g/cm
3.By black, be that layer comprises polyethylene-based resin as principal constituent, substrate layer can have thermotolerance, solvent resistance, flexible, surface protective plate of the present invention easily can be formed to the form of roller winding article.In the situation that black system layer comprises polyethylene-based resin as principal constituent, this polyethylene-based resin preferably comprises Low Density Polyethylene and straight chain shape Low Density Polyethylene.By above-mentioned polyethylene-based resin, comprise Low Density Polyethylene and straight chain shape Low Density Polyethylene, substrate layer can have thermotolerance, solvent resistance, flexible fully, surface protective plate of the present invention further easily can be formed to the form of roller winding article.
Polyolefin-based resins in black system layer containing proportional be preferably 60 % by weight more than, more preferably more than 70 % by weight, more preferably more than 80 % by weight, more than being particularly preferably 85 % by weight, more than most preferably being 90 % by weight.Such polyolefin-based resins can only be used a kind of, also can use two or more.
The thickness of black system layer can adopt suitable arbitrarily thickness according to object.Such thickness is preferably 2 μ m～100 μ m, 3 μ m～80 μ m more preferably, and more preferably 4 μ m～60 μ m, are particularly preferably 5 μ m～50 μ m.
Substrate layer can contain suitable additive arbitrarily.As such additive, for example can enumerate: antioxidant, UV light absorber, protective agent, 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 (order ヤ ニ prevents drug), lubricant, anti blocking agent etc.
Substrate layer preferably comprises photostabilizer.By substrate layer, comprise photostabilizer, can give sufficient weathering resistance to surface protective plate of the present invention.
As photostabilizer, in not damaging the scope of effect of the present invention, can adopt suitable arbitrarily photostabilizer.As such photostabilizer, for example can preferably enumerate hindered amine is photostabilizer (HALS).
In the situation that substrate layer comprises photostabilizer; this photostabilizer containing proportional with respect to the weight of surface protective plate integral body of the present invention, be preferably more than 0.10 % by weight; 0.20 % by weight～0.64 % by weight more preferably; more preferably 0.30 % by weight～0.60 % by weight, is particularly preferably 0.34 % by weight～0.55 % by weight.In the situation that substrate layer comprises photostabilizer, as long as the proportional weight with respect to surface protective plate integral body of the present invention that contains of this photostabilizer is contained in above-mentioned scope, just can give weathering resistance more fully to surface protective plate of the present invention.
Also can implement the back side to outermost layer substrate layer and bonding coat opposition side processes.The method of processing as the back side, in not damaging the scope of effect of the present invention, can adopt appropriate means arbitrarily.The method of processing as such back side, such as enumerating the surface working such as embossing processing or concavo-convex processing, the method that makes it to contain derivative of fatty acid etc.Such derivative of fatty acid can be only a kind of, also can be for two or more.
In the situation that substrate layer comprises derivative of fatty acid, derivative of fatty acid in this substrate layer containing proportional with respect to the resinous principle in substrate layer, be preferably 0.05 % by weight～1.00 % by weight, more preferably 0.10 % by weight～0.90 % by weight, more preferably 0.30 % by weight～0.80 % by weight.As long as by the derivative of fatty acid in substrate layer containing proportional with respect to the resinous principle in substrate layer; be contained in above-mentioned scope; can easily make to make the surface protective plate uncoiling of the present invention of roller shape; stripping result can be shown fully, the pollution causing because of oozing out of this derivative of fatty acid can be suppressed fully simultaneously.
As derivative of fatty acid, refer to the compound that comprises derivative of fatty acid structure in molecular structure.
As derivative of fatty acid, such as enumerating: 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 stearic amide, ethylenebis stearic amide, ethylenebisoleaamide, ethylenebis behenic acid acid amides, N, N-stearyl-N '-stearic amide, the Zinic stearass etc. such as N-bis-oleyl hexanodioic acid acid amides, N-stearyl-N '-stearic urea.
As derivative of fatty acid, be preferably fatty acid amide, be more preferably selected from least one in methylene-bis stearic amide, ethylenebis stearic amide, ethylenebis behenic acid acid amides, N-stearyl-N '-stearic amide.
The preferred fusing point of derivative of fatty acid is more than 100 ℃.Lower than the derivative of fatty acid of 100 ℃, the transfer printing in bonding coat surface becomes significantly fusing point, likely easily produces bounding force and reduces.
Bonding coat preferably comprises thermoplastic resin as principal constituent.Thermoplastic resin contained in bonding coat can be only a kind of, also can be for two or more.
As thermoplastic resin, can adopt suitable arbitrarily thermoplastic resin.As such thermoplastic resin, such as enumerating: ethylene series resin, the olefin/diene copolymers that contains aromatic group, phenylethylene resin series, ester are resin etc.In these thermoplastic resins, optimization styrene is resin, more preferably styrene series thermoplastic elastomer.
As styrene series thermoplastic elastomer, preferably can enumerate: hydrogenated styrene/divinyl rubber (HSBR), styrene block copolymer or its hydride.
As styrene block copolymer, such as enumerating: polystyrene ABA block polymer (triblock copolymer) such as styrene butadiene styrene multipolymer (SBS), styrene isoprene styrol copolymers (SIS); The polystyrene ABAB type segmented copolymers (Tetrablock copolymer) such as styrene butadiene styrene butadienecopolymer (SBSB), styrene isoprene styrene isoprene multipolymer (SISI); The polystyrene ABABA type segmented copolymers (five segmented copolymers) such as styrene butadiene styrene butadienestyrene copolymer (SBSBS), styrene isoprene styrene isoprene styrol copolymer (SISIS); There is the styrene block copolymer of its above AB repeating unit etc.
As the hydride of styrene block copolymer, such as enumerating: the multipolymer (SEB SEB) of styrene ethylene-butylene copolymer styrol copolymer (SEBS), styrene ethylene-propylene copolymer styrol copolymer (SEPS), styrene ethylene-butylene copolymer styrene ethylene-butylene copolymer etc.
Styrene series thermoplastic elastomer can only be used a kind of, also can use two or more.
The styrene content of styrene series thermoplastic elastomer (being styrene block content in the situation of styrene block copolymer) is preferably 5 % by weight～13 % by weight, 1 % by weight～20 % by weight more preferably, more preferably 2 % by weight～18 % by weight, are particularly preferably 3 % by weight～15 % by weight.By above-mentioned styrene content is adjusted in above-mentioned scope; even if what surface protective plate effects on surface of the present invention was asperities also can be shown fully and the high bonding force of appropriateness by adherend when peeling off at a high speed; and, when peeling off, high speed at low temperatures also can show fully and the high bonding force of appropriateness.When above-mentioned styrene content tails off, likely easily produce the cull that the cohesive force deficiency because of bonding coat causes.When above-mentioned styrene content becomes many, likely bonding coat hardening and cannot obtain good binding property to asperities.
As styrene series thermoplastic elastomer, be preferably the hydride (SEBS, SEBSEB, SEBSEBS etc.) of the styrene block copolymer with repeating structure (ABA type, ABAB type, ABABA type etc.) more than the triblock copolymer being formed by vinylbenzene (A) and divinyl (B).By adopting such styrene series thermoplastic elastomer, can further suitably improve by the bonding force of the sticking state of adherend, on the other hand, bonding force when peeling off after being pasted by adherend further suitably increases, therefore, can be by slight power more easily from being peeled off by adherend, and, can further suppress to be exposed in the situation that be stored in for a long time the rising of the bonding force of the environmental loads under comparatively high temps.
In the situation that styrene series thermoplastic elastomer is for having the hydride (SEBS, SEBSEB, SEBSEBS etc.) of the styrene block copolymer of repeating structure (ABA type, ABAB type, ABABA type etc.) more than the triblock copolymer consisting of vinylbenzene (A) and divinyl (B), more than in ethylene-butene copolymer block, the ratio of shared butylene structure is preferably 60 % by weight, more preferably more than 70 % by weight, more preferably more than 75 % by weight.By the ratio of butylene structure shared in above-mentioned ethylene-butene copolymer block is contained in above-mentioned scope, can further suitably improve by the bonding force of the sticking state of adherend, on the other hand, bonding force when peeling off after being pasted by adherend further suitably increases, therefore, can be by slight power more easily from being peeled off by adherend, and, can further suppress to be exposed in the situation that be stored in for a long time the rising of the bonding force of the environmental loads under comparatively high temps.In addition, in above-mentioned ethylene-butene copolymer block, the ratio of shared butylene structure is preferably below 90 % by weight.
For bonding coat, the fusible adjusting etc. of take is object, the styrene series thermoplastic elastomer that also can comprise other in the scope of not damaging object of the present invention.
As other styrene series thermoplastic elastomer, can enumerate: the styrene block copolymer beyond above-mentioned; The multipolymer (SEB) of styrene-butadiene-copolymer (SB), styrene isoprene multipolymer (SI), styrene ethylene-butylene copolymer, the AB type block polymers such as multipolymer (SEP) of styrene ethylene-propylene copolymer; The polystyrene random copolymerss such as styrene butadiene ribber (SBR); The vinylbenzene alkene crystal system block polymer of the A-B-C types such as multipolymer (SEBC) of styrene ethylene-butylene copolymer alkene crystallization; These hydride etc.
When forming bonding coat, the control etc. of adhesion characteristic of take is object, also as required suitable interpolation for example for tenderizer, tackifier, the polyolefin-based resins that substrate layer is such, silicone-based polymkeric substance, aqueous acrylic copolymer, phosphoric acid ester based compound, protective agent, 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 (for example, calcium oxide, magnesium oxide, silicon-dioxide, zinc oxide, titanium oxide etc.), metal powder, tinting material, pigment, the additives such as heat-resisting stabilizing agent.
Also can be as required bonding coat surface embodiment be take to the surface treatment that fusible control or sticking operation etc. are object as Corona discharge Treatment, uviolizing processing, flame treating, Cement Composite Treated by Plasma, sputter etching processing etc.
The cooperation of tackifier is effective to improving bounding force.But the cull problem that the use level of tackifier causes for fear of the reduction producing because of cohesive force, can have suitablely being determined by adherend of surface protective plate according to application.The use level of tackifier is preferably below 80 % by weight with respect to the base polymer of bonding coat, more preferably below 40 % by weight, more preferably below 20 % by weight.
The softening temperature of tackifier is preferably 90 ℃～120 ℃, more preferably 70 ℃～135 ℃, more preferably 80 ℃～130 ℃, is particularly preferably 85 ℃～125 ℃.By the softening temperature of above-mentioned tackifier is adjusted in above-mentioned scope; even if surface protective plate effects on surface of the present invention is asperities by adherend; also can when peeling off at a high speed, show fully and the high bonding force of appropriateness; and, when peeling off, high speed at low temperatures also can show fully and the high bonding force of appropriateness.
As tackifier, such as using without particular limitation the petroleum line resins such as aliphatics based copolymer, aromatic series based copolymer, aliphatics aromatic series based copolymer system or ester ring type based copolymer; Coumarone-indenes is that resin, terpenic series resin, terpenes phenolic aldehyde are the rosin series resins such as resin, polymerized rosin; (alkyl) phenolic aldehyde is that resin, diformazan benzene series resin, these hydride etc. are generally used for the material of tackiness agent.Tackifier can only be used a kind of, also can use two or more.In these tackifier, from the viewpoint of separability or weathering resistance etc., the tackifier that preferably hydrogenation is, particularly preferably C5 is hydrogenated aromatic petroleum resin.In addition, tackifier also can be used as the tackifier that are commercially available with the blend of olefin resin.
The cooperation of tenderizer is effective for the raising of bounding force.As tenderizer, such as enumerating: low-molecular-weight diene polymer, polyisobutene, hydrogenated polyisoprene, hydrogenated butadiene polymer, these derivative etc.As such derivative, for example, can be illustrated in the derivative on an end or two ends with OH base or COOH base, particularly, can enumerate: hydrogenated butadiene polymer glycol, hydrogenated butadiene polymer single methanol, hydrogenated polyisoprene glycol, hydrogenated polyisoprene single methanol etc.Particularly, from suppressing with respect to by the object of the fusible raising of adherend, the preferably hydride of the diene polymer such as hydrogenated butadiene polymer or hydrogenated polyisoprene or ethylene series tenderizer etc.As such tenderizer, particularly, can obtain the trade(brand)name " KurapreneLIR-200 " of (strain) Kuraray system etc.With regard to these tenderizers, can only use a kind ofly, also can use two or more.
The molecular weight of tenderizer can suitablely be set as suitable arbitrarily amount, when but molecular weight diminishes, likely becoming material moves to by the reason of adherend or re-separation etc. from bonding coat, on the other hand, when molecule quantitative change is large, the trend that has the raising effect of bounding force to become and lack, therefore, the number-average molecular weight of tenderizer is preferably 5000～100,000, and more preferably 10,000～50,000.
In the situation that using tenderizer, its addition can suitablely be set as suitable arbitrarily amount, when but interpolation quantitative change is many, the trend that has the cull while being exposed to high temperature or open air to increase, therefore, preferably the base polymer with respect to bonding coat is below 100 % by weight, more preferably below 60 % by weight, more preferably below 40 % by weight.
In bonding coat, take that to suppress bonding force rising etc. be object, also can add polyolefin-based resins.The resin that polyolefin-based resins is can illustration same with the resin of formation for substrate layer.This polyolefin-based resins can be only a kind of, also can be for two or more.The use level of this polyolefin-based resins is preferably below 50 % by weight with respect to the base polymer of bonding coat, more preferably below 30 % by weight, more preferably below 20 % by weight.
In bonding coat, as required, until during for practicality, also can temporary adhesion dividing plate etc. protect.
The manufacture method of surface protective plate of the present invention is preferably by coextrusion and is shaped and makes substrate layer and bonding coat form as one to manufacture.Thus, can be efficiently and manufacture at an easy rate the surface protective plate of the stepped construction of the thickness with regulation.As coextrusion, be shaped, can adopt the suitable coextrusion arbitrarily of the manufacture that is generally used for film, sheet material etc. to be shaped.As coextrusion, be shaped, such as adopting blow moulding, coextrusion T-modulus method etc.
According to coextrusion, be shaped, the outermost of the opposition side of the bonding coat of substrate layer and bonding coat do not join dissolving under heated condition, therefore, do not generate the by product that the outmost thermal degradation when because of the opposition side of the bonding coat of substrate layer produces, and by product does not move to bonding coat, show excellent uncoiling, can suppress the pollution on bonding coat surface.
Embodiment
Below, by embodiment, the present invention is specifically described, but the present invention is not subject to any restriction of these embodiment.
(mensuration of density)
Density (the g/cm of resin
3) value for measuring according to ISO1183.
(mensuration to the bonding force at 23 ℃, 5 ℃, 10 ℃ of SUS hairline plate)
Bonding force at 23 ℃, 5 ℃, 10 ℃ of SUS hairline plate is measured according to JIS-Z-0237 (2000).Particularly, as being used the SUS hairline plate in the scope that surface roughness Ra is 0.210～0.310 by adherend, with toluene, clean behind the surface of this SUS hairline plate, make 2kg roller carry out one and come and go roll-in sample for evaluation, after 30 minutes, with INSTRON type tensile testing machine (society of Shimadzu Seisakusho Ltd. system, Autograph), draw speed is set in to 10m/min, when peeling off for 180 °, measures initial stage bonding force.Now, measure environment and preserve environment set while being 23 ℃ 23 ℃/humidity of temperature 50%, 5 ℃/humidity of temperature 50% 5 ℃ time, 10 ℃/humidity of temperature 50% 10 ℃ time.
(coextrusion shaping condition)
In embodiment and comparative example, the temperature condition that dissolves according to following, forms by blow moulding.
Substrate layer: 165 ℃
Bonding coat: 165 ℃
Coextrusion temperature: 165 ℃
[embodiment 1]
Relative Low Density Polyethylene (Tosoh system, trade(brand)name: Petrothene186R, density=0.924g/cm
3), with table 1 containing proportional cooperation white pigment (titanium oxide, Dupont system, trade(brand)name: Ti-PureR103), hindered amine is photostabilizer (HALS, BASF system, trade(brand)name: Tinuvin783), obtain white color system layer and form material.
Then, with respect to by Low Density Polyethylene (Tosoh system, trade(brand)name: Petrothene 186R, density=0.924g/cm
3) 85 % by weight and straight chain shape Low Density Polyethylene (Sumitomo Chemical system, trade(brand)name: ExcellenFXFX307, density=0.890g/cm
3) resin compound that 10 % by weight form, coordinate carbon black MB (firmly changing color system, trade(brand)name: BlackSPEMB-865, carbon content 20%) 5 % by weight, obtain black system layer and form a material.
And then, coordinate HSBR (styrene content=10 % by weight, JSR system, trade(brand)name: Dynaron1321P) 82 % by weight and tackifier (C 5 is that water adds aromatic base crude oil Trees fat, eastman chemical system, trade(brand)name: EASTOTACC115W, softening temperature=115 ℃) 18 % by weight, obtain bonding coat and form material.
Use the white color system layer obtaining in above-mentioned to form that material, black system layer form a material, bonding coat forms material; utilize the coextrusion of blow moulding to be shaped, obtain surface protective plate (the 1) (thickness: white color system layer/black layer/bonding coat=20 μ m/35 μ m/5 μ m of system) of three-decker (white color system layer/black system layer/bonding coat).
Show the result in table 1.
[embodiment 2]
The thickness of black system layer is made as to 45 μ m; in addition; carry out similarly to Example 1, obtain surface protective plate (the 2) (thickness: white color system layer/black layer/bonding coat=20 μ m/45 μ m/5 μ m of system) of three-layer structure (white color system layer/black system layer/bonding coat).
Show the result in table 1.
[embodiment 3]
The mixing ratio of HSBR is set as to 80 % by weight; the mixing ratio of tackifier is set as to 20 % by weight; in addition; carry out similarly to Example 1 surface protective plate (the 3) (thickness: white color system layer/black layer/bonding coat=20 μ m/35 μ m/5 μ m of system) of three-layer structure (white color system layer/black system layer/bonding coat).
Show the result in table 1.
[embodiment 4]
The thickness of black system layer is made as to 45 μ m; in addition; carry out similarly to Example 3, obtain surface protective plate (the 4) (thickness: white color system layer/black layer/bonding coat=20 μ m/45 μ m/5 μ m of system) of three-layer structure (white color system layer/black system layer/bonding coat).
Show the result in table 1.
[embodiment 5]
The mixing ratio of HSBR is set as to 85 % by weight; the mixing ratio of tackifier is set as to 15 % by weight; in addition; carry out similarly to Example 1 surface protective plate (the 5) (thickness: white color system layer/black layer/bonding coat=20 μ m/35 μ m/5 μ m of system) of three-layer structure (white color system layer/black system layer/bonding coat).
Show the result in table 1.
[embodiment 6]
The thickness of black system layer is made as to 45 μ m; in addition; carry out similarly to Example 5, obtain surface protective plate (the 6) (thickness: white color system layer/black layer/bonding coat=20 μ m/45 μ m/5 μ m of system) of three-layer structure (white color system layer/black system layer/bonding coat).
Show the result in table 1.
[comparative example 1]
Coordinate SEBS (hydrogenation SEBS, styrene content=15 % by weight, JSR system, trade(brand)name: Dynaron 8600P) 82 % by weight and tackifier (C5 is that hydrogenated aromatic petroleum resin, bright dipping emergingly produce, trade(brand)name: 140 ℃ of Aimerb P140, softening temperatures) 18 % by weight; obtain bonding coat and form material; in addition; carry out in the same manner with embodiment 1, obtain surface protective plate (the C1) (thickness: white color system layer/black layer/bonding coat=20 μ m/35 μ m/5 μ m of system) of three-layer structure (white color system layer/black system layer/bonding coat).
Show the result in table 2.
[comparative example 2]
The thickness of black system layer is made as to 45 μ m; in addition; similarly carry out with comparative example 1, obtain surface protective plate (the C2) (thickness: white color system layer/black layer/bonding coat=20 μ m/45 μ m/5 μ m of system) of three-layer structure (white color system layer/black system layer/bonding coat).
Show the result in table 2.
[comparative example 3]
Coordinate HSBR (styrene content=10 % by weight, JSR system, trade(brand)name: Dynaron1321P) 82 % by weight and tackifier (C5 is that hydrogenated aromatic petroleum resin, bright dipping emergingly produce, trade(brand)name: 140 ℃ of Aimerb P140, softening temperatures) 18 % by weight; obtain bonding coat and form material; in addition; carry out in the same manner with embodiment 1, obtain surface protective plate (the C3) (thickness: white color system layer/black layer/bonding coat=20 μ m/35 μ m/5 μ m of system) of three-layer structure (white color system layer/black system layer/bonding coat).
Show the result in table 2.
[comparative example 4]
The thickness of black system layer is made as to 45 μ m; in addition; similarly carry out with comparative example 3, obtain surface protective plate (the C4) (thickness: white color system layer/black layer/bonding coat=20 μ m/45 μ m/5 μ m of system) of three-layer structure (white color system layer/black system layer/bonding coat).
Show the result in table 2.
[comparative example 5]
Coordinate SEBS (hydrogenation SEBS, styrene content=15 % by weight, JSR system, trade(brand)name: Dynaron 8600P) 82 % by weight and tackifier (C5 is hydrogenated aromatic petroleum resin, eastman chemical system, trade(brand)name: EASTOTAC C115W, softening temperature=115 ℃) 18 % by weight; obtain bonding coat and form material; in addition; carry out in the same manner with embodiment 1, obtain surface protective plate (the C5) (thickness: white color system layer/black layer/bonding coat=20 μ m/35 μ m/5 μ m of system) of three-layer structure (white color system layer/black system layer/bonding coat).
Show the result in table 2.
[comparative example 6]
The thickness of black system layer is made as to 45 μ m; in addition; similarly carry out with comparative example 5, obtain surface protective plate (the C6) (thickness: white color system layer/black layer/bonding coat=20 μ m/45 μ m/5 μ m of system) of three-layer structure (white color system layer/black system layer/bonding coat).
Show the result in table 2.
[comparative example 7]
The thickness of black system layer is made as to 90 μ m; the thickness of bonding coat is formed to 10 μ m; in addition; similarly carry out with comparative example 1, obtain surface protective plate (the C7) (thickness: white color system layer/black layer/bonding coat=20 μ m/90 μ m/10 μ m of system) of three-layer structure (white color system layer/black system layer/bonding coat).
Show the result in table 2.
[comparative example 8]
The thickness of black system layer is made as to 70 μ m; the thickness of bonding coat is formed to 10 μ m; in addition; similarly carry out with comparative example 1, obtain surface protective plate (the C8) (thickness: white color system layer/black layer/bonding coat=20 μ m/70 μ m/10 μ m of system) of three-layer structure (white color system layer/black system layer/bonding coat).
Show the result in table 2.
From table 1, table 2, even if surface protective plate effects on surface of the present invention is asperities by adherend, the bonding force of peeling off at a high speed fully and appropriateness high, and high speed at low temperatures also shows in peeling off fully and the high bonding force of appropriateness.
Utilizability in industry
Surface protective plate of the present invention, when the 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, pvdc layer laminated steel, sheet glass etc., can be used for sticking on purposes of protecting on these surface etc.Surface protective plate of the present invention particularly as effects on surface carry out the processing of hair line SUS hairline plate surface protective plate of great use.
Claims (4)
1. a surface protective plate, it comprises substrate layer and bonding coat, wherein,
To the bonding force at 23 ℃ of SUS hairline plate, as draw speed, be that the lower 180 ° of bonding forces while peeling off of 10m/min are more than 1.0N/20mm,
To the bonding force at 5 ℃ of SUS hairline plate, as draw speed, be that the lower 180 ° of bonding forces while peeling off of 10m/min are more than 1.5N/20mm.
2. a surface protective plate, it comprises substrate layer and bonding coat, wherein,
This bonding coat comprises styrene series thermoplastic elastomer and tackifier,
The styrene content of this styrene series thermoplastic elastomer is 5 % by weight～13 % by weight,
The softening temperature of these tackifier is 90 ℃～120 ℃.
3. surface protective plate as claimed in claim 1 or 2, wherein,
Described substrate layer and described bonding coat are shaped to form as one by coextrusion and form.
4. the surface protective plate as described in any one in claim 1～3, wherein,
Described substrate layer comprises polyolefin-based resins as principal constituent.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210369682.4A CN103709947A (en) | 2012-09-28 | 2012-09-28 | Surface protective sheet |
| PCT/JP2013/074021 WO2014050490A1 (en) | 2012-09-28 | 2013-09-06 | Surface protective sheet |
| TW102133697A TW201418400A (en) | 2012-09-28 | 2013-09-17 | Surface protective sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210369682.4A CN103709947A (en) | 2012-09-28 | 2012-09-28 | Surface protective sheet |
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| Publication Number | Publication Date |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1942313A (en) * | 2005-01-14 | 2007-04-04 | 日绊株式会社 | Surface protective sheet |
| CN101189317A (en) * | 2005-06-06 | 2008-05-28 | 积水化学工业株式会社 | Surface protective film |
| CN102227481A (en) * | 2008-12-01 | 2011-10-26 | 出光统一科技株式会社 | Surface protective film |
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2012
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1942313A (en) * | 2005-01-14 | 2007-04-04 | 日绊株式会社 | Surface protective sheet |
| CN101189317A (en) * | 2005-06-06 | 2008-05-28 | 积水化学工业株式会社 | Surface protective film |
| CN102227481A (en) * | 2008-12-01 | 2011-10-26 | 出光统一科技株式会社 | Surface protective film |
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Application publication date: 20140409 |