JPH0522744B2 - - Google Patents
Info
- Publication number
- JPH0522744B2 JPH0522744B2 JP59163367A JP16336784A JPH0522744B2 JP H0522744 B2 JPH0522744 B2 JP H0522744B2 JP 59163367 A JP59163367 A JP 59163367A JP 16336784 A JP16336784 A JP 16336784A JP H0522744 B2 JPH0522744 B2 JP H0522744B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- adhesive
- vinyl aromatic
- aromatic compound
- parts
- 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.)
- Expired - Lifetime
Links
- 239000000853 adhesive Substances 0.000 claims description 32
- 230000001070 adhesive effect Effects 0.000 claims description 32
- -1 vinyl aromatic compound Chemical class 0.000 claims description 24
- 229920002554 vinyl polymer Polymers 0.000 claims description 21
- 229920001400 block copolymer Polymers 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 14
- 150000001993 dienes Chemical class 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 150000002900 organolithium compounds Chemical class 0.000 claims description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 10
- 238000005520 cutting process Methods 0.000 description 10
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 150000003606 tin compounds Chemical class 0.000 description 6
- 239000012790 adhesive layer Substances 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000012943 hotmelt Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 150000003097 polyterpenes Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000013032 Hydrocarbon resin Substances 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 description 3
- 229920006270 hydrocarbon resin Polymers 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000010734 process oil Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 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
- 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
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- XKBAVCUSVIEVHR-UHFFFAOYSA-N dibromo(methyl)silane Chemical compound C[SiH](Br)Br XKBAVCUSVIEVHR-UHFFFAOYSA-N 0.000 description 2
- BYLOHCRAPOSXLY-UHFFFAOYSA-N dichloro(diethyl)silane Chemical compound CC[Si](Cl)(Cl)CC BYLOHCRAPOSXLY-UHFFFAOYSA-N 0.000 description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- XQBHAZDVLGNSOJ-UHFFFAOYSA-N 1-(4-ethenylphenyl)-n,n-dimethylmethanamine Chemical compound CN(C)CC1=CC=C(C=C)C=C1 XQBHAZDVLGNSOJ-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-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
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- DBKNQKMXXOSIOX-UHFFFAOYSA-N butyl(dichloro)silane Chemical compound CCCC[SiH](Cl)Cl DBKNQKMXXOSIOX-UHFFFAOYSA-N 0.000 description 1
- FYDLBBUBQFJOJT-UHFFFAOYSA-L butyl(dichloro)tin Chemical compound CCCC[Sn](Cl)Cl FYDLBBUBQFJOJT-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- LIQOCGKQCFXKLF-UHFFFAOYSA-N dibromo(dimethyl)silane Chemical compound C[Si](C)(Br)Br LIQOCGKQCFXKLF-UHFFFAOYSA-N 0.000 description 1
- VJIYRPVGAZXYBD-UHFFFAOYSA-N dibromosilane Chemical compound Br[SiH2]Br VJIYRPVGAZXYBD-UHFFFAOYSA-N 0.000 description 1
- NJKDOKBDBHYMAH-UHFFFAOYSA-N dibutyl(dichloro)silane Chemical compound CCCC[Si](Cl)(Cl)CCCC NJKDOKBDBHYMAH-UHFFFAOYSA-N 0.000 description 1
- YFAXVVMIXZAKSR-UHFFFAOYSA-L dichloro(diethyl)stannane Chemical compound CC[Sn](Cl)(Cl)CC YFAXVVMIXZAKSR-UHFFFAOYSA-L 0.000 description 1
- NRAYZPGATNMOSB-UHFFFAOYSA-N dichloro(dihexyl)silane Chemical compound CCCCCC[Si](Cl)(Cl)CCCCCC NRAYZPGATNMOSB-UHFFFAOYSA-N 0.000 description 1
- PKKGKUDPKRTKLJ-UHFFFAOYSA-L dichloro(dimethyl)stannane Chemical compound C[Sn](C)(Cl)Cl PKKGKUDPKRTKLJ-UHFFFAOYSA-L 0.000 description 1
- PFMKUUJQLUQKHT-UHFFFAOYSA-N dichloro(ethyl)silicon Chemical compound CC[Si](Cl)Cl PFMKUUJQLUQKHT-UHFFFAOYSA-N 0.000 description 1
- SYAXPJDYXAPBDK-UHFFFAOYSA-L dichloro(ethyl)tin Chemical compound CC[Sn](Cl)Cl SYAXPJDYXAPBDK-UHFFFAOYSA-L 0.000 description 1
- NYKYPUSQZAJABL-UHFFFAOYSA-N dichloro(hexyl)silane Chemical compound CCCCCC[SiH](Cl)Cl NYKYPUSQZAJABL-UHFFFAOYSA-N 0.000 description 1
- NENHTYKSUUMRCM-UHFFFAOYSA-L dichloro(hexyl)tin Chemical compound CCCCCC[Sn](Cl)Cl NENHTYKSUUMRCM-UHFFFAOYSA-L 0.000 description 1
- BQWHLOCBVNERCO-UHFFFAOYSA-L dichloro(methyl)tin Chemical compound C[Sn](Cl)Cl BQWHLOCBVNERCO-UHFFFAOYSA-L 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000013611 frozen food Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- CETVQRFGPOGIQJ-UHFFFAOYSA-N lithium;hexane Chemical compound [Li+].CCCCC[CH2-] CETVQRFGPOGIQJ-UHFFFAOYSA-N 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- SDYRIBONPHEWCT-UHFFFAOYSA-N n,n-dimethyl-2-phenylethenamine Chemical compound CN(C)C=CC1=CC=CC=C1 SDYRIBONPHEWCT-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
本発明は粘着剤組成物、特に熱溶融型粘着剤と
して好適な粘着剤組成物に関するものである。
一般に粘着剤はクラフトテープ等の粘着テー
プ、ラベルその他の粘着シートの粘着層を形成す
るために用いられる。このような粘着剤として
は、熱溶融させると適度の流動性を有し従つて有
機溶剤を用いずにそのまま基材に塗布して粘着層
を形成し得るものが望まれている。従来このよう
な熱溶融型粘着剤としては、例えば特公昭50−
56426号公報、特開昭54−33536号公報に記載され
たもの等が知られているが、これら従来の粘着剤
は、粘着シートの粘着層に要求される重要な特性
である初期粘着力および保持力等のすべてを同時
に満足するものでない。
本発明は以上の如き事情に基いて鋭意研究を重
ねた結果、特定構造のブロツク共重合体を２官能
のケイ素、またはスズ化合物でカツプリングした
ものを用いることにより、種々の特性において優
れた熱溶融型粘着剤が得られることを見出して完
成されたものであつて、その目的は、粘着シート
に適用されたときに、初期粘着力、はくり強度、
ダイカツト性および保持力のすべてにおいて優れ
た特性を有する熱溶融型の粘着剤組成物を提供す
ることにある。
即ち本発明の粘着剤組成物は、炭化水素溶媒中
で有機リチウム化合物を開始剤として得られる分
岐状ビニル芳香族化合物一共役ジエン共重合体に
おいて、該共重合体が一般式
（Ａ−Ｂ）２――Ｙ
［式中、Ａはビニル芳香族化合物重合体ブロツ
ク、Ｂは共役ジエンとビニル芳香族化合物との共
重合体であつて、Ｂ部分が
(a) ビニル芳香族化合物が漸増するテーパーブロ
ツクを０〜10個有し、
(b) ビニル芳香族化合物／共役ジエンの重量比が
０〜50／100〜50であり、
Ｙは一般式 R1R2MX2の残基
（式中R1R2はＨまたはCoH2o+1でｎ＝１〜20の整
数
Ｘはハロゲン
ＭはSiまたはSn）］
で表わされ、かつ該共重合体の全結合ビニル芳香
族化合物が５〜70重量％であることを特徴とする
ブロツク共重合体100重量部、粘着性付与剤20〜
200重量部および軟化剤０〜100重量部を含有して
なることを特徴とするものである。
本発明におけるブロツク共重合体の製造法は、
有機リチウム化合物を開始剤として用い、エーテ
ルまたは第３級アミン化合物の存在下で、
(a) まずビニル芳香族化合物の３〜70重量％を重
合し、重合が実質的に終了した後、
(b) 共役ジエン100〜50重量％とビニル芳香族化
合物０〜50重量％からなる混合物を１回または
２〜10回に分けて添加し、重合し、
(c) 最後に一般式
R1R2MX2
〔式中R1、R2はＨまたはCoH2o+1（ｎ＝１〜20
の整数）
ＸはClまたはBr
ＭはSiまたはSn〕
で表わされるケイ素またはスズ化合物を添加し
てカツプリング反応を行なわせることによつて
製造できる。
本発明のブロツク共重合体はビニル芳香族化合
物が５〜70重量％、好ましくは５〜50重量％、更
に好ましくは５〜40重量％である。ビニル芳香族
化合物が５重量％未満では粘着剤として用いた場
合保持力とダイカツト性が劣り、70重量％を超え
ると初期粘着力が劣る。
ここでいうダイカツト性とは、粘着ラベル製造
時に、はくり紙に貼り合わされた粘着シート上で
所望の形のラベルとなるようにダイで粘着基材を
打ち抜き、不要な部分をはくり紙から取り除く
が、この時、ダイカツト性が悪いとダイに粘着基
材が付着し、粘着ラベルとして必要な部分までが
はくり紙からはがれてしまうことを言う。このダ
イカツト性の悪さが熱可塑性ブロツク共重合体を
用いた熱溶融型粘着剤を粘着ラベル用途へ応用す
る時の最も大きな欠点となつている。
本発明の特徴はビニル芳香族化合物と共役ジエ
ンとを重合したのち、２官能のケイ素またはスズ
化合物を添加してこれによりカツプリングされた
ブロツク共重合体を用いることにある。
これらの特徴により本発明のブロツク共重合体
を粘着剤として用いた場合、粘着性保持力とはく
り強度とダイカツト性が著しく改善される。
本発明のブロツク共重合体を製造するにはまず
ビニル芳香族化合物を全モノマー使用量の５〜70
重量％重合する。
５重量％未満では粘着剤として用いた場合、保
持力とダイカツト性が劣り、70重量％を超えると
初期粘着力が劣る。
ビニル芳香族化合物が実質的に重合終了したの
ち、次に共役ジエン100〜50重量％とビニル芳香
族化合物０〜50重量％からなる混合物を重合す
る。
共役ジエンが50重量％未満では粘着剤として用
いた場合、接着力が劣る。
この重合は上記混合物を１回または２〜10回に
分けて添加し重合する。共役ジエンの重合が終了
したのち、２官能のケイ素またはスズ化合物を添
加してカツプリングされたブロツク共重合体を生
成する。
２官能のケイ素またはスズ化合物の添加量はリ
チウム末端ブロツク共重合体のリチウムを基準と
して0.3〜1.5当量である。
0.3当量未満ではまたは1.5当量を超えると粘着
剤として用いた場合保持力が劣る。
本発明に使用するビニル芳香族化合物として
は、スチレン、α−メチルスチレン、ｐ−メチル
スチレン、ｍ−メチルスチレン、ｏ−メチルスチ
レン、ｐ−tert−ブチルスチレン、ジメチルスチ
レン、ビニルナフタレン、ジメチルアミノスチレ
ン、ジメチルアミノメチルスチレン等が使用出来
る。このうちスチレンが好ましい。また共役ジエ
ンとしては、ブタジエン、イソプレン、ピペリレ
ンなどが使用出来る。このうちイソプレンが好ま
しいものとして挙げられる。
本発明のブロツク共重合体の重量平均分子量は
好ましくは10000〜500000、更に好ましくは50000
〜400000である。このうちビニル芳香族化合物ブ
ロツク部分の重量平均分子量は5000〜50000、共
役ジエンブロツク部分の重量平均分子量は10000
〜300000が好ましい。
本発明のブロツク共重合体は等温重合法でも、
断熱重合法でも得られる。また好ましい重合温度
範囲は30〜120℃である。
本発明のブロツク共重合体の製造に用いられる
炭化水素溶媒として、例えば「シクロペンタン、
シクロヘキサン、ベンゼン、エチルベンゼン、キ
シレン及びこれらとペンタン、ヘキサン、ヘプタ
ン、ブタン」などの混合物が用いられる。
有機リチウム化合物としては例えばｎ−ブチル
リチウム、sec−ブチルリチウム、tert−ブチル
リチウム、ｎ−ヘキシルリチウム、iso−ヘキシ
ルリチウム、フエニルリチウム、ナフチルリチウ
ム等があり、モノマー100重量部当り0.01〜1.0重
量部で用いられる。
本発明のブロツク共重合体の製造に用いられる
ケイ素またはスズ化合物としては一般式
R1R2MX2
〔式中R1、R2はＨ、またはCoH2o+1（ｎ＝１〜20
の整数）
ＸはClまたはBrなどのハロゲン、
ＭはSiまたはSn〕
で表わされるものであり、例えば
ジクロロシラン、モノメチルジクロロシラン、
ジメチルジクロロシラン、モノエチルジクロロシ
ラン、ジエチルジクロロシラン、モノブチルジク
ロロシラン、ジブチルジクロロシラン、モノヘキ
シルジクロロシラン、ジヘキシルジクロロシラ
ン、ジブロムシラン、モノメチルジブロムシラ
ン、ジメチルジブロムシラン、ジクロロスズ、モ
ノメチルジクロロスズ、ジメチルジクロロスズ、
モノエチルジクロロスズ、ジエチルジクロロス
ズ、モノブチルジクロロスズ、ジブチルジブロム
スズ、モノヘキシルジクロロスズ、等が用いられ
る。
特に好ましい具体例としてはモノメチルジクロ
ロシラン、ジメチルジクロロシラン、モノメチル
ジブロムシラン、ジブロムジクロロシランがあげ
られる。
以上の如きブロツク共重合体に粘着性付与剤が
配合される。この粘着性付与剤としては、ロジン
系樹脂、ポリテルペン系樹脂、合成ポリテルペン
系樹脂、脂環族系炭化水素樹脂、クモロン系樹
脂、フエノール系樹脂、テルペン−フエノール系
樹脂、芳香族炭化水素樹脂、脂肪族炭化水素樹脂
などが用いられる。これらのうち特にロジン系樹
脂、ポリテルペン系樹脂、脂環族系炭化水素樹脂
が好ましい。これらの粘着性付与剤は１種を単独
で、あるいは２種以上を混合して用いることがで
きる。粘着性付与剤の配合量は前記共重合体100
重量部に対して20〜200重量部、好ましくは50〜
150重量部である。この粘着性付与剤の配合量が、
上記の範囲外では、適切な初期粘着力および保持
力が十分でなくなるおそれがある。
本発明粘着剤組成物は更に軟化剤を配合するこ
とができ、この軟化剤としては、ナフテン系、パ
ラフイン系、アロマ系のプロセスオイルなどを単
独であるいは２種以上を混合して用いることがで
きる。軟化剤の配合量は、共重合体100重量部に
対して０〜100重量部、好ましくは20〜70重量部
である。軟化剤の配合量が100重量部を越える場
合には、時間の経過と共に軟化剤が粘着表面に浸
み出してきて好ましくない影響を与える。
本発明の粘着剤組成物には、更に上記以外に必
要に応じて酸化防止剤、紫外線吸収剤などの安定
剤、炭酸カルシウム、タルク、クレー、酸化チタ
ン、シリカ、炭酸マグネシウム、カーボンブラツ
クなどの無機充填剤、着色剤などを添加してもよ
い。
以上の粘着剤組成物の各成分は、一般の槽式混
合機、密閉式ニーダーなどで、加熱下において、
必要な場合には窒素ガス雰囲気中で混合される。
本発明の粘着剤組成物は、これを熱溶解させて
混合したものを直接塗布して粘着層を形成せしめ
る場合に最大の経済的効果を上げるものである。
しかし通常の溶剤による混合塗布、或いはエマル
ジヨン化させることによる混合塗布も可能であ
る。
このようにして得られる本発明の粘着剤組成物
は、基材に塗布されることにより粘着層を形成す
るので、各種粘着テープ、ラベル類、各種軽量プ
ラスチツク成形品固定用裏糊、カーペツト固定用
裏糊などとして有効であり、さらに冷凍食品類や
寒冷地で使用する粘着テープ、ラベルの粘着層形
成材料として有効である。
以下実施例によつて本発明を具体的に説明する
が、これらによつて本発明の範囲が制限されるも
のではない。
なお各種測定は下記の方法によつた。
初期粘着力は傾斜式ボールタツク測定法に拠つ
た。傾斜角度30°、測定温度25℃。
はくり強度JIS Z1522に準拠した。
（180°定速はくり強度試験、測定温度25℃）
保持力はJIS Z1524に準拠した。ただし、貼り
付け面積は15×10ｍ／ｍで、１Kgのおもりが落下
するまでの時間を測定した。測定温度25℃。
ダイカツト性の良否の判断は以下に示す方法で
行なつた。すなわち、上質紙に所定の厚みに粘着
剤をホツトメルトコーテイングし、これをはくり
紙に貼り合わせた後、20cm×４cmの大きさに切断
する。次に1.5cm×1.5cmの大きさの打ち抜き刃に
より、上質紙のみが切断されるように10個ずつ２
列合計20個の小片を打ち抜く、その後、余分な部
分を手ではくり紙よりはがす時、一緒にはがれた
粘着ラベルの数が０〜１枚のときに○印、２〜３
枚のときに△印、４枚以上のときに×印を付し、
ダイカツト性の良否を判定した。
全スチレン含量は赤外法により求めた。
実施例 １
洗滌、乾燥した撹拌機、ジヤケツト付きのオー
トクレープに窒素雰囲気下でシクロヘキサン4500
ｇ、テトラハイドロフラン１ｇを仕込んだ後、内
温を70℃にした。
次にｎ−ブチルリチウム0.4ｇを含むヘキサン
溶液を添加後スチレンを100ｇ添加し、60分重合
した。スチレンの重合転化率は100％であつた。
次いで、イソプレン500ｇを添加して60分重合し
た。イソプレンの重合転化率は100％であつた。
最後にモノメチルジクロロシランを0.36ｇ含
む、シクロヘキサン溶液を添加して、20分間カツ
プリング反応を行つた。
なお重合中は温度を常に70℃になる様に調節し
た。重合終了後、重合体溶液に２，６−ジ−tert
−ブチルｐ−クレゾールを添加した後、シクロヘ
キサンを加熱除去してブロツク共重合体を得た。
実施例２〜８ 比較例１〜５
表−１に示した所定量のスチレン、イソプレ
ン、ケイ素化合物等を用い、実施例１と同様の処
方によつて重合した。
The present invention relates to a pressure-sensitive adhesive composition, particularly to a pressure-sensitive adhesive composition suitable as a hot-melt pressure-sensitive adhesive. Generally, adhesives are used to form adhesive layers of adhesive tapes such as craft tapes, labels, and other adhesive sheets. It is desired that such an adhesive has appropriate fluidity when melted by heat and can be applied directly to a substrate to form an adhesive layer without using an organic solvent. Conventionally, such heat-melting adhesives include, for example,
56426 and JP-A-54-33536 are known, but these conventional adhesives do not have the initial adhesive strength and the important properties required for the adhesive layer of the adhesive sheet. It does not satisfy all aspects such as holding power at the same time. As a result of intensive research based on the above circumstances, the present invention has been developed by using a block copolymer with a specific structure coupled with a bifunctional silicon or tin compound to achieve thermal melting that is excellent in various properties. It was completed by discovering that a type adhesive could be obtained, and its purpose was to improve initial adhesive strength, peel strength, and
The object of the present invention is to provide a hot-melt pressure-sensitive adhesive composition having excellent properties in terms of both die-cutting properties and holding power. That is, the adhesive composition of the present invention is a branched vinyl aromatic compound-conjugated diene copolymer obtained in a hydrocarbon solvent using an organolithium compound as an initiator, and the copolymer has the general formula (A-B). 2 --Y [wherein A is a vinyl aromatic compound polymer block, B is a copolymer of a conjugated diene and a vinyl aromatic compound, and the B portion is (a) a taper in which the vinyl aromatic compound gradually increases. (b) the vinyl aromatic compound/conjugated diene weight ratio is 0 to 50/100 to 50, and Y is a residue of the general formula R 1 R 2 MX 2 (in the formula R 1 R2 is H or C o H 2o+1 , n is an integer of 1 to 20, X is halogen, M is Si or Sn), and the total bonded vinyl aromatic compound of the copolymer is 100 parts by weight of a block copolymer characterized in that it is 70% by weight, 20 to 20 parts by weight of a tackifier.
It is characterized by containing 200 parts by weight and 0 to 100 parts by weight of a softener. The method for producing a block copolymer in the present invention is as follows:
Using an organolithium compound as an initiator in the presence of an ether or a tertiary amine compound, (a) first polymerize 3 to 70% by weight of the vinyl aromatic compound, and after the polymerization has substantially completed, (b ) A mixture consisting of 100 to 50% by weight of a conjugated diene and 0 to 50% by weight of a vinyl aromatic compound is added once or in 2 to 10 portions and polymerized, (c) Finally, the general formula R 1 R 2 MX is added. 2 [In the formula, R 1 and R 2 are H or C o H 2o+1 (n = 1 to 20
X is Cl or Br M is Si or Sn] It can be produced by adding a silicon or tin compound to perform a coupling reaction. The block copolymer of the present invention has a vinyl aromatic compound content of 5 to 70% by weight, preferably 5 to 50% by weight, and more preferably 5 to 40% by weight. If the vinyl aromatic compound is less than 5% by weight, the holding power and die-cutting properties will be poor when used as an adhesive, and if it exceeds 70% by weight, the initial adhesive strength will be poor. Die-cutting here means that when manufacturing adhesive labels, a die is used to punch out the adhesive base material to form a label of the desired shape on the adhesive sheet attached to the release paper, and unnecessary parts are removed from the release paper. However, at this time, if the die-cutting properties are poor, the adhesive base material will adhere to the die, and the part needed as an adhesive label will peel off from the release paper. This poor die-cutting property is the biggest drawback when applying hot-melt pressure-sensitive adhesives using thermoplastic block copolymers to pressure-sensitive adhesive labels. The feature of the present invention is to use a block copolymer obtained by polymerizing a vinyl aromatic compound and a conjugated diene, adding a difunctional silicon or tin compound, and coupling the polymer with this. Due to these characteristics, when the block copolymer of the present invention is used as an adhesive, the adhesive retention, peel strength, and die-cutting properties are significantly improved. To produce the block copolymer of the present invention, a vinyl aromatic compound is first added in an amount of 5 to 70% of the total amount of monomers used.
% by weight polymerized. If it is less than 5% by weight, the holding power and die-cutting properties will be poor when used as an adhesive, and if it exceeds 70% by weight, the initial adhesive strength will be poor. After the polymerization of the vinyl aromatic compound is substantially completed, a mixture consisting of 100 to 50% by weight of the conjugated diene and 0 to 50% by weight of the vinyl aromatic compound is then polymerized. If the conjugated diene content is less than 50% by weight, the adhesive strength will be poor when used as an adhesive. This polymerization is carried out by adding the above mixture once or in 2 to 10 portions. After the polymerization of the conjugated diene is completed, a difunctional silicon or tin compound is added to produce a coupled block copolymer. The amount of the difunctional silicon or tin compound added is 0.3 to 1.5 equivalents based on lithium in the lithium-terminated block copolymer. If the amount is less than 0.3 equivalents, or if it exceeds 1.5 equivalents, the holding power will be poor when used as an adhesive. Examples of vinyl aromatic compounds used in the present invention include styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, p-tert-butylstyrene, dimethylstyrene, vinylnaphthalene, and dimethylaminostyrene. , dimethylaminomethylstyrene, etc. can be used. Among these, styrene is preferred. Further, as the conjugated diene, butadiene, isoprene, piperylene, etc. can be used. Among these, isoprene is preferred. The weight average molecular weight of the block copolymer of the present invention is preferably 10,000 to 500,000, more preferably 50,000.
~400000. Of these, the weight average molecular weight of the vinyl aromatic compound block part is 5,000 to 50,000, and the weight average molecular weight of the conjugated diene block part is 10,000.
~300000 is preferred. The block copolymer of the present invention can also be produced by isothermal polymerization.
It can also be obtained by adiabatic polymerization. Further, a preferable polymerization temperature range is 30 to 120°C. Examples of hydrocarbon solvents used in the production of the block copolymer of the present invention include "cyclopentane,
Cyclohexane, benzene, ethylbenzene, xylene, and mixtures thereof with pentane, hexane, heptane, butane, etc. are used. Examples of organic lithium compounds include n-butyllithium, sec-butyllithium, tert-butyllithium, n-hexyllithium, iso-hexyllithium, phenyllithium, naphthyllithium, etc., and the amount is 0.01 to 1.0 weight per 100 parts by weight of monomer. used in the department. The silicon or tin compound used in the production of the block copolymer of the present invention has the general formula R 1 R 2 MX 2 [wherein R 1 and R 2 are H, or C o H 2o+1 (n=1 to 20
X is a halogen such as Cl or Br, M is Si or Sn], for example, dichlorosilane, monomethyldichlorosilane,
Dimethyldichlorosilane, monoethyldichlorosilane, diethyldichlorosilane, monobutyldichlorosilane, dibutyldichlorosilane, monohexyldichlorosilane, dihexyldichlorosilane, dibromosilane, monomethyldibromosilane, dimethyldibromosilane, dichlorotin, monomethyldichlorotin, dimethyl dichlorotin,
Monoethyldichlorotin, diethyldichlorotin, monobutyldichlorotin, dibutyldibromtin, monohexyldichlorotin, etc. are used. Particularly preferred examples include monomethyldichlorosilane, dimethyldichlorosilane, monomethyldibromosilane, and dibromdichlorosilane. A tackifier is blended into the block copolymer as described above. Examples of the tackifier include rosin resin, polyterpene resin, synthetic polyterpene resin, alicyclic hydrocarbon resin, cumoron resin, phenol resin, terpene-phenol resin, aromatic hydrocarbon resin, and fatty acid. Group hydrocarbon resins are used. Among these, rosin resins, polyterpene resins, and alicyclic hydrocarbon resins are particularly preferred. These tackifiers can be used alone or in combination of two or more. The amount of tackifier added is 100% of the above copolymer.
20 to 200 parts by weight, preferably 50 to 200 parts by weight
It is 150 parts by weight. The amount of this tackifier is
Outside the above range, there is a risk that appropriate initial adhesive strength and retention strength will not be sufficient. The adhesive composition of the present invention can further contain a softener, and as the softener, naphthenic, paraffinic, aromatic process oils, etc. can be used alone or in combination of two or more. . The blending amount of the softener is 0 to 100 parts by weight, preferably 20 to 70 parts by weight, based on 100 parts by weight of the copolymer. If the blending amount of the softener exceeds 100 parts by weight, the softener will seep into the adhesive surface over time, causing undesirable effects. In addition to the above, the adhesive composition of the present invention may further contain stabilizers such as antioxidants and ultraviolet absorbers, and inorganic substances such as calcium carbonate, talc, clay, titanium oxide, silica, magnesium carbonate, and carbon black. Fillers, colorants, etc. may also be added. Each component of the above-mentioned pressure-sensitive adhesive composition is heated in a general tank mixer, closed kneader, etc.
If necessary, they are mixed in a nitrogen gas atmosphere. The pressure-sensitive adhesive composition of the present invention has the greatest economic effect when it is heat-melted and mixed and directly applied to form a pressure-sensitive adhesive layer.
However, mixed coating using a conventional solvent or by emulsion is also possible. The adhesive composition of the present invention obtained in this way forms an adhesive layer when applied to a base material, so it can be used for various adhesive tapes, labels, backing glue for fixing various lightweight plastic molded products, and for fixing carpets. It is effective as a backing glue, and is also effective as an adhesive layer forming material for frozen foods, adhesive tapes used in cold regions, and labels. The present invention will be specifically explained below with reference to Examples, but the scope of the present invention is not limited by these. In addition, various measurements were conducted according to the following methods. Initial adhesion strength was measured using a tilted ball tack measurement method. Tilt angle 30°, measurement temperature 25°C. Compliant with peel strength JIS Z1522. (180° constant speed peel strength test, measurement temperature 25°C) Holding force was in accordance with JIS Z1524. However, the pasting area was 15 x 10 m/m, and the time required for a 1 kg weight to fall was measured. Measurement temperature 25℃. The quality of die-cutting was determined by the method described below. That is, high-quality paper is hot-melt coated with an adhesive to a predetermined thickness, bonded to release paper, and then cut into a size of 20 cm x 4 cm. Next, a punching blade with a size of 1.5cm x 1.5cm is used to cut 10 pieces at a time so that only the high-quality paper is cut.
Punch out a total of 20 small pieces in a row, then peel off the excess from the paper by hand. If the number of adhesive labels that were peeled off together is 0 to 1, mark ○, 2 to 3.
When there are 4 or more pieces, mark △, and when there are 4 or more pieces, mark x.
The quality of die-cutting was judged. Total styrene content was determined by infrared method. Example 1 Cyclohexane 4500 ml under nitrogen atmosphere in a washed, dry, stirred, and jacketed autoclave.
After charging 1 g of tetrahydrofuran and 1 g of tetrahydrofuran, the internal temperature was brought to 70°C. Next, a hexane solution containing 0.4 g of n-butyllithium was added, and then 100 g of styrene was added and polymerized for 60 minutes. The polymerization conversion rate of styrene was 100%.
Next, 500 g of isoprene was added and polymerized for 60 minutes. The polymerization conversion rate of isoprene was 100%. Finally, a cyclohexane solution containing 0.36 g of monomethyldichlorosilane was added, and a coupling reaction was performed for 20 minutes. During the polymerization, the temperature was always adjusted to 70°C. After polymerization, add 2,6-di-tert to the polymer solution.
After adding -butyl p-cresol, cyclohexane was removed by heating to obtain a block copolymer. Examples 2 to 8 Comparative Examples 1 to 5 Polymerization was carried out according to the same recipe as in Example 1 using predetermined amounts of styrene, isoprene, silicon compounds, etc. shown in Table 1.
【表】【table】
【表】
ブロツク共重合体の構造を表−２、物性を表−
３に示す。
注
合成ポリテルペン樹脂、
日本ゼオン(株)製、クイントンＤ−100
ナフテン系プロセスオイル、出光興産(株)製、
ダイアナプロセスオイルNM−280
フエノール系老化防止剤、
大内新興化学(株)製、ノクラツクNS−６
実施例１〜８は比較例１〜５に比べ、初期粘着
力とはくり強度とダイカツト性のバランスの点で
優れている。[Table] Table 2 shows the structure of the block copolymer, and Table 2 shows the physical properties.
Shown in 3. Note: Synthetic polyterpene resin, manufactured by Nippon Zeon Co., Ltd., Quinton D-100 naphthenic process oil, manufactured by Idemitsu Kosan Co., Ltd.
Diana Process Oil NM-280 Phenol-based anti-aging agent, manufactured by Ouchi Shinko Kagaku Co., Ltd., Nokrac NS-6 Examples 1 to 8 had better initial adhesion strength, peel strength, and die-cutting properties than Comparative Examples 1 to 5. Excellent in terms of balance.
【表】【table】
【表】【table】
Claims (1)
ビニル芳香族化合物−共役ジエン共重合体におい
て、該共重合体が一般式 （Ａ−Ｂ）２――Ｙ ［式中、Ａはビニル芳香族化合物重合体ブロツ
ク、Ｂは共役ジエンとビニル芳香族化合物との共
重合体であつて、Ｂ部分が (a) ビニル芳香族化合物が漸増するテーパーブロ
ツクを０〜10個有し、 (b) ビニル芳香族化合物／共役ジエンの重量比が
０〜50／100〜50であり、 Ｙは一般式R1R2MX2の残基 （式中R1、R2はＨまたはCoH2o+1でｎ＝１〜20の
整数、 Ｘはハロゲン ＭはSiまたはSn）］ で表わされ、かつ該共重合体の全結合ビニル芳香
族化合物が５〜70重量％であることを特徴とする
ブロツク共重合体100重量部、粘着性付与剤20〜
200重量部および軟化剤０〜100重量部を含有して
成ることを特徴とする粘着剤組成物。[Scope of Claims] 1. A vinyl aromatic compound-conjugated diene copolymer obtained using an organolithium compound as an initiator, the copolymer having the general formula (A-B) 2 --Y [wherein A is The vinyl aromatic compound polymer block, B, is a copolymer of a conjugated diene and a vinyl aromatic compound, in which the B portion has (a) 0 to 10 tapered blocks in which the vinyl aromatic compound gradually increases; b) The weight ratio of vinyl aromatic compound/conjugated diene is 0 to 50/100 to 50, and Y is a residue of the general formula R 1 R 2 MX 2 (wherein R 1 and R 2 are H or C o H 2o+1 , where n is an integer of 1 to 20, 100 parts by weight of block copolymer, 20~20 parts by weight of tackifier
An adhesive composition comprising 200 parts by weight and 0 to 100 parts by weight of a softener.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16336784A JPS6142582A (en) | 1984-08-02 | 1984-08-02 | Hot-melt adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16336784A JPS6142582A (en) | 1984-08-02 | 1984-08-02 | Hot-melt adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6142582A JPS6142582A (en) | 1986-03-01 |
| JPH0522744B2 true JPH0522744B2 (en) | 1993-03-30 |
Family
ID=15772536
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16336784A Granted JPS6142582A (en) | 1984-08-02 | 1984-08-02 | Hot-melt adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6142582A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2254333B (en) * | 1989-11-01 | 1994-03-16 | Swift Adhesives Ltd | Crosslinkable polymers |
| GB8924619D0 (en) * | 1989-11-01 | 1989-12-20 | Swift Adhesives Ltd | Crosslinkable polymers |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5433536A (en) * | 1977-08-22 | 1979-03-12 | Asahi Chem Ind Co Ltd | Improved fusion type adehsive composition |
| JPS54127930A (en) * | 1978-03-29 | 1979-10-04 | Asahi Chem Ind Co Ltd | Hot-melt adhesive mass composition |
-
1984
- 1984-08-02 JP JP16336784A patent/JPS6142582A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5433536A (en) * | 1977-08-22 | 1979-03-12 | Asahi Chem Ind Co Ltd | Improved fusion type adehsive composition |
| JPS54127930A (en) * | 1978-03-29 | 1979-10-04 | Asahi Chem Ind Co Ltd | Hot-melt adhesive mass composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6142582A (en) | 1986-03-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |