JPH05239432A - Moisture-curable polyurethane adhesive - Google Patents
Moisture-curable polyurethane adhesiveInfo
- Publication number
- JPH05239432A JPH05239432A JP4543692A JP4543692A JPH05239432A JP H05239432 A JPH05239432 A JP H05239432A JP 4543692 A JP4543692 A JP 4543692A JP 4543692 A JP4543692 A JP 4543692A JP H05239432 A JPH05239432 A JP H05239432A
- Authority
- JP
- Japan
- Prior art keywords
- ethyl
- morpholino
- adhesive
- amine
- formula
- 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.)
- Pending
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 41
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 41
- 239000004814 polyurethane Substances 0.000 title claims description 13
- 229920002635 polyurethane Polymers 0.000 title claims description 13
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 3
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 abstract description 30
- 239000007983 Tris buffer Substances 0.000 abstract description 8
- 238000013329 compounding Methods 0.000 abstract description 3
- 125000005442 diisocyanate group Chemical group 0.000 abstract description 2
- 229920005862 polyol Polymers 0.000 abstract description 2
- 150000003077 polyols Chemical class 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 14
- 239000002318 adhesion promoter Substances 0.000 description 7
- -1 amine compound Chemical class 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 2
- ZMSQJSMSLXVTKN-UHFFFAOYSA-N 4-[2-(2-morpholin-4-ylethoxy)ethyl]morpholine Chemical compound C1COCCN1CCOCCN1CCOCC1 ZMSQJSMSLXVTKN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- DROMNWUQASBTFM-UHFFFAOYSA-N dinonyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCC DROMNWUQASBTFM-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、湿気硬化性ポリウレタ
ン系接着剤、さらに詳しくは、特定の硬化触媒と接着付
与剤とを配合することにより得られる、低温低湿度下の
例えば５℃−２０％ＲＨの条件下での硬化速度が速く、
また硬化後の接着強度に優れ、さらに高温高湿度下の例
えば３５℃−９０％ＲＨの条件下で、作業性に優れた湿
気硬化性ポリウレタン系接着剤に関する。FIELD OF THE INVENTION The present invention relates to a moisture-curable polyurethane adhesive, more specifically, a mixture of a specific curing catalyst and an adhesion promoter, which is obtained at a low temperature and a low humidity, for example, 5 ° C.-20. The curing speed is high under the condition of% RH,
Further, the present invention relates to a moisture-curable polyurethane-based adhesive having excellent adhesive strength after curing and excellent workability under high temperature and high humidity conditions such as 35 ° C.-90% RH.
【０００２】[0002]
【従来の技術】一液型の湿気硬化性ポリウレタン系接着
剤として、遊離のＮＣＯ基含有ウレタンプレポリマーを
主成分とするものがよく知られており、例えば自動車製
造工程での部材の接着、及びその窓ガラスの接着、さら
に詳しくは、特願平３−３２８９５記載の内外装用のパ
ネル類の取り付け固定など、多方面に使用されている。2. Description of the Related Art As a one-pack type moisture-curable polyurethane adhesive, one containing a free NCO group-containing urethane prepolymer as a main component is well known. For example, adhesion of members in automobile manufacturing process, and It is used in various fields such as adhesion of the window glass, and more specifically, attachment and fixation of inner and outer panels described in Japanese Patent Application No. 3-32895.
【０００３】本来このタイプのポリウレタン系接着剤
は、空気中の水分存在下で硬化するものであるが、作業
現場での能率を上げるため、より迅速な硬化速度及び良
好な接着性を有するポリウレタン系接着剤が望まれてお
り、通常各種の硬化触媒が配合されている。しかし反
面、従来の硬化触媒を配合した場合には、低温低湿度下
の例えば５℃−２０％ＲＨでの硬化速度が極端に遅く接
着性が不十分であり、作業能率が極端に低下し、ほぼ不
可能な場合もある。また高温高湿度下の例えば３５℃−
９０％ＲＨでは反応が極端に速くなり、通常の作業が著
しく行い難い。Originally, this type of polyurethane-based adhesive cures in the presence of water in the air, but in order to improve the efficiency at the work site, a polyurethane-based adhesive having a faster curing rate and good adhesiveness. Adhesives are desired, and usually various curing catalysts are blended. However, on the other hand, when a conventional curing catalyst is blended, the curing rate at low temperature and low humidity, for example, at 5 ° C.-20% RH is extremely slow, the adhesiveness is insufficient, and the work efficiency is extremely reduced. In some cases it is almost impossible. Also, under high temperature and high humidity, for example, 35 ° C-
At 90% RH, the reaction becomes extremely fast, and normal work is extremely difficult to perform.
【０００４】[0004]
【発明が解決しようとする課題】かかる背景下に、本発
明はポリウレタン系接着剤の硬化反応での触媒の働きに
よる硬化速度が、低温低湿度下で極端に遅く高温高湿度
下で極端に速いことに起因する作業性の欠点を解決しよ
うとするものである。また触媒と接着付与剤の相性の悪
さによる接着性の低下という欠点を解決しようとするも
のである。Against this background, the present invention provides that the curing rate of the catalyst in the curing reaction of the polyurethane adhesive is extremely slow at low temperature and low humidity and extremely fast at high temperature and high humidity. This is intended to solve the drawback of workability caused by the above. Further, the present invention is intended to solve the drawback that the adhesiveness is deteriorated due to the poor compatibility between the catalyst and the adhesion-imparting agent.
【０００５】[0005]
【課題を解決するための手段】本発明は、遊離のＮＣＯ
基含有ウレタンプレポリマーを主成分とし、これに硬化
触媒として、接着剤全量中０．０５〜１．００重量％の
式The present invention provides a free NCO.
Group-containing urethane prepolymer as a main component, and as a curing catalyst for this, a formula of 0.05 to 1.00 wt% in the total amount of the adhesive
【化３】 （式中、Ｒ1 、Ｒ2 、Ｒ3 、Ｒ4 、Ｒ5 、Ｒ6 は水素、
メチル基またはエチル基である。）で示されるアミン化
合物と、接着付与剤として、接着剤全量中０．０３〜
２．００重量％の式[Chemical 3] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are hydrogen,
It is a methyl group or an ethyl group. ) And an amine compound represented by the formula (3) as an adhesion-imparting agent in the total amount of the adhesive of 0.03 to
2.00 wt% formula
【化４】 で示される接着剤用ポリイソシアネートとを配合した湿
気硬化性ポリウレタン接着剤組成物を提供するものであ
る。[Chemical 4] The present invention provides a moisture-curable polyurethane adhesive composition containing the polyisocyanate for adhesives represented by
【０００６】本発明における遊離ＮＣＯ基含有ウレタン
プレポリマーとしては、この種のシーリング材主成分と
して用いられているものであれば、特に制限なく使用で
きるが、具体的には、例えば市販のポリオキシアルキレ
ンジオール（ポリオキシエチレングリコール、ポリオキ
シプロピレングリコール、ポリオキシブチレングリコー
ル、またはこれらの共重合体など）やポリオキシアルキ
レントリオール（エチレンオキサイド、プロピレンオキ
サイド、ブチレンオキサイドなどと、グリセリン、トリ
メチロールプロパンなどを付加重合させたもの）のポリ
オキシアルキレンポリオールと、過剰量の有機ジイソシ
アネート化合物（脂肪族、脂環式、アリール脂肪族また
は芳香族ジイソシアネート）を常法に従って反応させた
ものがあげられる。反応は５０℃〜１３０℃の温度下で
ゆっくり攪拌しながら行う。Urethane containing free NCO group in the present invention
As a prepolymer, the main component of this kind of sealing material
If it is used as it is, it can be used without particular limitation
However, specifically, for example, commercially available polyoxyalkylene
Diol (polyoxyethylene glycol, polyoxy
Cypropylene glycol, polyoxybutylene glyco
Or their copolymers) or polyoxyalkyl
Rentriol (ethylene oxide, propylene oxide
Side, butylene oxide, etc., with glycerin, tri
(Polymers obtained by addition polymerization of methylolpropane)
Oxyalkylene polyol and excess organic diisocyanate
Anate compound (aliphatic, cycloaliphatic, arylaliphatic or
Is an aromatic diisocyanate)
I can give you something. The reaction is performed at a temperature of 50 ° C to 130 ° C.
Perform with gentle stirring.
【０００７】本発明に係る湿気硬化性ポリウレタン系接
着剤は、上記主成分のウレタンプレポリマーに上記式
（Ｉ）の硬化触媒、及び上記式（II）の接着付与剤を配
合した系で構成されるが、更に必要に応じてＮＣＯ基に
対していずれも不活性な充填剤（カーボンブラック、炭
酸カルシウム、酸化チタンなど） 可塑剤（ジオクチルフタレート、ブチルベンジルフタレ
ート、ジノニルフタレートなど） 溶剤（トルエン、キシレン エーテル類、ケトン類、エ
ステル類など） を適量添加してもよい。一般式（Ｉ）においてＲ1 、Ｒ
2 、Ｒ3 、Ｒ4 、Ｒ5 、Ｒ6 、は同じでも異なっていて
もよい。好ましくはＲ1 、Ｒ2 、Ｒ3 、Ｒ4 、Ｒ5 、Ｒ
6 がメチル基である。The moisture-curable polyurethane adhesive according to the present invention comprises a system in which a urethane prepolymer as the main component is blended with a curing catalyst of the above formula (I) and an adhesion promoter of the above formula (II). However, if necessary, any filler that is inert to NCO groups (carbon black, calcium carbonate, titanium oxide, etc.) Plasticizer (dioctyl phthalate, butylbenzyl phthalate, dinonyl phthalate, etc.) Solvent (toluene, Xylene ethers, ketones, esters, etc.) may be added in an appropriate amount. In the general formula (I), R 1 and R
2 , R 3 , R 4 , R 5 , and R 6 may be the same or different. Preferably R 1 , R 2 , R 3 , R 4 , R 5 and R
6 is a methyl group.
【０００８】一般式（Ｉ）で示される化合物としては、
例えばトリス（２−（４−モルホリノ）エチル）アミ
ン、トリス（２−（２，６−ジメチル−４−モルホリ
ノ）エチル）アミン、トリス（２−（２，６−ジエチル
−４−モルホリノ）エチル）アミン、トリス（２−（２
−メチル−４−モルホリノ）エチル）アミン、トリス
（２−（２−エチル−４−モルホリノ）エチル）アミ
ン、ビス（２−（２，６−ジメチル−４−モルホリノ）
エチル）−（２−（４−モルホリノ）エチル）アミン、
ビス（２−（２，６−ジメチル−４−モルホリノ）エチ
ル）−（２−（２，６−ジエチル−４−モルホリノ）エ
チル）アミン、ビス（２−（２，６−ジメチル−４−モ
ルホリノ）エチル）−（２−（２−メチル−４−モルホ
リノ）エチル）アミン、ビス（２−（２，６−ジメチル
−４−モルホリノ）エチル）−（２−（２，６−エチル
−４−モルホリノ）エチル）アミン、ビス（２−（２，
６−ジエチル−４−モルホリノ）エチル）−（２−（４
−モルホリノ）エチル）アミン、ビス（２−（２，６−
ジエチル−４−モルホリノ）エチル）−（２−（２，６
−ジメチル−４−モルホリノ）エチル）アミン、ビス
（２−（２，６−ジエチル−４−モルホリノ）エチル）
−（２−（２−メチル−４−モルホリノ）エチル）アミ
ン、ビス（２−（２，６−ジエチル−４−モルホリノ）
エチル）−（２−（２−エチル−４−モルホリノ）エチ
ル）アミン、ビス（２−（２−メチル−４−モルホリ
ノ）エチル）−（２−（４−モルホリノ）エチル）アミ
ン、ビス（２−（２−メチル−４−モルホリノ）エチ
ル）−（２−（２，６−ジメチル−４−モルホリノ）エ
チル）アミン、ビス（２−（２−メチル−４−モルホリ
ノ）エチル）−（２−（２，６−ジエチル−４−モルホ
リノ）エチル）アミン、ビス（２−（２−メチル−４−
モルホリノ）エチル）−（２−（２−エチル−４−モル
ホリノ）エチル）アミン、ビス（２−（２−エチル−４
−モルホリノ）エチル）−（２−（４−モルホリノ）エ
チル）アミン、ビス（２−（２−エチル ４−モルホリ
ノ）エチル）−（２−２，６−ジメチル−４−モルホリ
ノ）エチル）アミン、ビス（２−（２−エチル−４−モ
ルホリノ）エチル）−（２−（２，６−ジエチル−４−
モルホリノ）エチル）アミン、ビス（２−（２−エチル
−４−モルホリノ）エチル）−（２−（２−メチル−４
−モルホリノ）エチル）アミン、（２−（２，６−ジメ
チル−４−モルホリノ）エチル）−ビス（２−（４−モ
ルホリノ）エチル）アミン、（２−（２，６−ジエチル
−４−モルホリノ）エチル）−ビス（２−（４−モルホ
リノ）エチル）アミン、（２−（２−メチル−４−モル
ホリノ）エチル）−ビス（２−（４−モルホリノ）エチ
ル）アミン、（２−（２−エチル−４−モルホリノ）エ
チル）−ビス（２−（４−モルホリノ）エチル）アミ
ン、ビス（２−（２−メチル−４−モルホリノ）エチ
ル）−（２−（４−モルホリノ）エチル）アミン、ビス
（２−（２−メチル−４−モルホリノ）エチル）−（２
−（２，６−ジエチル−４−モルホリノ）エチル）アミ
ンがあげられる。好ましくはトリス（２−（４−モルホ
リノ）エチル）アミン、トリス（２−（２，６−ジメチ
ル−４−モルホリノ）エチルアミンである。As the compound represented by the general formula (I),
For example, tris (2- (4-morpholino) ethyl) amine, tris (2- (2,6-dimethyl-4-morpholino) ethyl) amine, tris (2- (2,6-diethyl-4-morpholino) ethyl) Amine, Tris (2- (2
-Methyl-4-morpholino) ethyl) amine, tris (2- (2-ethyl-4-morpholino) ethyl) amine, bis (2- (2,6-dimethyl-4-morpholino))
Ethyl)-(2- (4-morpholino) ethyl) amine,
Bis (2- (2,6-dimethyl-4-morpholino) ethyl)-(2- (2,6-diethyl-4-morpholino) ethyl) amine, bis (2- (2,6-dimethyl-4-morpholino) ) Ethyl)-(2- (2-methyl-4-morpholino) ethyl) amine, bis (2- (2,6-dimethyl-4-morpholino) ethyl)-(2- (2,6-ethyl-4- Morpholino) ethyl) amine, bis (2- (2,2
6-Diethyl-4-morpholino) ethyl)-(2- (4
-Morpholino) ethyl) amine, bis (2- (2,6-
Diethyl-4-morpholino) ethyl)-(2- (2,6
-Dimethyl-4-morpholino) ethyl) amine, bis (2- (2,6-diethyl-4-morpholino) ethyl)
-(2- (2-Methyl-4-morpholino) ethyl) amine, bis (2- (2,6-diethyl-4-morpholino))
Ethyl)-(2- (2-ethyl-4-morpholino) ethyl) amine, bis (2- (2-methyl-4-morpholino) ethyl)-(2- (4-morpholino) ethyl) amine, bis (2 -(2-Methyl-4-morpholino) ethyl)-(2- (2,6-dimethyl-4-morpholino) ethyl) amine, bis (2- (2-methyl-4-morpholino) ethyl)-(2- (2,6-diethyl-4-morpholino) ethyl) amine, bis (2- (2-methyl-4-)
Morpholino) ethyl)-(2- (2-ethyl-4-morpholino) ethyl) amine, bis (2- (2-ethyl-4)
-Morpholino) ethyl)-(2- (4-morpholino) ethyl) amine, bis (2- (2-ethyl-4-morpholino) ethyl)-(2-2,6-dimethyl-4-morpholino) ethyl) amine, Bis (2- (2-ethyl-4-morpholino) ethyl)-(2- (2,6-diethyl-4-
Morpholino) ethyl) amine, bis (2- (2-ethyl-4-morpholino) ethyl)-(2- (2-methyl-4)
-Morpholino) ethyl) amine, (2- (2,6-dimethyl-4-morpholino) ethyl) -bis (2- (4-morpholino) ethyl) amine, (2- (2,6-diethyl-4-morpholino) ) Ethyl) -bis (2- (4-morpholino) ethyl) amine, (2- (2-Methyl-4-morpholino) ethyl) -bis (2- (4-morpholino) ethyl) amine, (2- (2 -Ethyl-4-morpholino) ethyl) -bis (2- (4-morpholino) ethyl) amine, bis (2- (2-methyl-4-morpholino) ethyl)-(2- (4-morpholino) ethyl) amine , Bis (2- (2-methyl-4-morpholino) ethyl)-(2
Examples include-(2,6-diethyl-4-morpholino) ethyl) amine. Preferred are tris (2- (4-morpholino) ethyl) amine and tris (2- (2,6-dimethyl-4-morpholino) ethylamine.
【０００９】硬化触媒（Ｉ）の配合量は、接着剤全量中
０．０５〜１．００重量％、好ましくは、０．１０〜
０．７０重量％の範囲で選定する。通常湿気硬化性ポリ
ウレタン系接着剤の可使時間は、最低３分間、望ましく
は４分間以上が必要であり、また次工程を考慮すると、
長くとも６０分間位が望まれる。０．０５重量％未満で
あると、特に低温低湿度下での所望の硬化促進が得られ
ず、また１．００重量％を越えると、高温高湿度下での
硬化速度が速くなり作業が困難になる。The curing catalyst (I) is blended in an amount of 0.05 to 1.00% by weight, preferably 0.10 to 10% by weight based on the total amount of the adhesive.
Select in the range of 0.70% by weight. Generally, the pot life of the moisture-curable polyurethane adhesive must be at least 3 minutes, preferably 4 minutes or more. Considering the next step,
At least 60 minutes is desired. If it is less than 0.05% by weight, the desired curing acceleration cannot be obtained especially at low temperature and low humidity, and if it exceeds 1.00% by weight, the curing speed becomes high under high temperature and high humidity and the work is difficult. become.
【００１０】一般式（II）で示される化合物の特徴は、
ＮＣＯ基含有率１６．０〜１７．０％、不揮発分７３．
０〜７７．０％、粘度１００〜３００ｃｐｓである。接
着付与剤（II）の配合量は、組成物全量中０．０３〜
２．００重量％、好ましくは、０．１０〜１．５０重量
％の範囲で選定する。湿気硬化性ポリウレタン系接着剤
の初期接着性は高いことが望まれるが、通常９０分後で
０．１kg／cm2 以上あれば十分である。０．０３重量％
未満であると、特に低温低湿度下での初期接着性が低下
し、実用に供し難い。また２．００重量％を越えると、
初期接着力がほぼ飽和に達し、２．５０重量％を越える
と、触媒の働きを阻害し硬化速度をも遅くなることが見
られたので、あまり望ましくない。The characteristics of the compound represented by the general formula (II) are as follows:
NCO group content 16.0 to 17.0%, nonvolatile 73.
The viscosity is 0 to 77.0% and the viscosity is 100 to 300 cps. The compounding amount of the adhesion-imparting agent (II) is 0.03 to the total amount of the composition.
It is selected in the range of 2.00% by weight, preferably 0.10 to 1.50% by weight. It is desired that the moisture-curable polyurethane adhesive has a high initial adhesiveness, but normally 90 minutes later, 0.1 kg / cm 2 or more is sufficient. 0.03% by weight
If it is less than the above range, the initial adhesiveness is lowered particularly at low temperature and low humidity, and it is difficult to put it to practical use. If it exceeds 2.00% by weight,
When the initial adhesive strength reaches almost saturation and exceeds 2.50% by weight, it is observed that the function of the catalyst is hindered and the curing rate is slowed down, which is not desirable.
【００１１】[0011]
【実施例】次に実施例および比較例を挙げて、本発明を
より具体的に説明する。実施例１〜７及び比較例１〜６ a) プレポリマーの合成 分子量４０００のポリオキシアルキレントリオール２０
００ｇに、ＭＤＩ３５０ｇを加え、６０℃で６時間反応
させて、遊離ＮＣＯ基含有量２．４％、粘度（２０℃）
３５０００ｃｐｓのウレタンプレポリマーを得る。 b) 基本ポリウレタン系接着剤の調整 上記a)のウレタンプレポリマー５００ｇに、乾燥したカ
ーボンブラック４００ｇを加え１０分間攪拌混合した
後、ジオクチルフタレート１２０ｇを加え、減圧下で１
５分間真空脱泡攪拌を行った後、接着付与剤１０ｇ（接
着剤全量中１．０重量％に相当）および硬化触媒４．０
ｇ（接着剤全量中０．４０重量％に相当）を加え、１５
分間脱泡攪拌を行う。EXAMPLES Next, the present invention will be described more specifically with reference to Examples and Comparative Examples. Examples 1 to 7 and Comparative Examples 1 to 6 a) Synthesis of prepolymer Polyoxyalkylene triol 20 having a molecular weight of 4000
350 g of MDI was added to 00 g and reacted at 60 ° C. for 6 hours to give a free NCO group content of 2.4% and a viscosity (20 ° C.)
A urethane prepolymer of 35000 cps is obtained. b) Preparation of Basic Polyurethane Adhesive To 500 g of the urethane prepolymer of the above a), 400 g of dried carbon black was added and mixed with stirring for 10 minutes, and then 120 g of dioctyl phthalate was added, and 1
After vacuum defoaming and stirring for 5 minutes, 10 g of an adhesion-imparting agent (corresponding to 1.0% by weight in the total amount of the adhesive) and a curing catalyst 4.0.
g (corresponding to 0.40% by weight in the total amount of the adhesive), and add 15
Degas and stir for a minute.
【００１２】c) 低温および高温におけるタックフリー
タイムの測定 ガラス板、幅９０mm、長さ３００mm、厚さ３mmの上に接
着剤を幅２５mm、長さ３００mm、厚さ５mmのビード状に
塗布し、試験片とする。接着剤塗布後からポリエチレン
フィルム（幅２５mm、長さ５０mm、厚み０．１〜０．１
５mm）を接着剤の上に押しつけ、ひきはがし、接着剤が
フィルムに付着しなくなる時間を測定する。接着剤がフ
ィルムに付着しなくなる時間をタックフリータイムとし
て、時間（分）で表示する。実施例として触媒および接
着付与剤の量を変え５℃−２０％ＲＨ、３５℃−９０％
ＲＨにおいてタックフリータイムを測定、また比較例と
して各接着剤を５℃−２０％ＲＨ、３５℃−９０％ＲＨ
においてタックフリータイムを測定し、結果を表１〜３
に示す。C) Measurement of tack free time at low and high temperatures A glass plate, width 90 mm, length 300 mm, thickness 3 mm, was coated with an adhesive in the form of beads having a width of 25 mm, a length of 300 mm and a thickness of 5 mm, Use as a test piece. After applying the adhesive, polyethylene film (width 25 mm, length 50 mm, thickness 0.1-0.1
5 mm) is pressed onto the adhesive, peeled off and the time at which the adhesive no longer adheres to the film is measured. The time when the adhesive does not adhere to the film is displayed as the tack free time in minutes. As an example, the amounts of the catalyst and the adhesion-imparting agent were changed to 5 ° C-20% RH, 35 ° C-90%.
The tack free time was measured at RH, and each adhesive was tested at 5 ° C-20% RH and 35 ° C-90% RH as a comparative example.
The tack free time was measured in Table 1, and the results are shown in Tables 1 to 3.
Shown in.
【００１３】d) 低温および高温における９０分後の引
張強度の測定 幅２５mm、長さ１００mm、厚さ５mmのガラス板と、幅２
５mm、長さ１００mm、厚さ０．８mmの塗装鋼板を使用
し、接着剤の厚さが３mm、面積が２．５cm2 となるよう
にせん断試験片を作製する。せん断試験片を５℃−２０
％ＲＨ、および３５℃−９０％ＲＨに９０分間保持した
後、ただちに引張試験機にとりつけ引張速度５０mm／ｍ
ｉｎで引張強度を測定する。測定値は破壊時の最大荷重
（ｋｇｆ）をとり破壊後接着面積を測定し、破壊荷重を
接着面積で割った値を引張強度とする。実施例として触
媒および接着付与剤の量を変え５℃−２０％ＲＨ、３５
℃−９０％ＲＨにおいて９０分後の引張強度を測定、ま
た比較例として各接着剤を５℃−２０％ＲＨ、３５℃−
９０％ＲＨにおいて９０分後の引張強度を測定し、結果
を表１〜３に示す。D) Measurement of tensile strength after 90 minutes at low temperature and high temperature A glass plate having a width of 25 mm, a length of 100 mm and a thickness of 5 mm, and a width of 2
Using a coated steel plate having a length of 5 mm, a length of 100 mm and a thickness of 0.8 mm, a shear test piece is prepared so that the adhesive has a thickness of 3 mm and an area of 2.5 cm 2 . Shear test piece at 5 ° C-20
% RH and 35 ° C-90% RH for 90 minutes, then immediately attach to a tensile tester and pull speed 50 mm / m.
Measure tensile strength in. For the measured value, the maximum load (kgf) at the time of breaking is taken, the adhesive area after breaking is measured, and the value obtained by dividing the breaking load by the adhesive area is taken as the tensile strength. As an example, the amount of the catalyst and the adhesion promoter was changed to 5 ° C.-20% RH, 35
Tensile strength after 90 minutes was measured at 90 ° C.-90% RH. As a comparative example, each adhesive was tested at 5 ° C.-20% RH, 35 ° C.-
Tensile strength after 90 minutes was measured at 90% RH, and the results are shown in Tables 1 to 3.
【００１４】[0014]
【表１】 [Table 1]
【００１５】[0015]
【表２】 [Table 2]
【００１６】[0016]
【表３】 [Table 3]
【００１７】注）各例で用いた硬化触媒、接着付与剤は
以下の通りである。 硬化触媒：実施例１〜７、比較例１、２、３、６Note) The curing catalyst and adhesion promoter used in each example are as follows. Curing catalyst: Examples 1-7, Comparative Examples 1, 2, 3, 6
【化５】 硬化触媒：比較例４ ジブチルチンジラウレート 硬化触媒：比較例５ ２，２−ジモルホリノジエチルエーテル 接着付与剤：実施例１〜７、比較例１〜５[Chemical 5] Curing catalyst: Comparative example 4 Dibutyltin dilaurate Curing catalyst: Comparative example 5 2,2-Dimorpholinodiethyl ether Adhesion imparting agent: Examples 1-7, Comparative examples 1-5
【化６】 接着付与剤：比較例６ トリフェニルメタン[Chemical 6] Adhesion imparting agent: Comparative Example 6 Triphenylmethane
【００１８】ここで、表１は、（II）式の接着付与剤
（１．００％）を用い（Ｉ）式の触媒量（％）を変えた
ときであって、触媒量の少ない比較例１の場合は、低温
時のタックフリータイムが長くかつ低温時の引張強度も
足りないし、また触媒量の多い比較例２は、高温時のタ
ックフリータイムが短すぎるが、実施例１〜３は、タッ
クフリータイム、引張強度共に問題がない。Here, Table 1 shows the case where the adhesion promoter (1.00%) of the formula (II) was used and the catalyst amount (%) of the formula (I) was changed. In the case of 1, the tack free time at low temperature is long and the tensile strength at low temperature is insufficient, and in Comparative Example 2 in which the amount of catalyst is large, the tack free time at high temperature is too short, but in Examples 1 to 3, There are no problems with tack free time and tensile strength.
【００１９】次に、表２は、（Ｉ）式の触媒（０．４０
％）と任意の接着付与剤を用いたときであって、接着付
与剤の多い比較例３は、高温時のタックフリータイムが
短すぎるが、実施例４〜７は、タックフリータイム、引
張強度のいずれも適切な値を示す。Next, Table 2 shows the catalyst of formula (I) (0.40
%) And an arbitrary adhesion-imparting agent are used, and Comparative Example 3 containing many adhesion-imparting agents has a too short tack free time at high temperature, but Examples 4 to 7 show tack free time and tensile strength. Shows an appropriate value.
【００２０】更に、表３は、任意の触媒（０．４０
％）、任意の接着付与剤（１．００％）を用いたときで
あって、触媒にジブチルチンジラウレート、接着付与剤
に（II）式のものを用いた比較例４は、低温時のタック
フリータイムが長くかつ低温時、高温時の引張強度が足
りないし、また触媒に２，２−ジモリホリノジエチルエ
ーテルを用い接着付与剤に（II）式のものを用いた比較
例５は、低温時のタックフリータイムが長くかつ低温時
の引張強度が足りず、さらに触媒に（Ｉ）式のもの、接
着付与剤にトリフェニルメタンを用いた比較例６は、低
温時の引張強度が足りないのである。Further, Table 3 shows that any catalyst (0.40
%), And when using an arbitrary adhesion-imparting agent (1.00%), Comparative Example 4 in which dibutyltin dilaurate was used as the catalyst and the compound of formula (II) was used as the adhesion-imparting agent, the tack at low temperature was used. Comparative Example 5 in which the free time is long and the tensile strength at low temperature and high temperature is insufficient, and 2,2-dimolifolino diethyl ether is used as the catalyst and the adhesion promoter of the formula (II) is used, Comparative Example 6 in which the tack-free time at low temperature is long and the tensile strength at low temperature is insufficient, and the catalyst of the formula (I) and triphenylmethane as the adhesion promoter are used, the tensile strength at low temperature is insufficient. There is no.
【００２１】[0021]
【発明の効果】以上のとおりであって、本発明の接着剤
は、低温高温また低湿度高湿度を問わず適切な硬化速度
を有するため作業性に優れ、しかも触媒と接着付与剤と
の間の相性の悪さによる接着性の低下という欠点もよく
克服できるものであるから、極めて有用である。EFFECTS OF THE INVENTION As described above, the adhesive of the present invention has an excellent curing rate regardless of low temperature and high temperature or low humidity and high humidity, and is excellent in workability. It is extremely useful because it can well overcome the drawback of reduced adhesiveness due to poor compatibility.
Claims (1)
ーを主成分とし、これに硬化触媒として、接着剤全量
中、０．０５〜１．００重量％の式 【化１】 （式中、Ｒ1 、Ｒ2 、Ｒ3 、Ｒ4 、Ｒ5 、Ｒ6 は水素、
メチル基またはエチル基である。）で示されるアミン化
合物と、接着付与剤として、接着剤全量中、０．０３〜
２．００重量％の式 【化２】 で示されるポリイソシアネートとを配合してなる湿気硬
化性ポリウレタン接着剤。1. A urethane prepolymer containing a free NCO group as a main component, which is used as a curing catalyst in an amount of 0.05 to 1.00% by weight based on the total amount of the adhesive. (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are hydrogen,
It is a methyl group or an ethyl group. ), As an adhesion-imparting agent, 0.03 to
2.00 wt% formula A moisture-curable polyurethane adhesive compounded with a polyisocyanate represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4543692A JPH05239432A (en) | 1992-03-03 | 1992-03-03 | Moisture-curable polyurethane adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4543692A JPH05239432A (en) | 1992-03-03 | 1992-03-03 | Moisture-curable polyurethane adhesive |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05239432A true JPH05239432A (en) | 1993-09-17 |
Family
ID=12719266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4543692A Pending JPH05239432A (en) | 1992-03-03 | 1992-03-03 | Moisture-curable polyurethane adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05239432A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000016985A (en) * | 1998-06-30 | 2000-01-18 | Toagosei Co Ltd | Men compound, isocyanate curing catalyst and adhesive composition |
-
1992
- 1992-03-03 JP JP4543692A patent/JPH05239432A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000016985A (en) * | 1998-06-30 | 2000-01-18 | Toagosei Co Ltd | Men compound, isocyanate curing catalyst and adhesive composition |
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