JPH0362747B2 - - Google Patents
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- Publication number
- JPH0362747B2 JPH0362747B2 JP56121265A JP12126581A JPH0362747B2 JP H0362747 B2 JPH0362747 B2 JP H0362747B2 JP 56121265 A JP56121265 A JP 56121265A JP 12126581 A JP12126581 A JP 12126581A JP H0362747 B2 JPH0362747 B2 JP H0362747B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- component
- monomer
- main component
- 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
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- 239000000178 monomer Substances 0.000 claims description 47
- 230000001070 adhesive effect Effects 0.000 claims description 30
- 239000000853 adhesive Substances 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 19
- 239000012190 activator Substances 0.000 claims description 18
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 18
- 229920002681 hypalon Polymers 0.000 claims description 13
- 150000001451 organic peroxides Chemical class 0.000 claims description 13
- -1 chlorinated sulfonyl compound Chemical class 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 239000003381 stabilizer Substances 0.000 claims description 9
- 239000004709 Chlorinated polyethylene Substances 0.000 claims description 8
- 239000007859 condensation product Substances 0.000 claims description 6
- 239000002075 main ingredient Substances 0.000 claims description 6
- 150000003512 tertiary amines Chemical class 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 3
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 2
- 125000001302 tertiary amino group Chemical group 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 13
- 150000003606 tin compounds Chemical class 0.000 description 10
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 7
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 4
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 3
- 150000002432 hydroperoxides Chemical class 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- 150000003335 secondary amines Chemical class 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 2
- HJKXLQIPODSWMB-UHFFFAOYSA-N 4-(4-chlorosulfonylphenoxy)benzenesulfonyl chloride Chemical compound C1=CC(S(=O)(=O)Cl)=CC=C1OC1=CC=C(S(Cl)(=O)=O)C=C1 HJKXLQIPODSWMB-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 1
- FEXBEKLLSUWSIM-UHFFFAOYSA-N 2-Butyl-4-methylphenol Chemical compound CCCCC1=CC(C)=CC=C1O FEXBEKLLSUWSIM-UHFFFAOYSA-N 0.000 description 1
- SFPNZPQIIAJXGL-UHFFFAOYSA-N 2-ethoxyethyl 2-methylprop-2-enoate Chemical compound CCOCCOC(=O)C(C)=C SFPNZPQIIAJXGL-UHFFFAOYSA-N 0.000 description 1
- HDECRAPHCDXMIJ-UHFFFAOYSA-N 2-methylbenzenesulfonyl chloride Chemical compound CC1=CC=CC=C1S(Cl)(=O)=O HDECRAPHCDXMIJ-UHFFFAOYSA-N 0.000 description 1
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000004823 Reactive adhesive Substances 0.000 description 1
- LCXXNKZQVOXMEH-UHFFFAOYSA-N Tetrahydrofurfuryl methacrylate Chemical compound CC(=C)C(=O)OCC1CCCO1 LCXXNKZQVOXMEH-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- YVHDRFKHKGNLNW-UHFFFAOYSA-L [dibutyl(octadecanoyloxy)stannyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCCCCCCCC YVHDRFKHKGNLNW-UHFFFAOYSA-L 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- PZGVVCOOWYSSGB-UHFFFAOYSA-L but-2-enedioate;dioctyltin(2+) Chemical compound CCCCCCCC[Sn]1(CCCCCCCC)OC(=O)C=CC(=O)O1 PZGVVCOOWYSSGB-UHFFFAOYSA-L 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 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
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229940120693 copper naphthenate Drugs 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 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
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GUAWMXYQZKVRCW-UHFFFAOYSA-N n,2-dimethylaniline Chemical compound CNC1=CC=CC=C1C GUAWMXYQZKVRCW-UHFFFAOYSA-N 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- UIEKYBOPAVTZKW-UHFFFAOYSA-L naphthalene-2-carboxylate;nickel(2+) Chemical compound [Ni+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 UIEKYBOPAVTZKW-UHFFFAOYSA-L 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- LNDJHRZUMNSRAV-UHFFFAOYSA-M tribenzylstannyl dodecanoate Chemical compound C=1C=CC=CC=1C[Sn](CC=1C=CC=CC=1)(OC(=O)CCCCCCCCCCC)CC1=CC=CC=C1 LNDJHRZUMNSRAV-UHFFFAOYSA-M 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Description
本発明はアクリル系単量体の主剤成分とその重
合を開始させる活性化剤から成る反応型２成分型
接着剤に関する。更に詳しくはその主剤成分の保
存安定性の改良に関するものである。実質的に溶
剤を含まず、モノマー成分の重合により硬化して
多種類の被着材を強力に接着する反応型の接着剤
は公知である。例えば二成分型接着剤であり、第
一の成分はアクリル単量体またはメタクリル単量
体とパーオキサイドまたはハイドロパーオキサイ
ドからなり、第二の成分は常温において、アクリ
ルまたはメタクリル単量体の重合を開始させる活
性化剤からなる。ここで活性化剤は単量体に対し
て非科学量論理的な量でも充分に接着強度がでる
ものが好都合である。
米国特許第3890407号（日本国対応特許は特開
昭49−132119号である）にはクロルスルホン化し
たポリエチレンおよび塩化スルホニルと塩素化ポ
リエチレンとの混合物よりなる群からえらばれた
含硫黄組成物をアクリル単量体およびメタクリル
単量体よりなる群から選ばれた少なくとも１種の
重合可能な単量体に溶解した溶液ならびに遊離基
生成剤よりなり接着剤組成物が示されている。
しかし、この種の接着剤組成物はすぐれた接合
を与えるものであるが、長時間の保存安定性に欠
けるところがあり、この点を改良する必要があ
る。接着剤は接着速度とか接着強度などの性能に
優れていることが必要であるが、この性能をでき
るだけ長時間保持していることが極めて重要であ
る。しばしば、この種接着剤が比較的短期間のう
ちにゲル化するとか、接着速度が非常におそくな
つたり、接着強度が低下するといつた現象が観察
される。
米国特許第3962372号（日本国対応特許は特公
昭57−20347号である）には、米国特許第3890407
号の接着剤組成物の保存性を改良する方法が提案
これている。これによると安定剤として２，６−
ジ−ｔ−ブチル−４−メチルフエノール（BHT）
を用い、有機ヒドロパーオキサイドとの使用比を
１：１〜１：４の重量比にすれば保存性が良くな
るとのべられている。これについて本発明者らが
調べたところによると確かに安定性は改良されて
いるが保存性の促進試験において、50℃で７〜10
日でゲル化することが観察された。しかしながら
この種接着剤における保存安定性は促進試験にお
いて50℃で７−10日では不十分であつて少なくと
も20日〜30日もつことが要望されている。
本発明者らはかかる不十分な保存安定性を大巾
に改良すべく、いろんな角度から検討を加えた結
果、BHTなどの安定剤だけでは、も早や改善が
望めず有機スズ化合物の添加が極めて有効である
ことを見出した。
すなわち本願第１発明は
アクリル単量体またはメタクリル単量体と有機
過酸化物からなる主成分と
常温においてアクリル単量体またはメタクリル
単量体の重合を開始させる活性化剤と
からなる反応型２成分型接着剤において主剤成分
が
(A) アクリル単量体またはメタクリル単量体から
成る群から選ばれた少なくとも１種の単量体
(B) クロルスルホン化ポリエチレンまたは有機塩
化スルホニル化合物と塩素化ポリエチレンとの
混合物（Ａ成分とＢ成分の割合はＢ成分100重
量部当たり、Ａ成分50〜500重量部である）
(C) 有機過酸化物（主剤成分の0.01〜10重量％）
(D) フエノール系安定剤（主剤成分の0.01〜10重
量％）
(E) 有機スズ化合物（主剤成分の0.01〜20重量
％）
からなる組成物であり、かつ活性化剤が第３級ア
ミンまたはアルデヒドと第１級アミンもしくは第
２級アミンとの縮合生成物であることを特徴とす
る反応型２成分型接着剤。
であり、その主剤成分は極めて長期間経時しても
ゲル化することなく、また接着速度および強度の
低下も認められなかつた。
本発明で用いるアクリル単量体またはメタクリ
ル単量体としては例えば、メチル（メタ）アクリ
レート、エチル（メタ）アクリレート、ブチル
（メタ）アクリレート、シクロヘキシル（メタ）
アクリレート、２−エチルヘキシル（メタ）アク
リレート、ラウリル（メタ）アクリレート、ステ
アリル（メタ）アクリレート、メトキシエチル
（メタ）アクリレート、エトキシエチル（メタ）
アクリレート、ブトキシエチル（メタ）アクリレ
ート、テトラヒドロフルフリル（メタ）アクリレ
ート、（メタ）アクリル酸、エチレングリコール
ジメタクリレート、トリメチロールプロパントリ
メタクリレート等が挙げられ、これらの単量体は
単独または混用して使用することが出来る。
本発明に使用するクロルスルホン化ポリエチレ
ン又は有機塩化スルホニル化合物と塩素化ポリエ
チレンの混合体は重合体100ｇ当り25〜75重量％
の塩素および、３〜160ミリモルの塩化スルホニ
ル部分を含み且つ、クロルスルホン化ポリエチレ
ン及び塩素化ポリエチレンは４〜500の溶融係数
を有するポリエチレンからつくられたものであ
る。有機塩化スルホニル化合物は、例えばトルエ
ンスルホニルクロリド、ジフエニルエーテル−
４，4′−ジスルホニルクロリド等が適している。
クロロスルホン化ポリエチレン又は有機塩化スル
ホニル化合物と塩素化ポリエチレンの混合体と重
合可能な単量体との比率は重合体100重量部当り
単量体50〜500重量部である。または本発明で遊
離基生成剤として有機パーオキサイド及び有機ハ
イドロパーオキサイドを使用する。具体的には例
えばベンゾイルパーオキサイド、ｔ−ブチルハイ
ドロパーオキサイド、キユメンハイドパーオキサ
イドのどが挙げられ、これらの有機過酸化物の量
は主剤成分の0.01〜10重量％である。
本発明に用いれる有機スズ化合物には例えばジ
ブチルスズマレート、ジ−ｎ−オクチルスズマレ
ート、ジブチルスズジステアレート、ジブチルス
ズジノニレート、ジブチルスズジラウレート、ト
リベンジルスズラウレートのなどがあげられる。
これら有機スズ化合物の好ましい配合量は、主剤
成分の0.01〜20重量％である。これ以う加えると
接着力が低くなるので好ましくない。
本発明で使用される保存寿命を良くするフエノ
ール系安定剤としては、ハイドロキノン、ハイド
ロキノンモノメチルエーテル、２，６−ジ−ｔ−
ブチル−４−メチルフエノール等が挙げられる
が、最も好ましい安定剤は、２，６−ジ−ｔ−ブ
チル−４−メチルフエノールである。安定剤の好
ましい量は、主剤成分の0.01〜10重量％である。
本願の第１発明の主剤成分はアクリル単量体ま
たはメタクリル単量体、クロルスルホン化ポリエ
チレンまたは塩化スルホニルと塩素化ポリエチレ
ンとの混合物、有機過酸化物、安定剤及び有機ス
ズ化合物を均一に混合すれば容易に製造すること
ができる。
また、本発明者らは上述の本願の第１発明の主
剤成分に対してエポキシ樹脂を添加することによ
つてさらにその保存性を向上させることを知つ
た。この新な現象は有機スズ化合物とエポキシ樹
脂とを併用するときにのみ発現しエポキシ樹脂単
独の使用では何等の効果も認めない。
すなわち本願の第２発明は
アクリル単量体またはメタクリル単量体と有機
過酸化物からなる主成分と
常温においてアクリル単量体またはメタクリル
単量体の重合を開始させる活性化剤と
からなる反応型２成分型接着剤において主剤成分
が
(A) アクリル単量体またはメタクリル単量体から
成る群から選ばれた少なくとも１種の単量体
(B) クロルスルホン化ポリエチレンまたは有機塩
化スルホニル化合物と塩素化ポリエチレンとの
混合物（Ａ成分とＢ成分の割合はＢ成分100重
量当たり、Ａ成分50〜500重量部である）
(C) 有機過酸化物（主剤成分の0.01〜10重量％）
(D) フエノール系安定剤（主剤成分の0.01〜10重
量％）
(E) 有機スズ化合物（全組成物の0.01〜20重量
％）
(F) エポキシ化合物（主組成物の0.01〜20重量
％）
からなる組成物であり、かつ活性化剤が第３級ア
ミンまたはアルデヒドと第１級アミンもしくは第
２級アミンとの縮合生成物であることを特徴とす
る反応型２成分型接着剤
であり、その主剤成分は本願の第１発明の主剤成
分よりも優れた経時安定性を有する。
本発明に用いられるエポキシ樹脂は通常市販さ
れているエポキシ樹脂が適しており、その例とし
てはポリグリシジルエーテル、ポリグリシジルエ
ステルなどが挙げられ、液状または固形状の何れ
でも良い。本願の第１発明の主剤成分にエポキシ
樹脂を添加混合すれば本願の第２発明の主剤成分
が得られるが、その好ましい配合量は主剤成分の
0.01〜20重量％である。
かくして得られたアクリル単量体又はメタクリ
ル単量体からなる主剤成分を重合開始させる活性
化剤化合物は、例えば第三級アミン（例えばＮ，
N′−ジメチルアニリン、Ｎ，N′ジイソプロピル
−Ｐ−トルイジン）またはアルデヒドと第１級も
しくは第二級アミンとの縮合生成物（例えばブチ
ルアルデヒドとアニリンもしくはブチルアミンと
の縮合生成物であり、これらの例示化合物にはデ
ユポン社の活性化剤808および833が含まれる。
接着は主剤成分を被着剤の一方に塗布し、活性
化剤を他方に薄く塗布して、その両面を圧着させ
ることにより直ちに重合が起り、数分内に接着し
24時間で最強接着強度に達する。活性化剤の使用
量は主剤成分100重量部に対し、最大15重量部好
ましくは0.01〜1.5重量部が好適である。
本発明に従えば接着硬化速度を大ならしめるた
めに活性化剤とともに促進剤を用いる。好適な促
進剤としては遷移金属の酸化性化合物が含まれ
る。例えばナフテン酸銅、ナフテン酸コバルト、
ナフテン酸鉄、ナフテン酸ニツケル、または、ア
セチルアセトンと鉄、銅、コバルトもしくはバナ
ジウムの錯化合物が含まれる。
本発明の接着剤はその接着強度が大きいので、
鋼−鋼の接着等の構造用接着剤として適する。
以下に本発明の効果を実施例により示すが、使
用した活性化剤化合物はデユポン社の活性化剤
808を用いた。また接着効果は下記のとおりの促
進試験法により評価した。
実施例１〜９、比較例１〜２
メチルメタクリレート50重量部、２−エチルヘ
キシルメタクリレート10重量部、エチレングリコ
ールメタクリレート２重量部、トリメチロールプ
ロパントリメタクリレート１重量部及びメタクリ
ル酸７重量部を均一に混合した単量体組成物70重
量部に対し、表１に示すクロルスルホン化ポリエ
チレン、有機過酸化物、BHT及び有機スズ化合
物または、さらにエピコート828を加えて均一に
混合し各接着剤を得た。
これらの接着剤を使用し、保存試験を行なつた
結果を表１に示した。
The present invention relates to a reactive two-component adhesive comprising a main component of an acrylic monomer and an activator for initiating polymerization thereof. More specifically, it relates to improving the storage stability of the main ingredient. Reactive adhesives that substantially do not contain a solvent and are cured by polymerization of monomer components to strongly bond various types of adherends are known. For example, it is a two-component adhesive, in which the first component consists of an acrylic or methacrylic monomer and a peroxide or hydroperoxide, and the second component allows the polymerization of the acrylic or methacrylic monomer at room temperature. Consists of an activator to initiate. Here, the activator is preferably one that can provide sufficient adhesive strength even in a non-scientific amount relative to the monomer. U.S. Patent No. 3,890,407 (Japanese equivalent patent is JP-A-49-132119) discloses a sulfur-containing composition selected from the group consisting of chlorosulfonated polyethylene and a mixture of sulfonyl chloride and chlorinated polyethylene. An adhesive composition is shown comprising a solution of at least one polymerizable monomer selected from the group consisting of acrylic monomers and methacrylic monomers and a free radical generator. However, although this type of adhesive composition provides excellent bonding, it lacks long-term storage stability, and there is a need to improve this point. Adhesives need to have excellent performance such as adhesion speed and adhesive strength, and it is extremely important to maintain this performance for as long as possible. It is often observed that such adhesives gel in a relatively short period of time, that the adhesion speed becomes very slow, and that the adhesion strength decreases. U.S. Patent No. 3962372 (Japanese equivalent patent is Japanese Patent Publication No. 57-20347), U.S. Patent No. 3890407
A method for improving the shelf life of adhesive compositions has been proposed. According to this, 2,6-
Di-tert-butyl-4-methylphenol (BHT)
It is stated that the storage stability is improved if the weight ratio of organic hydroperoxide to organic hydroperoxide is 1:1 to 1:4. According to the inventors' investigation, the stability has certainly been improved, but in an accelerated storage test, 7 to 10
It was observed that it gelled within a few days. However, storage stability of this type of adhesive at 50 DEG C. for 7 to 10 days is insufficient in an accelerated test, and is required to last for at least 20 to 30 days. The present inventors conducted studies from various angles in order to significantly improve such insufficient storage stability, and as a result, they found that it was difficult to expect improvement with stabilizers such as BHT alone, and that the addition of organic tin compounds was necessary. It was found to be extremely effective. That is, the first invention of the present application is a reaction type 2 consisting of a main component consisting of an acrylic monomer or methacrylic monomer and an organic peroxide, and an activator that initiates polymerization of the acrylic monomer or methacrylic monomer at room temperature. In the component type adhesive, the main component is (A) at least one monomer selected from the group consisting of acrylic monomers or methacrylic monomers (B) chlorosulfonated polyethylene or organic chlorinated sulfonyl compound and chlorinated polyethylene (The ratio of component A and component B is 50 to 500 parts by weight of component A per 100 parts by weight of component B) (C) Organic peroxide (0.01 to 10% by weight of the main component) (D) Phenol System stabilizer (0.01 to 10% by weight of the main component) (E) A composition consisting of an organic tin compound (0.01 to 20% by weight of the main component), and the activator is a tertiary amine or aldehyde and a primary A reactive two-component adhesive characterized by being a condensation product with a primary amine or a secondary amine. The main component did not gel even after an extremely long period of time, and no decrease in adhesion speed or strength was observed. Examples of the acrylic monomer or methacrylic monomer used in the present invention include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and cyclohexyl (meth)acrylate.
Acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate
Examples include acrylate, butoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (meth)acrylic acid, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and these monomers can be used alone or in combination. You can. The mixture of chlorosulfonated polyethylene or organic chlorinated sulfonyl compound and chlorinated polyethylene used in the present invention is 25 to 75% by weight per 100 g of polymer.
of chlorine and 3 to 160 mmol of sulfonyl chloride moieties, and the chlorosulfonated polyethylene and chlorinated polyethylene are made from polyethylene having a melting coefficient of 4 to 500. Organic sulfonyl chloride compounds include, for example, toluenesulfonyl chloride, diphenyl ether-
4,4'-disulfonyl chloride and the like are suitable.
The ratio of the chlorosulfonated polyethylene or the mixture of the organic sulfonyl chloride compound and the chlorinated polyethylene to the polymerizable monomer is 50 to 500 parts by weight of monomer per 100 parts by weight of the polymer. Alternatively, organic peroxides and organic hydroperoxides are used as free radical generating agents in the present invention. Specific examples include benzoyl peroxide, t-butyl hydroperoxide, and yumenehydroperoxide, and the amount of these organic peroxides is 0.01 to 10% by weight of the base ingredient. Examples of the organic tin compounds used in the present invention include dibutyltin maleate, di-n-octyltin maleate, dibutyltin distearate, dibutyltin dinonylate, dibutyltin dilaurate, and tribenzyltin laurate.
The preferred amount of these organic tin compounds is 0.01 to 20% by weight of the main ingredient. Adding more than this is not preferable because the adhesive strength will decrease. The phenolic stabilizers used in the present invention to improve shelf life include hydroquinone, hydroquinone monomethyl ether, 2,6-di-t-
Examples include butyl-4-methylphenol, but the most preferred stabilizer is 2,6-di-t-butyl-4-methylphenol. The preferred amount of stabilizer is 0.01 to 10% by weight of the base ingredient. The main component of the first invention of the present application is a uniform mixture of acrylic monomer or methacrylic monomer, chlorosulfonated polyethylene or a mixture of sulfonyl chloride and chlorinated polyethylene, an organic peroxide, a stabilizer, and an organic tin compound. It can be easily manufactured. In addition, the present inventors have found that by adding an epoxy resin to the main component of the first invention of the present application described above, the storage stability can be further improved. This new phenomenon occurs only when an organic tin compound and an epoxy resin are used together, and no effect is observed when the epoxy resin is used alone. That is, the second invention of the present application is a reactive type consisting of a main component consisting of an acrylic monomer or methacrylic monomer and an organic peroxide, and an activator that initiates polymerization of the acrylic monomer or methacrylic monomer at room temperature. In a two-component adhesive, the main component is (A) at least one monomer selected from the group consisting of acrylic monomers or methacrylic monomers (B) chlorosulfonated polyethylene or organic chlorinated sulfonyl compound and chlorinated Mixture with polyethylene (ratio of component A and component B is 50 to 500 parts by weight of component A per 100 weight of component B) (C) Organic peroxide (0.01 to 10% by weight of the main component) (D) Phenol A composition consisting of a system stabilizer (0.01 to 10% by weight of the main component) (E) an organic tin compound (0.01 to 20% by weight of the total composition) (F) an epoxy compound (0.01 to 20% by weight of the main composition) It is a reactive two-component adhesive characterized in that the activator is a condensation product of a tertiary amine or aldehyde and a primary amine or secondary amine, and its main component is It has better stability over time than the main ingredient of the first invention of the present application. Commercially available epoxy resins are suitable as the epoxy resin used in the present invention, examples of which include polyglycidyl ether and polyglycidyl ester, and they may be in either liquid or solid form. By adding and mixing an epoxy resin to the base component of the first invention of the present application, the base component of the second invention of the present application can be obtained.
It is 0.01-20% by weight. The activator compound that initiates the polymerization of the main component consisting of the acrylic monomer or methacrylic monomer obtained in this way is, for example, a tertiary amine (for example, N,
N'-dimethylaniline, N,N'diisopropyl-P-toluidine) or condensation products of aldehydes with primary or secondary amines (e.g. condensation products of butyraldehyde with aniline or butylamine; Exemplary compounds include DuPont's Activators 808 and 833. Adhesion is achieved immediately by applying the base component to one side of the adherend, applying a thin layer of activator to the other side, and pressing both sides together. Polymerization occurs and the bond forms within a few minutes.
Maximum adhesive strength is reached in 24 hours. The amount of the activator to be used is preferably 15 parts by weight at most, preferably 0.01 to 1.5 parts by weight, per 100 parts by weight of the main ingredient. According to the present invention, an accelerator is used in conjunction with an activator to increase the rate of adhesive curing. Suitable promoters include oxidizing compounds of transition metals. For example, copper naphthenate, cobalt naphthenate,
Included are complex compounds of iron naphthenate, nickel naphthenate, or acetylacetone with iron, copper, cobalt, or vanadium. Since the adhesive of the present invention has high adhesive strength,
Suitable as a structural adhesive for steel-to-steel bonding, etc. The effects of the present invention will be shown below through examples. The activator compound used was Dupont's activator.
808 was used. Further, the adhesive effect was evaluated by the following accelerated test method. Examples 1 to 9, Comparative Examples 1 to 2 50 parts by weight of methyl methacrylate, 10 parts by weight of 2-ethylhexyl methacrylate, 2 parts by weight of ethylene glycol methacrylate, 1 part by weight of trimethylolpropane trimethacrylate, and 7 parts by weight of methacrylic acid were uniformly mixed. To 70 parts by weight of the monomer composition prepared above, chlorosulfonated polyethylene, organic peroxide, BHT, and organic tin compound shown in Table 1, or Epicoat 828 were added and mixed uniformly to obtain each adhesive. Table 1 shows the results of a storage test using these adhesives.
【表】【table】
【表】
表１の結果から有機スズ化合物の添加が保存安
定性に極めて良好な効果を示していることがわか
る。
(1) 塩素29％および硫黄1.4％を含みムーニー粘
度30のクロルスルホン化ポリエチレンを使用。
(2) 44％の塩素分を含み、溶融粘度150のポリエ
チレンからつくられた塩素化ポリエチレンとジ
フエニールエーテル−４，4′−ジスルホニルク
ロリドの10：１重量比の混合物。
促進試験法60mlのガラスビンに主剤組成物を50
ｇ入れ密栓して、50℃の恒温乾燥器に入れ、所定
の期間放置する。一週間毎にサンプルをとり出
し、鋼−鋼の引張剪断強度（Kgｆ／cm2、JIS
K6850）を測定する。引張剪断強度は５分養成お
よび24時間養成後の強度を測定する。
接着試験法
試験片の一方に主剤成分を塗布し、他方に活性
化剤をうすく塗布し、両方の塗布面を合せて圧接
着し、５分後及び24時間後の引張剪断強度（Kg
ｆ／cm2）を測定した。（JIS K6850）
実施例10〜11、比較例３〜４
ブチルメタクリレート20重量部、テロラヒドロ
フルフリルメタクリレート20重量部、エトキシエ
チルメタクリレート20重量部、エチレングリコー
ルジメタクリレート２重量部、トリメチロールプ
ロパントリメタクリレート１重量部、メタクリル
酸７重量部、クロルスルホン化ポリエチレン40重
量部、キユメンハイドロパーオキサイド１重量部
及びBHT1.5重量部を均一に混合して得た組成物
112.5重量部に対し表２に示すジブチルスズマー
レートまたはさらにエピコート828を加えて接着
剤を調製し、保存試験した結果を表２に示す。[Table] From the results in Table 1, it can be seen that the addition of an organic tin compound has an extremely good effect on storage stability. (1) Uses chlorosulfonated polyethylene containing 29% chlorine and 1.4% sulfur and a Mooney viscosity of 30. (2) A 10:1 weight ratio mixture of chlorinated polyethylene and diphenyl ether-4,4'-disulfonyl chloride made from polyethylene containing 44% chlorine and a melt viscosity of 150. Accelerated test method: Add 50% of the base composition to a 60ml glass bottle.
Put it in a thermostatic dryer at 50℃ and leave it for a specified period of time. Samples are taken out every week and the steel-to-steel tensile shear strength (Kgf/cm 2 , JIS
K6850). The tensile shear strength is measured after 5 minutes of curing and 24 hours of curing. Adhesion test method: Apply the main component to one side of the test piece, apply a thin layer of activator to the other side, press-bond both coated surfaces together, and measure the tensile shear strength (Kg) after 5 minutes and 24 hours.
f/cm 2 ) was measured. (JIS K6850) Examples 10 to 11, Comparative Examples 3 to 4 20 parts by weight of butyl methacrylate, 20 parts by weight of telorahydrofurfuryl methacrylate, 20 parts by weight of ethoxyethyl methacrylate, 2 parts by weight of ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate A composition obtained by uniformly mixing 1 part by weight, 7 parts by weight of methacrylic acid, 40 parts by weight of chlorosulfonated polyethylene, 1 part by weight of kyumene hydroperoxide, and 1.5 parts by weight of BHT.
Table 2 shows the results of a storage test of an adhesive prepared by adding dibutyl tin merate shown in Table 2 or Epicoat 828 to 112.5 parts by weight.
【表】
実施例12〜16、比較例５
メチルメタクリレート20重量部、２−エチルヘ
キシルメタクリレート10重量部、テトラヒドロフ
ルフリルメタクリレート30重量部、エチレングリ
コールジメタクリレート２重量部、トリメチロー
ルプロパントリメタクリレート１重量部およびメ
タクリル酸５重量部を均一に混合した単量体組成
物68重量部に対し表−３に示すクロルスルホン化
ポリエチレン、有機過酸化物、BHTおよび有機
ズズ化合物またはさらにエピコート828又はエピ
コート815を加えて均一に混合し各接着剤を得た。
これらの接着剤を使用し、保存試験を行なつた結
果を表−３に示した。[Table] Examples 12 to 16, Comparative Example 5 20 parts by weight of methyl methacrylate, 10 parts by weight of 2-ethylhexyl methacrylate, 30 parts by weight of tetrahydrofurfuryl methacrylate, 2 parts by weight of ethylene glycol dimethacrylate, 1 part by weight of trimethylolpropane trimethacrylate To 68 parts by weight of a monomer composition uniformly mixed with 5 parts by weight of methacrylic acid, chlorosulfonated polyethylene, organic peroxide, BHT, and organic tin compounds shown in Table 3, or in addition Epicote 828 or Epicote 815 were added. The mixture was mixed uniformly to obtain each adhesive.
Table 3 shows the results of a storage test using these adhesives.
Claims (1)
機過酸化物からなる主剤成分と 常温においてアクリル単量体またはメタクリル
単量体の重合を開始させる活性化剤と からなる反応型２成分型接着剤において主剤成分
が (A) アクリル単量体またはメタクリル単量体から
成る群から選ばれた少なくとも１種の単量体 (B) クロルスルホン化ポリエチレンまたは有機塩
化スルホニル化合物と塩素化ポリエチレンとの
混合物（Ａ成分とＢ成分の割合はＢ成分100重
量部当たり、Ａ成分50〜500重量部である） (C) 有機過酸化物（主剤成分の0.01〜10重量％） (D) フエノール系安定剤（主剤成分の0.01〜10重
量％） (E) 有機スズ化合物（主成分の0.01〜20重量％） からなる組成物であり、かつ活性化剤が第３級ア
ミンまたはアルデヒドと第１級アミンもしくは第
２級アミンとの縮合生成物であることを特徴とす
る反応型２成分型接着剤。 ２ アクリル単量体またはメタクリル単量体と有
機過酸化物から成る主剤成分と 常温においてアクリル単量体またはメタクリル
単量体の重合を開始させる活性化剤と からなる反応型２成分型接着剤において、主剤成
分が (A) アクリル単量体またはメタクリル単量体から
成る群からえらばれた少なくとも１種の単量体 (B) クロルスルホン化ポリエチレンまたは有機塩
化スルホニル化合物と塩素化ポリエチレンとの
混合物（Ａ成分とＢ成分の割合はＢ成分100重
量部当たり、Ａ成分50〜500重量部である） (C) 有機過酸化物（主剤成分の0.01〜10重量％） (D) フエノール系安定剤（主剤成分の0.01〜10重
量％） (E) 有機スズ化合物（主成分の0.01〜20重量％） (F) エポキシ化合物（主剤成分の0.01〜20重量
％） からなる組成物であり、かつ活性化剤が第３級ア
ミンまたはアルデヒドと第１級アミンもしくは第
２級アミンとの縮合生成物であることを特徴とす
る反応型２成分型接着剤。[Scope of Claims] 1. A reactive type consisting of a main component consisting of an acrylic monomer or methacrylic monomer and an organic peroxide, and an activator that initiates polymerization of the acrylic monomer or methacrylic monomer at room temperature. In a two-component adhesive, the main component is (A) at least one monomer selected from the group consisting of acrylic monomers or methacrylic monomers (B) chlorosulfonated polyethylene or organic chlorinated sulfonyl compound and chlorinated Mixture with polyethylene (the ratio of component A and component B is 50 to 500 parts by weight of component A per 100 parts by weight of component B) (C) Organic peroxide (0.01 to 10% by weight of the main component) (D) A composition consisting of a phenolic stabilizer (0.01 to 10% by weight of the main component) (E) an organotin compound (0.01 to 20% by weight of the main component), and the activator is a tertiary amine or aldehyde and a tertiary amine or aldehyde. A reactive two-component adhesive characterized by being a condensation product with a primary amine or a secondary amine. 2. In a reactive two-component adhesive consisting of a main component consisting of an acrylic monomer or methacrylic monomer and an organic peroxide, and an activator that initiates polymerization of the acrylic monomer or methacrylic monomer at room temperature. , the main ingredient is (A) at least one monomer selected from the group consisting of acrylic monomers or methacrylic monomers (B) a mixture of chlorosulfonated polyethylene or an organic chlorinated sulfonyl compound and chlorinated polyethylene ( The ratio of component A and component B is 50 to 500 parts by weight of component A per 100 parts by weight of component B.) (C) Organic peroxide (0.01 to 10% by weight of the main ingredient) (D) Phenol stabilizer ( (0.01 to 10% by weight of the main component) (E) Organotin compound (0.01 to 20% by weight of the main component) (F) Epoxy compound (0.01 to 20% by weight of the main component) and activated A reactive two-component adhesive characterized in that the agent is a condensation product of a tertiary amine or aldehyde and a primary amine or secondary amine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12126581A JPS5821469A (en) | 1981-07-31 | 1981-07-31 | Adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12126581A JPS5821469A (en) | 1981-07-31 | 1981-07-31 | Adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5821469A JPS5821469A (en) | 1983-02-08 |
| JPH0362747B2 true JPH0362747B2 (en) | 1991-09-26 |
Family
ID=14806966
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12126581A Granted JPS5821469A (en) | 1981-07-31 | 1981-07-31 | Adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5821469A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6040176A (en) * | 1983-08-15 | 1985-03-02 | Dainippon Printing Co Ltd | Pressure-sensitive adhesive composition |
| GB8522042D0 (en) * | 1985-09-05 | 1985-10-09 | Permabond Adhesives | Acrylic adhesives & sealants |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49132119A (en) * | 1972-07-20 | 1974-12-18 | ||
| JPS5088132A (en) * | 1973-11-30 | 1975-07-15 |
-
1981
- 1981-07-31 JP JP12126581A patent/JPS5821469A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49132119A (en) * | 1972-07-20 | 1974-12-18 | ||
| JPS5088132A (en) * | 1973-11-30 | 1975-07-15 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5821469A (en) | 1983-02-08 |
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