CN103834314A - Surface protection sheet - Google Patents
Surface protection sheet Download PDFInfo
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- CN103834314A CN103834314A CN201210477884.0A CN201210477884A CN103834314A CN 103834314 A CN103834314 A CN 103834314A CN 201210477884 A CN201210477884 A CN 201210477884A CN 103834314 A CN103834314 A CN 103834314A
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- substrate layer
- surface protective
- white color
- protective plate
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Abstract
The invention provides a surface protection sheet, the outermost surface of a base material layer is roughed to a degree that the presence of a foreign body between the surface protection sheet and an adherend is unobvious, and whether an adherend with a smooth surface or an adherend with a rough surface both can exhibit sufficient and appropriate adhesion to the surface protection sheet. The surface protection sheet successively comprises a white series base material layer, a black series base material layer and an adhesive layer, the white series base material layer is the outermost layer, the surface roughness Ra of the outermost surface of the white series base material layer is above 0.30 mum, and the surface gloss, at 60 degree gloss, of the outermost surface of the white series base material layer is below 65.
Description
Technical field
The present invention relates to a kind of surface protective plate.Specifically, the present invention relates to comprise successively white color system substrate layer, black is the surface protective plate of substrate layer and bonding coat, and this white color system substrate layer is outermost layer.Surface protective plate of the present invention; for example carrying, when optics, the electronic units etc. such as parts, polarizing coating, liquid crystal panel such as processing or maintenance metal sheet, coated plate, aluminum alloy frame, resin board, decorative steel plate, pvdc layer laminated steel, sheet glass, the surface that can be used for sticking on these is with purposes of protecting etc.
Background technology
Surface protective plate is provided with bonding coat in a side of substrate layer conventionally.As the method for manufacturing such surface protective plate that comprises substrate layer and bonding coat, propose to have a kind of by the coextrusion method (for example,, with reference to patent documentation 1) that substrate layer and bonding coat are formed as one that is shaped.
From rakish viewpoint, the outmost surface of the substrate layer in surface protective plate is preferably smoothly sometimes.But; if the outmost surface of the substrate layer in surface protective plate is too level and smooth; can cause the problem that the foreign matter being present between this surface protective plate and adherend is obvious, sense of touch variation is such, also can cause the such problem of precise decreasing of visual inspection, also can have influence on productivity.
In addition, with regard to existing surface protective plate, the insufficient and immoderation to the bonding force under the attaching state of adherend.Therefore,, while processing etc. having attached the adherend of existing surface protective plate, exist a part for this surface protective plate can peel off such problem.The situation of the insufficient and immoderation of the bonding force that for example, exists the low speed 23 DEG C time to peel off, paste the situation of the insufficient and immoderation of same bonding force after 1 week.
And then existing surface protective plate exists the low such problem of the cementability of uneven surface.For example, carry out in the case of pasting effects on surface the SUS hairline plate of hairline processing, had to add to peel off in man-hour etc. or break etc. and cannot show the such problem of abundant and appropriate cementability.
Prior art document
Patent documentation 1: Japanese kokai publication sho 61-103975 communique
Summary of the invention
Problem of the present invention is, even if the outmost surface that substrate layer is provided by asperities change into foreign matter be present between surface protective plate and adherend also unconspicuous degree, no matter be the surface protective plate that the adherend of surface smoothing or the adherend of uneven surface can show to it abundant and appropriate bonding force.
Surface protective plate of the present invention, its for comprising white color system substrate layer successively, black is the surface protective plate of substrate layer and bonding coat,
This white color system substrate layer is outermost layer,
The surface roughness Ra of the outmost surface of this white color system substrate layer is more than 0.30 μ m,
The surface gloss of 60 ° of gloss of the outmost surface of this white color system substrate layer is below 65.
In a preferred embodiment, in above-mentioned white color system substrate layer, comprise inorganic particulate.
In a preferred embodiment, the inorganic particulate in above-mentioned white color system substrate layer containing proportional be 2 % by weight～8 % by weight.
In a preferred embodiment, the median size of above-mentioned inorganic particulate is 5 μ m～10 μ m.
In a preferred embodiment, above-mentioned inorganic particulate is from SiO
2and CaCO
3at least a kind of middle selection.
In a preferred embodiment, be that substrate layer and above-mentioned bonding coat are shaped to form as one by coextrusion and form by above-mentioned white color system substrate layer, above-mentioned black.
In a preferred embodiment, above-mentioned white color system substrate layer comprises polyethylene-based resin as main component.
In a preferred embodiment, above-mentioned polyethylene-based resin comprises Low Density Polyethylene.
In a preferred embodiment, above-mentioned black is that substrate layer comprises polyethylene-based resin as main component.
In a preferred embodiment, above-mentioned polyethylene-based resin comprises Low Density Polyethylene.
In a preferred embodiment, above-mentioned polyethylene-based resin comprises straight chain shape Low Density Polyethylene.
In a preferred embodiment, for surface protective plate of the present invention, the initial stage bonding force with respect to SUS430BA plate 23 DEG C time is 0.3m/min at draw speed 180 ° be more than 1.0N/20mm in peeling off.
In a preferred embodiment, for surface protective plate of the present invention, the bonding force of the stickup with respect to SUS430BA plate 23 DEG C time after 1 week is 0.3m/min at draw speed 180 ° be more than 2.0N/20mm in peeling off.
In a preferred embodiment, for surface protective plate of the present invention, the initial stage bonding force with respect to SUS304 hairline plate 23 DEG C time is 0.3m/min at draw speed 180 ° be more than 1.5N/20mm in peeling off.
In a preferred embodiment, for surface protective plate of the present invention, the bonding force of the stickup with respect to SUS304 hairline plate 23 DEG C time after 1 week is 0.3m/min at draw speed 180 ° be more than 2.0N/20mm in peeling off.
In a preferred embodiment, for surface protective plate of the present invention, breaking tenacity is more than 20N/20mm.
In a preferred embodiment, for surface protective plate of the present invention, when fracture, elongation is more than 200%.
Invention effect
According to the present invention, even if the outmost surface that substrate layer can be provided by asperities change into foreign matter be present between surface protective plate and adherend also unconspicuous degree, no matter be the surface protective plate that the adherend of surface smoothing or the adherend of uneven surface can both show to it abundant and appropriate bonding force.
Brief description of the drawings
Fig. 1 is the sectional view that schematically shows a configuration example of surface protective plate of the present invention.
Embodiment
Surface protective plate of the present invention be comprise successively white color system substrate layer, black is the surface protective plate of substrate layer and bonding coat.An outermost side of surface protective plate of the present invention is white color system substrate layer.Surface protective plate of the present invention can also comprise other suitable arbitrarily layers in the scope of not damaging effect of the present invention.
The integral thickness of surface protective plate of the present invention is preferably 30 μ m～150 μ m, more preferably 35 μ m～140 μ m, 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 integral thickness of surface protective plate of the present invention is adjusted in above-mentioned scope, can become operability excellent and there is the surface protective plate of sufficient physical strength.
White color system substrate layer is the layer of the tone of display white system, and for example, the whiteness specifying 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 substrate layer preferably comprises white pigment.As white pigment, can adopt suitable white pigment arbitrarily.As such white pigment, for example, can enumerate titanium oxide.In the situation that white color system substrate layer contains white pigment, with respect to the resinous principle that forms white color system substrate layer, it is containing proportional 0.1 % by weight～50 % by weight that is preferably, more preferably 1 % by weight～40 % by weight, more preferably 2 % by weight～30 % by weight.By by white pigment with respect to form white color system substrate layer resinous principle containing proportional being adjusted in above-mentioned scope, can make the surface protective plate of weathering resistance excellence, the plasticity such as extrudability is also excellent.
The resinous principle that forms white color system substrate layer is preferably polyolefin-based resins.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, the propylene resin being formed by propylene composition and ethene composition, poly-1-butylene, poly--4-methyl-1-pentene, 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-methyl methacrylate methyl terpolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-vinyl alcohol copolymer etc.Form the resinous principle of white color system substrate layer, more preferably acrylic polymer, ethylene-based polymer.As the resinous principle that forms white color system substrate layer, particularly, preferably can 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 substrate layer preferably comprises vinylite as main component.As the density of this polyethylene-based resin, be preferably 0.880g/cm
3～0.940g/cm
3, more preferably 0.880g/cm
3～0.923g/cm
3, more preferably 0.880g/cm
3～0.915g/cm
3.By comprising polyethylene-based resin as main component in white color system substrate layer, white color system substrate layer can have thermotolerance, solvent resistance, flexible thus, and can be by easily coiling tubular of surface protective plate of the present invention.The in the situation that of comprising polyethylene-based resin as main component in white color system substrate layer, this polyethylene-based resin preferably comprises Low Density Polyethylene.By comprise Low Density Polyethylene in above-mentioned polyethylene-based resin, can make thus white color system substrate layer there is sufficient thermotolerance, solvent resistance, flexible, can be by more easily coiling tubular of surface protective plate of the present invention.
At this, more than in the present invention, " main component " refers to and be 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.
Polyolefin-based resins in white color system substrate 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 use a kind, also can use two or more.
The thickness of white color system substrate layer, can adopt suitable thickness arbitrarily according to object.Such thickness is preferably 2 μ m～100 μ m, more preferably 3 μ m～80 μ m, and more preferably 4 μ m～60 μ m, are particularly preferably 5 μ m～50 μ m.
Black is that substrate layer is the layer that shows the tone of black system.Black is that substrate layer preferably comprises black pigment.As black pigment, can adopt suitable black pigment arbitrarily.As such black pigment, for example, can enumerate carbon black.Be the in the situation that of containing black pigment in substrate layer at black, with respect to the resinous principle that forms black system layer, it is containing proportional 0.01 % by weight～10 % by weight that is preferably, more preferably 0.1 % by weight～5 % by weight, more preferably 0.5 % by weight～3 % by weight.By by black pigment with respect to form black be substrate layer resinous principle containing proportional being adjusted in above-mentioned scope, can make the surface protective plate of weathering resistance excellence, the plasticity such as extrudability is also excellent.
Formation black is that the resinous principle of substrate layer is preferably polyolefin-based resins.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, the propylene resin being formed by propylene composition and ethene composition, poly-1-butylene, poly--4-methyl-1-pentene, 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-methyl methacrylate methyl terpolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-vinyl alcohol copolymer etc.Forming black is more preferably acrylic polymer, the ethylene-based polymer of resinous principle of substrate layer.Be the resinous principle of substrate layer as forming black, particularly, preferably can 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 is that substrate layer preferably comprises polyethylene-based resin as main component.As the density of this polyethylene-based resin, be preferably 0.880g/cm
3～0.940g/cm
3, more preferably 0.880g/cm
3～0.923g/cm
3, more preferably 0.880g/cm
3～0.915g/cm
3.By being to comprise polyethylene-based resin in substrate layer as main component at black, substrate layer can have thermotolerance, solvent resistance, flexible, and can be by easily coiling tubular of surface protective plate of the present invention.Be the in the situation that of comprising polyethylene-based resin as main component in substrate layer at black, this polyethylene-based resin preferably comprises at least a kind that from Low Density Polyethylene and straight chain shape Low Density Polyethylene, selects.By comprise at least a kind that selects from Low Density Polyethylene and straight chain shape Low Density Polyethylene in above-mentioned polyethylene-based resin; black is that substrate layer can have sufficient thermotolerance, solvent resistance, flexible thus, and can be by more easily coiling tubular of surface protective plate of the present invention.
Black be polyolefin-based resins in substrate 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 use a kind, also can use two or more.
Black is the thickness of substrate layer, can adopt suitable thickness arbitrarily according to object.Such thickness is preferably 2 μ m～100 μ m, more preferably 3 μ m～80 μ m, and more preferably 4 μ m～60 μ m, are particularly preferably 5 μ m～50 μ m.
In white color system substrate layer, preferably comprise inorganic particulate.As such inorganic particulate, as long as just applying usually used as the known material of inorganic particulate, but in order to fully demonstrate effect of the present invention, be preferably from SiO
2and CaCO
3at least a kind of middle selection.
Fig. 1 is the sectional view that schematically shows a configuration example of the surface protective plate of the present invention of the situation that comprises inorganic particulate in white color system substrate layer.In Fig. 1, schematically illustrated surface protective plate 100 of the present invention has a configuration example of the situation of the stacked formation of " white color system substrate layer 21/ black is substrate layer 22/ bonding coat 10 ".In white color system substrate layer 21, comprise inorganic particulate 30.
The in the situation that of comprising inorganic particulate in white color system substrate layer, the inorganic particulate in white color system substrate layer containing proportional 2 % by weight～8 % by weight that are preferably, more preferably 2 % by weight～7 % by weight, more preferably 2 % by weight～6 % by weight.By by the inorganic particulate in white color system substrate layer containing proportional being adjusted within the scope of this, even if the outmost surface that can make thus substrate layer fully asperities change into foreign matter and be present between surface protective plate and adherend also unconspicuous degree.Inorganic particulate in white color system substrate layer containing proportional being less than 2 % by weight, if having foreign matter between surface protective plate and adherend,, in the time observing the outmost surface of substrate layer, foreign matter likely can be obvious.Inorganic particulate in white color system substrate layer containing proportional while exceeding 8 % by weight, the dispersion that not only easily causes white pigment is bad, the coming off of inorganic particulate, and likely makes thin film strength physical property decline and add the damage to adherend that film fracture occurs man-hour or follow with it at adherend.
The in the situation that of comprising inorganic particulate in white color system substrate layer, the median size of inorganic particulate is preferably 5 μ m～10 μ m, more preferably 5 μ m～9 μ m, more preferably 6 μ m～10 μ m.By the median size of inorganic particulate is adjusted within the scope of this, even if the outmost surface that can make thus substrate layer fully asperities change into foreign matter and be present between surface protective plate and adherend also unconspicuous degree.In the time that the median size of inorganic particulate is less than 5 μ m, if inside has foreign matter between surface protective plate and adherend,, in the time observing the outmost surface of substrate layer, foreign matter likely can be obvious.In the time that the median size of inorganic particulate exceedes 10 μ m, the dispersion that not only easily causes white pigment is bad, the coming off of inorganic particulate, and likely makes thin film strength physical property decline and add the damage to adherend that film fracture occurs man-hour or follow with it at adherend.
Different from white color system substrate layer, black is in substrate layer, preferably not comprise inorganic particulate.Black be inorganic particulate in substrate layer containing proportional being preferably below 1 % by weight, more preferably, below 0.1 % by weight, be more preferably essentially 0 % by weight.By by black be inorganic particulate in substrate layer containing proportional being adjusted within the scope of this, be present between surface protective plate and adherend also unconspicuous degree even if can make thus the abundant asperities of the outmost surface of substrate layer change into foreign matter.
White color system substrate layer, black are that substrate layer can contain any suitable additive.As such additive, for example can enumerate antioxidant, UV light absorber, antiaging agent, photostabilizer, antistatic agent, 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 (Japanese: order ヤ ニ prevents drug), lubrication prescription, antiblocking agent etc.
White color system substrate layer, black are that substrate layer preferably comprises Photostabilised dose.Be that substrate layer comprises Photostabilised dose by making white color system substrate layer, black, can give sufficient weathering resistance to surface protective plate of the present invention.
As Photostabilised dose, not damaging in the scope of effect of the present invention, can adopt any suitable Photostabilised dose.As such Photostabilised dose, for example preferably can enumerate hindered amine is Photostabilised dose (HALS).
Be that substrate layer is comprise Photostabilised dose in the situation that at white color system substrate layer, black; with respect to the weight of surface protective plate entirety of the present invention; this Photostabilised dose containing proportional be preferably 0.10 % by weight more than; more preferably 0.20 % by weight～0.64 % by weight; more preferably 0.30 % by weight～0.60 % by weight, is particularly preferably 0.34 % by weight～0.55 % by weight.Be that substrate layer is comprise Photostabilised dose in the situation that at white color system substrate layer, black; as long as by this Photostabilised dose be adjusted to respect to the weight of surface protective plate entirety of the present invention to be in above-mentioned scope, can to give weathering resistance more fully to surface protective plate of the present invention containing proportional.
Can implement the back side to the outmost surface of white color system substrate layer processes.The method of processing as the back side can adopt any appropriate means in the scope of not damaging effect of the present invention.The method of processing as such back side, the method that for example can enumerate the surface working such as embossing processing or concavo-convex processing, makes it to contain derivative of fatty acid etc.Such derivative of fatty acid can be only a kind of, can be also two or more.
In the situation that white color system substrate layer comprises derivative of fatty acid, with respect to the resinous principle in white color system substrate layer, derivative of fatty acid in white color system substrate layer containing proportional 0.05 % by weight～1.00 % by weight that is preferably, 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 white color system substrate layer to be adjusted to respect to the resinous principle in white color system substrate layer be in above-mentioned scope containing proportional; can easily make to make the surface protective plate uncoiling of the present invention of drum; embody fully stripping result, can suppress fully because of the pollution due to the oozing out of this derivative of fatty acid 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, for example, can enumerate saturated fatty acid bisamide, unsaturated fatty acids bisamide, fragrant family bisamide, substituted ureas, 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 '-stearyl urea.
As derivative of fatty acid, be preferably fatty acid amide, more preferably from methylene-bis stearic amide, ethylenebis stearic amide, ethylenebis behenic acid acid amides, N-stearyl-N '-stearic amide, select at least a kind.
The preferred fusing point of derivative of fatty acid is more than 100 DEG C.The derivative of fatty acid that fusing point is less than 100 DEG C, becomes significantly to the transfer printing on bonding coat surface, and the decline of bounding force likely easily occurs.
The thickness of bonding coat is preferably 1 μ m～50 μ m, more preferably 2 μ m～40 μ m, 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, in the time utilizing coextrusion to be shaped manufacture surface protective plate of the present invention, the control transfiguration that layer forms is easy, in addition, can obtain having the surface protective plate of sufficient physical strength thus.
Bonding coat preferably comprises thermoplastic resin as main component.The contained thermoplastic resin of bonding coat can be only a kind, can be also two or more.
As thermoplastic resin, can adopt suitable thermoplastic resin arbitrarily.As such thermoplastic resin, for example can enumerate ethylene series resin, the olefin/diene copolymers that contains aromatic group, phenylethylene resin series, ester is 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, for example, can enumerate the polystyrene ABA block polymer (triblock copolymer) such as styrene-butadiene-styrene (SBS), styrene-isoprene-styrene copolymer-(SIS); The polystyrene ABAB type segmented copolymers (Tetrablock copolymer) such as styrene-butadiene-styrene-butadienecopolymer (SBSB), styrene-isoprene-phenylethene-isoprene copolymer (SISI); The polystyrene ABABA type segmented copolymers (five segmented copolymers) such as styrene-butadiene-styrene-butadiene-styrene copolymer (SBSBS), styrene-isoprene-phenylethene-isoprene-styrol copolymer (SISIS); There is the styrene block copolymer of its above AB repeating unit; Deng.
As the hydride of styrene block copolymer, for example, can enumerate the multipolymer (SEBSEB) of styrene-ethylene-butylene copolymer-styrol copolymer (SEBS), styrene-ethylene-propylene copolymer-styrol copolymer (SEPS), styrene-ethylene-butylene copolymer-styrene-ethylene-butylene copolymer; Deng.
Styrene series thermoplastic elastomer can only use a kind, also can use two or more.
Styrene content (being styrene block content in the situation that of styrene block copolymer) in styrene series thermoplastic elastomer is preferably 5 % by weight～13 % by weight, more preferably 1 % by weight～20 % by weight, 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, thus for surface protective plate of the present invention, no matter be that the adherend of surface smoothing or the adherend of uneven surface can show abundant and appropriate bonding force to it.If above-mentioned styrene content tails off, likely easily there is the not enough caused cull of cohesive force because of bonding coat.If it is many that above-mentioned styrene content becomes, bonding coat hardening, likely cannot obtain the binding property good with respect to uneven surface.
As styrene series thermoplastic elastomer, preferably there is 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 being formed by vinylbenzene (A) and divinyl (B).By adopting such styrene series thermoplastic elastomer, more fully and moderately show thus the bonding force under the attaching state of adherend, on the other hand, the bonding force attaching to while peeling off after adherend is more abundant and appropriate size, therefore just can easily peel off from adherend with the slight power of appropriateness, and then, can fully and moderately show the bonding force exposing to the sun in the carrying capacity of the environment of long-term preservation.
At styrene series thermoplastic elastomer for to have the hydride (SEBS, SEBSEB, SEBSEBS etc.) of styrene block copolymer of repeating structure (ABA type, ABAB type, ABABA type etc.) more than the triblock copolymer being formed by vinylbenzene (A) and divinyl (B), butylene structure is more than in ethylene-butene copolymer block, shared ratio is preferably 60 % by weight, more preferably more than 70 % by weight, more preferably more than 75 % by weight.By butylene structure shared ratio in above-mentioned ethylene-butene copolymer block is adjusted in above-mentioned scope, bonding force while more fully and moderately showing thus the attaching state to adherend, on the other hand, the bonding force attaching to while peeling off after adherend is more abundant and appropriate size, therefore, just can more easily peel off from adherend with the power that appropriateness is slight, and then, can fully and moderately show the bonding force exposing to the sun in the carrying capacity of the environment of long-term preservation.It should be noted that, above-mentioned butylene structure shared ratio in ethylene-butene copolymer block is preferably below 90 % by weight.
In order to carry out fusible adjusting etc., bonding coat can contain other styrene series thermoplastic elastomers in the scope of not damaging object of the present invention.
As other styrene series thermoplastic elastomer, can enumerate above-mentioned styrene block copolymer in addition; The AB type block polymers such as the multipolymer (SEB) of styrene-butadiene copolymer (SB), styrene-isoprene copolymer (SI), styrene-ethylene-butylene copolymer, the multipolymer (SEP) of styrene-ethylene-propylene copolymer; The polystyrene random copolymerss such as styrene butadiene rubbers (SBR); Vinylbenzene-alkene crystal system block polymer of the A-B-C types such as the multipolymer (SEBC) of styrene-ethylene-butylene copolymer-alkene crystallization; The hydride of these materials; Deng.
In the time forming bonding coat, in order to carry out control of adhesion characteristic etc., can suitably add as required for example tenderizer, tackifier, the such polyolefin-based resins using in substrate layer, silicone-based polymkeric substance, aqueous acrylic copolymer, phosphoric acid ester based compound, antiaging agent, Photostabilised dose, 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.
Can also to bonding coat surface as required embodiment if Corona discharge Treatment, uviolizing processing, flame treating, Cement Composite Treated by Plasma, sputter etching processing etc. are to control binding property or to attach the surface treatment as object such as workability.
Tackifier be engaged in improve bounding force aspect be effective.Wherein, about the use level of tackifier, for fear of the caused cull problem of decline occurring because of cohesive force, and can suitably determine according to the adherend of application surface screening glass.With respect to the base polymer of bonding coat, the use level of tackifier is preferably below 80 % by weight, more preferably below 40 % by weight, more preferably below 20 % by weight.
The softening temperature of tackifier is preferably 90 DEG C～120 DEG C, more preferably 70 DEG C～135 DEG C, more preferably 80 DEG C～130 DEG C, is particularly preferably 85 DEG C～125 DEG C.By the softening temperature of above-mentioned tackifier is adjusted in above-mentioned scope, no matter be the adherend of surface smoothing or the adherend of uneven surface, surface protective plate of the present invention can further show abundant and appropriate bonding force to it thus.
As tackifier, can use ad lib petroleum line resin, the coumarone-indenes such as aliphatics based copolymer such as, aromatic series based copolymer, aliphatic-aromatic based copolymer system or ester ring type based copolymer is that resin, terpenic series resin, terpenes phenolic aldehyde are that the rosin series such as resin, polymerized rosin resin, (alkyl) phenolic aldehyde are that resin, diformazan benzene series resin, these hydride etc. are generally used for the material of tackiness agent.Tackifier can only use a kind, also can use two or more.In these tackifier, from the viewpoint of separability, weathering resistance etc., the preferably tackifier of hydrogenation system, especially preferably C5 is hydrogenated aromatic petroleum resin.It should be noted that, tackifier also can use with the form of the mixture of olefin resin and commercially available product.
The cooperation of tenderizer is effective to improving bounding force.As tenderizer, for example, can enumerate low-molecular-weight diene polymer, polyisobutene, hydrogenated polyisoprene, hydrogenated butadiene polymer, their derivative etc.As such derivative, for example can be illustrated in single end or two ends and have the material of 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.Especially to the object being suppressed with respect to the fusible raising of adherend, preferably hydride or the ethylene series tenderizer etc. of the diene polymer such as hydrogenated butadiene polymer, hydrogenated polyisoprene.As such tenderizer, particularly, can obtain the trade(brand)name " KurapreneLIR-200 " of (strain) Kuraray system etc.These tenderizers can only use a kind, also can use two or more.
The molecular weight of tenderizer can suitably be set as the amount of any suitable, if molecular weight diminishes, likely become that material from bonding coat to adherend is divided a word with a hyphen at the end of a line or the reason of re-separation etc., on the other hand, if molecule quantitative change is large, have and become the tendency of raising effect that lacks bounding force, 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 suitably be set as the amount of any suitable, if but it is many to add quantitative change, there is the tendency that while exposure, cull increases outside high temperature or room, therefore,, with respect to the base polymer of bonding coat, be preferably below 100 % by weight, more preferably below 60 % by weight, more preferably below 40 % by weight.
Taking the rising etc. that suppresses bonding force as object, in bonding coat, can also add polyolefin-based resins.Polyolefin-based resins can exemplify the resin same with the resin using in the formation of substrate layer.This polyolefin-based resins can be only a kind, can be also 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.
For surface protective plate of the present invention, the surface roughness Ra of the outmost surface of white color system substrate layer is more than 0.30 μ m, is preferably 0.30 μ m～1.0 μ m, and more preferably 0.30 μ m～0.8 μ m, is particularly preferably 0.3 μ m～0.60 μ m.By the surface roughness Ra of the outmost surface of the white color system substrate layer in surface protective plate of the present invention is adjusted in above-mentioned scope; for surface protective plate of the present invention, be present between surface protective plate and adherend also unconspicuous degree even if can make the outmost surface asperities of substrate layer change into foreign matter.It should be noted that, about the measuring method of surface roughness Ra, as described later.
For surface protective plate of the present invention, the surface gloss of 60 ° of gloss of the outmost surface of white color system substrate layer is below 65, is preferably 20～65, more preferably 25～60, be particularly preferably 25～55.By the surface gloss of 60 ° of gloss of the outmost surface of the white color system substrate layer in surface protective plate of the present invention is adjusted in above-mentioned scope; for surface protective plate of the present invention, between surface protective plate and adherend, also can become very not obvious even if there is foreign matter to be present in.It should be noted that, about the measuring method of surface gloss, as described later.
For surface protective plate of the present invention; the initial stage bonding force with respect to SUS430BA plate 23 DEG C time; be 0.3m/min at draw speed 180 ° be preferably 1.0N/20mm in peeling off more than; more preferably 1.0N/20mm～3.0N/20mm; more preferably 1.2N/20mm～2.8N/20mm, is particularly preferably 1.4N/20mm～2.5N/20mm.By the above-mentioned initial stage bonding force in surface protective plate of the present invention is adjusted in above-mentioned scope, during surface protective plate of the present invention low speed is at room temperature peeled off, can show fully and the high bonding force of appropriateness.It should be noted that, about the measuring method of the various bonding forces with respect to SUS430BA plate, as described later.
For surface protective plate of the present invention; the bonding force of the stickup with respect to SUS430BA plate 23 DEG C time after 1 week; be 0.3m/min at draw speed 180 ° be preferably 2.0N/20mm in peeling off more than; more preferably 2.0N/20mm～4.0N/20mm; more preferably 2.0N/20mm～3.8N/20mm, is particularly preferably 2.0N/20mm～3.5N/20mm.By the above-mentioned bonding force in surface protective plate of the present invention is adjusted in above-mentioned scope; with regard to surface protective plate of the present invention; in the low speed exposing to the sun in the carrying capacity of environment of long-term preservation is peeled off, surface protective plate of the present invention can show fully and the high bonding force of appropriateness.It should be noted that, about the measuring method of the various bonding forces with respect to SUS430BA plate, as described later.
For surface protective plate of the present invention; the initial stage bonding force with respect to SUS304 hairline plate 23 DEG C time; be 0.3m/min at draw speed 180 ° be preferably 1.5N/20mm in peeling off more than; more preferably 1.5N/20mm～3.0N/20mm; more preferably 1.5N/20mm～2.8N/20mm, is particularly preferably 1.5N/20mm～2.5N/20mm.By the above-mentioned initial stage bonding force in surface protective plate of the present invention is adjusted in above-mentioned scope; during surface protective plate of the present invention low speed is at room temperature peeled off, even if the adherend that is uneven surface with respect to surface also can show fully and the high bonding force of appropriateness.It should be noted that, about the measuring method of the various bonding forces with respect to SUS304 hairline plate, as described later.
For surface protective plate of the present invention; the bonding force of the stickup with respect to SUS304 hairline plate 23 DEG C time after 1 week; be 0.3m/min at draw speed 180 ° be preferably 2.0N/20mm in peeling off more than; more preferably 2.0N/20mm～4.0N/20mm; more preferably 2.0N/20mm～3.8N/20mm, is particularly preferably 2.0N/20mm～3.5N/20mm.By the above-mentioned bonding force of surface protective plate of the present invention is adjusted in above-mentioned scope; with regard to surface protective plate of the present invention; in the low speed exposing to the sun in the carrying capacity of environment of long-term preservation is peeled off, even if the adherend that surface protective plate of the present invention is uneven surface with respect to surface also can show fully and the high bonding force of appropriateness.It should be noted that, about the measuring method of the various bonding forces with respect to SUS304 hairline plate, as described later.
It should be noted that, the material that in this specification sheets, is called " SUS hairline plate " is surperficial by the finished SUS plate of hairline, is to have the SUS plate that surface roughness Ra is the uneven surface of 0.210 μ m～0.310 μ m.This surface roughness Ra is to use contact surfaceness meter (SJ400: Mitutoyo Corp (MITUTOYO) system), measures (condition determination: taking JIS-B-0601:(2001) and measures as benchmark having carried out ridge orientation SUS plate, hairline and the right angle orientation of hairline processing.Specifically, under the condition of contact pilotage radius 2 μ m, cut-off (cut off) value 0.8mm, measured length 4mm, measure) time value.
For surface protective plate of the present invention, more than breaking tenacity is preferably 20N/20mm, more preferably 20N/20mm～50N/20mm, more preferably 20N/20mm～45N/20mm, is particularly preferably 20N/20mm～40N/20mm.By the breaking tenacity in surface protective plate of the present invention is adjusted in above-mentioned scope, surface protective plate of the present invention can show sufficient physical strength.It should be noted that, about the measuring method of breaking tenacity, as described later.
For surface protective plate of the present invention, when fracture, elongation is preferably more than 200%, and more preferably 200%～600%, more preferably 200%～500%, be particularly preferably 200%～400%.Elongation is adjusted in above-mentioned scope when by fracture in surface protective plate of the present invention, for surface protective plate of the present invention, can show sufficient physical strength.It should be noted that, the measuring method of elongation during about fracture, as described later.
For surface protective plate of the present invention, be preferably that substrate layer and bonding coat are shaped to form as one by coextrusion and form by white color system substrate layer, black.Be shaped as coextrusion, can adopt normally used suitable coextrusion arbitrarily in the manufacture of film, sheet material etc. to be shaped.Be shaped as coextrusion, can adopt such as blow moulding, coextrusion T-modulus method etc.From cost aspect or productivity aspect consider, preferably these coextrusion are shaped.
The manufacture method of surface protective plate of the present invention, preferably making white color system substrate layer, black is that substrate layer and bonding coat are shaped and are formed as one and manufactured by coextrusion.Thus, can high-level efficiency and manufacture at an easy rate the surface protective plate of the stepped construction with specific thickness.Be shaped as coextrusion, can adopt normally used suitable coextrusion arbitrarily in the manufacture of film, sheet material etc. to be shaped.Be shaped as coextrusion, can adopt such as blow moulding, coextrusion T-modulus method etc.
Be shaped according to coextrusion, because white color system substrate layer and bonding coat do not join under melting heated condition, therefore do not generate the by product producing because of the thermal degradation when of white color system substrate layer, and there is no its by product dividing a word with a hyphen at the end of a line to bonding coat, demonstrate 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) for measure the value obtaining according to ISO1183.
(mensuration of surface roughness Ra)
Surface protective plate is carried out to round attaching on SUS430BA plate with 2kg roller.Based on JIS B0601 (2001), (μ m) measures the surface roughness Ra of the outmost surface of the white color system substrate layer with contact pilotage front end footpath 2 μ m, measured length 4mm, cutoff 0.8mm to the surface protective plate after attaching.
(mensuration of surface gloss)
Use the Micro TRIgloss processed of GUARDNER company, carried out the mensuration of 60 ° of corner reflection rates.
(with respect to the mensuration of the initial stage bonding force of SUS430BA plate)
Draw speed is the initial stage bonding forces with respect to SUS430BA plate during 180 ° of 0.3m/min are peeled off, 23 DEG C time, measures according to following.
, bonding force of above-mentioned initial stage is measured according to JIS-Z-0237 (2000).Particularly, use SUS430BA plate as adherend, behind surface with this SUS430BA plate of toluene wash, make 2kg roller round trip crimping sample for evaluation, after 30 minutes, use INSTRON type tensile testing machine (company of Shimadzu Seisakusho Ltd. system, Autograph (オ mono-ト グ ラ Off)), draw speed is set as to above-mentioned speed, peels off and measured initial stage bonding force with 180 °.Now, measure environment and preserve environment and carry out with 23 DEG C/humidity of temperature 50%.
(with respect to mensuration SUS430BA plate, that paste the bonding force after 1 week)
Draw speed be during 180 ° of 0.3m/min are peeled off, 23 DEG C time with respect to the stickup of SUS430BA plate the bonding force after 1 week, measure according to following.
, above-mentioned bonding force is measured according to JIS-Z-0237 (2000).Particularly, use SUS430BA plate as adherend, behind surface with this SUS430BA plate of toluene wash, make 2kg roller round trip crimping sample for evaluation, after between above-mentioned preservation period, use INSTRON type tensile testing machine (company of Shimadzu Seisakusho Ltd. system, Autograph), draw speed is set as to above-mentioned speed, peels off and measured bonding force with 180 °.Now, measuring environment carries out with 23 DEG C/humidity of temperature 50%.
(with respect to the mensuration of the initial stage bonding force of SUS304 hairline plate)
Draw speed is the initial stage bonding forces with respect to SUS304 hairline plate during 180 ° of 0.3m/min are peeled off, 23 DEG C time, measures according to following.
, bonding force of above-mentioned initial stage is measured according to JIS-Z-0237 (2000).Particularly, use SUS304 hairline plate as adherend, behind surface with this SUS304 hairline plate of toluene wash, make 2kg roller round trip crimping sample for evaluation, after 30 minutes, use INSTRON type tensile testing machine (company of Shimadzu Seisakusho Ltd. system, Autograph), draw speed is set as to above-mentioned speed, peels off and measured initial stage bonding force with 180 °.Now, measure environment and preserve environment and carry out with 23 DEG C/humidity of temperature 50%.
(with respect to mensuration SUS304 hairline plate, that paste the bonding force after 1 week)
Draw speed is the bonding forces of the stickups with respect to SUS304 hairline plate during 180 ° of 0.3m/min are peeled off, 23 DEG C time after 1 week, measures according to following.
, above-mentioned bonding force is measured according to JIS-Z-0237 (2000).Particularly, use SUS304 hairline plate as adherend, behind surface with this SUS304 hairline plate of toluene wash, make 2kg roller round trip crimping sample for evaluation, after between above-mentioned preservation period, use INSTRON type tensile testing machine (company of Shimadzu Seisakusho Ltd. system, Autograph), draw speed is set as to above-mentioned speed, peels off and measured bonding force with 180 °.Now, measuring environment carries out with 23 DEG C/humidity of temperature 50%.
(mensuration of breaking tenacity)
Breaking tenacity is measured according to following.
Carry out tension test based on JIS-K-7127.Measure the surface protective plate that sample uses the shape of the test film type 2 that is cut into JIS-K-7127 record, carry out with grip separation 50mm, test film width 10mm, trial speed 300mm/min.In addition, the trier using in mensuration is INSTRON type tensile testing machine (company of Shimadzu Seisakusho Ltd. system, Autograph).Intensity when sample fracture taking N/20mm when unit calculates tension test.
(mensuration of elongation when fracture)
When fracture, elongation is measured according to following.
Carry out tension test based on JIS-K-7127.Measure the surface protective plate that sample uses the shape of the test film type 2 that is cut into JIS-K-7127 record, carry out with grip separation 50mm, test film width 10mm, trial speed 300mm/min.In addition, the trier using in mensuration is INSTRON type tensile testing machine (company of Shimadzu Seisakusho Ltd. system, Autograph).Elongation when sample fracture taking spacing jig from 50mm when benchmark calculates tension test with %.
(pliability test)
Pliability test is measured according to following.
Carrying out crimping with 2kg roller is attached on the stainless steel plate (304HL) of thickness 2.0mm surface protective plate; after the mode of the opposition side that is drift according to surface protective plate is arranged, carry out metal V bending machining test (V-block method) (JIS-Z-2248).Now; with die orifice V angle: 88 degree, die orifice V width (L width): 16 or 12mm, die orifice R:2.0 or 1.0mm, drift angle: the condition of 88 degree, drift R:0.6 is carried out, after bending machining, there is the cracked situation of surface protective plate to be designated as ×, situation about not occurring is designated as zero.In addition, the surface protective plate after processing is peeled off, confirmed that stainless steel plate surface has or not scar.There is the situation of scar to be designated as ×, situation about not occurring is designated as zero.
(foreign matter identification)
Aluminium oxide particles (median size=10 μ m, clear and electrician's system, CB-A10S) is sticked in swab stick, make it be attached to the surface of SUS430BA plate.There is wall-attached surface screening glass on the SUS430BA plate of this aluminium oxide particles in surface attachment, carry out, after lamination, having or not by visual observation the particle of nipping with 0.4MPa.The situation of observing the particle of nipping is designated as ×, unobserved situation is designated as zero.
(coextrusion shaping condition)
In embodiment and comparative example, utilize blow moulding to form according to following melt temperature condition.
White color system substrate layer: 165 DEG C
Black is substrate layer: 165 DEG C
Bonding coat: 165 DEG C
Coextrusion temperature: 165 DEG C
(embodiment 1)
As shown in table 1, to Low Density Polyethylene (eastern Cao's system, trade(brand)name: Petrothene 186R, density=0.924g/cm
3) coordinate silicon-dioxide (median size=6.8 μ m, Unimin system, MINEX4) 2 weight parts in 80 weight parts, and then coordinate white pigment (titanium oxide, Dupont system, trade(brand)name: Ti-PureR103) 18 weight parts, obtain white color system substrate layer and formed material.
Then, as shown in table 1, to Low Density Polyethylene (eastern Cao's system, trade(brand)name: Petrothene 186R, density=0.924g/cm
3) coordinate straight chain shape Low Density Polyethylene (Sumitomo Chemical system, trade(brand)name: Excellen FX FX307, density=0.890g/cm in 89 weight parts
3) 10 weight parts, and then coordinate carbon black MB (firmly change Color system, trade(brand)name: Black SPEMB-865, carbon content 20%) 5 weight parts, having obtained black is that substrate layer forms material.
And then, as shown in table 1, coordinate HSBR (styrene content=10 % by weight, JSR system, trade(brand)name: DYNARON 1321P) 82 weight parts and tackifier (C5 is that hydrogenated aromatic petroleum resin, bright dipping emergingly produce, trade(brand)name: I-MARV P140, softening temperature=140 DEG C) 18 weight parts, obtained bonding coat and formed material.
Using white color system substrate layer formation material obtained above, black is that substrate layer forms material, bonding coat forms material; by utilize blow moulding coextrusion be shaped, obtain 3-tier architecture (white color system substrate layer/black is substrate layer/bonding coat) surface protective plate (1) (thickness: white color system substrate layer/black be substrate layer/bonding coat=20 μ m/35 μ m/5 μ m).
The results are shown in table 1.
(embodiment 2)
As shown in table 1, to Low Density Polyethylene (eastern Cao's system, trade(brand)name: Petrothene 186R, density=0.924g/cm
3) coordinate silicon-dioxide (median size=6.8 μ m, Unimin system, MINEX4) 3.5 weight parts in 78.5 weight parts, and then coordinate white pigment (titanium oxide, Dupont system, trade(brand)name: Ti-Pure R103) 18 weight parts, obtain white color system substrate layer and formed material.
Then, as shown in table 1, to Low Density Polyethylene (eastern Cao's system, trade(brand)name: Petrothene 186R, density=0.924g/cm
3) coordinate straight chain shape Low Density Polyethylene (Sumitomo Chemical system, trade(brand)name: Excellen FX FX307, density=0.890g/cm in 89 weight parts
3) 10 weight parts, and then coordinate carbon black MB (firmly change Color system, trade(brand)name: Black SPEMB-865, carbon content 20%) 5 weight parts, having obtained black is that substrate layer forms material.
And then, as shown in table 1, coordinate HSBR (styrene content=10 % by weight, JSR system, trade(brand)name: DYNARON 1321P) 82 weight parts and tackifier (C5 is that hydrogenated aromatic petroleum resin, bright dipping emergingly produce, trade(brand)name: I-MARV P140, softening temperature=140 DEG C) 18 weight parts, obtained bonding coat and formed material.
Using white color system substrate layer formation material obtained above, black is that substrate layer forms material, bonding coat forms material; by utilize blow moulding coextrusion be shaped, obtained 3-tier architecture (white color system substrate layer/black is substrate layer/bonding coat) surface protective plate (2) (thickness: white color system substrate layer/black be substrate layer/bonding coat=20 μ m/35 μ m/5 μ m).
The results are shown in table 1.
(embodiment 3)
As shown in table 1, to Low Density Polyethylene (eastern Cao's system, trade(brand)name: Petrothene 186R, density=0.924g/cm
3) coordinate silicon-dioxide (median size=6.8 μ m, Unimin system, MINEX4) 7 weight parts in 75 weight parts, and then coordinate white pigment (titanium oxide, Dupont system, trade(brand)name: Ti-PureR103) 18 weight parts, obtain white color system substrate layer and form material.
Then, as shown in table 1, to Low Density Polyethylene (eastern Cao's system, trade(brand)name: Petrothene 186R, density=0.924g/cm
3) coordinate straight chain shape Low Density Polyethylene (Sumitomo Chemical system, trade(brand)name: Excellen FX FX307, density=0.890g/cm in 89 weight parts
3) 10 weight parts, and then coordinate carbon black MB (firmly change Color system, trade(brand)name: Black SPEMB-865, carbon content 20%) 5 weight parts, obtaining black is that substrate layer forms material.
And then, as shown in table 1, coordinate HSBR (styrene content=10 % by weight, JSR system, trade(brand)name: DYNARON 1321P) 82 weight parts and tackifier (C5 is that hydrogenated aromatic petroleum resin, bright dipping emergingly produce, trade(brand)name: I-MARV P140, softening temperature=140 DEG C) 18 weight parts, obtain bonding coat and form material.
Using white color system substrate layer formation material obtained above, black is that substrate layer forms material, bonding coat forms material; by utilize blow moulding coextrusion be shaped, obtain 3-tier architecture (white color system substrate layer/black is substrate layer/bonding coat) surface protective plate (3) (thickness: white color system substrate layer/black be substrate layer/bonding coat=20 μ m/35 μ m/5 μ m).
The results are shown in table 1.
(embodiment 4)
As shown in table 1, to Low Density Polyethylene (eastern Cao's system, trade(brand)name: Petrothene 186R, density=0.924g/cm
3) coordinate silicon-dioxide (median size=8.7 μ m, Unimin system, MINEX4F) 2 weight parts in 80 weight parts, and then coordinate white pigment (titanium oxide, Dupont system, trade(brand)name: Ti-Pure R103) 18 weight parts, obtain white color system substrate layer and formed material.
Then, as shown in table 1, to Low Density Polyethylene (eastern Cao's system, trade(brand)name: Petrothene 186R, density=0.924g/cm
3) coordinate straight chain shape Low Density Polyethylene (Sumitomo Chemical system, trade(brand)name: Excellen FX FX307, density=0.890g/cm in 89 weight parts
3) 10 weight parts, and then coordinate carbon black MB (firmly change Color system, trade(brand)name: Black SPEMB-865, carbon content 20%) 5 weight parts, having obtained black is that substrate layer forms material.
And then, as shown in table 1, coordinate HSBR (styrene content=10 % by weight, JSR system, trade(brand)name: DYNARON 1321P) 82 weight parts and tackifier (C5 is that hydrogenated aromatic petroleum resin, bright dipping emergingly produce, trade(brand)name: I-MARV P140, softening temperature=140 DEG C) 18 weight parts, obtained bonding coat and formed material.
Using white color system substrate layer formation material obtained above, black is that substrate layer forms material, bonding coat forms material; by utilize blow moulding coextrusion be shaped, obtain 3-tier architecture (white color system substrate layer/black is substrate layer/bonding coat) surface protective plate (4) (thickness: white color system substrate layer/black be substrate layer/bonding coat=20 μ m/35 μ m/5 μ m).
The results are shown in table 1.
(embodiment 5)
As shown in table 1, to Low Density Polyethylene (eastern Cao's system, trade(brand)name: Petrothene 186R, density=0.924g/cm
3) coordinate silicon-dioxide (median size=8.7 μ m, Unimin system, MINEX4F) 3.5 weight parts in 78.5 weight parts, and then coordinate white pigment (titanium oxide, Dupont system, trade(brand)name: Ti-Pure R103) 18 weight parts, obtain white color system substrate layer and formed material.
Then, as shown in table 1, to Low Density Polyethylene (eastern Cao's system, trade(brand)name: Petrothene 186R, density=0.924g/cm
3) coordinate straight chain shape Low Density Polyethylene (Sumitomo Chemical system, trade(brand)name: Excellen FX FX307, density=0.890g/cm in 89 weight parts
3) 10 weight parts, and then coordinate carbon black MB (firmly change Color system, trade(brand)name: Black SPEMB-865, carbon content 20%) 5 weight parts, having obtained black is that substrate layer forms material.
And then, as shown in table 1, coordinate HSBR (styrene content=10 % by weight, JSR system, trade(brand)name: DYNARON 1321P) 82 weight parts and tackifier (C5 is that hydrogenated aromatic petroleum resin, bright dipping emergingly produce, trade(brand)name: I-MARV P140, softening temperature=140 DEG C) 18 weight parts, obtained bonding coat and formed material.
Using white color system substrate layer formation material obtained above, black is that substrate layer forms material, bonding coat forms material; by utilize blow moulding coextrusion be shaped, obtain 3-tier architecture (white color system substrate layer/black is substrate layer/bonding coat) surface protective plate (5) (thickness: white color system substrate layer/black be substrate layer/bonding coat=20 μ m/35 μ m/5 μ m).
The results are shown in table 1.
(embodiment 6)
As shown in table 1, to Low Density Polyethylene (eastern Cao's system, trade(brand)name: Petrothene 186R, density=0.924g/cm
3) coordinate silicon-dioxide (median size=8.7 μ m, Unimin system, MINEX4F) 7 weight parts in 75 weight parts, and then coordinate white pigment (titanium oxide, Dupont system, trade(brand)name: Ti-Pure R103) 18 weight parts, obtain white color system substrate layer and formed material.
Then, as shown in table 1, to Low Density Polyethylene (eastern Cao's system, trade(brand)name: Petrothene 186R, density=0.924g/cm
3) coordinate straight chain shape Low Density Polyethylene (Sumitomo Chemical system, trade(brand)name: Excellen FX FX307, density=0.890g/cm in 89 weight parts
3) 10 weight parts, and then coordinate carbon black MB (firmly change Color system, trade(brand)name: Black SPEMB-865, carbon content 20%) 5 weight parts, having obtained black is that substrate layer forms material.
And then, as shown in table 1, coordinate HSBR (styrene content=10 % by weight, JSR system, trade(brand)name: DYNARON 1321P) 82 weight parts and tackifier (C5 is that hydrogenated aromatic petroleum resin, bright dipping emergingly produce, trade(brand)name: I-MARV P140, softening temperature=140 DEG C) 18 weight parts, obtained bonding coat and formed material.
Using white color system substrate layer formation material obtained above, black is that substrate layer forms material, bonding coat forms material; by utilize blow moulding coextrusion be shaped, obtain 3-tier architecture (white color system substrate layer/black is substrate layer/bonding coat) surface protective plate (6) (thickness: white color system substrate layer/black be substrate layer/bonding coat=20 μ m/35 μ m/5 μ m).
The results are shown in table 1.
(embodiment 7)
As shown in table 1, to Low Density Polyethylene (eastern Cao's system, trade(brand)name: Petrothene 186R, density=0.924g/cm
3) coordinate calcium carbonate (median size=8.0 μ m, standby northern efflorescence industry (strain) system, Softone BF300) 2 weight parts in 80 weight parts, and then coordinate white pigment (titanium oxide, Dupont system, trade(brand)name: Ti-Pure R103) 18 weight parts, obtain white color system substrate layer and formed material.
Then, as shown in table 1, to Low Density Polyethylene (eastern Cao's system, trade(brand)name: Petrothene 186R, density=0.924g/cm
3) coordinate straight chain shape Low Density Polyethylene (Sumitomo Chemical system, trade(brand)name: Excellen FX FX307, density=0.890g/cm in 89 weight parts
3) 10 weight parts, and then coordinate carbon black MB (firmly change Color system, trade(brand)name: Black SPEMB-865, carbon content 20%) 5 weight parts, having obtained black is that substrate layer forms material.
And then, as shown in table 1, coordinate HSBR (styrene content=10 % by weight, JSR system, trade(brand)name: DYNARON 1321P) 82 weight parts and tackifier (C5 is that hydrogenated aromatic petroleum resin, bright dipping emergingly produce, trade(brand)name: I-MARV P140, softening temperature=140 DEG C) 18 weight parts, obtained bonding coat and formed material.
Using white color system substrate layer formation material obtained above, black is that substrate layer forms material, bonding coat forms material; by utilize blow moulding coextrusion be shaped, obtain 3-tier architecture (white color system substrate layer/black is substrate layer/bonding coat) surface protective plate (7) (thickness: white color system substrate layer/black be substrate layer/bonding coat=20 μ m/35 μ m/5 μ m).
The results are shown in table 1.
(embodiment 8)
As shown in table 1, to Low Density Polyethylene (eastern Cao's system, trade(brand)name: Petrothene 186R, density=0.924g/cm
3) coordinate calcium carbonate (median size=8.0 μ m, standby northern efflorescence industry (strain) system, Softone BF300) 4 weight parts in 78 weight parts, and then coordinate white pigment (titanium oxide, Dupont system, trade(brand)name: Ti-Pure R103) 18 weight parts, obtain white color system substrate layer and formed material.
Then, as shown in table 1, to Low Density Polyethylene (eastern Cao's system, trade(brand)name: Petrothene 186R, density=0.924g/cm
3) coordinate straight chain shape Low Density Polyethylene (Sumitomo Chemical system, trade(brand)name: Excellen FX FX307, density=0.890g/cm in 89 weight parts
3) 10 weight parts, and then coordinate carbon black MB (firmly change Color system, trade(brand)name: Black SPEMB-865, carbon content 20%) 5 weight parts, having obtained black is that substrate layer forms material.
And then, as shown in table 1, coordinate HSBR (styrene content=10 % by weight, JSR system, trade(brand)name: DYNARON 1321P) 82 weight parts and tackifier (C5 is that hydrogenated aromatic petroleum resin, bright dipping emergingly produce, trade(brand)name: I-MARV P140, softening temperature=140 DEG C) 18 weight parts, obtained bonding coat and formed material.
Using white color system substrate layer formation material obtained above, black is that substrate layer forms material, bonding coat forms material; by utilize blow moulding coextrusion be shaped, obtain 3-tier architecture (white color system substrate layer/black is substrate layer/bonding coat) surface protective plate (8) (thickness: white color system substrate layer/black be substrate layer/bonding coat=20 μ m/35 μ m/5 μ m).
The results are shown in table 1.
(comparative example 1)
White color system substrate layer at embodiment 1 forms in the preparation of material, to Low Density Polyethylene (eastern Cao's system, trade(brand)name: Petrothene 186R, density=0.924g/cm
3) coordinate silicon-dioxide (median size=6.8 μ m, Unimin system, MINEX4) 1 weight part in 81 weight parts; and then cooperation white pigment (titanium oxide, Dupont system, trade(brand)name: Ti-Pure R103) 18 weight parts; in addition; carry out similarly to Example 1, obtain 3-tier architecture (white color system substrate layer/black is substrate layer/bonding coat) surface protective plate (C1) (thickness: white color system substrate layer/black be substrate layer/bonding coat=20 μ m/35 μ m/5 μ m).
The results are shown in table 2.
(comparative example 2)
White color system substrate layer at embodiment 1 forms in the preparation of material, to Low Density Polyethylene (eastern Cao's system, trade(brand)name: Petrothene 186R, density=0.924g/cm
3) coordinate silicon-dioxide (median size=3.5 μ m, Unimin system, MINEX7) 2 weight parts in 80 weight parts; and then cooperation white pigment (titanium oxide, Dupont system, trade(brand)name: Ti-Pure R103) 18 weight parts; in addition; carry out similarly to Example 1, obtain 3-tier architecture (white color system substrate layer/black is substrate layer/bonding coat) surface protective plate (C2) (thickness: white color system substrate layer/black be substrate layer/bonding coat=20 μ m/35 μ m/5 μ m).
The results are shown in table 2.
(comparative example 3)
White color system substrate layer at embodiment 1 forms in the preparation of material, to Low Density Polyethylene (eastern Cao's system, trade(brand)name: Petrothene 186R, density=0.924g/cm
3) coordinate silicon-dioxide (median size=3.5 μ m, Unimin system, MINEX7) 3.5 weight parts in 78.5 weight parts; and then cooperation white pigment (titanium oxide, Dupont system, trade(brand)name: Ti-Pure R103) 18 weight parts; in addition; carry out similarly to Example 1, obtain 3-tier architecture (white color system substrate layer/black is substrate layer/bonding coat) surface protective plate (C3) (thickness: white color system substrate layer/black be substrate layer/bonding coat=20 μ m/35 μ m/5 μ m).
The results are shown in table 2.
(comparative example 4)
White color system substrate layer at embodiment 1 forms in the preparation of material, to Low Density Polyethylene (eastern Cao's system, trade(brand)name: Petrothene 186R, density=0.924g/cm
3) coordinate silicon-dioxide (median size=3.5 μ m, Unimin system, MINEX7) 7 weight parts in 75 weight parts; and then cooperation white pigment (titanium oxide, Dupont system, trade(brand)name: Ti-Pure R103) 18 weight parts; in addition; carry out similarly to Example 1, obtain 3-tier architecture (white color system substrate layer/black is substrate layer/bonding coat) surface protective plate (C4) (thickness: white color system substrate layer/black be substrate layer/bonding coat=20 μ m/35 μ m/5 μ m).
The results are shown in table 2.
(comparative example 5)
White color system substrate layer at embodiment 7 forms in the preparation of material, to Low Density Polyethylene (eastern Cao's system, trade(brand)name: Petrothene 186R, density=0.924g/cm
3) coordinate calcium carbonate (median size=3.2 μ m, Bai Shi Calcium (strain) system, PO-150-B-10) 2 weight parts in 80 weight parts; and then cooperation white pigment (titanium oxide, Dupont system, trade(brand)name: Ti-Pure R103) 18 weight parts; in addition; carry out similarly to Example 7, obtain 3-tier architecture (white color system substrate layer/black is substrate layer/bonding coat) surface protective plate (C5) (thickness: white color system substrate layer/black be substrate layer/bonding coat=20 μ m/35 μ m/5 μ m).
The results are shown in table 2.
(comparative example 6)
White color system substrate layer at embodiment 7 forms in the preparation of material, to Low Density Polyethylene (eastern Cao's system, trade(brand)name: Petrothene 186R, density=0.924g/cm
3) coordinate calcium carbonate (median size=3.2 μ m, Bai Shi Calcium (strain) system, PO-150-B-10) 7 weight parts in 75 weight parts; and then cooperation white pigment (titanium oxide, Dupont system, trade(brand)name: Ti-Pure R103) 18 weight parts; in addition; carry out similarly to Example 7, obtain 3-tier architecture (white color system substrate layer/black is substrate layer/bonding coat) surface protective plate (C6) (thickness: white color system substrate layer/black be substrate layer/bonding coat=20 μ m/35 μ m/5 μ m).
The results are shown in table 2.
(comparative example 7)
White color system substrate layer at embodiment 7 forms in the preparation of material, to Low Density Polyethylene (eastern Cao's system, trade(brand)name: Petrothene 186R, density=0.924g/cm
3) coordinate calcium carbonate (median size=1.5 μ m, standby northern efflorescence industry (strain) system, Softone 1500) 2 weight parts in 80 weight parts; and then cooperation white pigment (titanium oxide, Dupont system, trade(brand)name: Ti-Pure R103) 18 weight parts; in addition; carry out similarly to Example 7, obtain 3-tier architecture (white color system substrate layer/black is substrate layer/bonding coat) surface protective plate (C7) (thickness: white color system substrate layer/black be substrate layer/bonding coat=20 μ m/35 μ m/5 μ m).
The results are shown in table 2.
(comparative example 8)
White color system substrate layer at embodiment 7 forms in the preparation of material, to Low Density Polyethylene (eastern Cao's system, trade(brand)name: Petrothene 186R, density=0.924g/cm
3) coordinate calcium carbonate (median size=1.5 μ m, standby northern efflorescence industry (strain) system, Softone 1500) 7 weight parts in 75 weight parts; and then cooperation white pigment (titanium oxide, Dupont system, trade(brand)name: Ti-Pure R103) 18 weight parts; in addition; carry out similarly to Example 7, obtain 3-tier architecture (white color system substrate layer/black is substrate layer/bonding coat) surface protective plate (C8) (thickness: white color system substrate layer/black be substrate layer/bonding coat=20 μ m/35 μ m/5 μ m).
The results are shown in table 2.
[table 1]
By table 1, table 2 is known, for surface protective plate of the present invention, the surface roughness Ra of the outmost surface of white color system substrate layer is more than 0.30 μ m, the surface gloss of 60 ° of gloss of the outmost surface of white color system substrate layer is below 65, can unconspicuous degree even if the outmost surface of substrate layer is changed into by asperities that foreign matter is present between surface protective plate and adherend also, no matter the adherend of surface smoothing or the adherend of uneven surface can show abundant and appropriate bonding force to it, breaking tenacity, the mechanical characteristics excellence such as elongation when fracture, bendability is also excellent.
In industry, utilize possibility
Surface protective plate of the present invention, for example carrying, when optics, the electronic units etc. such as parts, polarizing coating, liquid crystal panel such as processing or maintenance metal sheet, coated plate, aluminum alloy frame, resin board, decorative steel plate, pvdc layer laminated steel, sheet glass, can be used for sticking on purposes of protecting on these surface etc.
Nomenclature
100 surface protective plates
10 bonding coats
21 white color system substrate layers
22 black are substrate layer
30 inorganic particulates
Claims (17)
1. a surface protective plate, its for comprising white color system substrate layer successively, black is the surface protective plate of substrate layer and bonding coat, wherein,
This white color system substrate layer is outermost layer,
The surface roughness Ra of the outmost surface of this white color system substrate layer is more than 0.30 μ m,
The surface gloss of 60 ° of gloss of the outmost surface of this white color system substrate layer is below 65.
2. surface protective plate as claimed in claim 1, wherein,
In described white color system substrate layer, comprise inorganic particulate.
3. surface protective plate as claimed in claim 2, wherein,
Inorganic particulate in described white color system substrate layer containing proportional be 2 % by weight～8 % by weight.
4. surface protective plate as claimed in claim 2, wherein,
The median size of described inorganic particulate is 5 μ m～10 μ m.
5. surface protective plate as claimed in claim 2, wherein,
Described inorganic particulate is from SiO
2and CaCO
3at least a kind of middle selection.
6. surface protective plate as claimed in claim 1, wherein,
Described white color system substrate layer, described black are that substrate layer and described bonding coat are shaped to form as one by coextrusion and form.
7. surface protective plate as claimed in claim 1, wherein,
Described white color system substrate layer comprises polyethylene-based resin as main component.
8. surface protective plate as claimed in claim 7, wherein,
Described polyethylene-based resin comprises Low Density Polyethylene.
9. surface protective plate as claimed in claim 1, wherein,
Described black is that substrate layer comprises polyethylene-based resin as main component.
10. surface protective plate as claimed in claim 9, wherein,
Described polyethylene-based resin comprises Low Density Polyethylene.
11. surface protective plates as claimed in claim 9, wherein,
Described polyethylene-based resin comprises straight chain shape Low Density Polyethylene.
12. surface protective plates as claimed in claim 1, wherein,
The initial stage bonding force with respect to SUS430BA plate 23 DEG C time is 0.3m/min at draw speed 180 ° be more than 1.0N/20mm in peeling off.
13. surface protective plates as claimed in claim 1,
The bonding force of the stickup with respect to SUS430BA plate 23 DEG C time after 1 week is 0.3m/min at draw speed 180 ° be more than 2.0N/20mm in peeling off.
14. surface protective plates as claimed in claim 1, wherein,
The initial stage bonding force with respect to SUS304 hairline plate 23 DEG C time is 0.3m/min at draw speed 180 ° be more than 1.5N/20mm in peeling off.
15. surface protective plates as claimed in claim 1, wherein,
The bonding force of the stickup with respect to SUS304 hairline plate 23 DEG C time after 1 week is 0.3m/min at draw speed 180 ° be more than 2.0N/20mm in peeling off.
16. surface protective plates as claimed in claim 1, wherein,
Breaking tenacity is more than 20N/20mm.
17. surface protective plates as claimed in claim 1, wherein,
When fracture, elongation is more than 200%.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210477884.0A CN103834314A (en) | 2012-11-22 | 2012-11-22 | Surface protection sheet |
| PCT/JP2013/080615 WO2014080806A1 (en) | 2012-11-22 | 2013-11-13 | Surface protection sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210477884.0A CN103834314A (en) | 2012-11-22 | 2012-11-22 | Surface protection sheet |
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| Publication Number | Publication Date |
|---|---|
| CN103834314A true CN103834314A (en) | 2014-06-04 |
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ID=50798219
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210477884.0A Pending CN103834314A (en) | 2012-11-22 | 2012-11-22 | Surface protection sheet |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109790719A (en) * | 2017-03-30 | 2019-05-21 | 日吉华株式会社 | Building materials |
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| JPH06271821A (en) * | 1993-03-23 | 1994-09-27 | Lintec Corp | Removable type tacky protecting tape |
| CN102250560A (en) * | 2010-05-21 | 2011-11-23 | 日东电工株式会社 | Double-sealed pressure-sensitive adhesive tape and method of using thereof |
| CN103254819A (en) * | 2012-02-15 | 2013-08-21 | 日东电工株式会社 | Surface protection sheet |
| CN103254812A (en) * | 2012-02-15 | 2013-08-21 | 日东电工株式会社 | Surface protection sheet |
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- 2012-11-22 CN CN201210477884.0A patent/CN103834314A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06271821A (en) * | 1993-03-23 | 1994-09-27 | Lintec Corp | Removable type tacky protecting tape |
| CN102250560A (en) * | 2010-05-21 | 2011-11-23 | 日东电工株式会社 | Double-sealed pressure-sensitive adhesive tape and method of using thereof |
| CN103254819A (en) * | 2012-02-15 | 2013-08-21 | 日东电工株式会社 | Surface protection sheet |
| CN103254812A (en) * | 2012-02-15 | 2013-08-21 | 日东电工株式会社 | Surface protection sheet |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109790719A (en) * | 2017-03-30 | 2019-05-21 | 日吉华株式会社 | Building materials |
| CN109790719B (en) * | 2017-03-30 | 2022-10-14 | 日吉华株式会社 | Building material |
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Application publication date: 20140604 |