CN103254807A - Adhesive sheet - Google Patents
Adhesive sheet Download PDFInfo
- Publication number
- CN103254807A CN103254807A CN2012100361227A CN201210036122A CN103254807A CN 103254807 A CN103254807 A CN 103254807A CN 2012100361227 A CN2012100361227 A CN 2012100361227A CN 201210036122 A CN201210036122 A CN 201210036122A CN 103254807 A CN103254807 A CN 103254807A
- Authority
- CN
- China
- Prior art keywords
- propylene
- adhesive sheet
- layer
- copolymer
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000000853 adhesive Substances 0.000 title claims abstract description 38
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 38
- 229920001577 copolymer Polymers 0.000 claims abstract description 63
- 239000000758 substrate Substances 0.000 claims abstract description 38
- 239000004711 α-olefin Substances 0.000 claims abstract description 36
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 33
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 239000004793 Polystyrene Substances 0.000 claims description 11
- 229920002223 polystyrene Polymers 0.000 claims description 11
- 238000005227 gel permeation chromatography Methods 0.000 claims description 7
- 238000009826 distribution Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000010410 layer Substances 0.000 abstract description 101
- 239000012790 adhesive layer Substances 0.000 abstract description 4
- 238000004321 preservation Methods 0.000 abstract description 2
- 230000032683 aging Effects 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 230000035882 stress Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 43
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 27
- 230000015572 biosynthetic process Effects 0.000 description 21
- 230000001681 protective effect Effects 0.000 description 21
- 229920000642 polymer Polymers 0.000 description 20
- 229920005989 resin Polymers 0.000 description 19
- 239000011347 resin Substances 0.000 description 19
- 229910000831 Steel Inorganic materials 0.000 description 17
- 239000010959 steel Substances 0.000 description 17
- 239000005977 Ethylene Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- -1 isocyanate compound Chemical class 0.000 description 9
- 239000000049 pigment Substances 0.000 description 9
- 229920001684 low density polyethylene Polymers 0.000 description 8
- 239000004702 low-density polyethylene Substances 0.000 description 8
- 239000006096 absorbing agent Substances 0.000 description 7
- 239000006229 carbon black Substances 0.000 description 7
- 229920005672 polyolefin resin Polymers 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 239000004922 lacquer Substances 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000012463 white pigment Substances 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229920001903 high density polyethylene Polymers 0.000 description 4
- 239000004700 high-density polyethylene Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- 229920002873 Polyethylenimine Polymers 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- 229920001195 polyisoprene Polymers 0.000 description 3
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene Polymers 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 150000003440 styrenes Chemical class 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 238000002788 crimping Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920005629 polypropylene homopolymer Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- VCLWNCAUAKTVII-UHFFFAOYSA-N C=C.CC=C.C=CC1=CC=CC=C1 Chemical group C=C.CC=C.C=CC1=CC=CC=C1 VCLWNCAUAKTVII-UHFFFAOYSA-N 0.000 description 1
- PEMDHCGOAOHYTL-UHFFFAOYSA-N C=CCCCC.CC1=C(C=C(C(=O)O)C=C1)C(=O)O Chemical compound C=CCCCC.CC1=C(C=C(C(=O)O)C=C1)C(=O)O PEMDHCGOAOHYTL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical class CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- IANQTJSKSUMEQM-UHFFFAOYSA-N benzofuran Natural products C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000011243 crosslinked material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000026676 system process Effects 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000012725 vapour phase polymerization Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/10—Homopolymers or copolymers of propene
- C09J123/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2423/00—Presence of polyolefin
- C09J2423/10—Presence of homo or copolymers of propene
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesive Tapes (AREA)
Abstract
The invention provides an adhesive sheet. The adhesive sheet has the advantages of excellent weatherability, good initial adhesiveness, excellent peeling property and good age adhesiveness even the adhesive sheet is in the ageing process after outdoor exposure or high temperature preservation, and good stress relaxation property. The adhesive sheet is obtained through forming an adhesive layer on at least one surface of a substrate layer, the substrate layer includes at least one layer selected from a white series layer and a black series layer, the adhesive layer is formed by an adhesive containing a propylene system copolymer, the propylene system copolymer includes propylene and C2-12 alpha-olefin except propylene as copolymerization components, and there is no above 1J/g endothermic peak in the determination curve of the propylene system copolymer at 0-200DEG through utilizing a differential scanning calorimeter (DSC).
Description
Technical field
The present invention relates to a kind of adhesive sheet.Adhesive sheet of the present invention is useful as the adhesive sheet that surface protective plate, electronic component-use location adhesive sheet etc. has a releasable especially.Adhesive sheet of the present invention is for example on the surface of metal sheet, parts such as metal sheet, aluminum alloy frame, resin board, decorative steel plate, ethylene chloride laminate steel, sheet glass through covering with paint, lacquer, colour wash, etc. being carried, be attached to when processing, maintenance etc. these parts, for the protection of the purposes of parts surface etc.
Background technology
As the essential characteristic of surface protective plate, can enumerate to be attached to and do not arched upward by this surface protective plate after on the adherend or peel off, peel off that tackiness agent does not remain in by on the adherend when removing.Be placed under the high temperature during after particularly on being attached to by adherend before peel off or be exposed to severe condition such as outdoor following times, the degree that above-mentioned characteristic is required is higher.
Therefore; as the tackiness agent of the bonding coat that forms surface protective plate, used in the past do not lose on the fusible degree with isocyanate compound or methylol compound with acrylic copolymer the three-dimensional cross-linked material that improves cohesive force, in natural rubber or modified natural rubber, cooperated the material of an amount of tackifier etc.
The use that has in the surface protective plate relative chamber of such bonding coat does not have special problem.But, be under the situation of principal constituent and at tackiness agent to be to be combined with under the situation of composition of tackifier etc. with natural rubber or modified natural rubber at tackiness agent, because this tackiness agent constitutes by the composition with unsaturated double-bond, so be exposed to when outdoor, ultraviolet ray causes the molecular breakdown of this composition.Thereby, when the stripper surface protective membrane, exist adhesive residue by the problem on the adherend.Therefore, seek weathering resistance surface of good screening glass.
In order to address the above problem, a kind of surface protection sheet of weathering resistance excellence has been proposed, wherein formed the bonding coat (referring to patent documentation 1, patent documentation 2) that the polystyrene A-B-A type block polymer by hydrogenation constitutes at base material film.The polystyrene A-B-A type block polymer with hydrogenation like this is the surface protection of the bonding coat coated steel plate that is attached to the high acrylic resin board of metal sheet, polarity through mirror process, polycarbonate resin plate, acrylic acid series or polyester system with sheet etc. when going up, the problem of generation be cause peel off bad etc.Particularly be attached to and be coated with the such aromatics of polystyrene as on the coated steel plate of the coating of principal constituent the time, be easy to produce problem as described above, and, be present in polar component in the coating to bonding coat generation substance transfer, produce the problem of the surface deformation that makes coated steel plate.
Proposed that a kind of to be added with polyethylene imine based and phosphoric acid ester in polystyrene A-B-A type block polymer be surface protection film tensio-active agent, that do not have bonding rising (referring to patent documentation 3).But it is the problem that tensio-active agent etc. pollutes coated steel plate etc. that this surface protection film has as the phosphoric acid ester of peeling off composition.And polystyrene A-B-A type block polymer is owing to having the plan crosslinking structure of styrene-based structural domain, so lack the stress retentivity.Therefore, in the time of on surface protection film as described above being attached to coated steel plate etc., produce as inferior problem: the ladder that is easy to produce on the surface of coated steel plate due to the attaching trace of film is poor.
As bond strength through the time variation aspect the surface protection film of excellence, a kind of surface protection film (referring to patent documentation 4, patent documentation 5) that is pressed with ethylene/alpha-olefin copolymer on the base material film upper strata has been proposed.But such surface protection film produces: though so must be under the heating and pressurizing condition bonding problem, through the time binding property stable because initial adhesive strength under the normal temperature be when after attaching, transporting below the 0.5N/25mm or completion before be attached to mansion and cause the problem peeled off by the wind that is risen etc. when outdoor with outer plaque etc.Particularly when such surface protection film being attached to shaggy (asperities) metal sheet, having implemented the coated steel plate of embossing processing or resin steel plate etc. and go up, the reduction of described bond strength becomes problem.
Proposed a kind of in bonding coat, used alpha-olefin copolymer, show good fusible surface protection film (referring to patent documentation 6, patent documentation 7).But; in these surface protection films; the surface protection film that can obtain good adhesive strength contains the such polystyrene A-B-A type block polymer of SEBS, SEPS in bonding coat; because the influence of the styrene block in this block polymer produces the problem bad, substance transfer of peeling off under the prolonged preservation.And then, there is such problem in the bonding coat that is formed by the mixed stocker of the polystyrene A-B-A type block polymer of alpha-olefin copolymer and hydrogenation: since when initial the manufacturing tackiness agent by mechanically milling, so each polymkeric substance is the diffusing state of differential, but it is destroyed on the outdoor diffusing state time dependent ground of high temperature differential of following time that places for a long time, be separated, it is residual to produce slurries.In addition, be used for the alpha-olefin copolymer of these surface protection films owing to have crystallising part, so have the shortcoming of stress retentivity difference, when this surface protection film being attached to coated steel plate etc. surperficial, exist to be easy to produce the problem that film attaches trace.
The prior art document
The special fair 6-89312 communique of [patent documentation 1] Japan
The special fair 5-74627 communique of [patent documentation 2] Japan
[patent documentation 3] Japanese kokai publication hei 6-1958 communique
[patent documentation 4] Japanese kokai publication hei 7-258617 communique
[patent documentation 5] Japanese kokai publication hei 8-157791 communique
[patent documentation 6] Japanese kokai publication hei 7-233354 communique
[patent documentation 7] Japanese kokai publication hei 11-21519 communique
Summary of the invention
Invent problem to be solved
Problem of the present invention is to provide a kind of adhesive sheet, it shows excellent weathering resistance, even have good initial stage binding property and after outdoor exposure or high temperature after preserving through the time also can show excellent separability in the process good through the time binding property, have good stress retentivity.
Be used for solving the method for problem
Adhesive sheet of the present invention is the adhesive sheet that is formed with bonding coat at the single face at least of substrate layer, wherein, this substrate layer comprises the one deck at least that is selected from white color system layer and the black system layer, this bonding coat is formed by the tackiness agent that contains propylene series copolymer, described propylene series copolymer comprises the alpha-olefin of the carbonatoms 2～12 beyond propylene and the propylene as copolymer composition, and this propylene series copolymer does not have the endotherm(ic)peak more than the 1J/g in the mensuration of 0～200 ℃ of temperature range utilizing differential scanning calorimeter (DSC).
In preferred embodiment, the polystyrene conversion weight-average molecular weight (Mw) that gel permeation chromatography (GPC) method of passing through of aforesaid propylene based copolymer is measured is 2.0 * 10
5～10.0 * 10
5, molecular weight distribution (Mw/Mn) is that the JIS-A hardness under 1.5～3.5, the JIS-K6253 is 20～50.
In preferred embodiment, adhesive sheet of the present invention is used for the surface protection purposes.
The invention effect
According to the present invention, a kind of adhesive sheet can be provided, it shows excellent weathering resistance, though have good initial stage binding property and after outdoor exposure or high temperature after preserving through the time also can show excellent separability in the process good through the time binding property, have good stress retentivity.
Description of drawings
Fig. 1 is the DSC collection of illustrative plates of propylene series copolymer (1).
Fig. 2 is the DSC collection of illustrative plates of propylene series copolymer (2).
Fig. 3 is the DSC collection of illustrative plates of ethylene/alpha-olefin copolymer used in the comparative example.
Fig. 4 is the DSC collection of illustrative plates of ethylene/alpha-olefin copolymer used in the comparative example.
Embodiment
The tackiness agent (the following tackiness agent that also abbreviates as) that is used for the bonding coat that adhesive sheet of the present invention has contains propylene series copolymer, and it is that 2～12 alpha-olefin is as copolymer composition that described propylene series copolymer comprises carbonatoms beyond propylene and the propylene.Carbonatoms beyond the propylene is that 2～12 alpha-olefin can only be a kind both, also can be for more than 2 kinds.
Contain the carbonatoms that comprises beyond propylene and the propylene and be 2～12 alpha-olefin and have good initial stage binding property as the tackiness agent of the propylene series copolymer of copolymer composition, and can suppress bonding rising to metal sheet, coated steel plate, have through the time after good separability.And, comprise carbonatoms beyond propylene and the propylene and be 2～12 alpha-olefin as the propylene series copolymer of copolymer composition owing to do not have crystallising part in fact, so stress retentivity excellence, relax the stress that is produced by base material with bonding coat, do not attach trace even also do not produce film for coated steel plate etc.And it is good as the cohesive force of the propylene series copolymer of copolymer composition to comprise carbonatoms beyond propylene and the propylene and be 2～12 alpha-olefin, even also can well peel off under situation about being positioned under the high temperature.Carbonatoms beyond the preferred propylene of propylene series copolymer and the propylene be 2～12 alpha-olefin be oriented to the atactic structure.
Be 2～12 alpha-olefin as the carbonatoms beyond the propylene, can adopt suitable arbitrarily alpha-olefin.Be the concrete example of 2～12 alpha-olefin as the carbonatoms beyond the propylene, for example can enumerate ethene, carbonatoms and be 4～12 alpha-olefin.Be 4～12 alpha-olefin as carbonatoms, for example can enumerate 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecylene, 4-methyl-1-pentene, 4-methyl isophthalic acid-hexene.Be 4～12 alpha-olefin as carbonatoms, be preferably 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene.
Each components in proportions that constitutes propylene series copolymer can be adjusted according to purposes is suitable.
In order to obtain good binding property and releasable, the weight ratio that the content of the propylene in the propylene series copolymer is formed in monomer is preferably 40～95 weight %, more preferably 60～90 weight %, more preferably 76～85 weight %.Under this situation, in order to show good low temperature adhesion, be that preferably to share ethene and carbonatoms be 4～12 alpha-olefin for 2～12 alpha-olefin as the carbonatoms beyond the propylene.At this moment, in the propylene series copolymer, carbonatoms is containing of 4～12 alpha-olefin and ethene of the proportional weight ratio of forming in monomer, carbonatoms is 4～12 alpha-olefin: ethene is preferably 1: 1～40: 1, more preferably 2: 1～30: 1.
In order to obtain good soakage and light separability, the weight ratio that the content of the propylene in the propylene series copolymer is formed in monomer is preferably 1～40 weight %, more preferably 2～30 weight %, more preferably 3～20 weight %.Under this situation, in order to show good light separability, be that preferably to share ethene and carbonatoms be 4～12 alpha-olefin for 2～12 alpha-olefin as the carbonatoms beyond the propylene.At this moment, in the propylene series copolymer, carbonatoms is containing of 4～12 alpha-olefin and ethene of the proportional weight ratio of forming in monomer, carbonatoms is 4～12 alpha-olefin: ethene is preferably 1: 1～1: 20, more preferably 1: 2～1: 10.
As the manufacture method of propylene series copolymer, can adopt appropriate means arbitrarily.As such method, for example can enumerate solution polymerization, slurry polymerisation, vapour phase polymerization.More particularly, for example can make by using catalyzer that Japanese kokai publication hei 11-80233 communique puts down in writing etc. to carry out polymerization.
Propylene series copolymer does not have the endotherm(ic)peak more than the 1J/g in the mensuration of 0～200 ℃ of temperature range utilizing differential scanning calorimeter (DSC).Propylene series copolymer can show excellent binding property by do not have the endotherm(ic)peak more than the 1J/g in the mensuration of 0～200 ℃ of temperature range utilizing differential scanning calorimeter (DSC), can show excellent stress retentivity.Propylene series copolymer does not preferably have the endotherm(ic)peak more than the 0.5J/g in the mensuration of 0～200 ℃ of temperature range utilizing differential scanning calorimeter (DSC).
In addition, the endotherm(ic)peak that propylene series copolymer does not have more than the 1J/g in the mensuration of 0 ℃～200 ℃ of temperature ranges utilizing differential scanning calorimeter (DSC) refers to, when carrying out the dsc analysis of propylene series copolymer with the method shown in the embodiment (condition), do not confirm the endotherm(ic)peak of thinking based on more than the 1J/g of crystallization fusion 0 ℃～200 ℃ temperature ranges.
The polystyrene conversion weight-average molecular weight (Mw) that gel permeation chromatography (GPC) method of passing through of propylene series copolymer is measured is preferably 2.0 * 10
5～10.0 * 10
5, more preferably 2.0 * 10
5～9.0 * 10
5, more preferably 2.5 * 10
5～8.0 * 10
5Above-mentioned weight-average molecular weight (Mw) is 2.0 * 10
5Under the above situation, cohesive force is good, and it is residual that slurries do not take place, and can peel off well.And above-mentioned weight-average molecular weight (Mw) is 10.0 * 10
5Under the following situation, the good forming ability in the time of for example will comprising the tackiness agent extrusion molding of propylene series copolymer.
The molecular weight distribution of propylene series copolymer (Mw/Mn) is preferably 1.5～3.5, and more preferably 1.5～3.0.Above-mentioned molecular weight distribution (Mw/Mn) is under the situation below 3.5, and the low molecular weight compositions that can suppress to generate etc. causes to be peeled off badly, and can suppress high molecular weight components and is present in the bonding coat reason that forms foreign matter and become bad order.
JIS-A hardness under the JIS-K6253 of propylene series copolymer is preferably 20～50, and more preferably 22～40, more preferably 25～38.As long as above-mentioned JIS-A hardness is in above-mentioned scope, film is just soft, is difficult for producing film and attaches trace.。
Tackiness agent among the present invention is principal constituent with above-mentioned propylene series copolymer.Aforesaid propylene based copolymer in the tackiness agent of the present invention contain proportional being preferably more than the 80 weight %, more preferably more than the 90 weight %.
Tackiness agent of the present invention is except containing the aforesaid propylene based copolymer, and binding property also can contain styrene-ethylene butylene copolymer-cinnamic multipolymer (SEBS) in the scope of not damaging the object of the invention, styrene-ethylene propylene copolymer-such hydrogenated styrene of cinnamic multipolymer (SEPS) is A-B-A type block polymer in order to improve; The such hydrogenated styrene of multipolymer (SEP) of the multipolymer of styrene-ethylene butylene copolymer (SEB), styrene-ethylene propylene copolymer is A-B type block polymer; The such hydrogenated styrene of multipolymer (SEBC) of styrene-ethylene butylene copolymer-alkene crystalline blocks polymkeric substance is A-B-C type block polymer; The hydride of the random copolymers that is constituted by vinylbenzene and diolefin series hydrocarbon; Deng.These polymkeric substance can only be a kind both, also can be for more than 2 kinds.Can suiting, it is proportional to adjust containing of these block polymers with vinylbenzene composition, but when containing increasing proportion, produce detrimentally affect in bonding rising, dividing a word with a hyphen at the end of a line property of material, stress aspect anterethic, thereby these block polymers with vinylbenzene composition are preferably 0～40 weight % with respect to propylene series copolymer, more preferably 0～20 weight %, more preferably 0～10 weight %.These have the vinylbenzene composition block polymer contain proportional when surpassing 40 weight % with respect to propylene series copolymer, might damage the stress retentivity or be easy to produce influence by the vinylbenzene composition causes peel off bad.
For control of carrying out adhesion characteristic etc., can suit as required in the tackiness agent of the present invention for example to add, tenderizer, ethylene series resin, silicone-based polymkeric substance, propylene liquid acid based copolymer, tackifier, antiaging agent, hindered amine are photostabilizer, UV light absorber, polyethylene imine based, fatty acid amide, phosphoric acid ester, weighting agent or pigment additives such as (for example, calcium oxide, magnesium oxide, silicon-dioxide, zinc oxide, titanium oxide etc.).
To tackiness agent of the present invention as required can also embodiment such as Corona discharge Treatment, uviolizing processing, flame treating, Cement Composite Treated by Plasma, sputter etching processing etc. with fusible control or to attach operation etc. be the surface treatment of purpose.
Also can contain tenderizer in the tackiness agent of the present invention to improve bounding force etc.As tenderizer, for example can use low-molecular-weight polyisobutene, hydrogenated polyisoprene, hydrogenated butadiene polymer or their derivative.As the example of derivative, can enumerate terminal or two ends have OH base, COOH base, hydrogenated butadiene polymer glycol, hydrogenated butadiene polymer one alcohol, hydrogenated polyisoprene glycol, hydrogenated polyisoprene one alcohol etc.As such tenderizer, for the purpose that suppresses to rise to by the binding property of adherend, hydride, the ethylene series tenderizer of diene polymers such as preferred especially hydrogenated butadiene polymer or hydrogenated isoprene.As such tenderizer, specifically can obtain the trade(brand)name " Kuraprene LIR-200 " of (strain) KURARAY manufacturing etc.Such tenderizer can only be a kind both, also can be for more than 2 kinds.Can suiting, it is proportional to set containing of tenderizer, but with respect to propylene series copolymer, tenderizer is preferably 0～40 weight %, more preferably 0～20 weight %, more preferably 0～10 weight %.During the containing proportional and surpass 40 weight % of tenderizer, the slurries when high temperature or outdoor exposure are residual might to become remarkable.
Can suit to set the molecular weight of tenderizer, but number-average molecular weight is preferably 5000～100,000, more preferably 10,000～50,000.The number-average molecular weight of tenderizer is 5000 when following, might cause to by the substance transfer of adherend and heavy peeling off etc., and the number-average molecular weight of tenderizer is 100,000 when above, lacks the raising effect of bounding force.
Also can contain tackifier in the tackiness agent of the present invention to improve bounding force etc.The slurries residue problem that causes from the reduction of avoiding producing because of cohesive force and the aspect that bounding force is improved, containing of tackifier proportionally is preferably below the 50 weight % with respect to propylene series copolymer, more preferably below the 30 weight %, 5～20 weight % more preferably.
As tackifier, for example can adopt petroleum line resin, coumarone indenes such as fatty family or fragrant family, aliphatics aromatic copolymer system or alicyclic series is that resin or terpenic series resin, terpene aldehyde phenol resin or polymerized rosin are that resin, (alkyl) phenol resin or diformazan benzene series resin or their hydrogenation are suitable tackifier arbitrarily such as resin.Tackifier can only be a kind both, also can be for more than 2 kinds.As tackifier, consider the tackifier of preferred hydrogenation from aspects such as separability and weathering resistances.In addition, also sell the mixture of tackifier and olefin resin on the market, also can use.
During bonding coat that formation is made of tackiness agent of the present invention, utilize solution that solvent forms or the hot melt liquid that for example can enumerate tackiness agent are coated on method on the base material, based on this coating is formed on the method that the bonding coat on the spacer plate shifts, the formation material of bonding coat is extruded in the method for supporting that base material is coated with, the formation material of substrate layer and the formation material of bonding coat are carried out double-deck or multi-layer co-extruded method, the method of individual layer laminate adhesive layer on the substrate layer or on laminate layers again the laminate adhesive layer carry out the method for double-layer lamination, support base materials such as bonding coat and film or laminate layers formation material is carried out the method for bilayer or laminated multi-layer etc.In these methods, consider from aspects such as productivity and costs, preferably by blow moulding or T die head method with the formation material of bonding coat material carries out co-extrusion modling in the mode of bilayer or multilayer the method that forms together with the substrate layer that is constituted by thermoplastic resin.
The thickness of bonding coat can be according to suitable adjustment such as bounding forces.The thickness of bonding coat is preferably 3～50 μ m, more preferably 5～40 μ m, more preferably 7～35 μ m.
As required, also bonding coat can protected bonding coat for be attached to spacer plate etc. during before the practicality temporarily.
Adhesive sheet of the present invention is formed with bonding coat at the single face at least of substrate layer.
The thickness of substrate layer is preferably 5～300 μ m, more preferably 20～150 μ m.As the ultraviolet ray transmissivity of substrate layer, the transmitance under wavelength 365nm is preferably below 5%, more preferably below 1%.
As the material of substrate layer, for example can enumerate polyester; Polymeric amide, single system (homo-polypropylene) or with the acrylic polymer of ethene composition as the block system of copolymer composition, random system, grafting system etc.; Ethylene-based polymers such as Low Density Polyethylene, high density polyethylene(HDPE), linear low density polyethylene, ultra-low density polyethylene; Olefin polymers such as ethylene propylene copolymer; Paper; Metallic membrane; Non-woven fabrics; Deng.The material of substrate layer can only be a kind both, also can be for more than 2 kinds.
Material as substrate layer is preferably polyester; Polymeric amide, single system (homo-polypropylene) or with the acrylic polymer of ethene composition as the block system of copolymer composition, random system, grafting system etc.; Ethylene-based polymers such as Low Density Polyethylene, high density polyethylene(HDPE), linear low density polyethylene, ultra-low density polyethylene; Olefin polymers such as ethylene propylene copolymer; Deng plastic film.
When selecting plastic film as the material of substrate layer, in order to prevent deterioration etc., for example also can contain photostabilizers such as antioxidant, UV light absorber, hindered amine as light stabilizer, static inhibitor, weighting agent or pigment (carbon black, calcium oxide, magnesium oxide, silicon-dioxide, zinc oxide, titanium oxide etc.).
As antioxidant, for example can enumerate hindered phenol is that antioxidant, phosphorus system process thermo-stabilizer, lactone is that processing thermo-stabilizer, sulphur are heat-resisting stabilizing agent etc.Antioxidant is preferably below the 5 weight % with respect to the base resin (when substrate layer was mixture, this mixture was base resin) as the substrate layer material, more preferably below the 3 weight %, and 0.1～0.5 weight % more preferably.
As UV light absorber, for example can enumerate benzotriazole is that UV light absorber, triazine are UV light absorber, benzophenone series UV light absorber etc.UV light absorber is preferably below the 5 weight % with respect to the base resin (when substrate layer was mixture, this mixture was base resin) as the substrate layer material, more preferably below the 3 weight %, and 0.1～1 weight % more preferably.
As photostabilizer, can enumerate hindered amine is that photostabilizer, benzoic ether are photostabilizer etc.Photostabilizer is preferably below the 5 weight % with respect to the base resin (when substrate layer was mixture, this mixture was base resin) as the substrate layer material, more preferably below the 3 weight %, and 0.1～1 weight % more preferably.
Substrate layer comprises the one deck at least that is selected from white color system layer and the black system layer.Thus, can make the very excellent adhesive sheet of weathering resistance.
The white color system layer is that display white is the layer of tone, and for example, the whiteness of JIS-L-1015 regulation is preferably more than 60%, more preferably more than 70%, more preferably more than 80%, is preferably more than 85% especially.The white color system layer preferably comprises white pigment.As white pigment, can adopt suitable arbitrarily white pigment.As such white pigment, for example can enumerate titanium oxide.When the white color system layer contained white pigment, it contained proportional resinous principle with respect to formation white color system layer and is preferably 0.1～50 weight %, more preferably 1～30 weight %, more preferably 5～20 weight %.
The resinous principle that forms the white color system layer can be enumerated the material of above-mentioned substrate layer, is preferably polyolefin-based resins, more preferably is selected from least a in acrylic polymer and the ethylene-based polymer, more preferably density 0.88～0.93g/cm
3Ethylene-based polymer.As the resinous principle that forms the white color system layer, specifically, can preferably enumerate polypropylene, Low Density Polyethylene (LDPE), linear low density polyethylene (LLDPE).Polyolefin-based resins in the white color system layer contain proportional being preferably more than the 60 weight %, more preferably more than the 70 weight %, more preferably more than the 80 weight %, be preferably especially more than the 85 weight %, most preferably be more than the 90 weight %.Such polyolefin-based resins both can only use a kind, also can use more than 2 kinds.
The thickness of white color system layer can adopt suitable arbitrarily thickness according to purpose.Such thickness is preferably 1～50 μ m, 3～40 μ m more preferably, and more preferably 5～30 μ m are preferably 10～30 μ m especially.
Black system layer is to show that black is the layer of tone.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.When black system layer contained black pigment, it contained proportional resinous principle with respect to formation black system layer and is preferably 0.01～10 weight %, more preferably 0.1～5 weight %, more preferably 0.5～3 weight %.
The resinous principle that forms black system layer can be enumerated the material of above-mentioned substrate layer, is preferably polyolefin-based resins, more preferably is selected from least a in acrylic polymer and the ethylene-based polymer, more preferably density 0.88～0.93g/cm
3Ethylene-based polymer.As the resinous principle that forms black system layer, specifically can preferably enumerate polypropylene, Low Density Polyethylene (LDPE), linear low density polyethylene (LLDPE).Polyolefin-based resins in the black system layer contain proportional being preferably more than the 60 weight %, more preferably more than the 70 weight %, more preferably more than the 80 weight %, be preferably especially more than the 85 weight %, most preferably be more than the 90 weight %.Such polyolefin-based resins both can only use a kind, also can use more than 2 kinds.
The thickness of black system layer can adopt suitable arbitrarily thickness according to purpose.Such thickness is preferably 1～100 μ m, 5～70m more preferably, and more preferably 10～60 μ m are preferably 20～50 μ m especially.
Also can add fatty acid amide or polyethylene imine based etc. carry out the demoulding and handle or arrange coating that the stripper that suited by silicone-based, chain alkyl system, fluorine system etc. constitutes with the coiling body that forms easy uncoiling etc. the face that bonding coat is not set of substrate layer.
Adhesive sheet of the present invention can pass through appropriate means manufacturing arbitrarily.Consider from aspects such as productivity and costs, be preferably by blow moulding or T die head method the formation material of bonding coat is formed material with the method for the mode co-extrusion modling of bilayer or multilayer together with the substrate layer that is made of thermoplastic resin.
Substrate layer comprise white color system layer and black system layer this when two-layer, form the formation material of substrate layer for more than at least 2 kinds, therefore, can obtain adhesive sheet of the present invention in the following way: use to form the formation material more than 2 kinds of substrate layer and form the formation material of bonding coat, by substrate layer and bonding coat are carried out coextrusion with multilayer method film forming.Formation as adhesive sheet of the present invention is not particularly limited, and can adopt arbitrary formation of " white color system layer/bonding coat ", " black system layer/bonding coat ", " white color system layer/black system layer/bonding coat ", " black system layer/white color system layer/bonding coat ".In addition, as substrate layer, can also be set at the layer more than 3 layers that is formed with black system layer and white color system layer layer in addition and constitute.Specifically, can also be set at the formation of " transparent resin layer/white color system layer/black system layer/bonding coat " etc.In addition, the thickness of white color system layer and black system layer can be identical, also can be different thickness (the white color system layer constitutes than the black system thin thickness of layer, and the white color system layer is that the thickness of bed thickness constitutes than black).
Adhesive sheet of the present invention is preferred for requiring the purposes of releasable or interim adhibit quality, and be preferably used as the surface protective plate that has the protection purposes on the surface of metal sheet, parts such as metal sheet, aluminum alloy frame, resin board, decorative steel plate, ethylene chloride laminate steel, sheet glass through covering with paint, lacquer, colour wash, etc. being carried, be attached to when processing, maintenance etc. these parts especially, the adhesive sheet that is reduced to purpose during to the adhesive sheet of the positioning parts of tame electrical article, with manufacturings such as electronic units etc. has the adhesive sheet of releasable.
Embodiment
Below, specify the present invention by embodiment, but the present invention is not subjected to any restriction of these embodiment.
(propylene copolymer)
The characteristic value of the propylene series copolymer that uses is listed in table 1.
[table 1]
In the table 1, P: B: E represents propylene: 1-butylene: ethene.In addition, weight-average molecular weight (Mw), molecular weight distribution (Mw/Mn) are the values that records by GPC method (post: eastern Cao makes, TSKgel GMH-H (S) * 2, solvent: tetrahydrofuran (THF), by polystyrene conversion), and JIS-A is the value that records according to JIS-K6253.
The DSC collection of illustrative plates of propylene series copolymer (1) is shown in Fig. 1, the DSC collection of illustrative plates of propylene series copolymer (2) is shown in Fig. 2.Propylene series copolymer (1), (2) do not have the above endotherm(ic)peak of 1J/g in 0 ℃～200 ℃.Do not see fusing point, Heat of fusion.In addition, the DSC collection of illustrative plates is to use differential scanning calorimeter (the Seiko electronics is made, and DSC2000), with temperature :-40～200 ℃, atmosphere gas: nitrogen (200ml/ minute), heat-up rate: 10 ℃/minute condition determination is measured and obtained.Intensification during mensuration and temperature-fall period carry out with 10 ℃/minute speed.
(embodiment 1)
Formation material as bonding coat uses propylene series copolymer (1); material use as the black system layer that forms substrate layer is added with (the Mitsubishi Chemical's manufacturing of 1 weight % carbon black; carbon black " #45 ") Low Density Polyethylene (Dong Caoshe manufacturing, Petrothene172); use the Low Density Polyethylene that is added with 20 weight % white pigments (refine big day society makes, HCM2035W) (Dong Caoshe makes, Petrothene172) as the material of the white color system layer that forms substrate layer; each material by the coextrusion of the T die head method of forming, is obtained surface protective plate (1).
Surface protection is white color system layer/layer/bonding coat=30 μ m/30 μ m/20 μ m of black system with the thickness of sheet (1).
(embodiment 2)
Material use as the black system layer that forms substrate layer is added with (the Mitsubishi Chemical's manufacturing of 1 weight % carbon black; carbon black " #45 ") (bright dipping petroleum chemistry society makes polypropylene; IDEMITSU PPF-744NP); material use as the white color system layer that forms substrate layer is added with (the society's manufacturing of refining big day of 20 weight % white pigments; HCM2035W) (bright dipping petroleum chemistry society makes polypropylene; IDEMITSU PP F-744NP); each material is passed through the coextrusion of the T die head method of forming; make the white black two-layer substrate layer of thickness 40 μ m (the white color system layer/layer=20 μ m/20 μ m of black system); at the toluene solution of its black layer side as adhesive coated propylene series copolymer (2); dry back forms bonding coat, obtains surface protective plate (2).
Surface protection is white color system layer/layer/bonding coat=20 μ m/20 μ m/15 μ m of black system with the thickness of sheet (2).
(comparative example 1)
In embodiment 1, as the formation material use ethylene/alpha-olefin copolymer (manufacturing of society of Du Pont, AFFINITY PF-1140) of bonding coat, operate similarly to Example 1 in addition, obtain surface protective plate (C1).
In addition, the above-mentioned ethylene/alpha-olefin copolymer as the formation material of bonding coat has 95.7 ℃ of endotherm(ic)peaks (40.5J/g) under the said determination condition.Its DSC collection of illustrative plates is shown in Fig. 3.
(comparative example 2)
In embodiment 1, as the formation material use ethylene/alpha-olefin copolymer (manufacturing of Sumitomo Chemical society, Esprene201) of bonding coat, operate similarly to Example 1 in addition, obtain surface protective plate (C2).
In addition, the above-mentioned ethylene/alpha-olefin copolymer as the formation material of bonding coat does not have endotherm(ic)peak under the said determination condition.
(comparative example 3)
In embodiment 2, as the toluene solution of tackiness agent use ethylene/alpha-olefin copolymer (manufacturing of society of Du Pont, AFFINITY PF-1140), operate similarly to Example 2 in addition, obtain surface protective plate (C3).
(comparative example 4)
In embodiment 2, ((strain) KURARAY makes, and toluene solution SEPTON2043) is operated in addition similarly to Example 2, obtains surface protective plate (C4) to use SEPS as tackiness agent.
(comparative example 5)
In embodiment 2; (the chemical society in waste river makes to be combined with 40 weight % hydrogenation petroleum line resins as the tackiness agent use with respect to propylene/alpha-olefins copolymer (manufacturing of Mitsui Chemicals society, TAFMER XR107L); the toluene solution of material Alcon P-100); operate similarly to Example 2 in addition, obtain surface protective plate (C5).
In addition, the ethylene/alpha-olefin copolymer as the formation material of bonding coat has 108.3 ℃ of endotherm(ic)peaks (24.1J/g) under the said determination condition.Its DSC collection of illustrative plates is shown in Fig. 4.
(comparative example 6)
In embodiment 1, in substrate layer, do not add carbon black and white pigment, operate similarly to Example 1 in addition, obtain surface protective plate (C6).
Carry out following evaluation for the surface protective plate that obtains by embodiment and comparative example.Evaluation result is shown in table 2.
(initial stage bounding force)
By twice the crimping of coming and going of 2kg roller, surface protective plate is attached to after on the metal sheet that the polyester melamine is covered with paint, lacquer, colour wash, etc., measure in 23 ℃ of bond strengths (N/25mm) after placing 1 hour.
Condition determination: 23 ℃, 65%RH
Stripping conditions: draw speed 300mm/ minute, 180 the degree peel off
(through the time bounding force)
By 2 times the crimping of coming and going of 2kg roller, surface protective plate is attached to after on the metal sheet that the polyester melamine is covered with paint, lacquer, colour wash, etc., measure in 80 ℃ of bond strengths (N/25mm) after placing 30 days down.
Condition determination: 23 ℃, 65%RH
Stripping conditions: draw speed 300mm/ minute, 180 the degree peel off
(stress retentivity)
Surface protective plate is attached on the metal sheet that the polyester melamine is covered with paint, lacquer, colour wash, etc. in the mode that produces bubble (diameter is the circle of 2cm) and fold (length 5em, height 5mm); placed 30 days at 80 ℃, have or not slurries residual (compendency) and have or not film to attach trace (trace tack) on the metal sheet when visual observation is peeled off the sheet material after placing.In addition, after placing 14 days under the environment of 60 ℃/95%RH, peel off, place filming after 24 hours under the visual observation room temperature and have or not reduce (observation that the thin degree that attaching portion produces because of substance transfer reduces).
(mensuration of weathering resistance)
Surface protective plate is cut into the strip of wide 20mm, makes to estimate and use sample.Make the roller round trip of 2kg, after being crimped on this sample on the SUS430BA plate, dropped in the weather-proof machine of sunlight carbon arc (SUGA TEST INSTRUMENTS Co., Ltd. goods) 1000 hours, next, on 180 ° of directions, peel off length to 100mm from an end of sample with 0.3m/ minute draw speed.
With the above-mentioned result of following benchmark evaluation.
Zero: sample does not have fragmentation, can peel off extremely well.
*: because of the base material deterioration, sample fragmentation or adhesive residue is halfway being polluted by adherend.
[table 2]
In the table 2, (-) expression does not produce bubble and fold because bonding force is not enough, does not have film to attach trace yet.As shown in Table 2, among the embodiment, show excellent weathering resistance, has the initial stage bounding force, and high temperature through the time bounding force the rising degree also little, have stable by the time bond strength, separability might as well, bonding coat has the stress retentivity, and aspects such as compendency at high temperature, substance transfer are all excellent.
Utilize possibility on the industry
Adhesive sheet of the present invention, particularly surface protective plate be for example on the surface of metal sheet, parts such as metal sheet, aluminum alloy frame, resin board, decorative steel plate, ethylene chloride laminate steel, sheet glass through covering with paint, lacquer, colour wash, etc. being carried, be attached to when processing, maintenance etc. these parts, for the protection of the purposes of parts surface etc.
Claims (3)
1. adhesive sheet, it is the adhesive sheet that is formed with bonding coat in the one side at least of substrate layer,
This substrate layer comprises the one deck at least that is selected from white color system layer and the black system layer,
This bonding coat is formed by the tackiness agent that contains propylene series copolymer, and described propylene series copolymer comprises the alpha-olefin of the carbonatoms 2～12 beyond propylene and the propylene as copolymer composition,
This propylene series copolymer does not have the endotherm(ic)peak more than the 1J/g in the mensuration of 0～200 ℃ of temperature range utilizing differential scanning calorimeter (DSC).
2. adhesive sheet according to claim 1, wherein,
The polystyrene conversion weight-average molecular weight (Mw) that gel permeation chromatography (GPC) method of passing through of described propylene series copolymer is measured is 2.0 * 10
5～10.0 * 10
5, molecular weight distribution (Mw/Mn) is 1.5～3.5, is 20～50 based on the JIS-A hardness of JIS-K6253.
3. adhesive sheet according to claim 1 and 2, wherein,
Described adhesive sheet is used for the surface protection purposes.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100361227A CN103254807A (en) | 2012-02-15 | 2012-02-15 | Adhesive sheet |
| PCT/JP2013/051524 WO2013121855A1 (en) | 2012-02-15 | 2013-01-25 | Adhesive sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100361227A CN103254807A (en) | 2012-02-15 | 2012-02-15 | Adhesive sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103254807A true CN103254807A (en) | 2013-08-21 |
Family
ID=48959036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100361227A Pending CN103254807A (en) | 2012-02-15 | 2012-02-15 | Adhesive sheet |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN103254807A (en) |
| WO (1) | WO2013121855A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106256864A (en) * | 2015-06-19 | 2016-12-28 | 日东电工株式会社 | Surface protective film |
| CN109536059A (en) * | 2018-11-08 | 2019-03-29 | 宁波激智科技股份有限公司 | A kind of novel optical protective film |
| CN115431615A (en) * | 2021-06-02 | 2022-12-06 | 尼洛科技农业合作社有限公司 (尼尔大卫) | A connection component with a layered structure |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112778923B (en) * | 2019-11-07 | 2024-12-27 | 日东电工株式会社 | Dicing tape and dicing die-bonding film |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06271821A (en) * | 1993-03-23 | 1994-09-27 | Lintec Corp | Removable type tacky protecting tape |
| JP2002226814A (en) * | 2001-02-05 | 2002-08-14 | Nitto Denko Corp | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
| JP2002226813A (en) * | 2001-02-05 | 2002-08-14 | Nitto Denko Corp | Adhesive and adhesive sheet |
| CN101058700A (en) * | 2006-04-17 | 2007-10-24 | 日东电工株式会社 | Base material for pressure-sensitive adhesive tape or sheet, pressure-sensitive adhesive tape or sheet having light-reflective property or light-shielding property and liquid crystal display apparatus |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003213485A (en) * | 2002-01-15 | 2003-07-30 | Nitto Denko Corp | Masking tape for metal plating |
-
2012
- 2012-02-15 CN CN2012100361227A patent/CN103254807A/en active Pending
-
2013
- 2013-01-25 WO PCT/JP2013/051524 patent/WO2013121855A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06271821A (en) * | 1993-03-23 | 1994-09-27 | Lintec Corp | Removable type tacky protecting tape |
| JP2002226814A (en) * | 2001-02-05 | 2002-08-14 | Nitto Denko Corp | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
| JP2002226813A (en) * | 2001-02-05 | 2002-08-14 | Nitto Denko Corp | Adhesive and adhesive sheet |
| CN101058700A (en) * | 2006-04-17 | 2007-10-24 | 日东电工株式会社 | Base material for pressure-sensitive adhesive tape or sheet, pressure-sensitive adhesive tape or sheet having light-reflective property or light-shielding property and liquid crystal display apparatus |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106256864A (en) * | 2015-06-19 | 2016-12-28 | 日东电工株式会社 | Surface protective film |
| CN109536059A (en) * | 2018-11-08 | 2019-03-29 | 宁波激智科技股份有限公司 | A kind of novel optical protective film |
| CN115431615A (en) * | 2021-06-02 | 2022-12-06 | 尼洛科技农业合作社有限公司 (尼尔大卫) | A connection component with a layered structure |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2013121855A1 (en) | 2013-08-22 |
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Application publication date: 20130821 |