JPS6225166B2 - - Google Patents
Info
- Publication number
- JPS6225166B2 JPS6225166B2 JP55109213A JP10921380A JPS6225166B2 JP S6225166 B2 JPS6225166 B2 JP S6225166B2 JP 55109213 A JP55109213 A JP 55109213A JP 10921380 A JP10921380 A JP 10921380A JP S6225166 B2 JPS6225166 B2 JP S6225166B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- weight
- epoxy
- epoxy resin
- resin composition
- 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
- 239000003822 epoxy resin Substances 0.000 claims description 32
- 229920000647 polyepoxide Polymers 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 11
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 229920000459 Nitrile rubber Polymers 0.000 claims description 8
- 229920001971 elastomer Polymers 0.000 claims description 8
- 239000005060 rubber Substances 0.000 claims description 8
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 8
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- 239000001361 adipic acid Substances 0.000 claims description 5
- 235000011037 adipic acid Nutrition 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 5
- 229920002857 polybutadiene Polymers 0.000 claims description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- 239000005062 Polybutadiene Substances 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 239000000539 dimer Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920005906 polyester polyol Polymers 0.000 claims description 2
- 229920005749 polyurethane resin Polymers 0.000 claims description 2
- 125000005442 diisocyanate group Chemical group 0.000 claims 1
- 239000011342 resin composition Substances 0.000 claims 1
- 239000000853 adhesive Substances 0.000 description 13
- 230000001070 adhesive effect Effects 0.000 description 13
- 238000009835 boiling Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 239000004800 polyvinyl chloride Substances 0.000 description 11
- 229920000915 polyvinyl chloride Polymers 0.000 description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 239000002318 adhesion promoter Substances 0.000 description 5
- 239000010425 asbestos Substances 0.000 description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 229910052895 riebeckite Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
- 239000004567 concrete Substances 0.000 description 4
- 229920006332 epoxy adhesive Polymers 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000009408 flooring Methods 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000010454 slate Substances 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- -1 aliphatic amines Chemical class 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、室温硬化型のエポキシ樹脂系接着剤
に関し、さらに詳しくは軟質、半硬質ポリ塩化ビ
ニルを接着すると共に、湿潤面モルタル、スレー
ト、コンクリートなどに接着可能な新規エポキシ
樹脂組成物である。その用途は、主に軟質、半硬
質塩ビ長尺床材用接着剤とし開発したものであ
る。その他用途としては人工芝などの接着剤に利
用される。
従来、市販されているエポキシ系接着剤は、金
属、木材、コンクリート、およびモルタルなどの
被着体には良く接着するが、軟質塩ビへは、直接
接着することはできなかつた。従来のエポキシ系
床材用接着剤で軟質塩ビシートを接着する場合、
軟質塩ビシート面に塩ビ―酢ビ系、アクリル系な
どのプライマーを塗付し、プライマーに含まれて
いる溶剤を乾燥後、エポキシ系接着剤を塗付する
など、作業が繁雑であつた。又軟質、半硬質ポリ
塩化ビニルに対するエポキシ系接着剤として特公
昭49―9609（エポキシ樹脂接着剤組成物）があげ
られるが、ポリ酢酸ビニル、ポリビニルアルコー
ルなどが配合されているため、耐水性や耐アルカ
リ性に難点があつた。また本発明者は特開昭54―
26845に示されるように、軟質塩ビシートに接着
するエポキシ樹脂組成物を発明した。しかし上記
エポキシ樹脂組成物は、軟質塩ビシートに良く接
着するが、十分硬化する迄、25℃×７日と時間が
かかりすぎ、屋外などで床へ軟質塩ビシートを接
着する際、エポキシ樹脂組成物が未硬化状態で、
水分が接着界面に浸入する為、接着不良をおこす
ことがあつた。この接着不良の要因として、エポ
キシ樹脂組成物が被着体に接着する結合が主とし
て水素結合のため、水などの存在で、その結合が
弱められ、はく離現象をおこした為と推定され
る。
本発明は、室温硬化二液型エポキシ樹脂系接着
剤で、その特徴は、軟質ポリ塩化ビニルにプライ
マーなしで直接接着できると共に、湿潤面モルタ
ルにも良好に接着可能で、用途として軟質ポリ塩
化ビニルとモルタル、コンクリートなどを接着す
るエポキシ系長尺床材用接着剤ならびに人工芝な
どの接着剤等に利用できる新規エポキシ樹脂組成
物を提供することを目的とする。
本発明のエポキシ樹脂組成物は、(1)エポキシ樹
脂100重量部、(2)熱可塑性ポリウレタン樹脂５〜
30重量部、(3)ニトリルゴム５〜30重量部、(4)分子
鎖末端にアミノ基またはエポキシ基を有するポリ
ブタジエンまたはアクリロニトリル・ブタジエン
共重合体で分子量6000以下の液状ゴム５〜50重量
部、好ましくは10〜45重量部、(5)硬化剤の必要量
および単独溶剤あるいは混合溶剤（高沸点溶剤／
低沸点溶剤の重量比１：９〜４：６）50〜90重量
部から成ることを特徴とする。
本発明のエポキシ樹脂組成物はエポキシ樹脂
に、軟質ポリ塩化ビニルに対する接着付与剤とし
て、溶解パラメーターが上記被着体に近い熱可塑
性ポリウレタン樹脂と、ニトリルゴム、分子鎖末
端にアミノ基またはエポキシ基を有するポリブタ
ジエンまたはアクリロニトリル・ブタジエン共重
合体で分子量6000以下の液状ゴム（以下、本発明
で用いる特定の液状ゴムという）と、更にエタノ
ール、アセトンなどの低沸点（b.p.80℃以下）の
溶剤あるいはその低沸点溶剤とトルエン、メチル
イソブチルケトン（MIBK）などの高沸点（b.
p.110゜〜170℃）の混合溶剤と、ポリアミン、ポ
リサルフアイドなどの硬化剤とから成るものであ
る。本発明に使用されるエポキシ樹脂はビスフエ
ノールＡ、ハロゲン化ビスフエノールＡ、パラヒ
ドロキシ安息香酸、またはグリセリンなどに対し
てエピクロルヒドリンを付加したものか、または
更にこれらをダイマー酸変性、ウレタン変性させ
たものである。硬化剤としてはジエチレントリア
ミン、トリエチレンテトラミン如き脂肪族アミン
及びその変性化合物、またポリアミド、複素環状
ポリアミン及びその変性物などエポキシ樹脂と室
温で反応硬化する硬化剤が使用できる。なお、硬
化剤の使用量は、硬化に必要な通常の必要量であ
る。通常30〜60重量部が用いられる。接着付与剤
としての熱可塑ウレタン樹脂は、アジピン酸と
１，４―ブタンジオール又はエチレングリコール
とよりなる末端にヒドロキシ基を有するポリエス
テルポリオールとトリレンジイソシアネートとの
重付加で生成する線状ポリエステルタイプのポリ
ウレタン樹脂であり、好ましくは分子量約２万程
度の樹脂である。ニトリルゴムはアクリロニトリ
ルとブタジエンとの共重合体であつて、いわゆる
中、高ニトリルと称せられるアクリロニトリルの
含有量が比較的高いものが好ましい。また本発明
で用いる特定の液状ゴムは、上述のように、分子
鎖末端にアミノ基またはエポキシ基を有するポリ
ブタジエンまたはアクリロニトリル・ブタジエン
共重合体で分子量6000以下の液状ゴムであるが、
分子鎖末端にアミノ基またはエポキシ基を有する
ポリイソプレンで分子量6000以下の液状ゴムも使
用可能である。これらの接着付与剤は、主剤（エ
ポキシ樹脂を含む液）中に加えても、硬化剤中に
加えてもよい。また接着付与剤としては必要に応
じて塩化ビニルと酢酸ビニルとの共重合体を配合
しても良い。本発明における低、高沸点の混合溶
剤としては、沸点80℃以下のアセトン、塩化メチ
レン、１，１，１―トリクロルエタン、ジクロル
エタン、エチルアルコール、メチルアルコール、
酢酸エチル、メチルエチルケトンなどの低沸点溶
剤と沸点110〜170℃を有するトルエン、キシレ
ン、シクロヘキサノン、メチルイソブチルケト
ン、ジイソブチルケトンなどの高沸点溶剤との混
合溶剤である。本発明における混合溶剤におい
て、本発明接着剤を塗付したのち、まず低沸点溶
剤が揮発して塗付面に皮膜を形成し塗付面に残存
する高沸点溶剤が“ぬれ”効果を与えるものであ
る。更にエポキシ樹脂への配合剤として一般に知
られているジグリシジルエーテルなどの反応性稀
釈剤、トリクレゾールフオスフエートなどの非反
応性稀釈剤、又、シリカ粉、炭酸カルシウム、ク
レー、アスベスト、セメント、タルクなどの充填
剤も添加することができる。本発明の接着付与剤
は、重量基準で、エポキシ樹脂100部に対して５
〜50部配合したものが最適である。50部より多く
配合しても接着性向上に寄与しないと共に反応を
遅くし、粘度が増して塗布が困難になり、作業性
にも難点がでてくる。本発明に使用している本発
明で用いる特定の液状ゴム単独では、エポキシ樹
脂又はポリアミンおよびポリアミドなどとの硬化
反応は緩慢である。しかし実施例の如きエポキシ
樹脂組成物にするとその組成物諸成分の相乗効果
などにより、硬化反応がより速くなり、比較的短
時間で実用強度が発揮され、特開昭54―26865の
エポキシ樹脂組成物に見られたような接着不良は
生じない。
以下本発明を実施例により詳説するが、本発明
はこれのみに限定されないことは勿論である。な
お、実施例中、部は重量基準である。
実施例 １
DER331（ダウケミカル社製：エポキシ当量
192のビスフエノール型エポキシ樹脂）100部、デ
スモコール400（バイエル社製：エレングリコー
ル／アジピン酸／トルエンジイソシアネートより
成る熱可塑性ウレタン）10部、ハイカー1041（ビ
ーエフ、グツドリツチ、ケミカル社製：高アクリ
ルニトリルのニトリルゴム）15部、炭酸カルシウ
ム100部およびメチルエチルケトン40部より成る
主剤100部に対して、硬化剤としてサンマイドＸ
―963（三和化学社製：アミン価570の変性ポリア
ミン）100部、ハイカー1300×16（ビーエフ、グ
ツドリツチ、ケミカル社製：アミン当量1000のジ
エン系液状ゴム）40部、２，４，６―トリス（ジ
メチルアミノメチル）フエノール５部、炭酸カル
シウム100部、アスベスト10部、トルエン15部お
よびエタノール５部を混合して成るエポキシ樹脂
組成物とする。上記実施例の組成物につき、以下
の方法により接着性能を測定した。
１ 試験片作製
スレート板（50mm×100mm×５mm）ヘクシ目
ゴテにてエポキシ樹脂組成物３ｇを塗付し、25
℃でオープンタイムを30分とる。オープンタイ
ム30分後、軟質ビニル樹脂（50mm×150mm×３
mm）をハンドローラーにて、エポキシ樹脂組成
物を介してスレート板と圧着し、25℃で所定時
間（24時間と168時間）硬化させる。
２ 90度はく離強さ
上記試験片を所定条件で処理した後、引張ス
ピード20mm／min・で室温時の90度はく離強さ
を測定する。得られた結果は第１表に示す。
実施例 ２
DER331（ダウケミカル社製：エポキシ当量
192のビスフエノール型エポキシ樹脂）100部、デ
スモコール400（バイエル社製：エチレングリコ
ール／アジピン酸／トリレンジイソシアネートよ
り成る熱可塑性ウレタン）20部、ハイカー1041
（ビーエフ、グツドリツチ、ケミカル社製高アク
リルニトリルのニトリルゴム）５部、ポリブタジ
エンR45EPT（出光石油化学社製：末端エポキシ
基化したポリブタジエンゴム）30部、炭酸カルシ
ウム100部およびメチルエチルケトン50部より成
る主剤100部に対して、硬化剤としてサンマイド
Ｘ―963（三和化学社製アミン価570の変性ポリア
ミン）100部、２，４，６―トリス（ジメチルア
ミノメチル）フエノール６部、炭酸カルシウム
100部、アスベスト10部およびエタノール20部を
加えて成るエポキシ樹脂組成物とする。上記エポ
キシ樹脂組成物を実施例１と同じ条件で処理し次
いで性能試験を行なつた。得られた結果は第１表
に示す。
なお、次の各比較例の組成物についても実施例
１と同様に、試験片を作製し性能試験を行なつ
た。試験結果は、第１表に示す。
比較例 １
DER331（ダウケミカル社製：エポキシ当量
192のビスフエノール型エポキシ樹脂）100部、デ
スモコール400（バイエル社製：エチレングリコ
ール／アジピン酸／トルエンジイソシアネートよ
り成る熱可塑性ポリウレタン）15部、ハイカー
1041（ビーエフ、グツドリツチ、ケミカル社製：
高アクリルニトリルのニトリルゴム）10部、炭酸
カルシウム100部、およびメチルエチルケトン50
部より成る主剤100部に対して、硬化剤としてサ
ンマイドＸ―963（三和化学社製：アミン価570の
変性ポリアミン）100部、２，４，６―トリス
（ジメチルアミノメチル）フエノール５部、炭酸
カルシウム100部、アスベスト10部およびメタノ
ール20部を混合して成るエポキシ樹脂組成物とす
る。
The present invention relates to a room-temperature curing epoxy resin adhesive, and more specifically to a novel epoxy resin composition capable of adhering to soft and semi-hard polyvinyl chloride, as well as wet surfaces such as mortar, slate, and concrete. It was developed primarily as an adhesive for soft and semi-hard PVC long flooring materials. Other uses include adhesives for artificial turf, etc. Conventionally, commercially available epoxy adhesives adhere well to adherends such as metal, wood, concrete, and mortar, but cannot directly adhere to soft PVC. When bonding soft PVC sheets with conventional epoxy flooring adhesive,
The work involved applying a PVC-PVC, acrylic, etc. primer to the surface of a soft PVC sheet, drying the solvent contained in the primer, and then applying an epoxy adhesive, which was a complicated process. In addition, as an epoxy adhesive for soft and semi-hard polyvinyl chloride, JP-B No. 49-9609 (epoxy resin adhesive composition) can be mentioned, but since it contains polyvinyl acetate, polyvinyl alcohol, etc., it has poor water resistance and resistance. There was a problem with alkalinity. In addition, the inventor of the present invention is
No. 26845, an epoxy resin composition that adheres to flexible PVC sheets was invented. However, although the above-mentioned epoxy resin composition adheres well to soft PVC sheets, it takes too long (25°C x 7 days) to fully cure. is in an uncured state,
Moisture entered the adhesive interface, which sometimes caused adhesion failure. The reason for this poor adhesion is presumed to be that the bonds that allow the epoxy resin composition to adhere to the adherend are mainly hydrogen bonds, and the presence of water weakens these bonds, causing a peeling phenomenon. The present invention is a two-component epoxy resin adhesive that cures at room temperature, and its characteristics include the ability to directly adhere to soft polyvinyl chloride without a primer, as well as good adhesion to wet surface mortar. The purpose of the present invention is to provide a new epoxy resin composition that can be used as an epoxy adhesive for long flooring materials such as mortar, concrete, etc., and as an adhesive for artificial turf. The epoxy resin composition of the present invention comprises (1) 100 parts by weight of epoxy resin, (2) 5 to 5 parts by weight of thermoplastic polyurethane resin.
30 parts by weight, (3) 5 to 30 parts by weight of nitrile rubber, (4) 5 to 50 parts by weight of a liquid rubber of polybutadiene or acrylonitrile-butadiene copolymer having an amino group or epoxy group at the end of the molecular chain and having a molecular weight of 6000 or less; Preferably 10 to 45 parts by weight, (5) the required amount of curing agent and a single solvent or mixed solvent (high boiling point solvent/
It is characterized by comprising 50 to 90 parts by weight of a low boiling point solvent in a weight ratio of 1:9 to 4:6). The epoxy resin composition of the present invention contains an epoxy resin, a thermoplastic polyurethane resin whose solubility parameter is close to that of the adherend, and a nitrile rubber, as an adhesion promoter for soft polyvinyl chloride, a nitrile rubber, and an amino group or an epoxy group at the end of the molecular chain. liquid rubber with a molecular weight of 6000 or less (hereinafter referred to as the specific liquid rubber used in the present invention), and a solvent with a low boiling point (bp 80°C or less) such as ethanol or acetone, or its low boiling point. Solvents with high boiling points (b.
It consists of a mixed solvent (p. 110° to 170°C) and a curing agent such as polyamine or polysulfide. The epoxy resin used in the present invention is one obtained by adding epichlorohydrin to bisphenol A, halogenated bisphenol A, parahydroxybenzoic acid, or glycerin, or one obtained by further modifying these with dimer acid or urethane. It is. As the curing agent, aliphatic amines such as diethylenetriamine and triethylenetetramine and modified compounds thereof, as well as curing agents which react with epoxy resins and cure at room temperature, such as polyamides, heterocyclic polyamines and modified products thereof, can be used. The amount of curing agent used is the amount normally required for curing. Usually 30 to 60 parts by weight are used. The thermoplastic urethane resin used as an adhesion promoter is a linear polyester type resin produced by polyaddition of a polyester polyol having a hydroxyl group at the end, which is made of adipic acid and 1,4-butanediol or ethylene glycol, and tolylene diisocyanate. It is a polyurethane resin, preferably a resin with a molecular weight of about 20,000. The nitrile rubber is a copolymer of acrylonitrile and butadiene, and preferably has a relatively high content of acrylonitrile, so-called medium or high nitrile. In addition, as mentioned above, the specific liquid rubber used in the present invention is a polybutadiene or acrylonitrile-butadiene copolymer having an amino group or an epoxy group at the end of the molecular chain, and has a molecular weight of 6000 or less.
A liquid rubber of polyisoprene having an amino group or an epoxy group at the end of the molecular chain and having a molecular weight of 6000 or less can also be used. These adhesion promoters may be added to the base resin (liquid containing epoxy resin) or to the curing agent. Further, as an adhesion promoter, a copolymer of vinyl chloride and vinyl acetate may be blended as required. Examples of mixed solvents with low and high boiling points in the present invention include acetone, methylene chloride, 1,1,1-trichloroethane, dichloroethane, ethyl alcohol, methyl alcohol, with a boiling point of 80°C or less,
It is a mixed solvent of low boiling point solvents such as ethyl acetate and methyl ethyl ketone and high boiling point solvents such as toluene, xylene, cyclohexanone, methyl isobutyl ketone and diisobutyl ketone having a boiling point of 110 to 170°C. In the mixed solvent of the present invention, after the adhesive of the present invention is applied, the low boiling point solvent first evaporates to form a film on the applied surface, and the high boiling point solvent remaining on the applied surface gives a "wetting" effect. It is. Furthermore, reactive diluents such as diglycidyl ether, which are generally known as compounding agents for epoxy resins, non-reactive diluents such as tricresol phosphate, silica powder, calcium carbonate, clay, asbestos, cement, etc. Fillers such as talc can also be added. The adhesion promoter of the present invention is based on the weight of 5 parts per 100 parts of epoxy resin.
A mixture of ~50 parts is optimal. Even if more than 50 parts is added, it will not contribute to improving adhesion, will slow down the reaction, will increase viscosity, will make coating difficult, and will cause problems in workability. The specific liquid rubber used in the present invention alone exhibits a slow curing reaction with epoxy resins, polyamines, polyamides, and the like. However, when using an epoxy resin composition as in the example, the curing reaction becomes faster due to the synergistic effect of the various components of the composition, and practical strength is achieved in a relatively short time. There are no adhesion defects like those seen with other products. The present invention will be explained in detail below with reference to Examples, but it goes without saying that the present invention is not limited thereto. In addition, in the examples, parts are based on weight. Example 1 DER331 (manufactured by Dow Chemical Company: epoxy equivalent
192 bisphenol type epoxy resin) 100 parts, Desmocol 400 (manufactured by Bayer AG: thermoplastic urethane consisting of ethylene glycol/adipic acid/toluene diisocyanate) 10 parts, Hiker 1041 (manufactured by BF, Gutdrich, Chemical Company: high acrylonitrile) Sanmide
-963 (manufactured by Sanwa Kagaku Co., Ltd.: modified polyamine with amine value of 570) 100 parts, Hiker 1300 x 16 (manufactured by BF, Gutuduritsu, Chemical Co., Ltd.: diene-based liquid rubber with amine equivalent of 1000) 40 parts, 2,4,6- An epoxy resin composition is prepared by mixing 5 parts of tris(dimethylaminomethyl)phenol, 100 parts of calcium carbonate, 10 parts of asbestos, 15 parts of toluene, and 5 parts of ethanol. The adhesive performance of the compositions of the above examples was measured by the following method. 1 Preparation of test piece Slate plate (50 mm x 100 mm x 5 mm) Apply 3 g of epoxy resin composition with a hexagonal trowel,
Allow 30 minutes open time at °C. After 30 minutes of open time, soft vinyl resin (50mm x 150mm x 3
mm) with a hand roller through the epoxy resin composition and cured at 25°C for a predetermined period of time (24 hours and 168 hours). 2. 90 degree peel strength After processing the above test piece under the specified conditions, the 90 degree peel strength at room temperature is measured at a tensile speed of 20 mm/min. The results obtained are shown in Table 1. Example 2 DER331 (manufactured by Dow Chemical Company: epoxy equivalent
192 bisphenol type epoxy resin) 100 parts, Desmocol 400 (manufactured by Bayer: thermoplastic urethane consisting of ethylene glycol/adipic acid/tolylene diisocyanate) 20 parts, Hiker 1041
5 parts of high acrylonitrile nitrile rubber (manufactured by BF, Gutuduritsu, Chemical Co., Ltd.), 30 parts of polybutadiene R45EPT (manufactured by Idemitsu Petrochemical Co., Ltd.: polybutadiene rubber with terminal epoxy groups), 100 parts of main agent consisting of 100 parts of calcium carbonate and 50 parts of methyl ethyl ketone. 100 parts of Sanmide
100 parts of asbestos, 10 parts of asbestos, and 20 parts of ethanol to form an epoxy resin composition. The above epoxy resin composition was treated under the same conditions as in Example 1 and then subjected to a performance test. The results obtained are shown in Table 1. In the same manner as in Example 1, test pieces were prepared for the compositions of the following comparative examples and performance tests were conducted. The test results are shown in Table 1. Comparative example 1 DER331 (manufactured by Dow Chemical Company: epoxy equivalent
192 bisphenol type epoxy resin) 100 parts, Desmocol 400 (manufactured by Bayer: thermoplastic polyurethane consisting of ethylene glycol/adipic acid/toluene diisocyanate) 15 parts, Hiker
1041 (manufactured by BF, Gutsudoritsuchi, Chemical Company:
10 parts of high acrylonitrile (nitrile rubber), 100 parts of calcium carbonate, and 50 parts of methyl ethyl ketone
To 100 parts of the base resin, 100 parts of Sanmide An epoxy resin composition is prepared by mixing 100 parts of calcium carbonate, 10 parts of asbestos, and 20 parts of methanol.
【表】【table】
【表】
以上説明したように、本発明のエポキシ樹脂組
成物は、軟質塩化ビニル樹脂に対して、良好な初
期強さを有すると共に強力な接着性能を示すもの
である。以上の如く本発明のエポキシ樹脂組成物
は、ノンプライマーで軟質、半硬質塩化ビニルと
コンクリート、モルタル、スレート、木材、鉄板
などの接着剤に適するという利点がある。本発明
の実用例としてプールサイド及び高級マンシヨン
などの軟質塩化ビニル長尺床材、人工芝などの接
着剤として使用可能である。その他、室内の装
飾、ライニングの接着、陸橋のノンスリツプ止用
接着剤などにも好ましく使用できるものである。[Table] As explained above, the epoxy resin composition of the present invention has good initial strength and exhibits strong adhesion performance to soft vinyl chloride resin. As described above, the epoxy resin composition of the present invention has the advantage of being non-primer and suitable as an adhesive for soft and semi-hard vinyl chloride, concrete, mortar, slate, wood, iron plates, etc. As a practical example of the present invention, it can be used as an adhesive for soft vinyl chloride long flooring materials for poolsides and luxury condominiums, artificial turf, etc. In addition, it can be preferably used for interior decoration, adhesion of linings, and non-slip adhesives for overpasses.
Claims (1)
ウレタン樹脂５〜30重量部、(3)ニトリルゴム５〜
30重量部、(4)分子鎖末端にアミノ基またはエポキ
シ基を有するポリブタジエンまたはアクリロニト
リル・ブタジエン共重合体で分子量6000以下の液
状ゴム５〜50重量部、(5)硬化剤および溶剤50〜90
重量部からなることを特徴とするエポキシ樹脂組
成物。 ２ 前記熱可塑性ポリウレタン樹脂が、アジピン
酸と１，４―ブタンジオールまたはエチレングリ
コールとよりなる末端にヒドロキシル基を有する
ポリエステルポリオールとトリレンジイソシアネ
ートまたはその２量体からなるジイソシアネート
との重付加により生成する実質的に線状のポリエ
ステルタイプのポリウレタン樹脂であり、前記ニ
トリルゴムが、アクリロニトリル含有量の中、高
程度のアクリロニトリルとブタジエンとの共重合
体である前記特許請求の範囲第１項に記載のエポ
キシ樹脂組成物。[Claims] 1 (1) 100 parts by weight of epoxy resin, (2) 5 to 30 parts by weight of thermoplastic polyurethane resin, (3) 5 to 30 parts by weight of nitrile rubber.
30 parts by weight, (4) 5 to 50 parts by weight of a polybutadiene or acrylonitrile-butadiene copolymer liquid rubber having a molecular weight of 6,000 or less, having an amino group or epoxy group at the end of the molecular chain, (5) Curing agent and solvent 50 to 90 parts by weight
An epoxy resin composition comprising parts by weight. 2. The thermoplastic polyurethane resin is produced by polyaddition of a polyester polyol having a hydroxyl group at the terminal consisting of adipic acid and 1,4-butanediol or ethylene glycol, and a diisocyanate consisting of tolylene diisocyanate or a dimer thereof. The epoxy of claim 1, which is a substantially linear polyester type polyurethane resin, and wherein the nitrile rubber is a copolymer of acrylonitrile and butadiene with a medium to high acrylonitrile content. Resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10921380A JPS5734151A (en) | 1980-08-11 | 1980-08-11 | Epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10921380A JPS5734151A (en) | 1980-08-11 | 1980-08-11 | Epoxy resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5734151A JPS5734151A (en) | 1982-02-24 |
| JPS6225166B2 true JPS6225166B2 (en) | 1987-06-02 |
Family
ID=14504457
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10921380A Granted JPS5734151A (en) | 1980-08-11 | 1980-08-11 | Epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5734151A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102008053518A1 (en) * | 2008-10-28 | 2010-06-02 | Henkel Ag & Co. Kgaa | Epoxy-based structural foam with improved toughness |
| DE102008053520A1 (en) * | 2008-10-28 | 2010-05-06 | Henkel Ag & Co. Kgaa | Epoxy-based structural foam with thermoplastic polyurethanes |
| JP2010150437A (en) * | 2008-12-26 | 2010-07-08 | Toagosei Co Ltd | Adhesive composition, and cover lay film and flexible copper-clad laminate, both prepared by using the composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5426865A (en) * | 1977-08-01 | 1979-02-28 | Sumitomo Naugatuck Co Ltd | Production of plated articles |
| JPS5463152A (en) * | 1977-10-29 | 1979-05-21 | Denki Kagaku Kogyo Kk | Flexible epoxy resin composition |
-
1980
- 1980-08-11 JP JP10921380A patent/JPS5734151A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5426865A (en) * | 1977-08-01 | 1979-02-28 | Sumitomo Naugatuck Co Ltd | Production of plated articles |
| JPS5463152A (en) * | 1977-10-29 | 1979-05-21 | Denki Kagaku Kogyo Kk | Flexible epoxy resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5734151A (en) | 1982-02-24 |
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