CN103254817A - Surface protection sheet - Google Patents
Surface protection sheet Download PDFInfo
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- CN103254817A CN103254817A CN2012100362164A CN201210036216A CN103254817A CN 103254817 A CN103254817 A CN 103254817A CN 2012100362164 A CN2012100362164 A CN 2012100362164A CN 201210036216 A CN201210036216 A CN 201210036216A CN 103254817 A CN103254817 A CN 103254817A
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- substrate layer
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- protective plate
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Abstract
The invention provides a surface protection sheet including a substrate layer and an adhesive layer and having an excellent bending processability when the surface protection sheet is attached to an adhered object. The surface protection sheet includes the substrate layer and the adhesive layer, the thickness of the substrate layer is above 50mum, and the break elongation rate, the upper yield point, the tensile strength under 100% elongation and the tensile strength under 200% elongation of the surface protection sheet is above 400%, below 15N/20mm, below 18N/20mm and below 20N/20mm respectively.
Description
Technical field
The present invention relates to a kind of surface protective plate.Specifically, the present invention relates to comprise the surface protective plate of substrate layer and bonding coat.Surface protective plate of the present invention can be used for following purposes; for example; when opticses such as parts, polarizing coating, liquid crystal panel, electronic units etc. such as metal sheet, coated plate, aluminium windowframe, resin board, decorative steel plate, vinylchlorid laminate steel, sheet glass are carried, processed or maintain etc., stick on these parts surfaces and protect etc.
Background technology
With regard to surface protective plate, the side at substrate layer is provided with bonding coat usually.Comprise the method for the surface protective plate of such substrate layer and bonding coat as manufacturing, the method (for example, with reference to patent documentation 1) that has proposed to utilize coextrusion to be shaped substrate layer and bonding coat are formed as one.
But existing surface protective plate is poor at the bendability that is pasted on by under the state of adherend.Therefore, to pasted existing surface protective plate carried out bending machining by adherend the time, have the fracture of this surface protective plate, or produce the such problem of SUS damage.
The prior art document
Patent documentation 1: Japanese kokai publication sho 61-103975 communique
Summary of the invention
Problem of the present invention is, provide a kind of comprise substrate layer and bonding coat, be pasted on by the surface protective plate of the excellent in bending workability under the adherend status.
Surface protective plate of the present invention is the surface protective plate that comprises substrate layer and bonding coat; the thickness of this substrate layer is more than the 50 μ m; elongation at break is more than 400%; upper yield point is below the 15N/20mm; tensile strength during 100% elongation is below the 18N/20mm, and the tensile strength during 200% elongation is below the 20N/20mm.
In preferred embodiment, described substrate layer and described bonding coat utilize coextrusion to be shaped and form as one.
In preferred embodiment, described substrate layer comprises polyolefin-based resins as main component.
In preferred embodiment, described substrate layer is made of outermost substrate layer A and middle substrate layer B, at the configurable described bonding coat of this centre substrate layer B side.
In preferred embodiment, described outermost substrate layer A comprises polyethylene-based resin as main component.
In preferred embodiment, described polyethylene-based resin comprises Low Density Polyethylene.
In preferred embodiment, described middle substrate layer B comprises polyethylene-based resin as main component.
In preferred embodiment, described polyethylene-based resin comprises Low Density Polyethylene.
In preferred embodiment, described polyethylene-based resin comprises straight chain shape Low Density Polyethylene.
In preferred embodiment, the density of described straight chain shape Low Density Polyethylene is 0.880g/cm
3~0.910g/cm
3
In preferred embodiment, described in the middle of among the substrate layer B described straight chain shape Low Density Polyethylene to contain proportional be 30 weight %~5 weight %.
In preferred embodiment, described bonding coat comprises styrene series thermoplastic elastomer.
According to the present invention, can provide a kind of comprise substrate layer and bonding coat, be pasted on by the surface protective plate of the excellent in bending workability under the adherend status.
Description of drawings
Fig. 1 is the diagrammatic cross-section of a configuration example of expression surface protective plate of the present invention.
Description of reference numerals
100 surface protective plates
10 bonding coats
20 substrate layers
21 outermost substrate layer A
Substrate layer B in the middle of 22
Embodiment
Surface protective plate of the present invention is the surface protective plate that comprises substrate layer and bonding coat.For surface protective plate of the present invention, in the scope of not damaging effect of the present invention, also can comprise other suitable arbitrarily layer.
The thickness of substrate layer is more than the 50 μ m, is preferably 50 μ m~300 μ m, 50 μ m~250 μ m more preferably, and more preferably 50 μ m~200 μ m are preferably 50 μ m~150 μ m especially, most preferably are 50 μ m~100 μ m.If the thickness of substrate layer is in above-mentioned scope; then to pasted surface protective plate of the present invention carried out bending machining by adherend the time; this surface protective plate is not easy fracture; being not easy to produce SUS hinders; in addition, the hardness that can suppress substrate layer becomes big, therefore; surface protective plate of the present invention is pasted on by after the adherend, is not easy produce to 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 preferably 4 μ m~20 μ m especially, most preferably are 5 μ m~10 μ m.By with the thickness of bonding coat in above-mentioned scope, easy key-course constitutes when utilizing coextrusion to be shaped to make surface protective plate of the present invention, in addition, can obtain having the surface protective plate of sufficient mechanical.
The integral thickness of surface protective plate of the present invention is preferably 51 μ m~150 μ m, 53 μ m~140 μ m more preferably, and more preferably 55 μ m~130 μ m are preferably 57 μ m~120 μ m especially, most preferably are 60 μ m~110 μ m.By with the integral thickness of surface protective plate of the present invention in above-mentioned scope, can obtain the surface protective plate that the property handled is excellent and have sufficient mechanical.
With regard to surface protective plate of the present invention, preferred substrates layer and bonding coat utilize coextrusion to be shaped and form as one.Be shaped as coextrusion, can adopt the suitable coextrusion of the manufacturing that is generally used for film, sheet material etc. arbitrarily to be shaped.Be shaped as coextrusion, for example, can adopt inflation method, coextrusion T pattern method etc.These coextrusion be shaped aspect cost or the productivity aspect preferred.
The elongation at break of surface protective plate of the present invention is more than 400%, is preferably 400%~800%, more preferably 400%~700%, more preferably 400%~650%, be preferably 400%~600% especially, and most preferably be 400%~500%.In above-mentioned scope, surface protective plate of the present invention can show excellent bendability under being pasted on by the state of adherend by elongation at break.Need to prove the measuring method aftermentioned of elongation at break.
The upper yield point of surface protective plate of the present invention is below the 15N/20mm; be preferably 8N/20mm~15N/20mm; 8.5N/20mm~14N/20mm more preferably; 8.5N/20mm~13.5N/20mm more preferably; be preferably 9N/20mm~13N/20mm especially, most preferably be 9.5N/20mm~13N/20mm.In above-mentioned scope, surface protective plate of the present invention can show excellent bendability under being pasted on by the state of adherend by upper yield point.Need to prove the measuring method aftermentioned of upper yield point.
Tensile strength when 100% of surface protective plate of the present invention extends is below the 18N/20mm; be preferably 12N/20mm~18N/20mm; 12.5N/20mm~17N/20mm more preferably; 13N/20mm~16.5N/20mm more preferably; be preferably 13.5N/20mm~16.5N/20mm especially, most preferably be 14N/20mm~16.5N/20mm.Tensile strength during by 100% elongation is in above-mentioned scope, and surface protective plate of the present invention can show excellent bendability under being pasted on by the state of adherend.Need to prove the measuring method aftermentioned of the tensile strength during 100% elongation.
Tensile strength when 200% of surface protective plate of the present invention extends is below the 20N/20mm; be preferably 13N/20mm~20N/20mm; 14N/20mm~19N/20mm more preferably; 15N/20mm~19N/20mm more preferably; be preferably 15.5N/20mm~18.5N/20mm especially, most preferably be 16N/20mm~17.5N/20mm.Tensile strength during by 200% elongation is in above-mentioned scope, and surface protective plate of the present invention can show excellent bendability under being pasted on by the state of adherend.Need to prove the measuring method aftermentioned of the tensile strength during 200% elongation.
The preferred substrates layer comprises polyolefin-based resins as main component.Substrate layer comprises polyolefin-based resins as main component, can have thermotolerance, solvent resistance, flexible thus, can easily be wound into the roller shape.The polyolefin-based resins that comprises in the substrate layer can be just a kind of, also can be two or more.Substrate layer can be individual layer, also can be multilayer.
At this, in the present invention, so-called " main component " refers to be preferably more than the 50 weight %, more preferably more than the 60 weight %, more preferably more than the 70 weight %, is preferably especially more than the 80 weight %, most preferably is more than the 90 weight %.
As polyolefin-based resins, for example, can enumerate: polyethylene-based resin, the propylene resin that is constituted by propylene or propylene composition and ethene composition, ethylene-vinyl acetate copolymer etc.
As polyolefin-based resins, particularly, for example, can enumerate: high density polyethylene(HDPE) (HDPE), medium-density polyethylene, Low Density Polyethylene (LDPE), straight chain shape Low Density Polyethylene (LLDPE), polypropylene, poly-1-butylene, poly--4-methyl-1-pentene, ethylene propylene copolymer, the ethene butene-1 copolymer, ethene 1-hexene copolymer, the ethene 4 methyl 1 pentene copolymer, ethene 1-octene copolymer, ethylene methyl acrylate copolymer, the ethylene methacrylic acid methyl terpolymer, ethylene vinyl acetate copolymer, ethylene ethyl acrylate copolymer, ethylene-vinyl alcohol copolymer etc.
Under the situation that substrate layer is made of the multilayer more than two-layer, for the layer of each adjacency, as the resinous principle that constitutes them, the preferred selection can form firm bonding resinous principle mutually by the fusion coextrusion.
With regard to substrate layer, preferably comprise outermost substrate layer A and middle substrate layer B, at the configurable above-mentioned bonding coat of this centre substrate layer B side.That is, the stepped construction of surface protective plate of the present invention is preferably the 3-tier architecture of " substrate layer B/ bonding coat in the middle of the outermost substrate layer A/ ".Fig. 1 has the diagrammatic cross-section of a configuration example of situation of the stacked formation of " substrate layer B22/ bonding coat 10 in the middle of the outermost substrate layer A21/ " for expression surface protective plate 100 of the present invention.Outermost substrate layer A21 and middle substrate layer B22 become substrate layer 20.
Outermost substrate layer A is preferably the white color system layer.Be the white color system layer by outermost substrate layer A, can form the surface protective plate that has excellent weather resistance.
Middle substrate layer B is preferably black system layer.Be black system layer by middle substrate layer B, can form the surface protective plate that has excellent weather resistance.
With regard to substrate layer, more preferably comprise outermost substrate layer A and middle substrate layer B, and outermost substrate layer A is the white color system layer, middle substrate layer B is black system layer.Comprise the two-layer of white color system layer and black system layer by substrate layer, can form the very excellent surface protective plate of weathering resistance.
The white color system layer is the layer of the tone of display white system, and for example, the whiteness of stipulating among the JIS-L-1015 is preferably more than 60%, more preferably more than 70%, more preferably more than 80%, is preferably more than 85% especially.The 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.The white color system layer contains under the situation of white pigment, and it contains proportional resinous principle with respect to formation white color system layer and is preferably 0.1 weight %~50 weight %, more preferably 1 weight %~40 weight %, more preferably 2 weight %~30 weight %.Proportional in above-mentioned scope with respect to containing of the resinous principle that forms the white color system layer by white pigment, can form the surface protective plate that has excellent weather resistance, also can make plasticity such as extrudability become excellent.
The resinous principle that forms outermost substrate layer A is preferably polyolefin-based resins, more preferably acrylic polymer, ethylene-based polymer.As the resinous principle that forms outermost substrate layer A, 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).Outermost substrate layer A preferably comprises polyethylene-based resin as main component.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
3A comprises polyethylene-based resin as main component by the outermost substrate layer; substrate layer can have thermotolerance, solvent resistance, flexible; can easily surface protective plate of the present invention be wound into the roller shape, and, under being pasted on by the state of adherend, can show excellent bendability.Outermost substrate layer A comprises under the situation of polyethylene-based resin as main component, and this polyethylene-based resin preferably comprises Low Density Polyethylene.Comprise Low Density Polyethylene by above-mentioned polyethylene-based resin; substrate layer can have thermotolerance, solvent resistance, flexible fully; can further easily surface protective plate of the present invention be wound into the roller shape; and, under being pasted on by the state of adherend, can further show excellent bendability.
Polyolefin-based resins among the outermost substrate layer A contain proportional being preferably more than the 60 weight %, more preferably more than the 70 weight %, more preferably more than the 80 weight %, be preferably especially more than the 85 weight %, most preferably be more than the 90 weight %.Polyolefin-based resins like this can only use a kind ofly, also can use two or more.
With regard to the thickness of outermost substrate layer A, according to purpose, can adopt suitable arbitrarily thickness.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 preferably 5 μ m~50 μ m especially.
Black system layer is for showing the layer of the tone that black is.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.Black system layer contains under the situation of black pigment, and it contains proportional resinous principle with respect to formation black system layer and is preferably 0.01 weight %~10 weight %, more preferably 0.1 weight %~5 weight %, more preferably 0.5 weight %~3 weight %.Proportional in above-mentioned scope with respect to containing of the resinous principle that forms black system layer by black pigment, can form the surface protective plate that has excellent weather resistance, plasticity such as extrudability is also excellent.
The resinous principle of substrate layer B is preferably polyolefin-based resins in the middle of forming, more preferably acrylic polymer, ethylene-based polymer.Resinous principle as substrate layer B in the middle of forming, 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 main component.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
3Comprise polyethylene-based resin as main component by middle substrate layer B; substrate layer can have thermotolerance, solvent resistance, flexible; can easily surface protective plate of the present invention be wound into the roller shape, and, under being pasted on by the state of adherend, can show excellent bendability.
Middle substrate layer B comprises under the situation of polyethylene-based resin as main component, and this polyethylene-based resin preferably comprises Low Density Polyethylene.Comprise Low Density Polyethylene by above-mentioned polyethylene-based resin; substrate layer can have thermotolerance, solvent resistance, flexible fully; can further easily surface protective plate of the present invention be wound into the roller shape; and, under being pasted on by the state of adherend, can further show excellent bendability.
Middle substrate layer B comprises under the situation of polyethylene-based resin as main component, and this polyethylene-based resin preferably comprises straight chain shape Low Density Polyethylene.Comprise straight chain shape Low Density Polyethylene by above-mentioned polyethylene-based resin, under being pasted on by the state of adherend, can further show very excellent bendability.
The density of above-mentioned straight chain shape Low Density Polyethylene is preferably 0.880g/cm
3~0.910g/cm
3, 0.880g/cm more preferably
3~0.905g/cm
3, 0.885g/cm more preferably
3~0.905g/cm
3, be preferably 0.890g/cm especially
3~0.900g/cm
3By with the density of above-mentioned straight chain shape Low Density Polyethylene in above-mentioned scope, under being pasted on by the state of adherend, can further show very excellent bendability.
Middle substrate layer B comprises under the situation of straight chain shape Low Density Polyethylene, this straight chain shape Low Density Polyethylene among the substrate layer B of this centre contain the proportional 30 weight %~5 weight % that are preferably, 25 weight %~5 weight % more preferably, more preferably 20 weight %~10 weight % are preferably 15 weight %~10 weight % especially.By with containing of the straight chain shape Low Density Polyethylene among the middle substrate layer B proportional in above-mentioned scope, under being pasted on by the state of adherend, can further show very excellent bendability.
Polyolefin-based resins among the middle substrate layer B contain proportional being preferably more than the 60 weight %, more preferably more than the 70 weight %, more preferably more than the 80 weight %, be preferably especially more than the 85 weight %, most preferably be more than the 90 weight %.Polyolefin-based resins like this can only use a kind ofly, also can use two or more.
With regard to the thickness of middle substrate layer B, according to purpose, can adopt suitable arbitrarily thickness.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 preferably 5 μ m~50 μ m especially.
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, plugging inhibitor, lubricant, anti-hard caking agent etc.
The outermost layer of a side opposite with bonding coat of substrate layer also can be implemented the back side and handle.Method as handle at the back side in the scope of not damaging effect of the present invention, can adopt appropriate means arbitrarily.As the method that handle at such back side, for example, can enumerate surface working such as embossing processing or concavo-convex processing, make its method that contains derivative of fatty acid etc.Derivative of fatty acid like this can be just a kind of, also can be two or more.
Substrate layer comprises under the situation of derivative of fatty acid, containing of derivative of fatty acid in this substrate layer proportionally is preferably 0.05 weight %~1.00 weight % with respect to the resinous principle in the substrate layer, more preferably 0.10 weight %~0.90 weight %, more preferably 0.30 weight %~0.80 weight %.As long as the derivative of fatty acid in the substrate layer contain proportional with respect to the resinous principle in the substrate layer in above-mentioned scope; thereby just the surface protective plate of the present invention that has formed the roller shape easily can be rewinded and manifest stripping result fully; and, can suppress the pollution that spills generation by this derivative of fatty acid fully.
As derivative of fatty acid, refer to comprise in the molecular structure compound of derivative of fatty acid structure.
As derivative of fatty acid, for example, can enumerate: saturated fatty acid bisamide, unsaturated fatty acids bisamide, fragrant family bisamide, replacement urea, fatty acid metal salt etc.As derivative of fatty acid, particularly, for example, can enumerate: methylene bis stearic amide, ethylene bis stearic acid amide, the two amine hydroxybenzenes of ethylene, N, N-two oleoyl hexanodioic acid acid amides, N-stearyl-N '-N-stearyl-N '-stearic amide, Zinic stearass etc. such as stearyl urea.
As derivative of fatty acid, be preferably fatty acid amide, more preferably be selected from least a in methylene bis stearic amide, ethylene bis stearic acid amide, N-stearyl-N '-stearic amide.
The fusing point of derivative of fatty acid is preferably more than 100 ℃.With regard to the derivative of fatty acid that fusing point is lower than 100 ℃, become significantly to the transfer printing on bonding coat surface, might be easy to cause bounding force to reduce.
Bonding coat preferably comprises thermoplastic resin as main component.With regard to the thermoplastic resin that comprises in the bonding coat, can be just a kind of, also can be two or more.
As thermoplastic resin, can adopt suitable arbitrarily thermoplastic resin.As such thermoplastic resin, for example, can enumerate: 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 styrene block copolymer or its hydride.
As styrene block copolymer, for example, can enumerate: styrene butadiene styrene multipolymer (SBS), styrene isoprene styrol copolymer polystyrene ABA block polymer (triblock copolymer) such as (SIS); Styrene butadiene styrene butadienecopolymer (SBSB), styrene isoprene styrene isoprene multipolymer polystyrene ABAB type segmented copolymers (Tetrablock copolymer) such as (SISI); Styrene butadiene styrene butadienestyrene copolymer (SBSBS), styrene isoprene styrene isoprene styrol copolymer polystyrene ABABA type segmented copolymers (five segmented copolymers) such as (SISIS); Has the styrene block copolymer of its above AB repeating unit etc.
Hydride as 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 etc.
With regard to styrene series thermoplastic elastomer, can only use a kind ofly, also can use two or more.
Styrene series thermoplastic elastomer is under the situation of styrene block copolymer or its hydride, styrene block content in this styrene series thermoplastic elastomer is preferably 5 weight %~40 weight %, more preferably 7 weight %~30 weight %, more preferably 9 weight %~20 weight %.When above-mentioned styrene block content tails off, may occur easily because of the not enough adhesive paste that causes of the cohesive force of bonding coat residual.Above-mentioned styrene block contains quantitative change for a long time, may make the bonding coat hardening, and uneven surface can't obtain good binding property relatively.
As styrene series thermoplastic elastomer, hydride (the SEBS that preferably has the styrene block copolymer of the repeating structure (ABA type, ABAB type, ABABA type etc.) more than the triblock copolymer that comprises vinylbenzene (A) and divinyl (B), SEBSEB, SEBSEBS etc.).By adopting such styrene series thermoplastic elastomer, can further suitably fully improve and be pasted on by the bonding force under the state of adherend, on the other hand, can make the bonding force that is pasted on when being peeled off after the adherend be more suitable size, thereby, with slight power just can be more easily from being peeled off by adherend, and the bonding force that can further suppress to be exposed to the carrying capacity of the environment of the prolonged preservation under the higher temperatures rises.
Under the situation of styrene series thermoplastic elastomer for the hydride (SEBS, SEBSEB, SEBSEBS etc.) of styrene block copolymer with the repeating structure (ABA type, ABAB type, ABABA type etc.) more than the triblock copolymer that is constituted by vinylbenzene (A) and divinyl (B), the shared ratio of butylene structure is preferably more than the 60 weight % in the ethylene-butene copolymer block, more preferably more than the 70 weight %, more preferably more than the 75 weight %.By the shared ratio of butylene structure in the above-mentioned ethylene-butene copolymer block in above-mentioned scope, can further suitably fully improve and be pasted on by the bonding force under the state of adherend, on the other hand, can make the bonding force that is pasted on when being peeled off after the adherend be more suitable size, thereby, with slight power just can be more easily from being peeled off by adherend, and the bonding force that can further suppress to be exposed to the carrying capacity of the environment of the prolonged preservation under the higher temperatures rises.Need to prove that the shared ratio of butylene structure is preferably below the 90 weight % in the above-mentioned ethylene-butene copolymer block.
With regard to bonding coat, be purpose to regulate binding property etc., in the scope of not damaging purpose of the present invention, also can comprise other styrene series thermoplastic elastomer.
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 multipolymer AB type block polymers such as (SEP) of styrene ethylene-propylene copolymer; Styrene butadiene ribber polystyrene random copolymerss such as (SBR); The vinylbenzene alkene crystal system block polymer of the multipolymer A-B-C types such as (SEBC) of styrene ethylene-butylene copolymer alkene crystallization; The hydride of these polymkeric substance etc.
When forming bonding coat, in order to control adhesion characteristic etc., as required, for example, can suitably add tenderizer, bonding imparting agent, the such polyolefin-based resins that is used for substrate layer, the silicone-based polymkeric substance, aqueous acrylic copolymer, the 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 (calcium oxide for example, magnesium oxide, silicon-dioxide, zinc oxide, titanium oxide etc.), metal powder, tinting material, pigment, additives such as heat-resisting stabilizing agent.
For the bonding coat surface, in order to control binding property or paste operation etc., as required can embodiment such as surface treatment such as Corona discharge Treatment, uviolizing processing, flame treating, Cement Composite Treated by Plasma, sputter etching processing.
The cooperation of bonding imparting agent is effective to improving bounding force.Wherein, with regard to the use level of bonding imparting agent, in order to evade the generation of the adhesive paste residue problem that is caused by the cohesive force reduction, can be according to suitably being determined by adherend that surface protective plate will be used.The use level of bonding imparting agent is preferably below the 80 weight % with respect to the matrix polymer of bonding coat, more preferably below the 40 weight %, more preferably below the 20 weight %.Need to prove that what will use at surface protective plate is under the situation of metal sheet by adherend, preferably when forming bonding coat, do not add bonding imparting agent.
As bonding imparting agent, for example, can use petroleum line resins such as aliphatics based copolymer, aromatic series based copolymer, aliphatics aromatic series based copolymer system or ester ring type based copolymer with being not particularly limited; Coumarone-indenes is rosin series resins such as resin, terpenic series resin, terpenes phenol resin, polymerized rosin; The hydride of (alkyl) phenol resin, diformazan benzene series resin, these resins etc. generally are used for the material of tackiness agent.With regard to bonding imparting agent, can only use a kind ofly, also can use two or more.In these bonding imparting agents, consider the bonding imparting agent of preferred hydrogenation system from viewpoints such as separability or weathering resistancies.Need to prove that bonding imparting agent also can use with the material commercially available with the form of the adulterant of olefin resin.
The cooperation of tenderizer is effective to improving bounding force.As tenderizer, for example, can enumerate: the derivative of low-molecular-weight diene polymer, polyisobutene, hydrogenated polyisoprene, hydrogenated butadiene polymer, these polymkeric substance etc.As such derivative, for example, can end of illustration or two ends have the derivative 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.Particularly from suppressing considered the hydride of diene polymers such as preferred hydrogenated butadiene polymer or hydrogenated polyisoprene or ethylene series tenderizer etc. by the purpose of the fusible raising of adherend.As such tenderizer, particularly, can obtain the trade(brand)name " Kuraprene LIR-200 " of Amada Co., Ltd.'s Kuraray manufacturing etc.With regard to these tenderizers, can only use a kind ofly, also can use two or more.
The molecular weight of tenderizer can suitably be set at appropriate vol arbitrarily, when but molecular weight diminishes, may become material from bonding coat to being shifted by adherend or the heavy reason of peeling off etc., on the other hand, when the molecule quantitative change is big, may make the raising effect of bounding force become not enough, therefore, the number-average molecular weight of tenderizer is preferably 5000~100,000, and more preferably 10,000~50,000.
Use under the situation of tenderizer, its addition can suitably be set at suitable arbitrarily amount, but add quantitative change for a long time, the residual trend that increase is arranged of adhesive paste when being exposed to high temperature or open air, therefore, matrix polymer with respect to bonding coat is preferably below the 100 weight %, more preferably below the 60 weight %, more preferably below the 40 weight %.Need to prove that what surface protective plate will be used is under the situation of metal sheet by adherend, does not add tenderizer when being preferably formed bonding coat.
In bonding coat, be purpose to suppress bonding force rising etc., also can add polyolefin-based resins.Polyolefin-based resins can illustration and the same resin of resin that is used to form substrate layer.With regard to this polyolefin-based resins, can be just a kind of, also can be two or more.The use level of this polyolefin-based resins is preferably below the 50 weight % with respect to the matrix polymer of bonding coat, more preferably below the 30 weight %, more preferably below the 20 weight %.
For bonding coat, as required, before being used for practicality, also can temporarily being adhered to distance piece etc. and protecting.
The manufacture method of surface protective plate of the present invention is preferably to be utilized coextrusion to be shaped substrate layer and bonding coat are formed as one and makes.Thus, can high-level efficiency and make the surface protective plate of the stepped construction of the thickness with regulation at an easy rate.Be shaped as coextrusion, can adopt the suitable coextrusion arbitrarily of the general manufacturing that is used for film, sheet material etc. to be shaped.Be shaped as coextrusion, for example, can adopt inflation method, coextrusion T pattern method etc.
Be shaped according to coextrusion, because the outermost with opposite side bonding coat substrate layer is not to be connected under the fusion heated condition with bonding coat, therefore, not the generation of the by product that causes because of outmost thermal degradation when substrate layer and opposite side bonding coat with and by product to the transfer of bonding coat, demonstrate excellent rewinding property, can suppress the pollution on bonding coat surface.
Embodiment
Below, specifically describe by the present invention of embodiment, but the present invention is not subjected to any restriction of these embodiment.
(mensuration of density)
Density (the g/cm of resin
3) value measured for foundation SO1183.
(mensuration of elongation at break)
Following time-and-motion study elongation at break.
Carry out tension test according to JIS-K-7127.Measure the surface protective plate that sample uses the shape of the 2 type test films that are cut to the JIS-K-7127 record, under the condition of clamp interval 50mm, test film width 10mm, trial speed 300mm/min, carry out tension test.In addition, be Instron type tensile testing machine (Shimadzu Scisakusho Ltd's system, Autograph) for the trier of measuring.In between clamp apart from 50mm be benchmark with %, the elongation during sample fracture when calculating tension test.
(mensuration of upper yield point)
Following time-and-motion study upper yield point.
Obtain by the tension test of carrying out according to JIS-K-7127.Measure the surface protective plate that sample uses the shape of the 2 type test films that are cut to the JIS-K-7127 record, under the condition of clamp interval 50mm, test film width 10mm, trial speed 300mm/min, carry out tension test.In addition, be Instron type tensile testing machine (Shimadzu Scisakusho Ltd's system, Autograph) for the trier of measuring.
(mensuration of tensile strength)
Tensile strength when the tensile strength when following time-and-motion study 100% is extended and 200% elongation.
Carry out according to JIS-K-7127.Measure the surface protective plate that sample uses the shape of the 2 type test films that are cut to the JIS-K-7127 record, under the condition of clamp interval 50mm, test film width 10mm, trial speed 300mm/min, carry out tension test.In addition, be Instron type tensile testing machine (Shimadzu Scisakusho Ltd's system, Autograph) for the trier of measuring.Elongation when calculating tension test by the S-S opisometer that obtains is 100% and 200% o'clock test power.
(pliability test)
Following time-and-motion study pliability test.
Carry out crimping at the stainless steel plate (304HL) of thickness 2.0mm with the 2kg roller and come the adhesive surface screening glass, after the mode of the opposition side of punching machine arranges, carry out metal V-shaped bending machining test (vee-block method) (JIS-Z-2248) with surface protective plate.At this moment; in mould V-arrangement angle: 88 degree, mould V-arrangement width (L width): 16 or 12mm, mould R:2.0 or 1.0mm, punching press angle: carry out pliability test under the condition of 88 degree, drift R:0.6, the situation that bending machining rear surface screening glass has been produced cracking is made as *, the situation that produces cracking is made as zero.In addition, peel off the surface protective plate after the processing, confirm that there is not damaged on the stainless steel plate surface.The situation that has produced damage is made as *, the situation that produces damage is made as zero.
(coextrusion shaping condition)
In embodiment and comparative example, the melt temperature condition according to following forms by inflation method.
Substrate layer: 165 ℃
Bonding coat: 165 ℃
Coextrusion temperature: 165 ℃
(embodiment 1)
According to containing of table 1 proportional cooperation Low Density Polyethylene (Japanese eastern Cao company makes, trade(brand)name: Petrothene 186R, density=0.924g/cm
3) and white pigment (titanium oxide, Dupont manufacturing, trade(brand)name: Ti-Pure R103), obtain the white color system layer and form material.
Then, according to containing of table 1 proportional cooperation Low Density Polyethylene (Japanese eastern Cao company makes, trade(brand)name: Petrothene 186R, density=0.924g/cm
3), (SUMITOMO CHEMICAL chemical company makes straight chain shape Low Density Polyethylene, trade(brand)name: Excellence FX FX307, density=0.890g/cm
3) and carbon black MB (Japanese Sumika Color Co., Ltd. makes, trade(brand)name: Black SPEMB-865, carbon content 20%), obtain black system layer and form material.
And then, (hydrogenation SEBS, styrene content=15 weight %, JSR company make, trade(brand)name: DYNARON 8600P) (C5 is that hydrogenated aromatic petroleum resin, Japanese Idemitsu Kosen Co., Ltd. make, trade(brand)name: 18 weight % I-MARV P140) obtain bonding coat and form material for 82 weight % and bonding imparting agent to cooperate SEBS.
Use the above-mentioned white color system layer that obtains to form material, black system layer formation material, bonding coat formation material; utilization obtains surface protective plate (the 1) (thickness: the white color system layer/layer/bonding coat=20 μ m/35 μ m/5 μ m of black system) of 3-tier architecture (white color system layer/black system layer/bonding coat) by the co-extrusion modling of inflation method.
Show the result in table 1.
(embodiment 2)
Form the cooperation of material as table 1 change white color system layer; in addition; similarly carry out with embodiment 1, obtain surface protective plate (the 2) (thickness: the white color system layer/layer/bonding coat=20 μ m/35 μ m/5 μ m of black system) of 3-tier architecture (white color system layer/black system layer/bonding coat).
Show the result in table 1.
(embodiment 3)
As the thickness of each layer of table 1 change, in addition and embodiment 1 similarly carry out, obtain the surface protective plate (3) (thickness: white color system layer/black is layer/bonding coat=15 μ m/40 μ m/5 μ m) of 3-tier architecture (white color system layer/black system layer/bonding coat).
Show the result in table 1.
(embodiment 4)
Form the cooperation of material as table 1 change white color system layer; thickness as each layer of table 1 change; in addition; similarly carry out with embodiment 1, obtain surface protective plate (the 4) (thickness: the white color system layer/layer/bonding coat=15 μ m/40 μ m/5 μ m of black system) of 3-tier architecture (white color system layer/black system layer/bonding coat).
Show the result in table 1.
(embodiment 5)
As the thickness of each layer of table 1 change, in addition and embodiment 1 similarly carry out, obtain the surface protective plate (5) (thickness: white color system layer/black is layer/bonding coat=20 μ m/45 μ m/5 μ m) of 3-tier architecture (white color system layer/black system layer/bonding coat).
Show the result in table 1.
(embodiment 6)
Form the cooperation of material as table 1 change white color system layer; thickness as each layer of table 1 change; in addition; similarly carry out with embodiment 1, obtain surface protective plate (the 6) (thickness: the white color system layer/layer/bonding coat=20 μ m/45 μ m/5 μ m of black system) of 3-tier architecture (white color system layer/black system layer/bonding coat).
Show the result in table 1.
(embodiment 7)
As the thickness of each layer of table 1 change, in addition and embodiment 1 similarly carry out, obtain the surface protective plate (7) (thickness: white color system layer/black is layer/bonding coat=15 μ m/50 μ m/5 μ m) of 3-tier architecture (white color system layer/black system layer/bonding coat).
Show the result in table 1.
(embodiment 8)
Form the cooperation of material as table 1 change white color system layer; thickness as each layer of table 1 change; in addition; similarly carry out with embodiment 1, obtain surface protective plate (the 8) (thickness: the white color system layer/layer/bonding coat=15 μ m/50 μ m/5 μ m of black system) of 3-tier architecture (white color system layer/black system layer/bonding coat).
Show the result in table 1.
(comparative example 1)
Form the cooperation of material as table 2 change white color system layer; form the cooperation of material as table 2 change black system layer; thickness as each layer of table 2 change; in addition; similarly carry out with embodiment 1, obtain surface protective plate (the C1) (thickness: the white color system layer/layer/bonding coat=55 μ m/15 μ m/5 μ m of black system) of 3-tier architecture (white color system layer/black system layer/bonding coat).
Show the result in table 2.
(comparative example 2)
Form the cooperation of material as table 2 change white color system layer; form the cooperation of material as table 2 change black system layer; thickness as each layer of table 2 change; in addition; similarly carry out with embodiment 1, obtain surface protective plate (the C2) (thickness: the white color system layer/layer/bonding coat=55 μ m/25 μ m/5 μ m of black system) of 3-tier architecture (white color system layer/black system layer/bonding coat).
Show the result in table 2.
(comparative example 3)
Form the cooperation of material as table 2 change white color system layer; form the cooperation of material as table 2 change black system layer; thickness as each layer of table 2 change; in addition; similarly carry out with embodiment 1, obtain surface protective plate (the C3) (thickness: the white color system layer/layer/bonding coat=60 μ m/15 μ m/5 μ m of black system) of 3-tier architecture (white color system layer/black system layer/bonding coat).
Show the result in table 2.
(comparative example 4)
Layer forms in the cooperation of material in black system, and (SUMITOMO CHEMICAL chemical company makes, trade(brand)name: Excellence FX FX307, density=0.890g/cm to replace straight chain shape Low Density Polyethylene
3), (SECCO company makes, trade(brand)name: LL0220AA, density=0.919g/cm and use straight chain shape Low Density Polyethylene
3), in addition and embodiment 1 similarly carry out, obtain the surface protective plate (C4) (thickness: white color system layer/black is layer/bonding coat=20 μ m/35 μ m/5 μ m) of 3-tier architecture (white color system layer/black system layer/bonding coat).
Show the result in table 2.
(comparative example 5)
Form the cooperation of material as table 2 change white color system layer; in addition; similarly carry out with comparative example 4, obtain surface protective plate (the C5) (thickness: the white color system layer/layer/bonding coat=20 μ m/35 μ m/5 μ m of black system) of 3-tier architecture (white color system layer/black system layer/bonding coat).
Show the result in table 2.
(comparative example 6)
As the thickness of each layer of table 2 change, in addition and comparative example 4 similarly carry out, obtain the surface protective plate C6 (thickness: white color system layer/black is layer/bonding coat=20 μ m/45 μ m/5 μ m) of 3-tier architecture (white color system layer/black system layer/bonding coat).
Show the result in table 2.
(comparative example 7)
As the thickness of each layer of table 2 change, in addition and comparative example 4 similarly carry out, obtain the surface protective plate (C7) (thickness: white color system layer/black is layer/bonding coat=15 μ m/50 μ m/5 μ m) of 3-tier architecture (white color system layer/black system layer/bonding coat).
Show the result in table 2.
By table 1, table 2 as can be known, surface protective plate of the present invention is the surface protective plate that comprises substrate layer and bonding coat, is pasted on by the excellent in bending workability under the state of adherend.
Industrial utilizability
Surface protective plate of the present invention can be used for following purposes; for example; when opticses such as parts, polarizing coating, liquid crystal panel, electronic units etc. such as metal sheet, coated plate, aluminium windowframe, resin board, decorative steel plate, vinylchlorid laminate steel, sheet glass are carried, processed or maintain etc., stick on these parts surfaces and protect etc.
Claims (12)
1. surface protective plate, it comprises substrate layer and bonding coat, it is characterized in that,
The thickness of this substrate layer is more than the 50 μ m,
Elongation at break is more than 400%,
Upper yield point is below the 15N/20mm,
Tensile strength during 100% elongation is below the 18N/20mm,
Tensile strength during 200% elongation is below the 20N/20mm.
2. surface protective plate according to claim 1, wherein, described substrate layer and described bonding coat utilize coextrusion to be shaped and form as one.
3. surface protective plate according to claim 1, wherein, described substrate layer comprises polyolefin-based resins as main component.
4. surface protective plate according to claim 1, wherein, described substrate layer comprises outermost substrate layer A and middle substrate layer B, and substrate layer B side disposes described bonding coat in this centre.
5. surface protective plate according to claim 4, wherein, described outermost substrate layer A comprises polyethylene-based resin as main component.
6. surface protective plate according to claim 5, wherein, described polyethylene-based resin comprises Low Density Polyethylene.
7. surface protective plate according to claim 4, wherein, described in the middle of substrate layer B comprise polyethylene-based resin as main component.
8. surface protective plate according to claim 7, wherein, described polyethylene-based resin comprises Low Density Polyethylene.
9. surface protective plate according to claim 7, wherein, described polyethylene-based resin comprises straight chain shape Low Density Polyethylene.
10. surface protective plate according to claim 9, wherein, the density of described straight chain shape Low Density Polyethylene is 0.880g/cm
3~0.910g/cm
3
11. surface protective plate according to claim 9, wherein, described in the middle of among the substrate layer B described straight chain shape Low Density Polyethylene to contain proportional be 30 weight %~5 weight %.
12. surface protective plate according to claim 1, wherein, described bonding coat comprises styrene series thermoplastic elastomer.
Priority Applications (3)
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CN2012100362164A CN103254817A (en) | 2012-02-15 | 2012-02-15 | Surface protection sheet |
PCT/JP2013/052139 WO2013121884A1 (en) | 2012-02-15 | 2013-01-31 | Surface-protecting sheet |
TW102104982A TW201402317A (en) | 2012-02-15 | 2013-02-07 | Surface-protecting sheet |
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CN2012100362164A CN103254817A (en) | 2012-02-15 | 2012-02-15 | Surface protection sheet |
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CN112048253A (en) * | 2020-09-04 | 2020-12-08 | 浙江洁美电子科技股份有限公司 | Self-adhesion type protection film |
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Application publication date: 20130821 |