JPH04309588A - Pressure-sensitive adhesive or adhesive composition - Google Patents
Pressure-sensitive adhesive or adhesive compositionInfo
- Publication number
- JPH04309588A JPH04309588A JP3103216A JP10321691A JPH04309588A JP H04309588 A JPH04309588 A JP H04309588A JP 3103216 A JP3103216 A JP 3103216A JP 10321691 A JP10321691 A JP 10321691A JP H04309588 A JPH04309588 A JP H04309588A
- Authority
- JP
- Japan
- Prior art keywords
- adhesive composition
- adhesive
- molecule
- isoprene
- conjugated diene
- 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
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 15
- 239000000853 adhesive Substances 0.000 title abstract description 35
- 230000001070 adhesive effect Effects 0.000 title abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 22
- -1 isocyanate compound Chemical class 0.000 claims abstract description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 15
- 239000012948 isocyanate Substances 0.000 claims abstract description 13
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims description 28
- 150000001993 dienes Chemical class 0.000 claims description 15
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 9
- VLLYOYVKQDKAHN-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene Chemical compound C=CC=C.CC(=C)C=C VLLYOYVKQDKAHN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 abstract description 14
- 238000000576 coating method Methods 0.000 abstract description 14
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 5
- 229920000428 triblock copolymer Polymers 0.000 abstract 1
- 229920001400 block copolymer Polymers 0.000 description 19
- 238000000034 method Methods 0.000 description 17
- 239000002904 solvent Substances 0.000 description 15
- 238000005984 hydrogenation reaction Methods 0.000 description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000000379 polymerizing effect Effects 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 239000002390 adhesive tape Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920001195 polyisoprene Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000005909 Kieselgur Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 150000003505 terpenes Chemical class 0.000 description 3
- 235000007586 terpenes Nutrition 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 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 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 2
- 239000010734 process oil Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 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 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-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
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- SGBDRKZSMKKNHE-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C Chemical compound N=C=O.N=C=O.N=C=O.C SGBDRKZSMKKNHE-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- VYBREYKSZAROCT-UHFFFAOYSA-N alpha-myrcene Natural products CC(=C)CCCC(=C)C=C VYBREYKSZAROCT-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 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
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 239000012765 fibrous filler Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 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
- 150000002576 ketones Chemical class 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- MSFGZHUJTJBYFA-UHFFFAOYSA-M sodium dichloroisocyanurate Chemical compound [Na+].ClN1C(=O)[N-]C(=O)N(Cl)C1=O MSFGZHUJTJBYFA-UHFFFAOYSA-M 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、塗工直後の初期凝集力
と高温時における凝集力の改良された２液硬化型粘・接
着剤に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a two-component curing adhesive/adhesive having improved initial cohesive force immediately after coating and cohesive force at high temperatures.
【０００２】0002
【従来の技術】従来より、天然ゴムなどを有機溶剤に溶
解して使用する溶剤型粘着剤が広く使用されている。し
かしながらこれらの粘着剤は、ポリマー中に架橋点を持
たないために、高温時における凝集力に問題があり、使
用される分野が限定されているのが現状である。2. Description of the Related Art Conventionally, solvent-based adhesives in which natural rubber or the like is dissolved in an organic solvent have been widely used. However, since these adhesives do not have crosslinking points in the polymer, they have problems with cohesive strength at high temperatures, and the fields in which they are used are currently limited.
【０００３】また、高温時における凝集力を発現させる
ために、混合、加熱することにより架橋点を形成させる
２液硬化型の粘着剤も市販されている。しかしながら、
これらの２液硬化型粘着剤は、硬化反応が速すぎるとポ
ットライフ、塗工性に問題が生じ、硬化反応が遅すぎる
と塗工直後の初期凝集力が不足するという問題が生じる
ため使用される分野が限定されているのが現状である。[0003] Furthermore, in order to develop cohesive force at high temperatures, two-component curing adhesives are also commercially available, which form crosslinking points by mixing and heating. however,
These two-component curing adhesives are not used because if the curing reaction is too fast, there will be problems with pot life and coating properties, and if the curing reaction is too slow, there will be a problem of insufficient initial cohesive force immediately after coating. Currently, the fields in which it can be used are limited.
【０００４】0004
【発明が解決しようとする課題】本発明は、塗工直後の
初期凝集力に優れ、かつ高温時における凝集力にも優れ
る２液硬化型粘・接着剤組成物を得ることを目的とする
。SUMMARY OF THE INVENTION An object of the present invention is to obtain a two-component curing adhesive/adhesive composition that has excellent initial cohesive force immediately after coating and also has excellent cohesive force at high temperatures.
【０００５】[0005]
【課題を解決するための手段】本発明者らは検討の結果
、（ａ）芳香族ビニルモノマーからなるブロックと、共
役ジエンモノマーからなるブロックと、芳香族ビニルモ
ノマーからなるブロックとからなるブロックから構成さ
れるブロック共重合体において、共役ジエンからなるブ
ロックの炭素−炭素二重結合の５０％以上が水素添加さ
れたブロック共重合体と、（ｂ）水酸基を有するイソプ
レンまたはイソプレン−ブタジエン混合物の重合体であ
って、分子中の炭素−炭素二重結合の５０％以上が水素
添加された液状重合体と、（ｃ）イソシアネート化合物
を必須成分とすることにより、（ａ）成分により塗工直
後の初期凝集力に優れ、（ｂ）成分と（ｃ）成分の混合
、加熱による架橋点の形成により高温時の凝集力にも優
れる粘・接着剤組成物が得られることを見出した。[Means for Solving the Problems] As a result of studies, the present inventors have found that (a) a block consisting of a block consisting of an aromatic vinyl monomer, a block consisting of a conjugated diene monomer, and a block consisting of an aromatic vinyl monomer; In the block copolymer constituted, a block copolymer in which 50% or more of the carbon-carbon double bonds of the block consisting of a conjugated diene is hydrogenated, and (b) a polymer of isoprene or an isoprene-butadiene mixture having a hydroxyl group. By combining a liquid polymer in which 50% or more of the carbon-carbon double bonds in the molecule are hydrogenated, and (c) an isocyanate compound as essential components, the (a) component immediately after coating It has been found that a pressure-sensitive adhesive composition that has excellent initial cohesive force and also has excellent cohesive force at high temperatures can be obtained by mixing components (b) and (c) and forming crosslinking points by heating.
【０００６】すなわち本発明によれば、上記目的は、（
ａ）少なくとも２つの芳香族ビニルモノマーからなるブ
ロックと少なくとも１つの共役ジエンモノマーからなる
ブロックからなり、該共役ジエンモノマーからなるブロ
ックの炭素−炭素二重結合の５０％以上が水素添加され
たブロック共重合体、（ｂ）１分子中に１．５〜５．０
個の水酸基を有するイソプレンまたはイソプレン−ブタ
ジエン混合物からなり、分子中の炭素−炭素二重結合の
５０％以上が水素添加された数平均分子量が７００〜７
０００の液状重合体、および（ｃ）イソシアネート化合
物を必須成分とする粘・接着剤組成物により達成される
。That is, according to the present invention, the above object is achieved by (
a) A block conjugate consisting of a block consisting of at least two aromatic vinyl monomers and a block consisting of at least one conjugated diene monomer, in which 50% or more of the carbon-carbon double bonds of the block consisting of the conjugated diene monomer are hydrogenated. Polymer, (b) 1.5 to 5.0 per molecule
It is made of isoprene or isoprene-butadiene mixture having hydroxyl groups, and has a number average molecular weight of 700 to 7, with at least 50% of the carbon-carbon double bonds in the molecule being hydrogenated.
000 liquid polymer and (c) an isocyanate compound as essential components.
【０００７】本発明において使用される、ブロック共重
合体（ａ）を構成する芳香族ビニルモノマーからなるブ
ロックは、スチレン、α−メチルスチレン、パラメチル
スチレン、ビニルナフタレンなどから選ばれた１種また
は２種以上のモノマーを重合することにより得られ、共
役ジエンモノマーからなるブロックはイソプレン、ブタ
ジエン、ミルセン、シクロペンタジエンなどから選ばれ
る１種または２種以上のモノマーを重合することにより
得られる。これらの共役ジエンモノマーのうち、得られ
るブロック共重合体の粘着性能、低温特性などの観点か
ら、イソプレンが最も好ましい。このブロック共重合体
は共役ジエンモノマーからなるブロックの炭素−炭素二
重結合の５０％以上が水素添加されていることが必要で
ある。水素添加率（水添率）が５０％より低い場合は、
得られる粘・接着剤組成物の耐候性、耐熱性などに問題
があり好ましくない。The block consisting of an aromatic vinyl monomer constituting the block copolymer (a) used in the present invention is one selected from styrene, α-methylstyrene, paramethylstyrene, vinylnaphthalene, etc. It is obtained by polymerizing two or more types of monomers, and a block consisting of a conjugated diene monomer is obtained by polymerizing one or more types of monomers selected from isoprene, butadiene, myrcene, cyclopentadiene, etc. Among these conjugated diene monomers, isoprene is most preferred from the viewpoint of adhesive performance, low temperature properties, etc. of the resulting block copolymer. In this block copolymer, it is necessary that 50% or more of the carbon-carbon double bonds in the block made of the conjugated diene monomer are hydrogenated. If the hydrogenation rate (hydrogenation rate) is lower than 50%,
This is not preferred because the resulting adhesive/adhesive composition has problems with weather resistance, heat resistance, etc.
【０００８】またこのブロック共重合体は、分子量が３
０，０００〜５００，０００の範囲にあることが好まし
く、また芳香族ビニルモノマーからなるブロックについ
ては分子量が４，０００〜８０，０００の範囲にあるこ
と、さらには芳香族ビニルモノマーからなるブロックと
共役ジエンモノマーからなるブロックの重量比が５／９
５〜５０／５０の範囲で、かつ共役ジエンモノマーから
なるブロックの１，４−結合量が５０％以上であること
が望ましい。Furthermore, this block copolymer has a molecular weight of 3
The molecular weight is preferably in the range of 0,000 to 500,000, and the molecular weight of the block made of aromatic vinyl monomer is preferably in the range of 4,000 to 80,000. The weight ratio of blocks consisting of conjugated diene monomers is 5/9
It is desirable that the ratio is in the range of 5 to 50/50, and that the amount of 1,4-bonds in the block consisting of the conjugated diene monomer is 50% or more.
【０００９】ブロック共重合体の分子量が上記範囲より
小さい場合は、得られる粘着剤の凝集力が十分でなく、
上記範囲より大きい場合は、得られる粘着剤の柔軟性が
十分でないことがある。また芳香族ビニルモノマーから
なるブロックの分子量が上記範囲より小さい場合は、粘
着剤の初期凝集力が十分でなく、逆に上記範囲より大き
い場合は、得られる粘着剤の低温特性が損なわれ好まし
くない。さらに芳香族ビニルモノマーからなるブロック
と共役ジエンモノマーからなるブロックの重量比が５／
９５より小さい場合も得られる粘着剤の凝集力が十分で
なく、５０／５０より大きい場合は、得られる粘着剤の
柔軟性が十分でないことがある。さらに共役ジエンモノ
マーからなるブロックの１，４−結合量が５０％より小
さい場合には低温での柔軟性が失われ、十分な粘着性能
が発現しないことがある。[0009] If the molecular weight of the block copolymer is smaller than the above range, the cohesive force of the resulting adhesive will not be sufficient;
If it is larger than the above range, the resulting adhesive may not have sufficient flexibility. In addition, if the molecular weight of the block consisting of aromatic vinyl monomer is smaller than the above range, the initial cohesive force of the adhesive will not be sufficient, and if it is larger than the above range, the low temperature properties of the obtained pressure sensitive adhesive will be impaired, which is undesirable. . Furthermore, the weight ratio of the block consisting of the aromatic vinyl monomer and the block consisting of the conjugated diene monomer is 5/5.
If it is smaller than 95, the resulting adhesive may not have sufficient cohesive force, and if it is larger than 50/50, the resulting adhesive may not have sufficient flexibility. Furthermore, if the amount of 1,4-bonds in the block made of the conjugated diene monomer is less than 50%, flexibility at low temperatures may be lost and sufficient adhesive performance may not be developed.
【００１０】かかるブロック共重合体の未水添物はアニ
オン重合により得られる。その合成例としてブチルリチ
ウムなどのアルキルリチウムを触媒として芳香族ビニル
モノマー、共役ジエンモノマーをそれぞれ順次重合する
方法、またはブチルリチウムなどのアルキルリチウムを
触媒として芳香族ビニルモノマー、共役ジエンモノマー
をそれぞれ順次重合したのち、カップリング剤により高
重合体を得る方法などが例示される。これらの方法にお
いて溶媒はシクロヘキサン、トルエンなどの炭化水素系
溶媒が用いられる。このブロック共重合体の水素添加は
公知の方法にしたがって行うことができる。その例とし
ては、例えば遷移金属有機化合物アルミニウム、アルカ
リ土類金属もしくはアルカリ金属などのアルキル化物と
の組み合わせによるチーグラー系触媒のような均一系触
媒、あるいはニッケル、銅−クロム、パラジウム、白金
などの金属を単独あるいは炭素、シリカ、けいそう土な
どに担持した不均一系触媒を用い、水素と反応させる方
法が採られる。反応条件としては常温〜２００℃、常圧
〜１００ｋｇ／ｃｍ２ の水素ガスと０．１〜１００時
間接触させる方法などが例示される。これらの水素添加
反応において反応の制御の点などから溶媒を用いてもよ
く、シクロヘキサンなどの炭化水素系溶媒が用いられる
。[0010] Such an unhydrogenated block copolymer can be obtained by anionic polymerization. As an example of its synthesis, an aromatic vinyl monomer and a conjugated diene monomer are sequentially polymerized using an alkyllithium such as butyllithium as a catalyst, or an aromatic vinyl monomer and a conjugated diene monomer are sequentially polymerized using an alkyllithium such as butyllithium as a catalyst. After that, a method of obtaining a high polymer using a coupling agent is exemplified. In these methods, hydrocarbon solvents such as cyclohexane and toluene are used as solvents. Hydrogenation of this block copolymer can be performed according to a known method. Examples include homogeneous catalysts such as Ziegler catalysts in combination with alkylated substances such as transition metal organic compounds aluminum, alkaline earth metals or alkali metals, or metals such as nickel, copper-chromium, palladium and platinum. A method of reacting with hydrogen using a heterogeneous catalyst, such as one or supported on carbon, silica, diatomaceous earth, etc., is adopted. Examples of reaction conditions include a method of contacting with hydrogen gas at room temperature to 200° C. and normal pressure to 100 kg/cm 2 for 0.1 to 100 hours. In these hydrogenation reactions, a solvent may be used from the viewpoint of reaction control, and hydrocarbon solvents such as cyclohexane are used.
【００１１】つぎに本発明において使用される液状重合
体（ｂ）の数平均分子量は７００〜７０００の範囲にあ
ることが必要である。数平均分子量が上記範囲より小さ
い場合は、得られる粘・接着剤組成物が良好な粘着性能
を示さないため好ましくない。また上記範囲より大きい
場合は、得られる粘・接着剤組成物の耐熱性が不十分と
なり好ましくない。また液状重合体（ｂ）は１分子中に
１．５〜５．０個の水酸基を有することが必要である。
１分子中の水酸基が１．５個より少ない場合、得られる
粘・接着剤組成物中の架橋密度が低すぎ、良好な耐熱性
が得られず好ましくない。１分子中の水酸基が５．０個
より多い場合は、得られる粘・接着剤組成物中の架橋密
度が高すぎ、良好なゴム弾性が得られず好ましくない。
なおこの水酸基は、分子鎖の末端、分子鎖中のいずれに
あってもよく、分子鎖と水酸基の間に両者をつなぐ官能
基を有していてもよい。さらにこの液状重合体（ｂ）は
分子中の炭素−炭素二重結合の５０％以上が水素添加さ
れていることが必要である。水素添加率が５０％より低
い場合は、炭素−炭素二重結合の劣化から得られる粘・
接着剤組成物の耐熱性が不十分となり好ましくない。さ
らにこの液状重合体（ｂ）の１，４−結合量は５０％以
上であることが望ましい。１，４−結合量が５０％より
小さい場合、得られる粘・接着剤組成物の低温での柔軟
性が失われ、十分な粘着性能が発現しないことがある。Next, the number average molecular weight of the liquid polymer (b) used in the present invention must be in the range of 700 to 7,000. If the number average molecular weight is smaller than the above range, the resulting pressure-sensitive adhesive composition will not exhibit good adhesive performance, which is not preferred. Moreover, if it is larger than the above range, the resulting adhesive/adhesive composition will have insufficient heat resistance, which is not preferable. Further, the liquid polymer (b) needs to have 1.5 to 5.0 hydroxyl groups in one molecule. If the number of hydroxyl groups in one molecule is less than 1.5, the crosslinking density in the resulting pressure-sensitive adhesive composition is too low and good heat resistance cannot be obtained, which is not preferable. If the number of hydroxyl groups in one molecule is more than 5.0, the crosslinking density in the resulting pressure-sensitive adhesive composition is too high and good rubber elasticity cannot be obtained, which is not preferable. The hydroxyl group may be located at the end of the molecular chain or within the molecular chain, and a functional group may be present between the molecular chain and the hydroxyl group to connect the two. Furthermore, it is necessary that 50% or more of the carbon-carbon double bonds in the molecule of this liquid polymer (b) be hydrogenated. If the hydrogenation rate is lower than 50%, the viscosity obtained from the deterioration of carbon-carbon double bonds
The heat resistance of the adhesive composition becomes insufficient, which is undesirable. Furthermore, it is desirable that the amount of 1,4-bonds in this liquid polymer (b) is 50% or more. If the amount of 1,4-bonds is less than 50%, the resulting pressure-sensitive adhesive composition may lose flexibility at low temperatures and may not exhibit sufficient adhesive performance.
【００１２】かかる液状重合体の未水添物は、例えばラ
ジカル重合により得られる。その合成例としてイソプレ
ンモノマーを過酸化水素、水酸基を有するアゾ化合物（
例えば、２，２′−アゾビス［２−メチル−Ｎ−（２−
ヒドロキシエチル）−プロピオンアミド］）などを重合
開始剤として重合する方法などがあげられる。これらの
方法において溶媒はエタノール、プロパノールなどのア
ルコール系溶媒などが用いられる。また、かかる液状重
合体の未水添物はアニオン重合によっても得られる。
その合成例としてイソプレンモノマーを、ジリチウム化
合物などをジアニオン系の重合開始剤として用いて重合
し、エチレンオキシド、プロピレンオキシドなどと反応
させる方法などがあげられる。これらの方法において溶
媒はヘキサン、シクロヘキサンなどの炭化水素系溶媒な
どが用いられる。この液状重合体の水素添加も公知方法
にしたがって行うことができる。その例としては、ニッ
ケル、銅−クロム、パラジウム、白金などの金属を単独
あるいは炭素、シリカ、けいそう土などに担持した不均
一系触媒を用い、水素と反応させる方法などが採られる
。反応条件としては常温〜２００℃、常圧〜１００ｋｇ
／ｃｍ２ の水素ガスと０．１〜１００時間接触させる
方法などが例示される。これらの水素添加反応において
反応の制御の点などから溶媒を用いてもよく、シクロヘ
キサンなどの炭化水素系溶媒、テトラヒドロフランなど
のエーテル系溶媒、エタノールなどのアルコール系溶媒
などが例示される。[0012] Such an unhydrogenated liquid polymer can be obtained, for example, by radical polymerization. As an example of its synthesis, isoprene monomer is converted into hydrogen peroxide, an azo compound having a hydroxyl group (
For example, 2,2'-azobis[2-methyl-N-(2-
Examples include a method of polymerizing using hydroxyethyl)-propionamide]) as a polymerization initiator. In these methods, alcoholic solvents such as ethanol and propanol are used as solvents. Moreover, such an unhydrogenated liquid polymer can also be obtained by anionic polymerization. An example of its synthesis is a method in which isoprene monomer is polymerized using a dilithium compound or the like as a dianionic polymerization initiator, and then reacted with ethylene oxide, propylene oxide, or the like. In these methods, hydrocarbon solvents such as hexane and cyclohexane are used as solvents. Hydrogenation of this liquid polymer can also be carried out according to known methods. An example of this is a method in which a heterogeneous catalyst in which a metal such as nickel, copper-chromium, palladium, or platinum is used alone or supported on carbon, silica, diatomaceous earth, or the like is used to react with hydrogen. Reaction conditions are room temperature to 200°C, normal pressure to 100 kg.
For example, a method of contacting with hydrogen gas of /cm2 for 0.1 to 100 hours is exemplified. In these hydrogenation reactions, a solvent may be used from the viewpoint of reaction control, and examples thereof include hydrocarbon solvents such as cyclohexane, ether solvents such as tetrahydrofuran, and alcohol solvents such as ethanol.
【００１３】さらに本発明においてイソシアネート化合
物（ｃ）は、１分子中に２個以上のイソシアネート基を
有するものが用いられる。１分子中に２個のイソシアネ
ート基を有する化合物としては、トリレンジイソシアネ
ート、ジフェニルメタンジイソシアネート、ヘキサメチ
レンジイソシアネート、イソホロンジイソシアネートな
どが挙げられ、１分子中に３個のイソシアネート基を有
する化合物としては、トリフェニルメタントリイソシア
ネートなどが挙げられるが、この限りではない。またイ
ソシアネート化合物は１種または２種以上を併用するこ
とも可能である。Furthermore, in the present invention, the isocyanate compound (c) used has two or more isocyanate groups in one molecule. Compounds having two isocyanate groups in one molecule include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc. Compounds having three isocyanate groups in one molecule include triphenyl diisocyanate. Examples include, but are not limited to, methane triisocyanate. Moreover, it is also possible to use one type or a combination of two or more types of isocyanate compounds.
【００１４】本発明の粘・接着剤組成物において使用さ
れるブロック共重合体（ａ）、液状重合体（ｂ）、イソ
シアネート化合物（ｃ）中、ブロック共重合体（ａ）と
液状重合体（ｂ）の好ましい配合の重量比率は（ａ）／
（ｂ）＝９５／５〜５／９５であり、また液状重合体（
ｂ）中の水酸基のモル数／イソシアネート化合物（ｃ）
中のイソシアネート基のモル数の比率＝１／０．５〜１
／１０が好ましい。Among the block copolymer (a), liquid polymer (b), and isocyanate compound (c) used in the pressure-sensitive adhesive composition of the present invention, the block copolymer (a) and the liquid polymer ( The preferred weight ratio of b) is (a)/
(b) = 95/5 to 5/95, and the liquid polymer (
Number of moles of hydroxyl groups in b)/isocyanate compound (c)
Ratio of the number of moles of isocyanate groups in it = 1/0.5 to 1
/10 is preferred.
【００１５】本発明の粘・接着剤組成物はその趣旨を損
なわない範囲内で、粘着付与樹脂、プロセスオイル、Ｄ
ＯＰなどの可塑剤、ＢＨＴなどの老化防止剤、炭酸カル
シウム、酸化チタンなどの粉末フィラー、ガラス繊維、
有機補強用繊維などの繊維状フィラーなどを含んでいて
もよい。The pressure-sensitive adhesive composition of the present invention may contain a tackifier resin, process oil, D
Plasticizers such as OP, anti-aging agents such as BHT, powder fillers such as calcium carbonate and titanium oxide, glass fiber,
It may also contain fibrous fillers such as organic reinforcing fibers.
【００１６】粘着付与樹脂はロジン系、テルペン系、テ
ルペンフェノール系などの天然樹脂系のものと、パラフ
ィン系、クマロン・インデン系、スチレン系、フェノー
ル系などの合成樹脂系のものに大別される。これらの粘
着付与樹脂のいずれもが使用可能であるが、水添ロジン
、スチレン系樹脂などが好適に用いられる。[0016] Tackifying resins are broadly classified into natural resins such as rosin, terpene, and terpene phenol, and synthetic resins such as paraffin, coumaron/indene, styrene, and phenol. . Although any of these tackifying resins can be used, hydrogenated rosin, styrene resin, etc. are preferably used.
【００１７】本発明の粘・接着剤組成物は通常、紙、セ
ロハン、ポリプロピレン、ポリエステルなどの基材に塗
工して用いられる。基材への塗工方法の一例を以下に示
す。The pressure-sensitive adhesive composition of the present invention is usually used by coating it on a substrate such as paper, cellophane, polypropylene, or polyester. An example of a method for coating the base material is shown below.
【００１８】ブロック共重合体（ａ）、液状重合体（ｂ
）および必要に応じて用いられるその他の配合剤の混合
は、ヘキサン、シクロヘキサンなどの飽和炭化水素ある
いはベンゼン、トルエンなどの芳香族系炭化水素、メチ
ルエチルケトン、メチルイソプロピルケトンなどのケト
ン類、酢酸エチル、酢酸ブチルなどのエステル類などを
溶媒として、通常常温で行う。この溶液とイソシアネー
ト化合物（ｃ）を常温で混合したのち、基材に塗工し、
加熱することにより、脱溶媒とともに液状重合体（ｂ）
とイソシアネート化合物（ｃ）との硬化を完了する。Block copolymer (a), liquid polymer (b)
) and other compounding agents used as necessary include saturated hydrocarbons such as hexane and cyclohexane, aromatic hydrocarbons such as benzene and toluene, ketones such as methyl ethyl ketone and methyl isopropyl ketone, ethyl acetate, and acetic acid. It is usually carried out at room temperature using esters such as butyl as a solvent. After mixing this solution and the isocyanate compound (c) at room temperature, coating it on the base material,
By heating, the liquid polymer (b) is removed as well as the solvent is removed.
and isocyanate compound (c) to complete curing.
【００１９】本発明の粘・接着剤組成物の硬化条件は、
使用する溶媒、使用するイソシアネート化合物（ｃ）の
種類によっても異なるが、通常常温〜２００℃の温度範
囲、１分〜数日の硬化時間の範囲である。基材に塗工後
の加熱途中あるいは直後の凝集力（初期凝集力）は、ブ
ロック共重合体（ａ）により発現し、かつ高温時の凝集
力は、液状重合体（ｂ）とイソシアネート化合物（ｃ）
とによる架橋点の生成により発現する。The curing conditions for the adhesive/adhesive composition of the present invention are as follows:
Although it varies depending on the solvent used and the type of isocyanate compound (c) used, the temperature range is normally room temperature to 200°C, and the curing time is usually within the range of 1 minute to several days. The cohesive force during or immediately after heating after coating on the substrate (initial cohesive force) is developed by the block copolymer (a), and the cohesive force at high temperatures is due to the liquid polymer (b) and the isocyanate compound ( c)
It is expressed by the generation of crosslinking points by
【００２０】[0020]
【実施例】以下実施例をもって本発明をさらに詳細に説
明するが、本発明はその趣旨を越えない限り、以下の実
施例に限定されるものではない。
参考例
ｓｅｃ−ブチルリチウムを触媒として用いてスチレン、
イソプレンを順次添加し重合させることにより、スチレ
ン−イソプレン−スチレントリブロック共重合体（ＳＩ
Ｓ）を得た。これらのブロック共重合体をオートクレー
ブ中でシクロヘキサンに溶解し、２０重量％の溶液とし
た。この溶液にパラジウム（５重量％）カーボン担持触
媒をブロック共重合体に対して１０重量％添加、分散さ
せ、水素により５０ｋｇ／ｃｍ２ に加圧し、５０℃で
水素添加反応を行った。反応終了後触媒を濾過により分
離し、真空乾燥することによりブロック共重合体の水素
添加物（＝水添ＳＩＳ、ブロック共重合体（Ａ））を得
た。各ブロック共重合体（Ａ）の分子量、スチレン／イ
ソプレン比、１，４−結合量、水素添加率を表１に示し
た。[Examples] The present invention will be explained in more detail with reference to the following examples, but the present invention is not limited to the following examples unless it exceeds the spirit thereof. Reference Example Styrene using sec-butyllithium as a catalyst,
By sequentially adding and polymerizing isoprene, a styrene-isoprene-styrene triblock copolymer (SI
S) was obtained. These block copolymers were dissolved in cyclohexane in an autoclave to form a 20% by weight solution. Palladium (5% by weight) carbon-supported catalyst was added and dispersed in this solution in an amount of 10% by weight based on the block copolymer, and the mixture was pressurized to 50 kg/cm2 with hydrogen to carry out a hydrogenation reaction at 50°C. After the reaction was completed, the catalyst was separated by filtration and vacuum dried to obtain a hydrogenated block copolymer (=hydrogenated SIS, block copolymer (A)). Table 1 shows the molecular weight, styrene/isoprene ratio, 1,4-bond content, and hydrogenation rate of each block copolymer (A).
【００２１】また、過酸化水素水を触媒として用いてイ
ソプレンを重合させることにより水酸基を有する液状ポ
リイソプレンを得た。これらの液状ポリイソプレンをオ
ートクレーブ中でシクロヘキサンに溶解し、５０重量％
の溶液とした。この溶液に還元ニッケル（３５重量％）
ケイソウ土担持触媒を液状ポリイソプレンに対して１０
重量％添加、分散させ、水素により５０ｋｇ／ｃｍ２
に加圧し、２００℃で水素添加を行った。反応終了後触
媒を濾過により分離し真空乾燥することにより、水酸基
を有する液状ポリイソプレンの水添物（液状重合体（Ｂ
））を得た。各液状重合体（Ｂ）の分子量、水酸基濃度
、ｆ値（１分子あたりの水酸基数）、水添率を表２に示
した。
実施例１〜４および比較例１〜２
表１に示したブロック共重合体（Ａ）と表２に示した液
状重合体（Ｂ）、そしてイソシアネート化合物、粘着付
与樹脂、可塑剤、老化防止剤、溶剤を表３に示す混合比
率でブレンドした。Furthermore, liquid polyisoprene having hydroxyl groups was obtained by polymerizing isoprene using hydrogen peroxide as a catalyst. These liquid polyisoprenes were dissolved in cyclohexane in an autoclave to give a concentration of 50% by weight.
A solution of Reduced nickel (35% by weight) is added to this solution.
diatomaceous earth supported catalyst to liquid polyisoprene
Weight% addition, dispersion, 50kg/cm2 with hydrogen
Hydrogenation was carried out at 200°C. After the reaction is completed, the catalyst is separated by filtration and vacuum dried to obtain a hydrogenated product of liquid polyisoprene having hydroxyl groups (liquid polymer (B
)) was obtained. Table 2 shows the molecular weight, hydroxyl group concentration, f value (number of hydroxyl groups per molecule), and hydrogenation rate of each liquid polymer (B). Examples 1 to 4 and Comparative Examples 1 to 2 Block copolymers (A) shown in Table 1 and liquid polymers (B) shown in Table 2, as well as isocyanate compounds, tackifying resins, plasticizers, and anti-aging agents. and solvents were blended at the mixing ratio shown in Table 3.
【００２２】この溶液を、室温中でコーターを用い、５
０μｍ 厚の市販ポリエステルフィルム上に８０μｍ
の塗布厚みでコーティングした後、１２０℃で５分間加
熱することにより粘着テープを作成した。得られた粘着
テープを各種基材に接着した後、性能を以下の方法によ
り評価した。
（１）初期凝集力
２５ｍｍ×２５ｍｍの面積に粘・接着剤組成物を塗工、
貼り合わせ、加熱処理した直後からの剪断接着力を経時
変化を測定する方法によった。
（２）高温時の凝集力
２５ｍｍ×２５ｍｍの面積で貼り合わせ、これに１２０
℃の温度雰囲気下で放置し、これに２００ｇ，５００ｇ
の荷重をかけ、落下時間あるいは、ずれ距離を測定する
方法によった。
（３）接着力
上記粘・接着テープを厚さ１ｍｍのステンレスあるいは
ポリエチレンシートに貼りつけ、１８０°剥離強度を測
定することによった。[0022] This solution was coated with a coater at room temperature for 5 minutes.
80μm on 0μm thick commercially available polyester film
An adhesive tape was prepared by coating the sample with a coating thickness of 100° C. and then heating it at 120° C. for 5 minutes. After adhering the obtained adhesive tape to various base materials, the performance was evaluated by the following method. (1) Coating the adhesive/adhesive composition on an area of 25 mm x 25 mm with initial cohesive force,
A method was used to measure changes in shear adhesive strength over time immediately after bonding and heat treatment. (2) Cohesive force at high temperature Bonded in an area of 25 mm x 25 mm,
Leave it in a temperature atmosphere of ℃, and add 200g and 500g to it.
The method was to apply a load of (3) Adhesive Strength The adhesive tape described above was attached to a 1 mm thick stainless steel or polyethylene sheet, and the 180° peel strength was measured.
【００２３】粘・接着剤組成物より作成した粘着テープ
の性能を前述の方法にしたがって測定し、その結果を表
４に示した。The performance of the pressure-sensitive adhesive tape prepared from the pressure-sensitive adhesive composition was measured according to the method described above, and the results are shown in Table 4.
【００２４】表４によれば、実施例に示した本発明の粘
・接着組成物による粘着テープ性能は、各比較例に示し
た粘・接着組成物による粘着テープ性能に比べ、初期凝
集力、高温時の凝集力に優れていることがわかる。According to Table 4, the adhesive tape performance of the adhesive/adhesive composition of the present invention shown in the Examples has a higher initial cohesive strength, It can be seen that it has excellent cohesive force at high temperatures.
【００２５】（１）カルボジイミド変性ジフェニルメタ
ンジイソシアネート（「ミリオネートＭＴＬ」日本ポリ
ウレタン工業（株）製）
（２）水添テルペン系樹脂（「クリアロンＰ−１０５」
ヤスハラケミカル（株）製）
（３）パラフィン系プロセスオイル（「ＰＷ−９０」出
光興産製）
（４）ペンタエリスリチル−テトラキス［３−（３，５
−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオ
ネート］（「イルガノックス１０１０」チバ−ガイギー
製）(1) Carbodiimide-modified diphenylmethane diisocyanate (“Millionate MTL” manufactured by Nippon Polyurethane Industries, Ltd.) (2) Hydrogenated terpene resin (“Clearon P-105”)
(manufactured by Yasuhara Chemical Co., Ltd.) (3) Paraffinic process oil (“PW-90” manufactured by Idemitsu Kosan) (4) Pentaerythrityl-tetrakis [3-(3,5
-di-t-butyl-4-hydroxyphenyl)propionate] (“Irganox 1010” manufactured by Ciba-Geigy)
【００２６】（１） ◎ ： 加熱開始より１分
以内に、
剪断接着力が２ｋｇ／ｃｍ２ に到達した。(1) ◎: The shear adhesive strength reached 2 kg/cm2 within 1 minute from the start of heating.
【００２７】○ ： 加熱開始より１分以上３分以
内に、
剪断接着力が２ｋｇ／ｃｍ２ に到達した。○: The shear adhesive strength reached 2 kg/cm2 within 1 minute or more and within 3 minutes from the start of heating.
【００２８】× ： 剪断接着力が２ｋｇ／ｃｍ２
に到達するのに、
加熱開始より３分以上を要した。×: Shear adhesive strength is 2 kg/cm2
It took more than 3 minutes from the start of heating to reach this point.
【００２９】（２） 条件Ａ １２０℃、荷重２０
０ｇ、４時間後のずれ距離（ｍｍ）
条件Ｂ １２０℃、荷重５００ｇ、落下時間（分）(2) Condition A 120°C, load 20
0g, displacement distance after 4 hours (mm) Condition B 120℃, load 500g, falling time (minutes)
【
００３０】[
0030
【発明の効果】本発明によれば、塗工直後の初期凝集力
に優れ、かつ高温時における凝集力にも優れる２液硬化
型粘・接着剤組成物が提供される。Effects of the Invention According to the present invention, a two-component curing pressure-sensitive adhesive composition is provided which has excellent initial cohesive force immediately after coating and also has excellent cohesive force at high temperatures.
Claims (1)
モノマーからなるブロックと少なくとも１つの共役ジエ
ンモノマーからなるブロックからなり、該共役ジエンモ
ノマーからなるブロックの炭素−炭素二重結合の５０％
以上が水素添加されたブロック共重合体、（ｂ）１分子
中に１．５〜５．０個の水酸基を有するイソプレンまた
はイソプレン−ブタジエン混合物からなり、分子中の炭
素−炭素二重結合の５０％以上が水素添加された数平均
分子量が７００〜７０００の液状重合体、および （ｃ）イソシアネート化合物 を必須成分とする粘・接着剤組成物。Claim 1: (a) consisting of a block consisting of at least two aromatic vinyl monomers and a block consisting of at least one conjugated diene monomer, and 50% of the carbon-carbon double bonds of the block consisting of the conjugated diene monomer;
(b) Consisting of isoprene or isoprene-butadiene mixture having 1.5 to 5.0 hydroxyl groups in one molecule, with 50 carbon-carbon double bonds in the molecule. A pressure-sensitive adhesive composition comprising, as essential components, a liquid polymer having a number average molecular weight of 700 to 7,000 and (c) an isocyanate compound which is hydrogenated at least %.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3103216A JPH04309588A (en) | 1991-04-08 | 1991-04-08 | Pressure-sensitive adhesive or adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3103216A JPH04309588A (en) | 1991-04-08 | 1991-04-08 | Pressure-sensitive adhesive or adhesive composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04309588A true JPH04309588A (en) | 1992-11-02 |
Family
ID=14348310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3103216A Pending JPH04309588A (en) | 1991-04-08 | 1991-04-08 | Pressure-sensitive adhesive or adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04309588A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0670864A4 (en) * | 1992-11-17 | 1995-07-25 | Korpman Ralf Ass | Pressure sensitive adhesives comprising liquid and solid rubbers. |
| JP2005298588A (en) * | 2004-04-08 | 2005-10-27 | Toyo Mooton Kk | High-solid type adhesive composition |
| JP2012177095A (en) * | 2011-02-04 | 2012-09-13 | Nitto Denko Corp | Adhesive and adhesive tape |
-
1991
- 1991-04-08 JP JP3103216A patent/JPH04309588A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0670864A4 (en) * | 1992-11-17 | 1995-07-25 | Korpman Ralf Ass | Pressure sensitive adhesives comprising liquid and solid rubbers. |
| EP0670864A1 (en) * | 1992-11-17 | 1995-09-13 | Ralf Korpman Associates | Pressure sensitive adhesives comprising liquid and solid rubbers |
| JP2005298588A (en) * | 2004-04-08 | 2005-10-27 | Toyo Mooton Kk | High-solid type adhesive composition |
| JP4530704B2 (en) * | 2004-04-08 | 2010-08-25 | 東洋モートン株式会社 | High solid adhesive composition |
| JP2012177095A (en) * | 2011-02-04 | 2012-09-13 | Nitto Denko Corp | Adhesive and adhesive tape |
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