JPH0119714B2 - - Google Patents
Info
- Publication number
- JPH0119714B2 JPH0119714B2 JP4819883A JP4819883A JPH0119714B2 JP H0119714 B2 JPH0119714 B2 JP H0119714B2 JP 4819883 A JP4819883 A JP 4819883A JP 4819883 A JP4819883 A JP 4819883A JP H0119714 B2 JPH0119714 B2 JP H0119714B2
- Authority
- JP
- Japan
- Prior art keywords
- hot melt
- weight
- adhesive
- general formula
- adhesives
- 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
- 239000004831 Hot glue Substances 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- MTELEIIKRPHJKA-UHFFFAOYSA-N 5-ethenyldioxazolidin-4-one Chemical class C=CC1OONC1=O MTELEIIKRPHJKA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 description 19
- 230000001070 adhesive effect Effects 0.000 description 19
- -1 amine imide Chemical class 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- JEAMWPJHRQVNFY-UHFFFAOYSA-N dioxazolidin-4-one Chemical group O=C1COON1 JEAMWPJHRQVNFY-UHFFFAOYSA-N 0.000 description 4
- 239000000806 elastomer Substances 0.000 description 4
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 2
- 239000012943 hotmelt Substances 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- CJLJMCAFJKKJCS-UHFFFAOYSA-N 1,2,4-dioxazol-3-one Chemical compound O=C1N=COO1 CJLJMCAFJKKJCS-UHFFFAOYSA-N 0.000 description 1
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- GDQZDVVGPJKEKV-UHFFFAOYSA-N 2-methylpentyl 2-methylprop-2-enoate Chemical compound CCCC(C)COC(=O)C(C)=C GDQZDVVGPJKEKV-UHFFFAOYSA-N 0.000 description 1
- SEDMFAYCVMLBFB-UHFFFAOYSA-N 2-methylpentyl prop-2-enoate Chemical compound CCCC(C)COC(=O)C=C SEDMFAYCVMLBFB-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- BBPSWYWJFWHIHC-UHFFFAOYSA-N 3,5,5-trimethylhexyl 2-methylprop-2-enoate Chemical compound CC(C)(C)CC(C)CCOC(=O)C(C)=C BBPSWYWJFWHIHC-UHFFFAOYSA-N 0.000 description 1
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 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
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 239000004823 Reactive adhesive Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- HRKWOOHVRHBXHJ-UHFFFAOYSA-N hexan-2-yl prop-2-enoate Chemical compound CCCCC(C)OC(=O)C=C HRKWOOHVRHBXHJ-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- 238000007757 hot melt coating Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Description
本発明は、新規な反応性ホツトメルト接着剤に
関する。更に詳しくはジオキサゾロン環を有する
アクリル系反応性ホツトメルト接着剤に関する。
接着剤の発展は近年目覚しいものがあり、その
用途は日用品から工業材料、医用材料にまで使わ
れており、その種類も多種多様である。
現在使用されているエラストマーとしては、ゴ
ム系、アクリル系、シリコン系が主なものである
が、ゴム系接着剤は耐久性が劣り、シリコン系は
接着力、耐久性ともに優れているが高価であるた
めに特殊な用途にしか用いられていない。アクリ
ル系接着剤は近年急速に伸びてきた接着剤であ
り、耐候性、耐油性、耐熱性が優れており、現
在、粘着シートに広く用いられている。このアク
リル系接着剤にも溶剤型、エマルジヨン型、ホツ
トメルト型等があり、近年環境保護、防災、省エ
ネルギー等の諸問題により溶剤型からエマルジヨ
ン型、ホツトメルト型へと移行しつつある。しか
しエマルジヨン型は、溶剤型と比較して耐水性、
耐熱性など劣る面がある。かかる理由から、最近
ではホツトメルト接着剤の進出がめざましいが、
このものは熱可塑性であるが故に耐熱性が劣つて
おり、高温での作業が不適となる。又、接着剤と
しての機能を発揮させるためには、数平均分子量
が20万から100万程度の高分子量化合物が必要と
なり、このものを塗工するには一般的なホツトメ
ルト塗工機では困難が生ずる。耐熱性を補強する
ためには、従来までのホツトメルト接着剤に官能
基をつけ、反応性を付与し、塗工後架橋せしめ
て、熱可塑性を消失せしめればよい。
反応性接着剤として頻繁にポリイソシアネート
が使用されるが、イソシアネート基は水分に対し
て極度に敏感であり、保存性が悪く適当な安定化
の工夫が必要である。
イソシアネート基の保護基としては、ウレタ
ン、アミンイミド等の形として保護されるものや
イミダゾール、カルボジイミドなどとの付加体が
挙げられるが、これらのものは分解温度や脱離化
合物がホツトメルト接着剤として用いるには不適
である。一方、ジオキサゾロン環は、最適な温
度、時間で分解し二酸化炭素を放出してイソシア
ネート基となるので、脱離化合物が粘着力や保持
力に影響を及ぼすことはない。
又、反応性を付与すると、高分子量エラストマ
ーを用いる必要はなく、低分子量から中分子量の
エラストマーを使用し、塗工、架橋後高分子量化
すれば所望の粘着力が得られることになる。
そこで本発明者らは上記の考えに基づき、従来
のホツトメルト接着剤の欠点を克服すべく鋭意検
討を行つた結果、イソシアネート基前駆体として
のジオキサゾロン環を有する低分子量又は中分子
量アクリル系エラストマーが塗工後熱湿架橋を行
い、粘着力、保持力のみならず、耐熱性、耐水
性、耐溶剤性等にも優れている事実を見い出し、
本発明に至つたわけである。
即ち、本発明は
一般式
（ただし、式中R1は水素又はメチル基、R2は
炭素数１〜13のアルキル基を示す。）
で表わされるビニル化合物の一種もしくは二種以
上50〜95重量％と、
一般式
（ただし、式中R3は水素、メチル基又はフエ
ニル基を示す）
で表わされるビニルジオキサゾロン化合物５〜50
重量％とを共重合せしめて得られるポリマーから
なる反応性ホツトメルト接着剤を提供するもので
ある。
本発明に用いられる一般式(1)で表わされるビニ
ル化合物の例としては、アクリル酸メチル、アク
リル酸エチル、アクリル酸ｎ―ブチル、アクリル
酸イソブチル、アクリル酸１―メチルペンチル、
アクリル酸２―メチルペンチル、アクリル酸ヘキ
シル、アクリル酸イソオクチル、アクリル酸３，
５，５―トリメチルヘキシル、アクリル酸ドデシ
ル等のアクリル酸エステル又はメタクリル酸メチ
ル、メタクリル酸エチル、メタクリル酸ｎ―ブチ
ル、メタクリル酸イソブチル、メタクリル酸１―
メチルペンチル、メタクリル酸２―メチルペンチ
ル、メタクリル酸ヘキシル、メタクリル酸イソオ
クチル、メタクリル酸３，５，５―トリメチルヘ
キシル、メタクリル酸ドデシル等のメタクリル酸
エステルから選ばれる一種もしくは二種以上のア
クリル酸エステル又はメタクリル酸エステルが用
いられる。なかでも、一般式(1)で示されるビニル
化合物成分の50〜80重量％のアルキル基が炭素数
５〜13のアクリル酸エステル又はメタクリル酸エ
ステルと20〜50重量％のアルキル基が炭素数１〜
３のアクリル酸エステル又はメタクリル酸エステ
ルを使用すると、粘着力、保持力の優れたエラス
トマーが生成し、好ましい。アルキル基の炭素数
が14以上のアクリル酸エステル、メタクリル酸エ
ステルを使用した場合には柔軟性が失われ、接着
剤としては適さない。
一般式(2)で表わされるビニルジオキサゾロン化
合物としては２―ビニル―１，３，４―ジオキサ
ゾリン―５―オン、２―イソプロペニル―１，
３，４―ジオキサゾリン―５―オン、２―（α―
スチリル）―１，３，４―ジオキサゾリン―５―
オンが使用されるが、その中でも重合性の面から
２―イソプロペニル―１，３，４―ジオキサゾリ
ン―５―オン、２―（α―スチリル）―１，３，
４―ジオキサゾリン―５―オンの使用が好まし
い。
一般式(2)で表わされるビニルジオキサゾロン化
合物を一般式(1)で表わされるビニル化合物と共重
合させるが、共重合体中のビニルジオキサゾロン
化合物の割合は、５〜50重量％であり、好ましく
は10〜30重量％である。これより少ない場合には
架橋速度が遅く、硬化効果が薄くなる。又、これ
より多い場合には、粘着性が劣る。共重合体の合
成法は認意であり、公知のラジカル重合法で行わ
れるが、重合触媒としてジベンゾイルパーオキサ
イド、ジクミルパーオキサイド、ジｔ―ブチルパ
ーオキサイド、α，α′―アゾビスイソブチロニト
リルやレドツクス系触媒等を用い、塊重合法で行
うのが最も好ましい。又、本発明の効果を害さな
い限り、上記二成分の他に任意の共重合し得るコ
モノマーを添加して共重合させてもよい。これら
コモノマーとしてはエチレン、プロピレン等のオ
レフイン、アクリロニトリル、酢酸ビニル、アク
リルアミド等が挙げられる。
かくして得られた共重合体の数平均分子量は
5000〜100000の範囲にあり、軟化点60〜100℃、
150℃での溶融粘度は1500〜100000cpsの白色固体
である。ビニルジオキサゾロンモノマーは、水と
反応し、ヒドロキサム酸となるが、本発明の共重
合体においては、空気中に１週間放置していても
反応することはなく、安定であつた。
本発明のホツトメルト接着剤の塗工装置として
は、窒素シール可能な溶融槽を有する一般的な塗
工機の使用が可能である。
使用法は先ず本発明の共重合体を窒素シールし
た溶融槽内で150℃で溶融させる。１時間、この
温度に保つた約50％のジオキサゾロン環が分解
し、二酸化炭素を放出してイソシアネート基とな
る。このものをロールコーター、又はスロツトダ
イコーター等の塗工機により基材に塗工してやる
と、室温で空気中の水分を吸収硬化し、粘着力、
保持力のみならず耐熱性、耐水性、耐溶剤性の優
れた接着剤となる。又、加熱処理せしめてもよ
く、塗工後130℃で湿加熱を行うと５分以内の短
時間で所望する粘着力を示すようになる。
本発明における接着剤は、粘着付与剤を添加す
ることなくして優れた粘着力を示すが、必要に応
じて、又、使用目的に応じてクマロンインデン系
樹脂、スチレン系樹脂等の公知の粘着付与剤を使
用することができる。又、軟化剤、酸化安定剤等
も必要に応じて使用可能である。
本発明の接着剤は、紙、布、プラスチツクフイ
ルム、複合材、金属箔など極めて多種の基材に対
し使用が可能であり、その応用範囲は広い。
以後、本発明を実施例により詳細に説明する
が、本発明は、この実施例に限られるものではな
い。尚、実施例中、「部」は断りのない限り「重
量部」を表わす。
実施例 １
アクリル酸ｎ―ヘキシル100部、メタクリル酸
メチル30部、２―イソプロペニル―１，３，４―
ジオキサゾリン―５―オン30部、α，α′―アゾビ
スイソブチロニトリル0.1部をセパラブルフラス
コに入れ、窒素気流下、70℃に加熱した。内部の
温度が70℃になるように調節し、この温度で12時
間かきまぜた。かくして得られた共重合体の軟化
点は82℃（JIS Ｋ 5902環球法）、150℃での溶融
粘度（Ｂ型粘度計）は7200cps、数平均分子量
9700であつた。
この共重合体を窒素シールした溶融槽内に入
れ、150℃で加熱溶融し、１時間この温度で加熱
し、その後ロールコーターにより、ポリエステル
フイルムに塗工した。その後、表―１に示した条
件で処理した。
The present invention relates to novel reactive hot melt adhesives. More specifically, the present invention relates to an acrylic reactive hot melt adhesive having a dioxazolone ring. The development of adhesives has been remarkable in recent years, and their applications range from daily necessities to industrial materials and medical materials, and they come in a wide variety of types. The main elastomers currently used are rubber-based, acrylic-based, and silicone-based, but rubber-based adhesives have poor durability, while silicone-based adhesives have excellent adhesive strength and durability, but are expensive. Because of this, it is only used for special purposes. Acrylic adhesives have been rapidly gaining popularity in recent years, and are currently widely used in pressure-sensitive adhesive sheets due to their excellent weather resistance, oil resistance, and heat resistance. There are various types of acrylic adhesives, such as solvent type, emulsion type, and hot melt type.In recent years, there has been a shift from solvent type to emulsion type and hot melt type due to various issues such as environmental protection, disaster prevention, and energy saving. However, emulsion type is more water resistant than solvent type.
It has some disadvantages such as heat resistance. For these reasons, hot melt adhesives have recently made remarkable advances.
Since this material is thermoplastic, it has poor heat resistance and is unsuitable for work at high temperatures. In addition, in order to function as an adhesive, a high molecular weight compound with a number average molecular weight of about 200,000 to 1,000,000 is required, and it is difficult to coat this compound with a general hot melt coating machine. arise. In order to enhance heat resistance, conventional hot melt adhesives may be added with functional groups to impart reactivity and crosslinked after coating to eliminate thermoplasticity. Polyisocyanates are frequently used as reactive adhesives, but the isocyanate groups are extremely sensitive to moisture, have poor shelf life, and require appropriate stabilization. Protective groups for isocyanate groups include those protected in the form of urethane, amine imide, etc., and adducts with imidazole, carbodiimide, etc., but these groups are difficult to use as hot melt adhesives due to the decomposition temperature and elimination compound. is inappropriate. On the other hand, the dioxazolone ring decomposes at the optimum temperature and time, releases carbon dioxide, and becomes an isocyanate group, so that the elimination compound does not affect the adhesion or retention force. Furthermore, if reactivity is imparted, there is no need to use a high molecular weight elastomer, and the desired adhesive strength can be obtained by using a low to medium molecular weight elastomer and increasing the molecular weight after coating and crosslinking. Based on the above idea, the present inventors conducted intensive studies to overcome the drawbacks of conventional hot melt adhesives, and as a result, a low or medium molecular weight acrylic elastomer having a dioxazolone ring as an isocyanate group precursor was developed. We performed hot-wet crosslinking after coating and discovered that it not only has excellent adhesive strength and holding power, but also has excellent heat resistance, water resistance, solvent resistance, etc.
This led to the present invention. That is, the present invention has the general formula (However, in the formula, R 1 is hydrogen or a methyl group, and R 2 is an alkyl group having 1 to 13 carbon atoms.) 50 to 95% by weight of one or more vinyl compounds represented by the general formula (However, in the formula, R 3 represents hydrogen, methyl group, or phenyl group.) Vinyldioxazolone compounds 5 to 50 represented by
The object of the present invention is to provide a reactive hot melt adhesive comprising a polymer obtained by copolymerizing % by weight. Examples of the vinyl compound represented by the general formula (1) used in the present invention include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 1-methylpentyl acrylate,
2-methylpentyl acrylate, hexyl acrylate, isooctyl acrylate, 3-acrylic acid,
Acrylic esters such as 5,5-trimethylhexyl and dodecyl acrylate, or methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and 1-methacrylate.
One or more acrylic esters selected from methacrylic esters such as methylpentyl, 2-methylpentyl methacrylate, hexyl methacrylate, isooctyl methacrylate, 3,5,5-trimethylhexyl methacrylate, dodecyl methacrylate, or Methacrylic acid esters are used. Among them, 50 to 80% by weight of the alkyl group of the vinyl compound component represented by general formula (1) is an acrylic ester or methacrylic ester having a carbon number of 5 to 13, and 20 to 50% by weight of an alkyl group is a carbon number of 1 ~
It is preferable to use the acrylic ester or methacrylic ester of No. 3 because it produces an elastomer with excellent adhesive strength and holding power. If an acrylic ester or methacrylic ester whose alkyl group has 14 or more carbon atoms is used, flexibility will be lost and it will not be suitable as an adhesive. Vinyldioxazolone compounds represented by general formula (2) include 2-vinyl-1,3,4-dioxazolin-5-one, 2-isopropenyl-1,
3,4-dioxazolin-5-one, 2-(α-
styryl)-1,3,4-dioxazoline-5-
Among them, 2-isopropenyl-1,3,4-dioxazolin-5-one, 2-(α-styryl)-1,3,
Preference is given to using 4-dioxazolin-5-one. The vinyldioxazolone compound represented by the general formula (2) is copolymerized with the vinyl compound represented by the general formula (1), and the proportion of the vinyldioxazolone compound in the copolymer is 5 to 50% by weight, Preferably it is 10 to 30% by weight. If the amount is less than this, the crosslinking speed will be slow and the curing effect will be weak. Moreover, when the amount is more than this, the adhesiveness is poor. The method for synthesizing the copolymer is a well-known radical polymerization method, but dibenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, α,α'-azobisisomer is used as a polymerization catalyst. It is most preferable to use a bulk polymerization method using butyronitrile, a redox catalyst, or the like. Further, as long as the effects of the present invention are not impaired, any comonomer that can be copolymerized may be added in addition to the above two components for copolymerization. Examples of these comonomers include olefins such as ethylene and propylene, acrylonitrile, vinyl acetate, and acrylamide. The number average molecular weight of the copolymer thus obtained is
In the range of 5000-100000, softening point 60-100℃,
It is a white solid with a melt viscosity of 1500-100000 cps at 150℃. Vinyldioxazolone monomer reacts with water to form hydroxamic acid, but the copolymer of the present invention did not react and was stable even when left in the air for one week. As a coating device for the hot melt adhesive of the present invention, a general coating machine having a melting tank that can be sealed with nitrogen can be used. The method of use is to first melt the copolymer of the present invention at 150°C in a nitrogen-sealed melting tank. Approximately 50% of the dioxazolone rings, kept at this temperature for 1 hour, decompose, releasing carbon dioxide and forming isocyanate groups. When this material is applied to a base material using a coating machine such as a roll coater or slot die coater, it hardens by absorbing moisture in the air at room temperature, increasing adhesive strength and
The adhesive has excellent heat resistance, water resistance, and solvent resistance as well as holding power. Alternatively, heat treatment may be performed, and if moist heating is performed at 130° C. after coating, the desired adhesive strength will be exhibited within a short time of 5 minutes. The adhesive of the present invention exhibits excellent adhesive strength without the addition of a tackifier, but if necessary or depending on the purpose of use, known adhesives such as coumaron indene resin, styrene resin, etc. Imparting agents can be used. Furthermore, softeners, oxidation stabilizers, etc. can also be used as necessary. The adhesive of the present invention can be used for a wide variety of substrates such as paper, cloth, plastic film, composite materials, and metal foil, and has a wide range of applications. Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples. In the examples, "parts" represent "parts by weight" unless otherwise specified. Example 1 100 parts of n-hexyl acrylate, 30 parts of methyl methacrylate, 2-isopropenyl-1,3,4-
30 parts of dioxazolin-5-one and 0.1 part of α,α'-azobisisobutyronitrile were placed in a separable flask and heated to 70°C under a nitrogen stream. The internal temperature was adjusted to 70°C and stirred at this temperature for 12 hours. The copolymer thus obtained had a softening point of 82°C (JIS K 5902 ring and ball method), a melt viscosity at 150°C (B-type viscometer) of 7200 cps, and a number average molecular weight.
It was 9700. This copolymer was placed in a melting tank sealed with nitrogen, heated and melted at 150°C, heated at this temperature for 1 hour, and then coated on a polyester film using a roll coater. Thereafter, it was processed under the conditions shown in Table 1.
【表】
これらの処理によりいずれも25μm厚さの接着
層が得られ、それぞれについて、被着体ステンレ
スでの180゜剥離力（引張速度300mm／min）、ロー
リングボールタツク、保持力（JIS Ｚ 0237）を
測定した。結果を表―２に示す。[Table] Adhesive layers with a thickness of 25 μm were obtained by these treatments, and for each, the 180° peel force (pulling speed 300 mm/min), rolling ball tack, and holding force (JIS Z 0237) on the adherend stainless steel were obtained. ) was measured. The results are shown in Table-2.
【表】
表―２からわかるように、いずれも良好な値を
示し、60℃にて剥離力測定の時にもほとんど剥離
力の低下はなかつた。
実施例 ２―４
表―３に示される配合組成で実施例１と同条件
で共重合体を製造した。[Table] As can be seen from Table 2, all showed good values, and there was almost no decrease in peel force even when peel force was measured at 60°C. Example 2-4 A copolymer was produced using the formulation shown in Table 3 under the same conditions as Example 1.
【表】
かくして得られた共重合体の軟化点150℃にお
ける溶融粘度、数平均分子量を表―４に示した。[Table] Table 4 shows the melt viscosity and number average molecular weight at a softening point of 150°C of the copolymer thus obtained.
【表】
各共重合体を実施例１と同じ方法でポリエステ
ルフイルムに塗工し、その後すぐ130℃、60％
RH、５分間の熱処理をした。これらの処理によ
り、いずれも25μm厚さの接着層が得られ、それ
ぞれについて被着体ステンレスでの180゜剥離力
（引つ張り速度300mm／min）、ローリングボール
タツク、保持力を測定した。結果を表―５に示
す。尚、被着体への貼合せは、20℃、60％RHで
２Kgの荷重を持つローラーで１往復して行つた。[Table] Each copolymer was coated on a polyester film in the same manner as in Example 1, and then immediately heated to 130℃ and 60%
Heat treatment was performed at RH for 5 minutes. Through these treatments, adhesive layers with a thickness of 25 μm were obtained in each case, and the 180° peel force (pulling speed 300 mm/min), rolling ball tack, and holding force on the stainless steel adherend were measured for each layer. The results are shown in Table-5. The bonding to the adherend was carried out at 20° C. and 60% RH by making one reciprocation using a roller with a load of 2 kg.
【表】
表―５に示す結果からわかるように、接着力、
タツク、保持力ともに優れ、耐熱性は従来のホツ
トメルト接着剤に比して著しく優れている。
次に実施例１―１，１―２，１―３，２，３，
４でそれぞれ得たポリエステル基材の粘着テープ
を実施例１と同じ方法でステンレスに貼り合せ、
耐水性、耐油性を調べた。試験法は圧着後20℃１
日放置し、20℃にて水又は油に24時間浸漬し、取
り出してすぐ180°剥離力を測定した（22℃、引つ
張り速度300mm／min）。その結果を表―６に示し
た。これから、耐水性、耐油性も優れていること
がわかる。[Table] As can be seen from the results shown in Table 5, adhesive strength,
It has excellent tack and holding power, and its heat resistance is significantly superior to conventional hot melt adhesives. Next, Examples 1-1, 1-2, 1-3, 2, 3,
The polyester-based adhesive tape obtained in each step 4 was attached to stainless steel in the same manner as in Example 1,
Water resistance and oil resistance were investigated. The test method is 20℃1 after crimping.
It was left in the sun, immersed in water or oil at 20°C for 24 hours, and immediately after being taken out, the 180° peel force was measured (22°C, tensile speed 300 mm/min). The results are shown in Table-6. From this, it can be seen that the water resistance and oil resistance are also excellent.
Claims (1)
が１〜13のアルキル基を示す。） で表わされるビニル化合物の一種又は二種以上50
〜95重量％と、 一般式(2) （式中、R3は水素、メチル基又はフエニル基
を示す。） で表わされるビニルジオキサゾロン化合物５〜50
重量％とを共重合せしめて得られるポリマーから
なるホツトメルト接着剤。 ２ ポリマーの数平均分子量が5000〜100000であ
る特許請求の範囲第１項記載のホツトメルト接着
剤。[Claims] 1 General formula (1) (In the formula, R 1 is hydrogen or a methyl group, and R 2 is an alkyl group having 1 to 13 carbon atoms.) One or more vinyl compounds represented by 50
~95% by weight, general formula (2) (In the formula, R 3 represents hydrogen, methyl group or phenyl group.) Vinyldioxazolone compounds 5 to 50
A hot melt adhesive made of a polymer obtained by copolymerizing % by weight. 2. The hot melt adhesive according to claim 1, wherein the polymer has a number average molecular weight of 5,000 to 100,000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4819883A JPS59174672A (en) | 1983-03-23 | 1983-03-23 | Hot-melt adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4819883A JPS59174672A (en) | 1983-03-23 | 1983-03-23 | Hot-melt adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59174672A JPS59174672A (en) | 1984-10-03 |
| JPH0119714B2 true JPH0119714B2 (en) | 1989-04-12 |
Family
ID=12796682
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4819883A Granted JPS59174672A (en) | 1983-03-23 | 1983-03-23 | Hot-melt adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59174672A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7405259B2 (en) | 2005-04-29 | 2008-07-29 | Momentive Performance Materials Inc. | Silylated polymer derived from butadiene and solvent-resistant pressure sensitive adhesive composition containing same |
| US7956123B2 (en) | 2005-10-24 | 2011-06-07 | Momentive Performance Materials Inc. | Solvent resistant polyurethane adhesive compositions |
| US8247079B2 (en) | 2006-09-01 | 2012-08-21 | Momentive Performance Materials Inc. | Laminate containing a silylated polyurethane adhesive composition |
| US8247514B2 (en) | 2006-09-01 | 2012-08-21 | Momentive Performance Materials Inc. | Silylated polyurethane compositions and adhesives therefrom |
| US7976951B2 (en) | 2006-11-14 | 2011-07-12 | Momentive Performance Materials Inc. | Laminate containing an adhesive-forming composition |
| US7829116B2 (en) | 2006-11-14 | 2010-11-09 | Momentive Performance Materials Inc. | Adhesive-forming composition and blend of adhesives obtained therefrom |
-
1983
- 1983-03-23 JP JP4819883A patent/JPS59174672A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59174672A (en) | 1984-10-03 |
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