CN105209566A - Hot-melt-adhesive composition - Google Patents
Hot-melt-adhesive composition Download PDFInfo
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- CN105209566A CN105209566A CN201480025871.7A CN201480025871A CN105209566A CN 105209566 A CN105209566 A CN 105209566A CN 201480025871 A CN201480025871 A CN 201480025871A CN 105209566 A CN105209566 A CN 105209566A
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- Prior art keywords
- styrene
- hot
- block copolymer
- adhesive composition
- nitrone
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 239000004831 Hot glue Substances 0.000 title claims abstract description 39
- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical class ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 38
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims abstract description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 15
- 239000000155 melt Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229960001866 silicon dioxide Drugs 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 4
- 229920006132 styrene block copolymer Polymers 0.000 abstract description 4
- -1 ammonia ester Chemical class 0.000 description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- 229910021529 ammonia Inorganic materials 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- PBZUAIHRZUBBAJ-UHFFFAOYSA-N 2-hydroxyiminoacetic acid Chemical compound ON=CC(O)=O PBZUAIHRZUBBAJ-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000004902 Softening Agent Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000003712 anti-aging effect Effects 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 238000006352 cycloaddition reaction Methods 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 125000004076 pyridyl group Chemical group 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 125000002769 thiazolinyl group Chemical group 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- MTFJSAGADRTKCI-UHFFFAOYSA-N N-(pyridin-2-ylmethylidene)hydroxylamine Chemical compound ON=CC1=CC=CC=N1 MTFJSAGADRTKCI-UHFFFAOYSA-N 0.000 description 3
- CKRZKMFTZCFYGB-UHFFFAOYSA-N N-phenylhydroxylamine Chemical compound ONC1=CC=CC=C1 CKRZKMFTZCFYGB-UHFFFAOYSA-N 0.000 description 3
- 235000002597 Solanum melongena Nutrition 0.000 description 3
- 244000061458 Solanum melongena Species 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000005012 oleoresinous Substances 0.000 description 3
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000003851 azoles Chemical class 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000012943 hotmelt Substances 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000010734 process oil Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound 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
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 239000013032 Hydrocarbon resin Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000006178 methyl benzyl group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- CLNYHERYALISIR-UHFFFAOYSA-N nona-1,3-diene Chemical class CCCCCC=CC=C CLNYHERYALISIR-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 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
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Inorganic Chemistry (AREA)
Abstract
Provided is a hot-melt-adhesive composition that is highly heat-stable and also exhibits good heat resistance. Said hot-melt-adhesive composition contains a styrene-butadiene block copolymer or copolymers, namely a styrene-butadiene-styrene block copolymer (SBS) and/or a styrene-butadiene-butylene-styrene block copolymer (SBBS), and 1 to 10 mass parts of a nitrone derivative per 100 mass parts of the styrene-butadiene block copolymer(s).
Description
Technical field
The present invention relates to a kind of hot-melt adhesive composition.
Background technology
There is the liquid moisture-curable ammonia ester system hot-melt adhesive of urethane prepolymer as principal constituent of isocyanate group in molecule, as being also referred to as reactive hot-melt caking agent, coat adherend in the molten state, after carrying out cooling curing, carried out the reaction of isocyanate group by the moisture existed in adherend or air, thus form crosslinking structure and solidify.
Therefore, in a liquid moisture-curable ammonia ester system hot-melt adhesive, reacted by the molecular growth of urethane prepolymer, the thermotolerance (such as with reference to patent documentation 1 and 2) higher than other hot-melt adhesive can be demonstrated.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2009-242557 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2011-190309 publication
Summary of the invention
Invent problem to be solved
The present inventor etc. are studied moisture-curable polyurethane hot-melt caking agent described in patent documentation 1 and 2, found that, property stability (hereinafter referred to as " thermostability ") under molten state is poor, there is the foreign matter being mixed with a part of gelation of composition.In addition, find the kind according to adherend, the stripping strength at 120 DEG C is low, thermotolerance is insufficient.
Therefore, problem of the present invention is, provides a kind of excellent heat stability, and the hot-melt adhesive composition that thermotolerance is also good.
For solving the means of problem
The present inventor etc. concentrate on studies to solve above-mentioned problem, found that, by coordinating the nitrone derivative of specified quantitative to the styrene-butadiene block copolymer of regulation, can excellent heat stability be formed, and the hot-melt adhesive composition that thermotolerance is good, thus complete the present invention.
That is, the present inventor waits discovery, solves above-mentioned problem by following integrant.
(1) a kind of hot-melt adhesive composition, containing styrene-butadiene block copolymer and nitrone derivative, above-mentioned styrene-butadiene block copolymer is styrene-butadiene-styrene block copolymer (SBS) and/or styrene butadiene-butylene-styrene segmented copolymer (SBBS), relative to above-mentioned styrene-butadiene block copolymer 100 mass parts, the content of above-mentioned nitrone derivative is 1 ~ 10 mass parts.
(2) the hot-melt adhesive composition according to above-mentioned (1), the ratio (120 DEG C of viscosity/180 DEG C viscosity) of the melt viscosity at the melt viscosity at 120 DEG C and 180 DEG C is more than 7.
(3) the hot-melt adhesive composition according to above-mentioned (2), the melt viscosity at 180 DEG C is below 4000mPas.
(4) the hot-melt adhesive composition according to any one of above-mentioned (1) ~ (3), above-mentioned nitrone derivative is the nitrone with aromatic hydrocarbyl or aromatic heterocycle, and described aromatic hydrocarbyl and aromatic heterocycle can have substituting group.
(5) the hot-melt adhesive composition according to above-mentioned (4), above-mentioned nitrone derivative has carboxyl as described substituting group.
(6) the hot-melt adhesive composition according to any one of above-mentioned (1) ~ (5), relative to above-mentioned styrene-butadiene block copolymer 100 mass parts, the content of silicon-dioxide is below 5 mass parts.
Invention effect
According to the present invention, a kind of excellent heat stability can be provided, and the hot-melt adhesive composition that thermotolerance is also good.
Embodiment
Hot-melt adhesive composition of the present invention is (following, also referred to as " adhesive composite of the present invention ") containing styrene-butadiene block copolymer and nitrone derivative, above-mentioned styrene-butadiene block copolymer is styrene-butadiene-styrene block copolymer (SBS) and/or styrene butadiene-butylene-styrene segmented copolymer (SBBS), relative to above-mentioned styrene-butadiene block copolymer 100 mass parts, the content of above-mentioned nitrone derivative is 1 ~ 10 mass parts.
In the present invention, as mentioned above, by coordinating the nitrone derivative of specified quantitative to the styrene-butadiene block copolymer of regulation, excellent heat stability can be formed, and the hot-melt adhesive composition that thermotolerance is also good.
Its details are not yet clear and definite, but think because under the molten state when mixing or when using, cycloaddition reaction (with reference to following formula (I) and (II)) occurs between the double bond of the divinyl of part or all and above-mentioned styrene-butadiene block copolymer of above-mentioned nitrone derivative, thus above-mentioned styrene-butadiene block copolymer interaction each other (intermolecular forces) improves.It also can be inferred by the following fact: as shown in comparative example described later, in the composition prepared not coordinating above-mentioned nitrone derivative, the melt viscosity at 120 DEG C is low.
In addition, after mixing above-mentioned nitrone derivative and above-mentioned styrene-butadiene block copolymer at the temperature (such as about 160 ~ 180 DEG C) of the molten state when assume that use, by the cleaning such as mixture hexanaphthene or ethyl acetate obtained, then carry out
1when H-NMR (proton magnetic resonance (PMR)) measures, by the chemical shift of the proton of the disappearance of the divinyl (double bond) with above-mentioned styrene-butadiene block copolymer, can confirm above-mentioned cycloaddition reaction occurs.
< styrene-butadiene block copolymer >
Above-mentioned styrene-butadiene block copolymer contained by adhesive composite of the present invention is styrene-butadiene-styrene block copolymer (SBS) and/or styrene butadiene-butylene-styrene segmented copolymer (SBBS).
The styrene content of above-mentioned styrene-butadiene block copolymer is not particularly limited, and about SBS, the mass ratio (phenylethylene/butadiene) of vinylbenzene and divinyl is preferably the amount of 20/80 ~ 50/50, is more preferably the amount of 30/70 ~ 45/55.
Equally, the melt flow rate (MFR) (MFR:200 DEG C, load 5.0kg) of above-mentioned styrene-butadiene block copolymer is not particularly limited, but is preferably less than 100, is more preferably 2 ~ 80.
In such styrene-butadiene block copolymer, as SBS, タ Off プ レ Application (registered trademark) A of Asahi Chemical Industry ケ ミ カ Le ズ Inc., the commercially available product such as 125 and 126S and ア サ プ レ Application (registered trademark) T-411, T-432, T-437, T-438 and T-439 can be used, as SBBS, the commercially available products such as タ Off テ ッ Network (registered trademark) P1000, P1500 and P2000 of Asahi Chemical Industry ケ ミ カ Le ズ Inc. can be used.
In the present invention, except SBS and/or SBBS, as other styrene-butadiene block copolymer, such as can also by styrene isoprene styrene block copolymer (SIS) (SIS), styrene ethylene-propylene-styrene block copolymer (SEPS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS) etc.
Wherein, become better reason from thermostability and consider, preferably and use SEBS.
< nitrone derivative >
Just be not particularly limited in the compound of the nitrogen-atoms of Schiff's base as long as the above-mentioned nitrone derivative contained by adhesive composite of the present invention is oxygen atoms bond.
In the present invention, above-mentioned nitrone derivative, all become better reason from thermostability and thermotolerance to consider, preferably there is the nitrone of aromatic hydrocarbyl or aromatic heterocycle, described aromatic hydrocarbyl and aromatic heterocycle can have substituting group, such as, can enumerate: the nitrone shown in following formula (a).
In formula (a), X and Y separately represents to have substituent aliphatics or aromatic alkyl, and at least one in X or Y represents to have substituent aromatic hydrocarbyl or aromatic heterocycle.
As the aliphatic alkyl shown in X and Y, such as, can enumerate: alkyl, cycloalkyl, thiazolinyl etc.As alkyl, such as can enumerate: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, tert-pentyl, 1-methyl butyl, 2-methyl butyl, 1,2-dimethyl propyl, n-hexyl, n-heptyl, n-octyl etc., wherein, the alkyl of preferred carbonatoms 1 ~ 18, the more preferably alkyl of carbonatoms 1 ~ 6.As cycloalkyl, such as, can enumerate: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl etc., wherein, the cycloalkyl of preferred carbonatoms 3 ~ 10, the more preferably cycloalkyl of carbonatoms 3 ~ 6.As thiazolinyl, such as, can enumerate: vinyl, 1-propenyl, allyl group, pseudoallyl, 1-butylene base, crotyl etc., wherein, the thiazolinyl of preferred carbonatoms 2 ~ 18, the more preferably thiazolinyl of carbonatoms 2 ~ 6.
As the aromatic hydrocarbyl shown in X and Y, such as, can enumerate: aryl, aralkyl etc.
As aryl, such as, can enumerate: phenyl, naphthyl, anthryl, phenanthryl, xenyl etc., wherein, the aryl of preferred carbonatoms 6 ~ 14, the more preferably aryl of carbonatoms 6 ~ 10, further preferred phenyl, naphthyl.
As aralkyl, such as, can enumerate: benzyl, styroyl, hydrocinnamyl etc., wherein, the aralkyl of preferred carbonatoms 7 ~ 13, the more preferably aralkyl of carbonatoms 7 ~ 11, further preferred benzyl.
As the aromatic heterocycle shown in X and Y, such as, can enumerate: pyrryl, furyl, thienyl, pyrazolyl, imidazolyl (imidazolyl),
azoles base, different
azoles base, thiazolyl, isothiazolyl, pyridyl (pyridyl), furyl, thienyl, pyridazinyl, pyrimidyl, pyrazinyl etc.Wherein, preferred pyridyl.
As the substituting group that the alkyl shown in X and Y can have, be not particularly limited and such as can enumerate: the low alkyl group, hydroxyl, amino, nitro, carbonyl, carboxyl, carbonate group, urethano, alkylsulfonyl, alkoxyl group, ester group, halogen atom etc. of carbonatoms 1 ~ 4.
In addition, as having so substituent aromatic hydrocarbyl, such as, can enumerate: tolyl, xylyl etc. have substituent aryl; Methyl-benzyl, Ethylbenzyl, methylphenethyl etc. have substituent aralkyl; Etc..
Nitrone shown in formula (a), as mentioned above, at least one in X or Y in solemnity (a) is for can have substituent aromatic hydrocarbyl or aromatic heterocycle, but improve from the viewpoint of thermotolerance, preferred X and Y is can have substituent aromatic hydrocarbyl or aromatic heterocycle.
In the present invention, above-mentioned nitrone derivative, better from thermostability, and the reason that can improve intermolecular forces is considered, preferably comprise the nitrone with the carboxyl alternatively aromatic hydrocarbyl of base or aromatic heterocycle (following, conveniently, also referred to as " carboxyl nitrone "), such as can enumerate: the nitrone shown in following formula (b).
In formula (b), m and n separately represents the integer of 0 ~ 5, m and n adds up to more than 1.
As the integer shown in m, become good and synthesis becomes easy reason considers, the preferably integer of 0 ~ 2, the more preferably integer of 0 ~ 1 from solubleness in a solvent during synthesis nitrone.
As the integer shown in n, become good and synthesis becomes easy reason considers, the preferably integer of 0 ~ 2, the more preferably integer of 0 ~ 1 from solubleness in a solvent during synthesis nitrone.
In addition, the total (m+n) of m and n, the reason becoming good and reactive excellence from solubleness is in the polymer considered, preferably 1 ~ 4, more preferably 1 ~ 2.
In the present invention, in above-mentioned, illustrative nitrone derivative can be used alone a kind, and also two or more kinds may be used.
Particularly better from thermotolerance, in addition, the reason that economy is also excellent is considered, preferably and with above-mentioned carboxyl nitrone and the nitrone (such as phenylbenzene nitrone etc.) with aromatic hydrocarbyl or the aromatic heterocycle can with functional group's (except carboxyl).
In addition, in the present invention, relative to above-mentioned styrene-butadiene block copolymer 100 mass parts, the content of above-mentioned nitrone derivative is 1 ~ 10 mass parts, from the viewpoint of economy, relative to above-mentioned styrene-butadiene block copolymer 100 mass parts, be preferably 1 ~ 5 mass parts.
The synthetic method > of < nitrone derivative
The synthetic method of above-mentioned nitrone derivative is not particularly limited, and can use existing known method.Such as by the compound with hydroxyl amino (-NHOH) and there is aldehyde radical (-CHO) compound with the mol ratio of 1.5:1 ~ 1:1.5 under organic solvent (such as methyl alcohol, ethanol, tetrahydrofuran (THF) etc.), at room temperature stir 1 ~ 24 hour, make two groups react thus, thus generation have formula "-N
+(-O
-)=CH-" shown in the nitrone of nitrone base.
< additive >
Adhesive composite of the present invention, except above-mentioned styrene-butadiene block copolymer and nitrone derivative, in the scope not damaging object of the present invention and effect, can also contain additive as required further.
As additive, such as, can enumerate: the diene series rubber beyond above-mentioned styrene-butadiene block copolymer and non-diene series rubber, thermoplastic elastomer, catalyzer, weighting agent, softening agent, tenderizer, bonding imparting agent, tackifier, wax, vulcanization accelerator, pigment, dyestuff, antiaging agent, antioxidant, static inhibitor, fire retardant, stablizer, spices, thixotropic agent, UV light absorber, silane coupling agent etc.
In above-mentioned additive, as weighting agent, specifically, such as can enumerate: calcium carbonate, talcum, white carbon black, silicon-dioxide, carbon black etc.
In the present invention, when using silicon-dioxide as weighting agent, the reason better from thermotolerance is considered, its content is preferably below 5 mass parts relative to above-mentioned styrene-butadiene block copolymer 100 mass parts, is more preferably below 4 mass parts.
In addition, as softening agent, specifically, such as can enumerate: the process oil of paraffin series, cycloalkanes hydrocarbon system or fragrant family; The fluid resin such as aqueous polybutene, aqueous polyhutadiene or aqueous polyisoprene; Whiteruss; Alkene operation wet goods.
In addition, as tackifier, such as, can enumerate: Gum Rosin, terpine resin, petroleum resin, coumarone-indene resin etc. or their modifier, hydride.
Wherein, as petroleum resin, can enumerate: using oil as the resin of the aliphatics of raw material, alicyclic, fragrant family, specifically, can preferably illustrate: C5 through-stone oleo-resinous, C9 through-stone oleo-resinous, copolymerization through-stone oleo-resinous, alicyclic saturated hydrocarbon resin, polystyrene petroleum resin etc.
In addition, as antiaging agent, specifically, such as can enumerate: hindered phenol based compound, hindered amine based compound.
The manufacture method of adhesive composite of the present invention is not particularly limited, such as, can enumerate: use known method, device (such as Banbury mixer, kneader, roller etc.) carries out mixing method etc. to above-mentioned each composition.
The ratio (120 DEG C of viscosity/180 DEG C viscosity) of the melt viscosity at the melt viscosity of adhesive material composition of the present invention at 120 DEG C and 180 DEG C is preferably more than 7, is more preferably more than 8.
Equally, the melt viscosity of adhesive material composition of the present invention at 180 DEG C is preferably below 4000mPas, is more preferably below 3000mPas.
If the viscosity at melt viscosity and 180 DEG C is in above-mentioned scope, operability when then adhesive composite of the present invention being applied to adherend (such as coating etc.) becomes good, stripping strength at 120 DEG C becomes higher, and thermotolerance becomes better.
As the parts (adherend) that can use adhesive composite of the present invention, such as, can enumerate: glass; The various metals of aluminium, anodised aluminium, iron, steel plate, steel plate galvanized, copper, stainless steel and so on; The porous part of Mortar Plates, stone material and so on; The parts of application have been carried out by fluorine galvanic deposit, vinylformic acid galvanic deposit or fluorine application, the application of ammonia ester, the application of vinylformic acid ammonia ester; The cured article of the sealing material of polysiloxane series, modified polyorganosiloxane system, ammonia ester system, polythioether system, polyisobutene system and so on; The resin of the polyolefine such as polyethylene, vinyl chloride resin, acrylic resin and so on; The rubber-like of NBR, EPDM and so on.
Embodiment
Below, enumerate embodiment to be specifically described the present invention.But the present invention is not limited to these embodiments.
The synthesis > of < nitrone derivative (carboxyl nitrone)
In 2L eggplant type flask, put into the methyl alcohol (900mL) being heated to 40 DEG C, add the terephthalaldehydic acid (30.0g) shown in following formula (2) wherein and dissolve.In this solution, add the solution phenylhydroxylamine (21.8g) shown in following formula (1) being dissolved in methyl alcohol (100mL), at room temperature stir 19 hours.After stirring terminates, by recrystallization from methyl alcohol, obtain the carboxyl nitrone (41.7g) shown in following formula (3).Yield is 86%.
The synthesis > of < nitrone derivative (pyridyl nitrone)
In 2L eggplant type flask, put into the methyl alcohol (900mL) being heated to 40 DEG C, add the pyridyl carboxylaldehyde acid (21.4g) shown in following formula (5) wherein and dissolve.In this solution, add the solution phenylhydroxylamine (21.8g) shown in following formula (4) being dissolved in methyl alcohol (100mL), at room temperature stir 19 hours.After stirring terminates, by recrystallization from methyl alcohol, obtain the pyridyl nitrone (39.0g) shown in following formula (6).Yield is 90%.
The synthesis > of < nitrone derivative (phenylbenzene nitrone)
The phenyl aldehyde (42.45g) shown in following formula (8) and ethanol (10mL) is put in 300mL eggplant type flask, add the solution phenylhydroxylamine (43.65g) shown in following formula (7) being dissolved in ethanol (70mL) wherein, at room temperature stir 22 hours.After stirring terminates, by recrystallization from ethanol, obtain the phenylbenzene nitrone (65.40g) shown in following formula (9) with the form of white crystals.Yield is 83%.
< embodiment 1 ~ 13>
Composition shown in following table 1 is coordinated with the ratio (mass parts) shown in following table 1.
Specifically, first, the temperature in container being set as adding styrene-butadiene block copolymer and softening agent in the Glass Containers of 160 DEG C, after mixing 5 minutes, nitrone derivative is added, more mixing 10 minutes.
Then, the temperature in Glass Containers is set as 130 DEG C, absorb fillers and tackifier, after mixing 10 minutes, adds antiaging agent, more mixing 5 minutes.
Then, take out mixture and cool, being prepared into hot-melt adhesive composition thus.
< embodiment 14>
Composition shown in following table 1 is coordinated with the ratio (mass parts) shown in following table 1.
Specifically, the temperature in Glass Containers during mixing styrene-butadiene block copolymer etc. is set as 130 DEG C, in addition, prepares hot-melt adhesive composition by method similarly to Example 1.
< comparative example 1 ~ 4>
Composition shown in following table 1 is coordinated with the ratio (mass parts) shown in following table 1.
Specifically, do not coordinate nitrone derivative, in addition, prepare hot-melt adhesive composition by the method same with embodiment 1 ~ 12.
< comparative example 5 and 6>
Use commercially available ammonia ester system hot-melt adhesive composition (ammonia ester system HM).
For each hot-melt adhesive composition, measure physical property shown below by method shown below.Their result is shown in following table 1.
(melt viscosity and melt viscosity ratio)
Single cylinder rotary viscosimeter is used to measure the melt viscosity of each hot-melt adhesive composition at 120 DEG C, 140 DEG C, 160 DEG C and 180 DEG C (mPas).
In addition, the ratio (120 DEG C of viscosity/180 DEG C viscosity) of the melt viscosity at melt viscosity at 120 DEG C and 180 DEG C is calculated by measurement result.
(softening temperature)
By measuring the softening temperature (DEG C) of each hot-melt adhesive composition according to the ring method employing glycerol bath of JISK6863:1994.
(stripping strength)
Make each hot-melt adhesive composition 180 DEG C of meltings, be coated in this condition on pet substrate (width: 25mm), and then the pet substrate of same size of fitting, slowly cool to room temperature, be made into test film.
At 25 DEG C, carry out 180 degree of stripping tests that the adherend in the test film of making (pet substrate) is peeled off each other, measure the intensity (g/25mm) when peeling off.
At 120 DEG C, carry out same stripping test, measure the intensity (g/25mm) when peeling off.
(thermostability)
Place under the state making the melting at 180 DEG C of each hot-melt adhesive composition 72 hours.
Confirm that placement has foreign (gelation shape thing) after 72 hours.If there is no foreign matter, then can be evaluated as excellent heat stability, if there is foreign matter, then can be evaluated as poor heat stability.
By the hot-melt adhesive composition cyclohexane of preparation in embodiment 1 and embodiment 14, only after isolating polymer, carry out
1h-NMR (proton magnetic resonance (PMR)) measures.
Comparative determination result, the polymkeric substance that result to be derived from embodiment 1 the hot-melt adhesive composition of preparation can confirm the chemical shift of the proton of the disappearance of the divinyl (double bond) with above-mentioned styrene-butadiene block copolymer, between the double bond that can confirm a part for nitrone derivative and the divinyl of styrene-butadiene block copolymer, cycloaddition reaction (with reference to above-mentioned formula (I)) occurs.
Table 1 (its 1)
Table 1 (its 2)
Table 1 (its 3)
The details of each composition shown in above-mentioned table 1 is as described below.
SBS1: ア サ プ レ Application T-439 (phenylethylene/butadiene mass ratio: 45/55, Asahi Chemical Industry ケ ミ カ Le ズ Inc.)
SBS2: ア サ プ レ Application T-432 (phenylethylene/butadiene mass ratio: 30/70, Asahi Chemical Industry ケ ミ カ Le ズ Inc.)
SBBS: タ Off テ ッ Network P1000 (phenylethylene/butadiene mass ratio: 30/70, Asahi Chemical Industry ケ ミ カ Le ズ Inc.)
Nitrone derivative: use carboxyl nitrone, pyridyl nitrone, the phenylbenzene nitrone by the synthesis of above-mentioned method.
Weighting agent (silicon-dioxide): ア エ ロ ジ Le 200 (Japanese ア エ ロ ジ Le Inc.)
Tackifier (terpine resin): Network リ ア ロ Application M105 (ヤ ス Ha ラ ケ ミ カ Le Inc.)
Tackifier (petroleum resin): ECR5600 (ト ー ネ ッ Network ス Inc.)
Softening agent (process oil): ダ イ ア Na Off レ シ ア S32 (bright dipping Xing Chan Inc.)
Antiaging agent (hindered phenol system): イ Le ガ ノ ッ Network ス 1010 (BASF AG's system)
Ammonia ester system HM1: タ イ フ ォ ー ス FH-100 (DIC Inc.)
Ammonia ester system HM2: Ha イ ボ Application 4832SA (Hitachi changes into Inc.)
From the result shown in above-mentioned table 1, if be used as the ammonia ester system hot-melt adhesive composition of commercially available product, then poor heat stability, in addition, the stripping strength (thermotolerance) at 120 DEG C poor (comparative example 5 and 6).
In addition, knownly do not coordinate nitrone derivative and the good thermal stability of the hot-melt adhesive composition of the comparative example 1 ~ 4 prepared, but stripping strength (thermotolerance) at 120 DEG C is poor.
On the other hand, the good thermal stability of the hot-melt adhesive composition of the embodiment 1 ~ 14 that the known styrene-butadiene block copolymer to regulation coordinates the nitrone derivative of specified quantitative and prepares, the stripping strength (thermotolerance) at 120 DEG C is also good.
If particularly comparing embodiment 1 and comparative example 1, the then known presence or absence according to nitrone derivative, melt viscosity at 120 DEG C rises nearly 2 times, and the melt viscosity at 180 DEG C is equal extent, by adding nitrone derivative, not only thermostability and thermotolerance improve, and the operability etc. during coating also significantly improves.
In addition, from the contrast of embodiment 6 and 7 and embodiment 13, if be below 5 mass parts as the content of the silicon-dioxide of weighting agent, then the stripping strength (thermotolerance) at having 120 DEG C becomes good tendency.
In addition, from the contrast of embodiment 1 and embodiment 14, if mixing time temperature high, then the stripping strength (thermotolerance) at having 120 DEG C becomes good tendency.Think that above-mentioned styrene-butadiene block copolymer interaction each other (intermolecular forces) improves thus because there is cycloaddition reaction (with reference to above-mentioned formula (I)) between the double bond of the divinyl of part or all and above-mentioned styrene-butadiene block copolymer of above-mentioned nitrone derivative described above.
Claims (6)
1. a hot-melt adhesive composition, containing styrene-butadiene block copolymer and nitrone derivative, described styrene-butadiene block copolymer is styrene-butadiene-styrene block copolymer and SBS and/or styrene butadiene-butylene-styrene segmented copolymer and SBBS, relative to described styrene-butadiene block copolymer 100 mass parts, the content of described nitrone derivative is 1 ~ 10 mass parts.
2. hot-melt adhesive composition according to claim 1, ratio i.e. 120 DEG C of viscosity/180 DEG C viscosity of the melt viscosity at the melt viscosity at 120 DEG C and 180 DEG C are more than 7.
3. hot-melt adhesive composition according to claim 2, the melt viscosity at 180 DEG C is below 4000mPas.
4. the hot-melt adhesive composition according to any one of claims 1 to 3, described nitrone derivative is the nitrone with aromatic hydrocarbyl or aromatic heterocycle, and described aromatic hydrocarbyl and aromatic heterocycle can have substituting group.
5. hot-melt adhesive composition according to claim 4, described nitrone derivative has carboxyl as described substituting group.
6. the hot-melt adhesive composition according to any one of Claims 1 to 5, relative to described styrene-butadiene block copolymer 100 mass parts, the content of silicon-dioxide is below 5 mass parts.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013046627A JP5578249B1 (en) | 2013-03-08 | 2013-03-08 | Hot melt adhesive composition |
| JP2013-046627 | 2013-03-08 | ||
| PCT/JP2014/055975 WO2014136940A1 (en) | 2013-03-08 | 2014-03-07 | Hot-melt-adhesive composition |
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| CN105209566A true CN105209566A (en) | 2015-12-30 |
| CN105209566B CN105209566B (en) | 2017-12-05 |
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| JP (1) | JP5578249B1 (en) |
| KR (1) | KR101622324B1 (en) |
| CN (1) | CN105209566B (en) |
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| JP6024781B2 (en) * | 2015-03-19 | 2016-11-16 | 横浜ゴム株式会社 | Rubber composition for tire tread and pneumatic tire |
| AU2017246738B2 (en) | 2016-04-08 | 2019-08-22 | Avery Dennison Corporation | Clear hot melt adhesives |
| WO2018070676A1 (en) * | 2016-10-14 | 2018-04-19 | 박희대 | Reactive hot melt resin composition and reactive hot melt film manufactured from resin |
| JP6716705B2 (en) * | 2017-02-17 | 2020-07-01 | 積水フーラー株式会社 | Hot melt adhesive and stretchable laminate |
| JP6621126B1 (en) * | 2018-09-25 | 2019-12-18 | 積水フーラー株式会社 | Hot melt coating agent for electronic circuit mounting boards |
| JP7060885B2 (en) * | 2019-12-11 | 2022-04-27 | 誠泰工業科技股▲分▼有限公司 | Eco-waterproof hot melt adhesive composition, its film material and manufacturing method |
| KR102309698B1 (en) | 2020-01-16 | 2021-10-07 | 주식회사 이레A.T (에이티) | Hot melt adhesive with excellent durability and adhesion |
| JPWO2022181690A1 (en) * | 2021-02-26 | 2022-09-01 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2137619A (en) * | 1983-03-30 | 1984-10-10 | Gerald Scott | Nitrone compounds and stabilised rubber compositions containing them |
| CN101932644A (en) * | 2007-12-12 | 2010-12-29 | 海因里希-海涅大学 | Polynitrons, and use thereof for cross-linking unsaturated polymers |
| WO2012010570A1 (en) * | 2010-07-22 | 2012-01-26 | Basf Se | Additive combination for sealants applications |
| JP2013032471A (en) * | 2011-08-03 | 2013-02-14 | Yokohama Rubber Co Ltd:The | Rubber composition |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1984003883A1 (en) * | 1983-03-30 | 1984-10-11 | Gerald Scott | Stabilised rubber compositions |
| JP4814047B2 (en) * | 2006-10-25 | 2011-11-09 | 三菱電機株式会社 | Liquid thermosetting resin composition and insulated coil using the same |
| JP5292891B2 (en) | 2008-03-31 | 2013-09-18 | Ｄｉｃ株式会社 | Moisture-cure polyurethane hot melt adhesive, and fabricated member using the same |
| JP5471639B2 (en) | 2010-03-12 | 2014-04-16 | Ｄｉｃ株式会社 | Moisture curable polyurethane hot melt adhesive and cosmetic product obtained using the same |
-
2013
- 2013-03-08 JP JP2013046627A patent/JP5578249B1/en active Active
-
2014
- 2014-03-07 WO PCT/JP2014/055975 patent/WO2014136940A1/en active Application Filing
- 2014-03-07 CN CN201480025871.7A patent/CN105209566B/en not_active Expired - Fee Related
- 2014-03-07 KR KR1020157025286A patent/KR101622324B1/en active IP Right Grant
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2015
- 2015-09-07 PH PH12015501989A patent/PH12015501989B1/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2137619A (en) * | 1983-03-30 | 1984-10-10 | Gerald Scott | Nitrone compounds and stabilised rubber compositions containing them |
| CN101932644A (en) * | 2007-12-12 | 2010-12-29 | 海因里希-海涅大学 | Polynitrons, and use thereof for cross-linking unsaturated polymers |
| WO2012010570A1 (en) * | 2010-07-22 | 2012-01-26 | Basf Se | Additive combination for sealants applications |
| JP2013032471A (en) * | 2011-08-03 | 2013-02-14 | Yokohama Rubber Co Ltd:The | Rubber composition |
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| JP2014172995A (en) | 2014-09-22 |
| KR20150142674A (en) | 2015-12-22 |
| PH12015501989A1 (en) | 2016-01-11 |
| CN105209566B (en) | 2017-12-05 |
| JP5578249B1 (en) | 2014-08-27 |
| PH12015501989B1 (en) | 2016-01-11 |
| WO2014136940A1 (en) | 2014-09-12 |
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