CN1311047C - Adhesive composition and method of bonding - Google Patents
Adhesive composition and method of bonding Download PDFInfo
- Publication number
- CN1311047C CN1311047C CNB2003801083675A CN200380108367A CN1311047C CN 1311047 C CN1311047 C CN 1311047C CN B2003801083675 A CNB2003801083675 A CN B2003801083675A CN 200380108367 A CN200380108367 A CN 200380108367A CN 1311047 C CN1311047 C CN 1311047C
- Authority
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- China
- Prior art keywords
- thermoplastic elastomer
- composition
- tackifier
- polyolefin
- binder composition
- Prior art date
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- Expired - Lifetime
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- 239000000203 mixture Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims description 7
- 239000000853 adhesive Substances 0.000 title abstract description 10
- 230000001070 adhesive effect Effects 0.000 title abstract description 10
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 29
- 229920000098 polyolefin Polymers 0.000 claims abstract description 21
- 229920005862 polyol Polymers 0.000 claims abstract description 20
- 150000003077 polyols Chemical class 0.000 claims abstract description 20
- 239000012948 isocyanate Substances 0.000 claims abstract description 17
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 239000011230 binding agent Substances 0.000 claims description 23
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 9
- 239000012530 fluid Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 238000004026 adhesive bonding Methods 0.000 claims description 2
- 229920005672 polyolefin resin Polymers 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 7
- 239000004615 ingredient Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 19
- 239000011347 resin Substances 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- -1 polyethylene Polymers 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 11
- 239000003208 petroleum Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 239000004831 Hot glue Substances 0.000 description 4
- 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 4
- 150000001875 compounds Chemical class 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000008676 import Effects 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 229920001195 polyisoprene Polymers 0.000 description 4
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 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 4
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229920006026 co-polymeric resin Polymers 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- MSFGZHUJTJBYFA-UHFFFAOYSA-M sodium dichloroisocyanurate Chemical compound [Na+].ClN1C(=O)[N-]C(=O)N(Cl)C1=O MSFGZHUJTJBYFA-UHFFFAOYSA-M 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- 239000013032 Hydrocarbon resin Substances 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 229920006270 hydrocarbon resin Polymers 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000003097 polyterpenes Chemical class 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 1
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 1
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 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
- FAIFRACTBXWXGY-JTTXIWGLSA-N COc1ccc2C[C@H]3N(C)CC[C@@]45[C@@H](Oc1c24)[C@@]1(OC)C=C[C@@]35C[C@@H]1[C@](C)(O)CCc1ccccc1 Chemical compound COc1ccc2C[C@H]3N(C)CC[C@@]45[C@@H](Oc1c24)[C@@]1(OC)C=C[C@@]35C[C@@H]1[C@](C)(O)CCc1ccccc1 FAIFRACTBXWXGY-JTTXIWGLSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 206010011968 Decreased immune responsiveness Diseases 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 1
- 229930006722 beta-pinene Natural products 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002397 thermoplastic olefin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
An adhesive with which polyolefin resins can be bonded while attaining a high initial bond strength and which has excellent adhesion durability especially at high temperatures. The adhesive is an adhesive composition comprising: a liquid composition obtained by dissolving or dispersing a carboxylated thermoplastic elastomer (A), a polyolefin polyol (B), and a tackifier (C) in an organic solvent; and a polyfunctional isocyanate (D). Preferably, the ratio of the weight of the carboxylated thermoplastic elastomer (A) to that of the polyolefin polyol (B) in the liquid composition is from 98/2 to 20/80 and the amount of the tackifier (C) is 5 to 150 parts by weight per 100 parts by weight of the sum of the ingredients (A) and (B).
Description
Technical field
The present invention relates to 2 liquid type fluid binder compositions,, have high initial adhesive strength and final bond strength, 2 liquid type binder compositions that adhesion durability is good in particular in bonding polyolefin resin.
Background technology
Usually, polyolefin resins such as known polyethylene and polypropylene are to be difficult to by tackiness agent adherent resin.But a lot of schemes have also been proposed for tackiness agent applicable to this class polyolefin resin.Particularly, the someone proposed styrene/isoprene/styrene segmented copolymer or styrene/butadiene/styrene block copolymers hydrogenation and the thermoplastic elastomers such as multipolymer that obtain as the scheme of the Hotmelt Adhesive of main component.
In Japanese kokai publication sho 62-48779 communique (claims), disclosed contain above-mentioned thermoplastic elastomer, hydrocarbon resin class tackifier, wax and the hydrocarbon synthetic rubber of yield point below 120 ℃ Hotmelt Adhesive applicable to polyolefinic bonding.In addition, in Japanese kokai publication hei 3-259981 communique (claims), disclosed the polyisoprene that contains same thermoplastic elastomer and hydroxyl and isocyanate reaction and the high temperature of isocyanate prepolymer the time improved Hotmelt Adhesive such as cohesive force and solvent resistance.Such Hotmelt Adhesive, solvent-free and be easier to base material is coated with, therefore have practicality, but bond strength is still waiting further raising.
Summary of the invention
The objective of the invention is to, providing can be with the bonding polyolefin resin of high initial adhesive strength, and the tackiness agent of the adhesion durability excellence under adhesion durability, the particularly high temperature.
The present invention contains carboxylic thermoplastic elastomer (A), polyolefin polyol (B) and tackifier (C) are dissolved or to be dispersed in fluid composition in the organic solvent, and polyfunctional isocyanate's (D) binder composition.
In preferred adhesive composition of the present invention, carboxylic thermoplastic elastomer (A) in the above-mentioned fluid composition is 98/2～20/80 with the mass ratio of polyolefin polyol (B), and per 100 mass parts of above-mentioned (A) and total amount (B), the ratio of tackifier (C) is 5～150 mass parts.
Preferred holographic recording of the present invention is with in the composition, and the thermoplastic elastomer (A) that contains carboxyl is the styrene analog thermoplastic elastomer that contains carboxyl.
In the present invention, use thermoplastic elastomer, promptly contain the thermoplastic elastomer of carboxyl with carboxyl.In the present invention, even being meant, so-called thermoplastic elastomer do not make sulfidizing, its moulding product also have the resin of caoutchouc elasticity at normal temperature, promptly becoming thermoplastic resin and have the material of caoutchouc elasticity, generally is to have the ABA type block or (A-B) multipolymer of the many block structures of n type on chemical structure.
The thermoplastic elastomer that contains carboxyl among the present invention obtains by carboxyl is imported thermoplastic elastomer.As the concrete example of preferred thermoplastic elastomer, can enumerate styrene-butadiene block copolymer, styrene-ethylene propylene-based block copolymer, styrene-butadiene-styrene block copolymer, styrene isoprene styrene block copolymer (SIS), styrene-ethylene butylene-styrene segmented copolymer, styrene-ethylene propylene-styrene segmented copolymer, ethylene-propylene copolymer, ethylene-propylene terpolymer.Below, the segmented copolymer that will have polystyrene units is called the styrenic elastomerics.
As the method that imports carboxyl to above-mentioned thermoplastic elastomer, when the monomer that is used to make thermoplastic elastomer carries out polymerization, normally make the method for copolymerization such as an amount of ethene unsaturated carboxylic acid, for example toxilic acid.For example, if styrenic elastomericss such as styrene isoprene styrene block copolymer (SIS) are maleic acid copolymerized by making, just can in elastomerics, import carboxyl (below, will import carboxyl to elastomerics and be called sour modification) when making the styrene monomer polymerization.
In the present invention, because of the solvability in used organic solvent is good, so preferably make carboxyl import the styrenic elastomerics.
The particularly preferred thermoplastic elastomer that contains carboxyl is a toxilic acid modified styrenics elastomerics among the present invention, is the toxilic acid modified styrenics elastomerics that contains styrene units 5～65 quality %, preferred 10～40 quality % in the multipolymer.As concrete example, can enumerate the Claiton of Claiton polymkeric substance Co., Ltd. production and the TuftecM series of Asahi Chemical Industry Co., Ltd's production etc., the skeleton of these products is styrene-ethylene butylene-styrene segmented copolymers (hereinafter referred to as SEBS).
Polyolefin polyol among the present invention has the stable hydrocarbon skeleton same with low-molecular-weight polyolefin, and has a plurality of hydroxyls.Its molecular weight is preferably in 500～5000 scope.Molecular weight is insoluble in organic solvent more than 5000; Molecular weight is below 500, and the gained binder composition descends easily to the binding property of polyolefin resin.As the concrete example of preferred polyolefin polyol, can enumerate the Polytel (trade(brand)name) of Mitsubishi chemical Co., Ltd's production etc.
The preferred usage ratio of above-mentioned thermoplastic elastomer and polyolefin polyol by quality ratio, is 98/2～20/80, more preferably 90/10～40/60.The ratio of polyolefin polyol by quality ratio, in case less than 2, just do not reach adhesion durability, on the other hand, in case greater than 80, bond strength just easily descends.
As the tackifier among the present invention, can enumerate polyterpene resinoid, rosin based resin, aliphatic category petroleum resin, alicyclic ring same clan petroleum resin, copolymerization class petroleum resin, hydrogenated petroleum resin etc.Wherein, in the present invention, according to adhesion durability, preferred hydrogenated hydrocarbon resins.
As the resinoid concrete example of polyterpene, can enumerate the multipolymer of α-Pai Xi polymkeric substance, beta-pinene polymer and these polymkeric substance and phenol or dihydroxyphenyl propane etc., trade(brand)name YS ResinPX, YS ResinA, YSPolystarT etc. that the commercially available prod of these resins has Yasuhara KCC to produce.
As the rosin based resin, can enumerate natural rosin, polymerized rosin and ester derivative thereof etc., as the commercially available prod, can enumerate Pensel D, SuperEsterA that Arakawa Chemical Industries, Ltd. produces.
The aliphatic category petroleum resin are by the common C 5 fraction synthetic resin by oil that is also referred to as the C5 class, as commercially available product, Quinton, the Wingtac that Good Year company produces etc. that have エ ス コ Star Star that Tonex Co., Ltd. produces, Japanese Zeon Co., Ltd. to produce.
Alicyclic ring same clan petroleum resin generally are the C9 cut synthetic resins by oil, as commercially available product, can enumerate the マ Le カ レ Star Star of Maruzen Petrochemical Co., Ltd.'s production etc.
Copolymerized petroleum resin is also referred to as the C5/C9 copolymer resins, as commercially available product, can enumerate the eastern High Resin of nation of Toho Chemical Industry Co., Ltd.'s production etc.
Hydrogenated petroleum resin is with the resin after the above-mentioned tackifier resins hydrogenation, as commercially available product, can enumerate ester rubber H and Alcom that Arakawa Chemical Industries, Ltd. produces, the エ ス コ Star Star that the Clearon that Yasuhara KCC produces, Tonex Co., Ltd. produce etc.
The preferred usage quantity of tackifier is, measures 100 mass parts with respect to the total of thermoplastic elastomer that contains carboxyl and polyolefin polyol, is 5～150 mass parts, 20～100 mass parts more preferably.The tackifier consumption is in case less than 5 mass parts, and adaptation will descend, and does not reach sufficient bond strength, and in case greater than 150 mass parts, adhesion durability is not enough easily.
The preferred organic solvent that uses among the present invention, be to make above-mentioned each composition dissolving or dispersion, and have suitable volatility, with the solvent of isocyanate group anergy, specifically can enumerate toluene, normal hexane, dimethylbenzene, hexanaphthene, methylcyclohexane and methyl ethyl ketone etc.
In the fluid composition that contains above-mentioned each composition and organic solvent, preferred solid component concentration is 5～50 quality %, 10～40 quality % more preferably.
In the present invention, and with the fluid composition and the polyfunctional isocyanate that contain above-mentioned each composition and organic solvent.Promptly, binder composition of the present invention is to utilize the cured with isocyanates reacted composition, polyfunctional isocyanate's usage quantity is preferably, be the amount of 1.0～10.0 scope with respect to the mol ratio (NCO/OH) of the isocyanate group of the hydroxyl in the polyolefin polyol, more preferably this mol ratio is 1.2～8.0 scope.NCO/OH was less than 1.0 o'clock, and adhesion durability reduces, and greater than 10.0 o'clock, bond strength descended easily.
Fluid composition mixes with the polyfunctional isocyanate's, preferably carries out before tackiness agent is about to use usually.After mixing these 2 kinds of compositions, if keep intact long-term the placement, phenomenons such as gelation will take place, become and can not use as tackiness agent.The time that can use as tackiness agent after the mixing be called the serviceable time (quality guaranteed period), and the quality guaranteed period of binder composition of the present invention is according to the kind of compound used therefor and difference is several minutes～a few hours.
As described above according to the polyfunctional isocyanate who uses with other composition blended using method before be about to using, can enumerate tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, isophorone diisocyanate etc., and addition compound modifiers such as tricarbimide is ester modified, biuret modified, TriMethylolPropane(TMP) etc.Specifically can enumerate the CORONET HX of Nippon Polyurethane Industry Co., Ltd.'s production that belongs to the chlorinated isocyanurates modifier and the TAKENATE D-170N of Mitsui Takeda Chemical Co., Ltd's production etc., belong to the TAKENATE D-165N of biuret modified thing etc., belong to CORONET L, the TAKENATE D-102 of TriMethylolPropane(TMP) addition compound modifier and TAKENATE D-140N etc.
Among the present invention, with the block agent isocyanate group is sheltered and the block type polyfunctional isocyanate of stabilization, also can use CORONET2507 that Nippon Polyurethane Industry Co., Ltd. for example produces and CORONET 2513 etc., at this moment, the mixing time to above-mentioned fluid composition and polyfunctional isocyanate is not particularly limited.That is, because placing, a kind of liquid has the secular quality guaranteed period, so also can be with tackiness agent as a kind of liquid manufacturing.
In the binder composition of the present invention that with above-mentioned various compositions serves as necessary composition, also can add other composition.For example, in order to promote polyolefin polyol and polyfunctional isocyanate's reaction, can be added with reaction accelerator, softening agent such as machine tin compound and not belong to the thermoplastic resin (also comprising elastomerics) of mentioned component (A)～(C).As such thermoplastic resin, optimal ethylene-vinyl acetate between to for plastic copolymer resins, ethylene-propylene acetoacetic ester copolymer resins, wax, SEBS or SEPS.As preferred plasticizer, can enumerate liquid rubber and processing wet goods such as polyisoprene, polybutene.
With binder composition adhesive substrate of the present invention the time, form the binder layer (drying) of 3～30 μ m at substrate surface, preferably on it, be called the operation of wanting other base material of bonded that adds hot pressing.The Heating temperature of this moment, preferred 60～150 ℃.Bonded like this base material is preferably being placed a few days thereafter again, is being promoted polyolefin polyol and polyfunctional isocyanate's reaction in 50～80 ℃ environment.
If adopt binder composition of the present invention, but polyolefin resin base materials such as the bonding polyethylene in high strength ground, polypropylene also can be used for the bonding of these materials and other material.For example, after resins such as polyethylene terephthalate or metallic surfaces such as aluminium, copper are coated with this tackiness agent, also can be on it easily bonding polyolefins material.
Embodiment
Below, enumerate embodiment and reference examples, specify the present invention.
(embodiment)
Embodiment 1
In the 500ml flask of condenser and whipping appts is housed, add toluene/methyl ethyl ketone=80/20 of 225g as solvent, 45g is as Tuftec M-1913 (the SEBS class of Asahi Chemical Industry Co., Ltd's production of the thermoplastic elastomer that contains carboxyl, styrene content 30 weight %), 5g is as the PolytelH (molecular weight 3000) of Mitsubishi chemical Co., Ltd's production of polyolefin polyol, 25g is as エ ス コ Star Star 5320HC (the hydrogenation Dicyclopentadiene (DCPD) resinoid of Tonex Co., Ltd. production of tackifier, 125 ℃ of softening temperatures), with respect to above-mentioned thermoplastic elastomer, polyolefin polyol, the total amount of tackifier, adding is as reaction accelerator dibutyltin dilaurate (being designated hereinafter simply as DBTL) 50ppm, 50 ℃ of following heated and stirred of interior temperature 3 hours, obtain composition.
Mix CORONET HX in the above-mentioned composition of cool to room temperature as Nippon Polyurethane Industry Co., Ltd.'s production of polyfunctional isocyanate, making the mol ratio (NCO/OH) of the hydroxyl of isocyanate group and polyolefin polyol is 2.0, obtains binder composition.
According to the bonding gained binder composition of following method, estimate its bond strength.
Zero is bonding: at the thick aluminium of 100 μ m or the single spreading binder solution of polyethylene terephthalate, making dried coating thickness was 10 μ m, according to 100 ℃ * 60 seconds condition drying.On the adhesive coated face, CPP (un-stretched polypropylene) film that the 40 μ m that superpose are thick adds hot pressing according to 80 ℃ * 3 seconds conditions, and is aging under 55 ℃ * 7 days condition.
Zero bond strength is measured: with pinblock speed (cross head speed) 100mm/min measure 23 ℃ with 80 ℃ under 180 ° of peel adhesion strength (N/15mm).
Zero adhesion durability: at bond area 150mm
2Under (15mm wide * 10mm lap), the 100 ℃ of environment, apply shear-type load 1kg, observe the stick portion state of having placed after 24 hours.
Embodiment 2～7
Use solvent, the thermoplastic elastomer that contains carboxyl, polyolefin polyol, tackifier, DBTL and polyfunctional isocyanate with ratio shown in the table 1, obtain binder composition.The binder composition that obtains is carried out similarly to Example 1 evaluation, its result of table 1 expression.And the relevant evaluation result of adhesion durability, the tackiness agent of embodiment 1～7 all is " no change ".
In addition, the details of the described compound of table 1 is as follows.
The carboxylic thermoplastic elastomer (SEBS class, styrene content are 30 quality %) that Claiton FG-1901X:Claiton polymkeric substance Co., Ltd. produces;
Tuftec M-1943: the elastomerics (SEBS class, styrene content are 20 quality %) that Asahi Chemical Industry Co., Ltd produces;
Polytel HA: the polyolefin polyol (molecular weight 2000) that Mitsubishi chemical Co., Ltd produces;
The tackifier (85 ℃ of hydrogenated terpene resin, softening temperatures) that Clearon P-85:Yasuhara KCC produces;
The tackifier (10 ℃ of aliphatic category C5 petroleum resin, softening temperatures) that Wingtac10:Good Year company produces;
CORONET L: the polyfunctional isocyanate that Nippon Polyurethane Industry Co., Ltd. produces.
In addition, in the table 1, the unit that has omitted the numerical value of unit is a mass parts, and Al/CPP has been to use the test film of aluminium and un-stretched polypropylene, and PET/CPP has been to use the test film of polyethylene terephthalate and un-stretched polypropylene.
Reference examples 1
The Clearon P-85 that adds Claiton FG-1901X, the 35g of 340g toluene/methyl ethyl ketone=80/20,50g 50 ℃ of following heated and stirred of interior temperature 3 hours, has obtained binder composition.Below, according to operation similarly to Example 1, estimate the rerum natura of binder composition, table 2 has been put down in writing its result.
Reference examples 2～4
The rerum natura of the binder composition of having estimated described each composition of cooperation table 2 and having obtained, table 2 has been put down in writing its result.In addition, the thermoplastic elastic body C laiton G-1652 that uses in the reference examples 2 is not carboxylic thermoplastic elastomer (a SEBS class).
In the tackiness agent of above-mentioned each reference examples, the evaluation result of the adhesion durability of the tackiness agent of reference examples 1 is " peeling off ".The adhesion durability of the tackiness agent of other reference examples all is " no change ".
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | |
| (A)TuftecM-1913 | 90 | 60 | 40 | 60 | 60 | - | - |
| Claiton FG-1901X | - | - | - | - | - | 60 | - |
| TuftecM-1943 | - | - | - | - | - | - | 60 |
| (B)Polytel H | 10 | - | 30 | - | - | - | - |
| Polytel HA | - | 40 | 30 | 40 | 40 | 40 | 40 |
| (C)エスコツツ5320HC | 50 | 50 | 50 | - | - | 50 | 50 |
| ClearonP-85 | - | - | - | 20 | - | - | - |
| Wingtac10 | - | - | - | - | 80 | - | - |
| Solvent (toluene/MEK) | 450 | 450 | 450 | 360 | 5l0 | 450 | 450 |
| DBTL(ppm) | 50 | 50 | 50 | 50 | 50 | 50 | 50 |
| (D) CORONET HX (NCO/OH mol ratio) | 2.0 | 3.0 | 1.5 | 4.5 | 3.0 | 3.0 | 3.0 |
| 23 ℃ of bond strength (N/15mm) AL/CPP | 9.2 | 8.6 | 7.0 | 7.5 | 6.1 | 9.0 | 7.8 |
| AL/CPP 80℃ | 4.1 | 1.3 | 1.0 | 1.2 | 1.0 | 1.2 | 1.0 |
| PET/CPP 23℃ | 12.9 | 3.9 | 4.1 | 3.5 | 3.5 | 4.2 | 3.7 |
| PET/CPP 80℃ | 3.4 | 3.0 | 2.9 | 2.8 | 2.5 | 2.8 | 2.5 |
Table 2
| Reference examples 1 | Reference examples 2 | Reference examples 3 | Reference examples 4 | |
| (A)TuftecFG-1901X | 100 | - | 60 | - |
| Claiton G-1652 | - | 60 | - | - |
| (B)Polytel H | - | - | 40 | - |
| Polytel HA | - | 40 | - | 100 |
| (C)ClearonP-85 | 70 | 20 | - | 50 |
| Solvent (toluene/MEK) | 510 | 480 | 400 | 450 |
| DBTL(ppm) | - | 50 | 50 | 50 |
| (D) CORONETHX (NCO/OH mol ratio) | - | 3.0 | 3.0 | 3.0 |
| Bond strength (N/15mm) | ||||
| AL/CPP 23℃ | 7.4 | 2.4 | 3.3 | 4.1 |
| AL/CPP 80℃ | 0.7 | 0.4 | 0.3 | 0.3 |
| PET/CPP 23℃ | 6.6 | 2.1 | 2.3 | 5.0 |
| PET/CPP 80℃ | 2.5 | 0.2 | 0.1 | 0.1 |
Utilize possibility on the industry
But the bonding polyolefin resin in adhesive composition high strength of the present invention ground.
Claims (4)
1. a binder composition is characterized in that, contains
Carboxylic thermoplastic elastomer (A), polyolefin polyol (B) and tackifier (C) are dissolved or be dispersed in fluid composition in the organic solvent, and polyfunctional isocyanate (D),
The molecular weight of described polyolefin polyol (B) is 500～5000.
2. binder composition as claimed in claim 1, it is characterized in that, carboxylic thermoplastic elastomer (A) in the described fluid composition is 98/2～20/80 with the mass ratio of polyolefin polyol (B), and the ratio of the tackifier (C) of per 100 mass parts of described (A) and total amount (B) is 5～150 mass parts.
3. binder composition as claimed in claim 1 or 2 is characterized in that, described carboxylic thermoplastic elastomer (A) is the styrene type thermoplastic elastomer that contains carboxyl.
4. the adhesive bonding method of a polyolefin-type base material is characterized in that, uses each described binder composition of claim 1～3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002322532 | 2002-11-06 | ||
| JP322532/2002 | 2002-11-06 |
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| CN1735672A CN1735672A (en) | 2006-02-15 |
| CN1311047C true CN1311047C (en) | 2007-04-18 |
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| CNB2003801083675A Expired - Lifetime CN1311047C (en) | 2002-11-06 | 2003-11-04 | Adhesive composition and method of bonding |
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| JP (1) | JP4360325B2 (en) |
| CN (1) | CN1311047C (en) |
| AU (1) | AU2003301859A1 (en) |
| WO (1) | WO2004041954A1 (en) |
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| JP5463228B2 (en) * | 2009-08-07 | 2014-04-09 | 日東電工株式会社 | Release agent, release material and adhesive tape |
| JP5323666B2 (en) * | 2009-09-29 | 2013-10-23 | 日東電工株式会社 | Release agent, release material and adhesive tape |
| TWI507494B (en) | 2010-12-28 | 2015-11-11 | Toagosei Co Ltd | An adhesive composition and a hot melt adhesive member using the composition |
| WO2012114776A1 (en) * | 2011-02-25 | 2012-08-30 | 東洋インキＳｃホールディングス株式会社 | Laminate for nonaqueous electrolyte secondary cell container, method for producing same, nonaqueous electrolyte secondary cell, and adhesive composition |
| JP2014185190A (en) * | 2011-07-19 | 2014-10-02 | Showa Denko Kk | Adhesive composition for battery exterior material |
| JP2013134823A (en) * | 2011-12-26 | 2013-07-08 | Showa Denko Kk | Battery exterior laminate, battery case using the laminate and battery |
| JPWO2013187216A1 (en) * | 2012-06-14 | 2016-02-04 | 昭和電工株式会社 | Adhesive composition |
| JP6794999B2 (en) | 2016-02-12 | 2020-12-02 | 東洋紡株式会社 | Adhesive composition for low energy surface substrates |
| JP6907927B2 (en) | 2017-01-11 | 2021-07-21 | 東洋インキＳｃホールディングス株式会社 | Adhesive compositions, laminates, packaging materials for power storage devices, containers for power storage devices and power storage devices |
| JP7206685B2 (en) * | 2018-08-09 | 2023-01-18 | 凸版印刷株式会社 | packaging bag |
| CN112708377A (en) * | 2020-12-25 | 2021-04-27 | 烟台德邦科技股份有限公司 | Adhesive for bonding polyolefin low-surface-energy material |
| CN114149735B (en) * | 2022-02-08 | 2022-06-24 | 拓迪化学(上海)有限公司 | Adhesive primer composition and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02145678A (en) * | 1988-11-28 | 1990-06-05 | Sunstar Eng Inc | Urethane rubber adhesive for polyolefin |
| JPH08165460A (en) * | 1994-12-13 | 1996-06-25 | Nitto Denko Corp | Prime-coating agent for tacky adhesive sheet and tacky adhesive sheet produced by using the agent |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07157742A (en) * | 1993-12-07 | 1995-06-20 | Honda Motor Co Ltd | Aqueous adhesive composition and its production |
| JP3503188B2 (en) * | 1994-05-31 | 2004-03-02 | 三菱化学株式会社 | Adhesive composition |
| JPH08157797A (en) * | 1994-12-01 | 1996-06-18 | Mitsubishi Chem Corp | Pressure-sensitive adhesive composition |
-
2003
- 2003-11-04 CN CNB2003801083675A patent/CN1311047C/en not_active Expired - Lifetime
- 2003-11-04 AU AU2003301859A patent/AU2003301859A1/en not_active Abandoned
- 2003-11-04 JP JP2004549596A patent/JP4360325B2/en not_active Expired - Lifetime
- 2003-11-04 WO PCT/JP2003/014044 patent/WO2004041954A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02145678A (en) * | 1988-11-28 | 1990-06-05 | Sunstar Eng Inc | Urethane rubber adhesive for polyolefin |
| JPH08165460A (en) * | 1994-12-13 | 1996-06-25 | Nitto Denko Corp | Prime-coating agent for tacky adhesive sheet and tacky adhesive sheet produced by using the agent |
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| Publication number | Publication date |
|---|---|
| WO2004041954A1 (en) | 2004-05-21 |
| JPWO2004041954A1 (en) | 2006-03-09 |
| AU2003301859A1 (en) | 2004-06-07 |
| JP4360325B2 (en) | 2009-11-11 |
| CN1735672A (en) | 2006-02-15 |
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