JPH0142313B2 - - Google Patents
Info
- Publication number
- JPH0142313B2 JPH0142313B2 JP56123083A JP12308381A JPH0142313B2 JP H0142313 B2 JPH0142313 B2 JP H0142313B2 JP 56123083 A JP56123083 A JP 56123083A JP 12308381 A JP12308381 A JP 12308381A JP H0142313 B2 JPH0142313 B2 JP H0142313B2
- Authority
- JP
- Japan
- Prior art keywords
- adhesive
- cyanoacrylate
- chloride
- present
- weight
- 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
Links
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical compound OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 claims description 24
- 239000004830 Super Glue Substances 0.000 claims description 14
- -1 Polysulfonyl chloride Polymers 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- UXJHQBVRZUANLK-UHFFFAOYSA-N azanylidyne(dichloro)-$l^{5}-phosphane Chemical compound ClP(Cl)#N UXJHQBVRZUANLK-UHFFFAOYSA-N 0.000 claims description 4
- ZYZDQXHUSKJJMK-UHFFFAOYSA-N 1,3,5-triazinane-2,4,6-trione trihydrochloride Chemical compound Cl.Cl.Cl.O=C1NC(=O)NC(=O)N1 ZYZDQXHUSKJJMK-UHFFFAOYSA-N 0.000 claims description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 150000007519 polyprotic acids Polymers 0.000 claims description 3
- 150000004756 silanes Chemical class 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- LIYZTOZNELDKQE-UHFFFAOYSA-N chloro-[2-[[chloro(hydroxy)phosphoryl]oxymethyl]-3-hydroxy-2-(hydroxymethyl)propoxy]phosphinic acid Chemical compound OP(=O)(Cl)OCC(CO)(CO)COP(O)(Cl)=O LIYZTOZNELDKQE-UHFFFAOYSA-N 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 description 30
- 239000000853 adhesive Substances 0.000 description 27
- 238000010438 heat treatment Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- BYLOHCRAPOSXLY-UHFFFAOYSA-N dichloro(diethyl)silane Chemical compound CC[Si](Cl)(Cl)CC BYLOHCRAPOSXLY-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- FGBJXOREULPLGL-UHFFFAOYSA-N ethyl cyanoacrylate Chemical compound CCOC(=O)C(=C)C#N FGBJXOREULPLGL-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- YVOFTMXWTWHRBH-UHFFFAOYSA-N pentanedioyl dichloride Chemical compound ClC(=O)CCCC(Cl)=O YVOFTMXWTWHRBH-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- ZLYYJUJDFKGVKB-OWOJBTEDSA-N (e)-but-2-enedioyl dichloride Chemical compound ClC(=O)\C=C\C(Cl)=O ZLYYJUJDFKGVKB-OWOJBTEDSA-N 0.000 description 1
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000005047 Allyltrichlorosilane Substances 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- PWAXUOGZOSVGBO-UHFFFAOYSA-N adipoyl chloride Chemical compound ClC(=O)CCCCC(Cl)=O PWAXUOGZOSVGBO-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
- CJPIDIRJSIUWRJ-UHFFFAOYSA-N benzene-1,2,4-tricarbonyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C(C(Cl)=O)=C1 CJPIDIRJSIUWRJ-UHFFFAOYSA-N 0.000 description 1
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- ALIQZUMMPOYCIS-UHFFFAOYSA-N benzene-1,3-disulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC(S(Cl)(=O)=O)=C1 ALIQZUMMPOYCIS-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- IRXBNHGNHKNOJI-UHFFFAOYSA-N butanedioyl dichloride Chemical compound ClC(=O)CCC(Cl)=O IRXBNHGNHKNOJI-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- ITVPBBDAZKBMRP-UHFFFAOYSA-N chloro-dioxido-oxo-$l^{5}-phosphane;hydron Chemical compound OP(O)(Cl)=O ITVPBBDAZKBMRP-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 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
- WMPOZLHMGVKUEJ-UHFFFAOYSA-N decanedioyl dichloride Chemical compound ClC(=O)CCCCCCCCC(Cl)=O WMPOZLHMGVKUEJ-UHFFFAOYSA-N 0.000 description 1
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 1
- UOZZKLIPYZQXEP-UHFFFAOYSA-N dichloro(dipropyl)silane Chemical compound CCC[Si](Cl)(Cl)CCC UOZZKLIPYZQXEP-UHFFFAOYSA-N 0.000 description 1
- YCEQUKAYVABWTE-UHFFFAOYSA-N dichloro-methyl-prop-2-enylsilane Chemical compound C[Si](Cl)(Cl)CC=C YCEQUKAYVABWTE-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 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
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-N n-Decanedioic acid Natural products OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- BCXWMIMRDMIJGL-UHFFFAOYSA-N naphthalene-1,5-disulfonyl chloride Chemical compound C1=CC=C2C(S(=O)(=O)Cl)=CC=CC2=C1S(Cl)(=O)=O BCXWMIMRDMIJGL-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000005054 phenyltrichlorosilane Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- SXYFKXOFMCIXQW-UHFFFAOYSA-N propanedioyl dichloride Chemical compound ClC(=O)CC(Cl)=O SXYFKXOFMCIXQW-UHFFFAOYSA-N 0.000 description 1
- ZTYMNUBYYQNBFP-UHFFFAOYSA-N propyl 2-cyanoprop-2-enoate Chemical compound CCCOC(=O)C(=C)C#N ZTYMNUBYYQNBFP-UHFFFAOYSA-N 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000008053 sultones Chemical class 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- SIPHWXREAZVVNS-UHFFFAOYSA-N trichloro(cyclohexyl)silane Chemical compound Cl[Si](Cl)(Cl)C1CCCCC1 SIPHWXREAZVVNS-UHFFFAOYSA-N 0.000 description 1
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 1
- HKFSBKQQYCMCKO-UHFFFAOYSA-N trichloro(prop-2-enyl)silane Chemical compound Cl[Si](Cl)(Cl)CC=C HKFSBKQQYCMCKO-UHFFFAOYSA-N 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Description
本発明は耐熱性を有する２―シアノアクリレー
ト系接着剤に関するものである。２―シアノアク
リレート系接着剤は被着材の表面に微量吸着され
ている水分で、常温にて瞬間的に硬化するため各
種産業分野において、プラスチツクス、ゴム、ガ
ラス、金属などの接着において瞬間接着剤として
利用されている。しかしながら２―シアノアクリ
レート系接着剤は高い抗張力と非常に速い接着速
度を有している反面、耐衝撃性、耐はく離性、耐
熱性に必ずしも満足できる性能をもつていないた
め、使用が制限される分野がある。２―シアノア
クリレート系接着剤は、２―シアノアクリレート
を主成分とし、極めて少量の安定剤、増粘剤、可
塑剤、架橋剤などが添加されてなるもので、一般
的には、２―シアノアクリレート系接着剤中の２
―シアノアクリレートの濃度が高い程、瞬間接着
剤としての性能が向上する傾向にあるため、この
接着剤を改質すべく、他の成分を種々添加する
と、２―シアノアクリレートの濃度が低下し瞬間
接着性を失なつたり、あるいは貯蔵安定性を欠い
たりする。そろため今迄に２―シアノアクリレー
ト系接着剤に他の成分を添加して接着剤の性能を
改質する試みは成功することがまれであつた。本
発明者等は、２―シアノアクリレート系接着剤に
その改質のために他の成分を添加すると瞬間接着
着剤としての性能が失われるという矛盾の中で２
―シアノアクリレート系接着剤に他の成分を添加
することにより、本来の接着性能を失なうことな
く、接着剤としての性能、特に耐熱性を改良すべ
く研究した結果、本発明を完成した。
即わち、本発明は２―シアノアクリレートと多
塩基酸クロリド、イソシアヌル酸トリクロリド、
ホスホニトリルクロリド、ポリスルホニルクロリ
ド、ペンタエリスリトールピス（クロロホスフエ
ート）、多価アルコールのポリクロロホーメート
及び塩素化シラン等の塩素含有化合物の一種以上
を含有する２―シアノアクリレート系接着剤組成
物に関するものであり、本発明者らが上記塩素含
有化合物を含有させることによつて耐熱性の改良
された２―シアノアクリレート系接着剤が得られ
ることを見い出して、本発明を完成させたもので
ある。
本発明に用いられる２―シアノアクリレートと
しては、通常のエステルがなんら支障なく使用で
きる。具体的には例えばメチル、エチル、ｎ―プ
ロピル、ｉ―プロピル、ｎ―ブチル、ｉ―ブチ
ル、sec―ブチル、ｔ―ブチル、アミル、ｎ―ヘ
キシル、シクロヘキシル、ヘブチル、ｎ―オクチ
ル、２―エチルヘキシル、ドデシル、アリル、プ
ロパギル、ベンジル、フエニル、２―メトキシエ
チル、２―エトキシエチル、２―クロロエチル、
ヘキサフルオロイソプロピル、トリフルオロエチ
ル、２―シアノエチル等の２―シアノアクリレー
トである。
本発明において改質剤として用いられる塩素含
有化合物は次の様なものである。
１ 多塩基酸クロリドは次の一般式で表わされる
もので
The present invention relates to a 2-cyanoacrylate adhesive having heat resistance. 2-Cyanoacrylate adhesive is a small amount of water adsorbed on the surface of the adherend, and because it instantly hardens at room temperature, it is used as an instant adhesive for bonding plastics, rubber, glass, metal, etc. in various industrial fields. It is used as a drug. However, while 2-cyanoacrylate adhesives have high tensile strength and extremely fast adhesion speed, they do not always have satisfactory performance in terms of impact resistance, peeling resistance, and heat resistance, which limits their use. There are fields. 2-cyanoacrylate adhesives are mainly composed of 2-cyanoacrylate, with the addition of very small amounts of stabilizers, thickeners, plasticizers, crosslinking agents, etc. 2 in acrylate adhesive
-The higher the concentration of cyanoacrylate, the better the performance as an instant adhesive. Therefore, when various other ingredients are added to modify this adhesive, the concentration of 2-cyanoacrylate decreases and instant adhesive properties improve. loses its properties or lacks storage stability. For this reason, attempts to modify the performance of 2-cyanoacrylate adhesives by adding other components to them have rarely been successful. The inventors of the present invention discovered 2-cyanoacrylate based on the contradiction that if other components were added to modify the adhesive, its performance as an instant adhesive would be lost.
-The present invention was completed as a result of research aimed at improving adhesive performance, especially heat resistance, without losing the original adhesive performance by adding other components to cyanoacrylate adhesives. That is, the present invention uses 2-cyanoacrylate, polybasic acid chloride, isocyanuric acid trichloride,
2-cyanoacrylate adhesive composition containing one or more chlorine-containing compounds such as phosphonitrile chloride, polysulfonyl chloride, pentaerythritol pis (chlorophosphate), polychloroformate of polyhydric alcohol, and chlorinated silane. The present invention was completed by the present inventors who discovered that a 2-cyanoacrylate adhesive with improved heat resistance could be obtained by incorporating the above-mentioned chlorine-containing compound. . As the 2-cyanoacrylate used in the present invention, ordinary esters can be used without any problem. Specifically, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, amyl, n-hexyl, cyclohexyl, hebutyl, n-octyl, 2-ethylhexyl. , dodecyl, allyl, propargyl, benzyl, phenyl, 2-methoxyethyl, 2-ethoxyethyl, 2-chloroethyl,
2-cyanoacrylates such as hexafluoroisopropyl, trifluoroethyl, and 2-cyanoethyl. The chlorine-containing compounds used as modifiers in the present invention are as follows. 1 Polybasic acid chloride is represented by the following general formula.
【式】【formula】
【式】
（但し、Ｒは脂肪族、芳香族の炭化水素残基
であり、ｎは２以上、ｍは１以上の整数であ
る。）具体的には例えば、マロン酸ジクロリド、
コハク酸ジクロリド、グルタル酸ジクロリド、
アジピン酸ジクロリド、セバシン酸ジクロリ
ド、フマル酸ジクロリド、フタル酸ジクロリ
ド、イソフタル酸ジクロリド、トリメリツト酸
トリクロリド、ピロメリツト酸テトラクロリ
ド、テレフタル酸ジクロリド、トリメリツト酸
モノクロリド酸無水物、などである。
２ イソシアヌル酸トリクロリド
３ ホスホニトリルクロリドは次の一般式で示さ
れる環状または鎖状化合物であり、
（―Ｎ＝PCl2）―p
（但しＰは３以上の整数である）
具体的には例えばホスホニトリルジクロリド
シクロトリマー、ホスホニトリルジクロリドシ
クロテトラマー、ホスホニトリルジクロリドポ
リマーなどである。
４ ポリスルホニルクロリドは次の一般式で表わ
されるもので、
Ｒ（―SO2Cl）o
（但し、Ｒは脂肪族、芳香族の炭化水素残基
であり、ｎは２以上の整数）
具体的には例えばｍ―ベンゼンジスルホニルク
ロリド、１，５―ナフタレンジスルホニルクロ
リドなど。
５ ペンタエリスリトールビス（クロロホスフエ
ート）
６ 多価アルコールのポリクロロホーメートは次
の一般式で表わされるもので、
（但し、Ｒは脂肪族、芳香族の炭化水素残基
であり、ｎは２以上の整数。）
具体的には例えば、エチレングリコールのジ
クロロホーメート、ジエチレングリコールのジ
クロロホーメート、１，４―ブタンジオールの
ジクロロホーメート、ビスフエノーール―Ａの
ジクロロホーメートなどである。
７ 塩素化シラン、次の一般式で表わされるもの
で、
（Ｒ）4-oSiClo
（但し、Ｒは脂肪族、芳香族炭化水素残基で
あり、ｎは２又は３）
具体的には例えばジメチルジクロロシラン、ジ
エチルジクロロシラン、ジプロピルジクロロシ
ラン、アリルメチルジクロロシラン、ジフエニ
ルジクロロシラン、メチルトリクロロシラン、
アリルトリクロロシラン、ベンジルトリクロロ
シラン、フエニルトリクロロシラン、シクロヘ
キシルトリクロロシラン、などである。
本発明において上記の塩素含有化合物がどのよ
うな作用により、２―シアノアクリレート系接着
剤の耐熱性を改善するのか明らかではないが、い
ずれも非常に活性な物質でありこれらの活性な物
質が、２―シアノアクリレートの硬化時において
重合体に組み込まれ、架橋結合などにより増強さ
れた、重合体構造を与えるものと考えられる。
かかる改質剤の添加量は２―シアノアクリレー
トとこれらの改質剤からなる接着剤中の0.0001重
量％以上10重量％以下、好ましくは0.001重量％
以上５重量％以下の範囲がよく、添加量が10重量
％を越えると溶解性が悪くなり、硬化速度が低下
し、さらに接着強さも下がる傾向にあり、また添
加量が0.0001重量％より少ないと耐熱性の向上は
みられない。
通常２―シアノアクリレート系接着剤は安定
剤、増粘剤、可塑剤、架橋剤を含有しているが、
本発明においてもこれらの添加剤は何ら支障をき
たすことはなく本発明の接着剤に併用できる。
これらの添加剤は一般的なものでよいが例え
ば、安定剤としてはSO2、スルホン酸類、サルト
ン、ラクトン、弗化水素、ハイドロキノン、ハイ
ドロキノンモノメチルエーテル、カテコール、ピ
ロガロール等を本発明の接着剤に１〜1000ppm添
加することができる。増粘剤としては、ポリメチ
ルメタクリレート、２―シアノアクリレートポリ
マー、アクリルゴム等のポリマーを要求される粘
度に応じて本発明の接着剤に対し数％程度添加す
ればよい。
又、２―シアノアクリレートポリマーは柔軟性
に欠けるため、ジオクチルフタレート、セバシン
酸エステル、リン酸エステル等の可塑剤を本発明
の接着剤に加え、硬化した接着剤の柔軟性を向上
させることもできる。
本発明で得られる接着剤は、鉄、ステンレスス
チール、銅、黄銅、アルミニウム、亜鉛、錫、フ
エライトなどの金属類、又これ以外のプラスチツ
クス、ガラス、陶器、ゴム等の接着に使用可能
で、耐熱性の要求される分野に使用される。
使用においては通常の２―シアノアクリレート
系接着剤と同様に瞬間接着剤としての使用が可能
である。
以下、本発明を実施例に従つて説明する。尚接
着強さの測定法はJISK6850の引張剪断接着強さ
測定法に準拠した。又以下の実施例の部はいずれ
も重量部を表わす。
実施例 １
エチル２―シアノアクリレート98部に対して、
グルタル酸ジクロリド２部を添加すると容易に均
一溶液となる。このものの瞬間接着性をみるた
め、１cm2の接着面積をもつ天然ゴム同志を接着し
たところ、５秒後に完全固着し、５Kgの引張荷重
に耐え瞬間接着性は、２―シアノアクリレート系
接着剤と同等であつた。
この接着剤を用いて鉄―鉄の接着を23℃、60％
RHの雰囲気下で行ない、同条件下で24時間養生
させた。
養生後120℃に設定した定温送風乾燥器内に接
着物を入れ、一定時間毎に取り出し、120℃加熱
下における引張剪断接着強さを測定したところ、
１時間加熱後で160Kg／cm2を示した。また、72時
間加熱後でも150Kg／cm2を示し、明らかに耐熱性
の向上が見られた。本発明の接着剤組成物の安定
性は充分に実用可能な範囲にあつて、60℃恒温槽
内で50日間安定であつた。
実施例 ２〜６
安定剤として、SO250ppmと塩素含有化合物を
表―１のように含有する２―シアノアクリレート
系接着剤を使用し実施例１と同様の操作により、
一定時間加熱後の接着強さを測定した。[Formula] (However, R is an aliphatic or aromatic hydrocarbon residue, n is an integer of 2 or more, and m is an integer of 1 or more.) Specifically, for example, malonic acid dichloride,
Succinic acid dichloride, glutaric acid dichloride,
These include adipic acid dichloride, sebacic acid dichloride, fumaric acid dichloride, phthalic acid dichloride, isophthalic acid dichloride, trimellitic acid trichloride, pyromellitic acid tetrachloride, terephthalic acid dichloride, trimellitic acid monochloride acid anhydride, and the like. 2 Isocyanuric acid trichloride 3 Phosphonitrile chloride is a cyclic or chain compound represented by the following general formula, (-N=PCl 2 )- p (where P is an integer of 3 or more) Specifically, for example, phosphonitrile chloride These include nitrile dichloride cyclotrimer, phosphonitrile dichloride cyclotetramer, phosphonitrile dichloride polymer, and the like. 4 Polysulfonyl chloride is represented by the following general formula: R(-SO 2 Cl) o (where, R is an aliphatic or aromatic hydrocarbon residue, and n is an integer of 2 or more) Specific Examples include m-benzenedisulfonyl chloride and 1,5-naphthalenedisulfonyl chloride. 5 Pentaerythritol bis(chlorophosphate) 6 Polychloroformate of polyhydric alcohol is represented by the following general formula, (However, R is an aliphatic or aromatic hydrocarbon residue, and n is an integer of 2 or more.) Specifically, for example, dichloroformate of ethylene glycol, dichloroformate of diethylene glycol, 1,4-butane These include dichloroformate of diol and dichloroformate of bisphenol-A. 7 Chlorinated silane, represented by the following general formula, (R) 4-o SiCl o (where R is an aliphatic or aromatic hydrocarbon residue, and n is 2 or 3) Specifically: For example, dimethyldichlorosilane, diethyldichlorosilane, dipropyldichlorosilane, allylmethyldichlorosilane, diphenyldichlorosilane, methyltrichlorosilane,
Allyltrichlorosilane, benzyltrichlorosilane, phenyltrichlorosilane, cyclohexyltrichlorosilane, etc. In the present invention, it is not clear how the above-mentioned chlorine-containing compounds improve the heat resistance of the 2-cyanoacrylate adhesive, but all of them are very active substances, and these active substances It is thought that it is incorporated into the polymer when the 2-cyanoacrylate is cured, giving it a polymer structure reinforced by crosslinking or the like. The amount of such a modifier added is 0.0001% by weight or more and 10% by weight or less, preferably 0.001% by weight in the adhesive consisting of 2-cyanoacrylate and these modifiers.
The range of 5% by weight or less is good; if the amount added exceeds 10% by weight, the solubility will deteriorate, the curing speed will decrease, and the adhesive strength will also tend to decrease, and if the amount added is less than 0.0001% by weight, No improvement in heat resistance was observed. Usually, 2-cyanoacrylate adhesives contain stabilizers, thickeners, plasticizers, and crosslinking agents.
In the present invention, these additives can be used in combination with the adhesive of the present invention without causing any problems. These additives may be common additives, but for example, stabilizers such as SO 2 , sulfonic acids, sultones, lactones, hydrogen fluoride, hydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol may be added to the adhesive of the present invention. ~1000ppm can be added. As a thickener, a polymer such as polymethyl methacrylate, 2-cyanoacrylate polymer, or acrylic rubber may be added in an amount of about several percent to the adhesive of the present invention depending on the required viscosity. Furthermore, since 2-cyanoacrylate polymers lack flexibility, a plasticizer such as dioctyl phthalate, sebacic acid ester, phosphoric acid ester, etc. can be added to the adhesive of the present invention to improve the flexibility of the cured adhesive. . The adhesive obtained in the present invention can be used to bond metals such as iron, stainless steel, copper, brass, aluminum, zinc, tin, and ferrite, as well as other materials such as plastics, glass, ceramics, and rubber. Used in fields that require heat resistance. In use, it can be used as an instant adhesive in the same way as ordinary 2-cyanoacrylate adhesives. Hereinafter, the present invention will be explained according to examples. The adhesive strength was measured in accordance with JISK6850 tensile shear adhesive strength measuring method. In addition, all parts in the following examples represent parts by weight. Example 1 For 98 parts of ethyl 2-cyanoacrylate,
Addition of 2 parts of glutaric acid dichloride easily results in a homogeneous solution. In order to check the instant adhesive properties of this product, we glued two pieces of natural rubber with an adhesion area of 1 cm 2 together. After 5 seconds, they completely adhered and withstood a tensile load of 5 kg, and the instant adhesive properties were comparable to those of 2-cyanoacrylate adhesives. It was the same. Using this adhesive, bond iron to iron at 23℃, 60%
It was carried out in an RH atmosphere and allowed to cure for 24 hours under the same conditions. After curing, the adhesive was placed in a constant temperature blow dryer set at 120°C, taken out at regular intervals, and the tensile shear adhesive strength was measured under heating at 120°C.
It showed 160Kg/cm 2 after heating for 1 hour. Moreover, even after heating for 72 hours, it showed 150 Kg/cm 2 , clearly showing an improvement in heat resistance. The stability of the adhesive composition of the present invention was within a sufficiently practical range, and was stable for 50 days in a constant temperature bath at 60°C. Examples 2 to 6 A 2-cyanoacrylate adhesive containing 50 ppm of SO 2 and a chlorine-containing compound as shown in Table 1 was used as a stabilizer, and the same procedure as in Example 1 was carried out.
The adhesive strength was measured after heating for a certain period of time.
【表】
比較例 １
エチル２―シアノアクリレートを用いて鉄―鉄
の接着を23℃、60％RHの雰囲気下でおこない、
同条件下で24時間養生させた。
この試験片を120℃で１時間加熱したのち、同
温度下で引張剪断接着強さを測定したところ50
Kg／cm2であつた。また120℃、72時間加熱したも
のは25Kg／cm2であつた。
比較例 ２
プロピル―２―シアノアクリレートを用いて比
較例１と同様の操作により一定時間加熱後の接着
強さを測定した。120℃、１時間加熱後測定した
ところ、40Kg／cm2、また120℃、72時間加熱後で
は15Kg／cm2であつた。
実施例 ７〜12
安定剤SO250ppmと塩素含有化合物を表―２の
ように含有する２―シアノアクリレートを使用
し、、実施例１と同様の操作により、一定時間加
熱後の接着強さを測定し、次の結果を得た。[Table] Comparative Example 1 Iron-iron bonding was performed using ethyl 2-cyanoacrylate in an atmosphere of 23°C and 60% RH.
It was cured for 24 hours under the same conditions. After heating this test piece at 120℃ for 1 hour, the tensile shear adhesive strength was measured at the same temperature.
It was Kg/ cm2 . Moreover, the weight was 25Kg/cm 2 when heated at 120°C for 72 hours. Comparative Example 2 Using propyl-2-cyanoacrylate, the adhesive strength after heating for a certain period of time was measured in the same manner as in Comparative Example 1. When measured after heating at 120°C for 1 hour, it was 40Kg/cm 2 , and after heating at 120°C for 72 hours, it was 15Kg/cm 2 . Examples 7 to 12 Using 2-cyanoacrylate containing 50 ppm of stabilizer SO 2 and a chlorine-containing compound as shown in Table 2, the adhesive strength after heating for a certain period of time was measured in the same manner as in Example 1. The following results were obtained.
【表】【table】
Claims (1)
0.0001重量％以上10重量％以下含有する２―シア
ノアクリレート系接着剤組成物。 (A) 多塩基酸クロリド (B) イソシアヌル酸トリクロリド (C) ホスホニトリルクロリド (D) ポリスルホニルクロリド (E) ペンタエリスリトールビス（クロロホスフエ
ート） (F) 多価アルコールのポリクロロホーメート (G) 塩素化シラン[Claims] 1. One or more of the following chlorine-containing compounds:
A 2-cyanoacrylate adhesive composition containing 0.0001% by weight or more and 10% by weight or less. (A) Polybasic acid chloride (B) Isocyanuric acid trichloride (C) Phosphonitrile chloride (D) Polysulfonyl chloride (E) Pentaerythritol bis(chlorophosphate) (F) Polychloroformate of polyhydric alcohol (G) chlorinated silane
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12308381A JPS5825377A (en) | 1981-08-07 | 1981-08-07 | Adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12308381A JPS5825377A (en) | 1981-08-07 | 1981-08-07 | Adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5825377A JPS5825377A (en) | 1983-02-15 |
| JPH0142313B2 true JPH0142313B2 (en) | 1989-09-12 |
Family
ID=14851770
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12308381A Granted JPS5825377A (en) | 1981-08-07 | 1981-08-07 | Adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5825377A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR9711198A (en) * | 1996-08-16 | 1999-08-17 | Loctite Ireland Ltd | Adhesive cyanoacrylate compositions for glass junction |
| JP2005162850A (en) * | 2003-12-02 | 2005-06-23 | Koatsu Gas Kogyo Co Ltd | Adhesive for thermoplastic elastomer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS48103633A (en) * | 1972-04-14 | 1973-12-26 | ||
| JPS57174368A (en) * | 1981-04-20 | 1982-10-27 | Taoka Chem Co Ltd | Heat-resistant adhesive composition |
-
1981
- 1981-08-07 JP JP12308381A patent/JPS5825377A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS48103633A (en) * | 1972-04-14 | 1973-12-26 | ||
| JPS57174368A (en) * | 1981-04-20 | 1982-10-27 | Taoka Chem Co Ltd | Heat-resistant adhesive composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5825377A (en) | 1983-02-15 |
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