JPH0153912B2 - - Google Patents
Info
- Publication number
- JPH0153912B2 JPH0153912B2 JP10564382A JP10564382A JPH0153912B2 JP H0153912 B2 JPH0153912 B2 JP H0153912B2 JP 10564382 A JP10564382 A JP 10564382A JP 10564382 A JP10564382 A JP 10564382A JP H0153912 B2 JPH0153912 B2 JP H0153912B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- weight
- polyvalent metal
- adhesive
- added
- 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
- 239000000203 mixture Substances 0.000 claims description 38
- 239000000853 adhesive Substances 0.000 claims description 30
- 230000001070 adhesive effect Effects 0.000 claims description 30
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 22
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 19
- 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 claims description 17
- 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 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 14
- 150000002736 metal compounds Chemical class 0.000 claims description 10
- 239000012736 aqueous medium Substances 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 2
- 150000003752 zinc compounds Chemical class 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000012790 adhesive layer Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- -1 phosphoric acid aluminum Chemical compound 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000004821 Contact adhesive Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 2
- 229940007718 zinc hydroxide Drugs 0.000 description 2
- YPGLTKHJEQHKSS-ASZLNGMRSA-N (1r,4ar,4bs,7r,8as,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,7,8,8a,9,10,10a-dodecahydrophenanthrene-1-carboxylic acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@@H](C(C)C)C[C@@H]2CC1 YPGLTKHJEQHKSS-ASZLNGMRSA-N 0.000 description 1
- UZZYXZWSOWQPIS-UHFFFAOYSA-N 3-fluoro-5-(trifluoromethyl)benzaldehyde Chemical compound FC1=CC(C=O)=CC(C(F)(F)F)=C1 UZZYXZWSOWQPIS-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000010237 calcium benzoate Nutrition 0.000 description 1
- 239000004301 calcium benzoate Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- HZQXCUSDXIKLGS-UHFFFAOYSA-L calcium;dibenzoate;trihydrate Chemical compound O.O.O.[Ca+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 HZQXCUSDXIKLGS-UHFFFAOYSA-L 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- ZADYMNAVLSWLEQ-UHFFFAOYSA-N magnesium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[Mg+2].[Si+4] ZADYMNAVLSWLEQ-UHFFFAOYSA-N 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920006173 natural rubber latex Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- KIOWHOMJXAQSMW-UHFFFAOYSA-N phenol;4,6,6-trimethylbicyclo[3.1.1]hept-3-ene Chemical compound OC1=CC=CC=C1.CC1=CCC2C(C)(C)C1C2 KIOWHOMJXAQSMW-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920006174 synthetic rubber latex Polymers 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229960000314 zinc acetate Drugs 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- JDLYKQWJXAQNNS-UHFFFAOYSA-L zinc;dibenzoate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 JDLYKQWJXAQNNS-UHFFFAOYSA-L 0.000 description 1
- NRINZBKAERVHFW-UHFFFAOYSA-L zinc;dicarbamate Chemical compound [Zn+2].NC([O-])=O.NC([O-])=O NRINZBKAERVHFW-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明はコンタクト型接着剤として用いて好適
な、カルボキシル化ポリクロロプレンを基本樹脂
とする耐水性にすぐれた接着剤組成物に関するも
のである。
コンタクト型接着剤とは一般に、被着体の接着
しようとする夫々の面に塗布した後暫く放置乾燥
しその後に該塗布面同志を単にコンタクト（接
触）させる丈で特に長時間の加熱加圧等の養生を
要せずに接着可能な接着剤をいう。
ポリクロロプレンを主成分とした固形分が水性
媒体中に分散された接着剤組成物は従来よりコン
タクト型接着剤として使用されており、カルボキ
シル化ポリクロロプレンラテツクスに多価金属の
酸化物又は水酸化物が添加されてなる接着剤組成
物が知られている。この組成物は、常温において
上記カルボキシル化ポリクロロプレンと多価金属
酸化物等との架橋反応が進行し接着剤としてすぐ
れた高温接着力を示すが、一方、経時により、粘
着性が著しく低下しコンタクト接着性が損われる
ので、上記架橋反応の速度を緩やかにするという
目的で水酸化ナトリウムや水酸化カリウム等のア
ルカリが多価金属の酸化物等と共に添加されてい
た。従つてこの組成物を用いると被着体間に形成
される接着剤層にもアルカリ分が残留する為、耐
水性が極めて悪く、接着部分に水が接触するよう
な用途には実用的に使用出来ないのが現状であつ
た。
本発明は固形分が水性媒体中に分散された上記
従来の接着剤組成物の欠点に鑑み、特に耐水性に
すぐれた水性媒体に分散された接着剤組成物を提
供することを目的としてなされたものでその要旨
は、水性媒体にカルボキシル化ポリクロロプレ
ン、多価金属化合物、ロジンフエノール及びアン
モニアもしくは炭素数が５以下の有機アミンが添
加分散されてなる接着剤組成物に存する。
本発明におけるカルボキシル化ポリクロロプレ
ンは分子中にカルボキシル基を有し、好ましくは
１分子中に２個以上のカルボキシル基を有するポ
リクロロプレンであり、例えばクロロブタジエン
とメタクリル酸等のカルボキシル基含有重合性単
量体とを乳化重合法等の従来公知の方法で重合す
ることにより得られる。
本発明における多価金属化合物とは第〜第
族の金属陽イオンの酸化物、水酸化物又は無機酸
もしくは有機酸との塩を意味し、具体例としては
酸化マグネシウム、酸化カルシウム、酸化亜鉛、
酸化アルミニウムなどの金属酸化物、水酸化マグ
ネシウム、水酸化カルシウム、水酸化亜鉛、水酸
化アルミニウムなどの金属水酸化物、硫酸マグネ
シウム、硫酸カルシウム、硫酸亜鉛、硫酸アルミ
ニウム、リン酸マグネシウム、リン酸カルシウ
ム、リン酸アルミニウム、ケイ酸マグネシウム、
ケイ酸アルミニウムなどの無機酸塩、酢酸カルシ
ウム、酢酸アルミニウム、酢酸亜鉛、安息香酸カ
ルシウム、安息香酸亜鉛、カルバミン酸亜鉛等の
有機酸塩が挙げられ、特に亜鉛化合物が好適に用
いられる。
これらの金属化合物は単独で又は適宜組合わせ
て用いられ、その使用量は金属化合物の種類、被
着体の種類、用途等によつて異なるが、少な過ぎ
ると最終的に形成される接着剤層の強度が弱く又
耐水性に劣つたものとなり、多過ぎると接着剤層
が脆くなつたりするので、上記カルボキシル化ポ
リクロロプレン100重量部に対し、一般に0.3〜15
重量部、好ましくは0.5〜６重量部とされる。
本発明におけるロジンフエノールとはロジンと
芳香族系アルコールとの反応生成物を意味し、そ
の殆んどは縮合生成物であると推定される。特に
樹脂酸として、アビエチン酸、ジヒドロアビエチ
ン酸、テトラヒドロアビエチン酸もしくはデキス
トロビマル酸を多量に含有するロジンとフエノー
ル類との反応物が、組成物に粘着性を与えると共
に被着体表面に対する接着力を付与する性質が大
きい点で好ましい。
ロジンフエノールは、クマロン−インデン樹
脂、脂肪族及び芳香族系石油樹脂、テルペン類等
の他の粘着性付与樹脂と併用されてもよく、その
使用量はカルボキシル化ポリクロロプレン100重
量部に対し一般に５〜200重量部、好ましくは20
〜100重量部とされ、通常はトルエン、キシレン
等の溶剤に予め溶解もしくは分散した形で用いら
れる。
本発明におけるアンモニアもしくは炭素数が５
以下の有機アミンは、通常水溶液として用いら
れ、有機アミンの具体例としてはメチルアミン、
エチルアミン等の脂肪族アミンの他モルホリン等
が挙げられ、特にアンモニアが好適に用いられ
る。
その使用量は上記カルボキシル化ポリクロロプ
レンのカルボキシル基１モルに対し一般に0.8〜
2.5モル、好ましくは1.0〜1.7モルとされる。
本発明組成物には、被着体への接着性や形成さ
れた接着剤層の耐水性等を改善することを目的と
して微粒子状シリカが添加分散されていてもよ
い。
かかるシリカは予め水中に分散されてコロイド
状をなしアルカリイオンによつてシリカ微粒子の
回りに電気二重層が形成された状態のものが使用
されるが、場合によつては、カルボキシル化ポリ
クロロプレン等の本発明における必須成分が添加
混合された水分散組成物中に直接添加されてもよ
い。
又、本発明組成物には更にヒンダードフエノー
ル系等の酸化防止剤、着色剤、充填剤、界面活性
剤、可塑剤、増粘剤、造膜形成促進剤、天然もし
くは合成ゴムラテツクス等が添加されていてもよ
い。
本発明組成物中の水性媒体即ち水と必要により
加えられた溶剤の量は特に限定されるものではな
いが、少な過ぎると組成物の粘度が高くて被着体
に塗布する際の作業性が悪く又多過ぎると乾燥に
要する工数が大となるので一般に30〜80重量％と
される。又、水性媒体中の水の量は通常50重量％
以上とされる。しかして被着体としては通常鉄等
の金属や各種合成樹脂が用いられるが木材等にも
使用可能である。
本発明組成物が耐水性に優れた接着剤層を形成
する理由は充分に明らかではないが、例えば、ア
ンモニアが上記多価金属化合物よりもカルボキシ
ル化ポリクロロプレンと反応し易い為、水性媒体
に分散されてなる組成物中でカルボキシル化ポリ
クロロプレンはアンモニウム塩を形成し金属化合
物と該ポリクロロプレンによる架橋反応は阻害さ
れるが、この組成物が被着体に塗布、乾燥される
と共にアンモニア分が揮発し、その後例えば塗布
された被着体同志が接触した状態で、常温下にカ
ルボキシル化ポリクロロプレンと上記多価金属と
の架橋反応が進行していくことと、粘着性付与樹
脂としてロジンフエノールを用いたことによるも
のと推定される。
本発明接着剤組成物は上述の通りの構成になさ
れており、優れた常態接着力を有し且つ従来のポ
リクロロプレン含有コンタクト型接着剤に比して
良好な耐熱性及び優れた耐水性を有する接着剤層
を形成するのである。
以下本発明を実施例によつて更に詳細に説明す
る。
実施例 １
ロジンフエノール（レジンSP560、スケネクタ
デイケミカル社製）50重量部をトルエン25重量部
に溶解した溶液に界面活性剤としてポリエチレン
グリコールアルキルフエニルエーテル５重量部及
び水30重量部を加え高速撹拌機にて混合しロジン
フエノールのエマルジヨンを得た。このエマルジ
ヨンにカルボキシル化ポリクロロプレンラテツク
ス（ネオプレンラテツクス115、固型分47％、昭
和ネオプレン社製）200重量部を加えよく撹拌し、
撹拌しながら28重量％アンモニア水３重量部（ア
ンモニア対カルボキシル化ポリクロロプレンのカ
ルボキシル基のモル比は1.5）を加え、更に、活
性亜鉛華３重量部を水４重量部に分散させた分散
液を加えて撹拌し、水性媒体に分散したコンタク
ト型接着剤組成物を得た。
この接着剤を25mm×125mm×0.6mmのアルミニウ
ム板と25mm×125mmの綿布に塗布（３回塗り）し
80℃で乾燥後ハンドロールで圧着してアルミニウ
ム板と綿布を接着し試験片とした。
室温にて試験片を４日間放置したのち20℃で
180゜剥離強度を測定し常態接着力を求めた。又、
残つた未測定の試験片を常温水中に４日間投入し
取り出した直後に20℃で180゜剥離強度を測定し耐
水接着力を求めた。その結果を第１表に示す。
実施例 ２
実施例１において活性亜鉛華３重量部の代りに
水酸化亜鉛３重量部を用いた以外は全て実施例１
と同様にして接着剤組成物を調整した。この組成
物を用い実施例１と同様にして試験片を作成し常
態接着力と耐水接着力を求めた。
その結果を第１表に示す。
実施例 ３
ロジンフエノールとして実施例１で用いたレジ
ンSP560，50重量部の代りにバーカムTD2615（大
日本インキ化学社製）50重量部を用いた以外は実
施例１と同様にして接着剤組成物を調整し、その
物性を測定し、結果を第１表に示した。
実施例 ４
ロジンフエノールとしてレジンSP560，50重量
部の代りにタマノール803（荒川化学工業社製）50
重量部を用いた以外は実施例１と同様にして接着
剤組成物を調整し、その物性を測定し、結果を第
１表に示した。
実施例 ５，６
第１表の５，６欄に示される組成の接着剤組成
物を調整し、その物性を測定し、結果を第１表に
示した。
実施例 ７
実施例１のロジンフエノール50重量部の代りに
ロジンフエノール25重量部と重合ロジン（ダイマ
レツクス、ハーキユレス社製）25重量部とを用い
た以外は実施例１と同様にして接着剤組成物を調
整し、その物性を測定し、結果を第１表に示し
た。
The present invention relates to an adhesive composition having excellent water resistance and containing carboxylated polychloroprene as a basic resin and suitable for use as a contact adhesive. Contact-type adhesives are generally adhesives that are applied to each surface of an adherend to be bonded, left to dry for a while, and then the coated surfaces are simply brought into contact (contact), especially by applying heat and pressure for a long time. An adhesive that can be bonded without requiring curing. Adhesive compositions in which a solid content mainly composed of polychloroprene is dispersed in an aqueous medium have traditionally been used as contact adhesives. Adhesive compositions containing additives are known. This composition exhibits excellent high-temperature adhesive strength as an adhesive due to the progress of the crosslinking reaction between the carboxylated polychloroprene and the polyvalent metal oxide at room temperature. Since adhesion is impaired, an alkali such as sodium hydroxide or potassium hydroxide has been added together with a polyvalent metal oxide in order to slow down the speed of the crosslinking reaction. Therefore, when this composition is used, alkaline content remains in the adhesive layer formed between the adherends, resulting in extremely poor water resistance, making it difficult to use in practical applications where water comes into contact with the adhesive part. The current situation was that it was not possible. The present invention was made in view of the drawbacks of the above-mentioned conventional adhesive compositions in which the solid content is dispersed in an aqueous medium, and an object of the present invention is to provide an adhesive composition in which the solid content is dispersed in an aqueous medium and has particularly excellent water resistance. The gist of the adhesive composition is an adhesive composition in which carboxylated polychloroprene, a polyvalent metal compound, rosin phenol, and ammonia or an organic amine having a carbon number of 5 or less are added and dispersed in an aqueous medium. The carboxylated polychloroprene in the present invention has a carboxyl group in the molecule, preferably two or more carboxyl groups in one molecule, and is, for example, a carboxyl group-containing polymerizable monomer such as chlorobutadiene and methacrylic acid. mer by a conventionally known method such as an emulsion polymerization method. In the present invention, the polyvalent metal compound refers to an oxide, hydroxide, or salt of a metal cation of group 1 to 3 with an inorganic or organic acid, and specific examples include magnesium oxide, calcium oxide, zinc oxide,
Metal oxides such as aluminum oxide, metal hydroxides such as magnesium hydroxide, calcium hydroxide, zinc hydroxide, aluminum hydroxide, magnesium sulfate, calcium sulfate, zinc sulfate, aluminum sulfate, magnesium phosphate, calcium phosphate, phosphoric acid aluminum, magnesium silicate,
Examples include inorganic acid salts such as aluminum silicate, and organic acid salts such as calcium acetate, aluminum acetate, zinc acetate, calcium benzoate, zinc benzoate, and zinc carbamate, and zinc compounds are particularly preferably used. These metal compounds are used alone or in appropriate combinations, and the amount used varies depending on the type of metal compound, type of adherend, purpose, etc., but if it is too small, the adhesive layer that is finally formed will be damaged. If the amount is too large, the adhesive layer may become brittle, so it is generally added between 0.3 and 15 parts by weight per 100 parts by weight of the carboxylated polychloroprene.
The amount is preferably 0.5 to 6 parts by weight. In the present invention, rosin phenol means a reaction product of rosin and an aromatic alcohol, and most of the rosin phenol is presumed to be a condensation product. In particular, the reaction product of phenols and rosin containing a large amount of abietic acid, dihydroabietic acid, tetrahydroabietic acid, or dextrobimaric acid as a resin acid gives the composition adhesiveness and adhesive strength to the adherend surface. It is preferable because it has a large property of imparting . Rosin phenol may be used in combination with other tackifying resins such as coumaron-indene resins, aliphatic and aromatic petroleum resins, and terpenes, and the amount used is generally 5 parts by weight per 100 parts by weight of carboxylated polychloroprene. ~200 parts by weight, preferably 20
~100 parts by weight, and is usually used in the form of a pre-dissolved or dispersed solution in a solvent such as toluene or xylene. Ammonia in the present invention or carbon number is 5
The following organic amines are usually used as aqueous solutions, and specific examples of organic amines include methylamine,
In addition to aliphatic amines such as ethylamine, morpholine and the like may be mentioned, and ammonia is particularly preferably used. The amount used is generally 0.8 to 1 mole of carboxyl group of the above carboxylated polychloroprene.
The amount is 2.5 mol, preferably 1.0 to 1.7 mol. Particulate silica may be added and dispersed in the composition of the present invention for the purpose of improving adhesion to adherends and water resistance of the formed adhesive layer. Such silica is used in the form of a colloid that has been dispersed in water in advance and an electric double layer is formed around the silica particles by alkali ions, but in some cases carboxylated polychloroprene, etc. The essential components of the present invention may be added directly to the aqueous dispersion composition. In addition, the composition of the present invention may further contain antioxidants such as hindered phenols, colorants, fillers, surfactants, plasticizers, thickeners, film formation promoters, natural or synthetic rubber latex, etc. You can leave it there. The amount of the aqueous medium, ie, water, and the solvent added as necessary in the composition of the present invention is not particularly limited, but if it is too small, the viscosity of the composition will be high and the workability when applying it to the adherend will be impaired. If the amount is too high, the number of steps required for drying will increase, so it is generally set at 30 to 80% by weight. Also, the amount of water in the aqueous medium is usually 50% by weight.
This is considered to be the above. As the adherend, metals such as iron and various synthetic resins are usually used, but wood and the like can also be used. The reason why the composition of the present invention forms an adhesive layer with excellent water resistance is not fully clear, but for example, ammonia reacts more easily with carboxylated polychloroprene than with the polyvalent metal compound, so it is dispersed in an aqueous medium. In the composition, the carboxylated polychloroprene forms an ammonium salt, and the crosslinking reaction between the metal compound and the polychloroprene is inhibited, but as the composition is applied to the adherend and dried, the ammonia content evaporates. Then, for example, when the coated adherends are in contact with each other, the crosslinking reaction between the carboxylated polychloroprene and the polyvalent metal proceeds at room temperature, and rosin phenol is used as the tackifying resin. It is presumed that this was due to the fact that The adhesive composition of the present invention has the above-mentioned structure, and has excellent normal adhesive strength, and has better heat resistance and water resistance than conventional contact adhesives containing polychloroprene. This forms an adhesive layer. The present invention will be explained in more detail below with reference to Examples. Example 1 5 parts by weight of polyethylene glycol alkyl phenyl ether and 30 parts by weight of water as surfactants were added to a solution of 50 parts by weight of rosin phenol (Resin SP560, manufactured by Schenecta Day Chemical Co., Ltd.) dissolved in 25 parts by weight of toluene and heated at high speed. The mixture was mixed using a stirrer to obtain a rosin phenol emulsion. 200 parts by weight of carboxylated polychloroprene latex (Neoprene Latex 115, solid content 47%, manufactured by Showa Neoprene Co., Ltd.) was added to this emulsion and stirred well.
While stirring, add 3 parts by weight of 28% ammonia water (the molar ratio of ammonia to the carboxyl group of carboxylated polychloroprene is 1.5), and then add a dispersion of 3 parts by weight of activated zinc white in 4 parts by weight of water. The mixture was added and stirred to obtain a contact type adhesive composition dispersed in an aqueous medium. Apply this adhesive to a 25mm x 125mm x 0.6mm aluminum plate and a 25mm x 125mm cotton cloth (3 coats).
After drying at 80°C, the aluminum plate and cotton cloth were bonded together using a hand roll to form a test piece. After leaving the test piece at room temperature for 4 days, it was heated to 20℃.
The 180° peel strength was measured to determine the normal adhesive strength. or,
The remaining unmeasured test pieces were placed in water at room temperature for 4 days, and immediately after being taken out, the 180° peel strength was measured at 20°C to determine the water-resistant adhesive strength. The results are shown in Table 1. Example 2 The same as Example 1 except that 3 parts by weight of zinc hydroxide was used instead of 3 parts by weight of activated zinc white in Example 1.
An adhesive composition was prepared in the same manner as above. A test piece was prepared using this composition in the same manner as in Example 1, and the normal adhesive strength and water-resistant adhesive strength were determined. The results are shown in Table 1. Example 3 An adhesive composition was prepared in the same manner as in Example 1 except that 50 parts by weight of Barcam TD2615 (manufactured by Dainippon Ink Chemical Co., Ltd.) was used instead of 50 parts by weight of Resin SP560 used in Example 1 as the rosin phenol. were prepared and their physical properties were measured, and the results are shown in Table 1. Example 4 As rosin phenol, 50 parts by weight of Tamanol 803 (manufactured by Arakawa Chemical Industry Co., Ltd.) was used instead of 50 parts by weight of Resin SP560.
An adhesive composition was prepared in the same manner as in Example 1 except that parts by weight were used, and its physical properties were measured. The results are shown in Table 1. Examples 5 and 6 Adhesive compositions having the compositions shown in columns 5 and 6 of Table 1 were prepared, and their physical properties were measured, and the results are shown in Table 1. Example 7 An adhesive composition was prepared in the same manner as in Example 1, except that 25 parts by weight of rosin phenol and 25 parts by weight of polymerized rosin (Dimarex, manufactured by Hercules) were used instead of 50 parts by weight of rosin phenol in Example 1. were prepared and their physical properties were measured, and the results are shown in Table 1.
【表】【table】
【表】
比較例 １
実施例１においてロジンフエノール（レジン
SP560）50重量部の代りにαピネンフエノール
（YSポリスター2130、安原油脂工業社製）50重量
部を用いた以外は実施例１と同様にして接着剤組
成物を調整し、その物性を求め、結果を第２表に
示した。
比較例 ２〜７
第２表に示される種々の組成の接着剤組成物を
調整し、その物性を測定し、結果を第２表に示し
た。[Table] Comparative Example 1 In Example 1, rosin phenol (resin
An adhesive composition was prepared in the same manner as in Example 1, except that 50 parts by weight of α-pinene phenol (YS Polyster 2130, manufactured by Yasushi Kogyo Co., Ltd.) was used instead of 50 parts by weight (SP560), and its physical properties were determined. The results are shown in Table 2. Comparative Examples 2 to 7 Adhesive compositions having various compositions shown in Table 2 were prepared and their physical properties were measured, and the results are shown in Table 2.
【表】【table】
Claims (1)
ン、多価金属化合物、ロジンフエノール及びアン
モニアもしくは炭素数が５以下の有機アミンが添
加分散されてなる接着剤組成物。 ２ 多価金属化合物が亜鉛化合物である第１項記
載の組成物。 ３ 多価金属化合物が多価金属の酸化物又は水酸
化物である第１項又は第２項記載の組成物。 ４ 多価金属化合物の添加量がカルボキシル化ポ
リクロロプレン100重量部に対し0.3〜15重量部で
ある第１項〜第４項何れか１項に記載の組成物。 ５ ロジンフエノールの添加量がカルボキシル化
ポリクロロプレン100重量部に対し５〜200重量部
である第１項〜第４項何れか１項に記載の組成
物。 ６ アンモニアもしくは有機アミンの添加量がカ
ルボキシル化ポリクロロプレンのカルボキシル基
１モルに対して0.8〜2.5モルである第１項〜第５
項何れか１項に記載の組成物。[Scope of Claims] 1. An adhesive composition comprising carboxylated polychloroprene, a polyvalent metal compound, rosin phenol, and ammonia or an organic amine having 5 or less carbon atoms added and dispersed in an aqueous medium. 2. The composition according to item 1, wherein the polyvalent metal compound is a zinc compound. 3. The composition according to item 1 or 2, wherein the polyvalent metal compound is a polyvalent metal oxide or hydroxide. 4. The composition according to any one of Items 1 to 4, wherein the amount of the polyvalent metal compound added is 0.3 to 15 parts by weight based on 100 parts by weight of carboxylated polychloroprene. 5. The composition according to any one of Items 1 to 4, wherein the amount of rosin phenol added is 5 to 200 parts by weight per 100 parts by weight of carboxylated polychloroprene. 6 Items 1 to 5, wherein the amount of ammonia or organic amine added is 0.8 to 2.5 mol per mol of carboxyl group of carboxylated polychloroprene.
The composition according to any one of the above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10564382A JPS58222169A (en) | 1982-06-18 | 1982-06-18 | Adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10564382A JPS58222169A (en) | 1982-06-18 | 1982-06-18 | Adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58222169A JPS58222169A (en) | 1983-12-23 |
| JPH0153912B2 true JPH0153912B2 (en) | 1989-11-16 |
Family
ID=14413132
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10564382A Granted JPS58222169A (en) | 1982-06-18 | 1982-06-18 | Adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58222169A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3718867B2 (en) * | 1994-05-09 | 2005-11-24 | 東ソー株式会社 | Latex for adhesive and chloroprene adhesive composition using the same |
| JP2776248B2 (en) * | 1994-05-13 | 1998-07-16 | 荒川化学工業株式会社 | Hot melt adhesive |
| JPH08188761A (en) * | 1995-01-06 | 1996-07-23 | Tosoh Corp | Latex for heat resistance-improved adhesive and chloroprene-based adhesive composition using the same |
| US5527846A (en) * | 1995-03-27 | 1996-06-18 | E. I. Du Pont De Nemours And Company | Polychloroprene adhesive latex composition |
| EP0817805B1 (en) * | 1995-03-27 | 2010-09-08 | E.I. Du Pont De Nemours And Company | Polychloroprene composition |
| JPH093423A (en) * | 1995-06-21 | 1997-01-07 | Tosoh Corp | Polychloroprene latex for adhesive, its production and adhesive composition used therefor |
| JP3884781B2 (en) * | 1995-07-18 | 2007-02-21 | 東ソー株式会社 | Chloroprene rubber latex for adhesive, method for producing the same, and adhesive composition using the same |
| JP2006160909A (en) * | 2004-12-08 | 2006-06-22 | Showa Highpolymer Co Ltd | Chloroprene rubber adhesive composition |
-
1982
- 1982-06-18 JP JP10564382A patent/JPS58222169A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58222169A (en) | 1983-12-23 |
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