JPS60179407A - Cure accelerator solution - Google Patents
Cure accelerator solutionInfo
- Publication number
- JPS60179407A JPS60179407A JP3433784A JP3433784A JPS60179407A JP S60179407 A JPS60179407 A JP S60179407A JP 3433784 A JP3433784 A JP 3433784A JP 3433784 A JP3433784 A JP 3433784A JP S60179407 A JPS60179407 A JP S60179407A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- accelerator solution
- curing
- curing accelerator
- hydrazide
- 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.)
- Granted
Links
- 239000013522 chelant Substances 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000004391 aryl sulfonyl group Chemical group 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 7
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 abstract description 24
- 230000001070 adhesive effect Effects 0.000 abstract description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 14
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 abstract description 4
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- VJRITMATACIYAF-UHFFFAOYSA-N benzenesulfonohydrazide Chemical compound NNS(=O)(=O)C1=CC=CC=C1 VJRITMATACIYAF-UHFFFAOYSA-N 0.000 abstract description 2
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 11
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- -1 amine salts Chemical class 0.000 description 6
- 150000001451 organic peroxides Chemical class 0.000 description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 4
- 239000003522 acrylic cement Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- MFWFDRBPQDXFRC-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;vanadium Chemical compound [V].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MFWFDRBPQDXFRC-LNTINUHCSA-N 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000005147 toluenesulfonyl group Chemical group C=1(C(=CC=CC1)S(=O)(=O)*)C 0.000 description 2
- HHQAGBQXOWLTLL-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC1=CC=CC=C1 HHQAGBQXOWLTLL-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- TYQCGQRIZGCHNB-JLAZNSOCSA-N l-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
Landscapes
- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
【発明の詳細な説明】
本発明はラジカル重合開始剤を配合した（メタ）アクリ
ル系硬化性組成物の硬化を促進するための硬化促進剤溶
液に関する。４′ｆに、嫌気性接着剤や第２世代アクリ
ル接着剤に適した高性能の硬化促進剤溶液を提供するも
のである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a curing accelerator solution for accelerating the curing of a (meth)acrylic curable composition containing a radical polymerization initiator. 4'f, a high performance curing accelerator solution suitable for anaerobic adhesives and second generation acrylic adhesives is provided.
嫌気性接着剤は空気と接触している限りは安定で長期間
硬化しないが、金属二表面間に入って空気を遮断される
と短時間で硬化するという独特の性能を有する接着剤で
ネジ部のゆるみ止めや配管部のシール用等に広く使用さ
れている。通常は一族で使用されているが、ライン作業
で速硬性が要求される場合やメッキ材質等の難接着性材
料の接着に当ってはその機能を充分発揮することができ
ないため、硬化促進剤を含有ずろプライマーを併用し二
液型としてその欠点を補っている。第２世代アクリル接
着剤は（メタ）アクリレート単量体、エラストマー及び
有機過１伎化物等からなるＡ液と硬化促進剤な配合した
Ｂ液からなる速硬性の二液型接着剤であり、作業性と接
着性能に優れ近年大きな注目を集めている接着剤である
。Anaerobic adhesives are stable and do not harden for long periods of time as long as they are in contact with air, but once they are placed between two metal surfaces and the air is blocked, they harden in a short period of time. It is widely used to prevent loosening of pipes, seal piping parts, etc. Although it is usually used in the industry, it cannot fully demonstrate its function when fast curing is required in line work or when bonding difficult-to-bond materials such as plated materials, so a curing accelerator is used. This drawback is compensated for as a two-component type by using a primer containing Zuro. The second generation acrylic adhesive is a fast-curing two-component adhesive consisting of liquid A consisting of (meth)acrylate monomer, elastomer, and organic peroxide, and liquid B containing a curing accelerator. It is an adhesive that has been attracting a lot of attention in recent years due to its excellent adhesiveness and adhesive performance.
これらにおける硬化促進剤は殆んどが嫌気性接着剤、ま
たは第２世代アクリル接着剤のＡ液中に含まれる有機過
酸化物とレドックスを形成することができる還元剤であ
り、たとえば、金属石けん、メルカプタン類、チオ尿素
、アスコルビン酸、金属キレート化合物、３級アミン等
であり、その何れもが公知である。このような還元剤の
使用によって前述の如くＣメタ）アクリル系硬化性組成
物を速硬性にすることができるが、近年においては組み
立て工程の高速化等に伴ない更に性能の向上が望まれて
いる。即ち、硬化速度がより速いこと、接着に当っては
被着体表面に影響されずどのよりな月質に対しても速硬
性であること、悪臭がないことなどである。Most of the curing accelerators in these are anaerobic adhesives or reducing agents that can form redox with organic peroxides contained in liquid A of second generation acrylic adhesives. , mercaptans, thiourea, ascorbic acid, metal chelate compounds, tertiary amines, etc., all of which are known. As mentioned above, the use of such a reducing agent makes it possible to make the C meth)acrylic curable composition quick-curing, but in recent years, as assembly processes have become faster, further improvements in performance have been desired. There is. That is, the curing speed is faster, the adhesion is not affected by the surface of the adherend, and it hardens quickly to any rough surface, and there is no bad odor.
本発明者等はこの目的に合致した硬化促進剤について鋭
意研究の結果、銅またはバナジウムのキレート化合物と
０−ベンゾイックスルフィミドまたはアリールスルホニ
ルヒドラジドの組み合せからなる還元剤系が著しく良好
な性能を有していることを見出し本発明に至ったもので
ある。As a result of intensive research into curing accelerators that meet this purpose, the present inventors have found that a reducing agent system consisting of a combination of a copper or vanadium chelate compound and 0-benzoic sulfimide or arylsulfonyl hydrazide has extremely good performance. This discovery led to the present invention.
即ち本発明は、下記（１）および（２）を有機溶剤に溶
解して得られる（メタ）アクリル系硬化性組成物用の硬
化促進剤溶液に関するものである。That is, the present invention relates to a curing accelerator solution for a (meth)acrylic curable composition obtained by dissolving the following (1) and (2) in an organic solvent.
（１）会同および／またはバナジウムのキレート化合物
（２）０−ベンゾイックスルフィミドおよび／またはア
リールスルホニルヒドラジド
硬化促進剤の成分として金属キレート化合物を用いた例
としては特公昭４４−３１８３０．同４９−２１０９３
、同４９−４８６７８ 、特開昭４１’ｌ−２１７８６
等の各公報に記載されているが接着速度の点で不充分で
ある。更に髄公昭３９−２９１９５号公報においてはバ
ナジウム化合物と主としてメルカプタン類との組み合わ
せからなる硬化促進剤により不飽和ポリエステル樹脂の
硬化速度を改善しており、また特公昭５５−１７０４１
号公報においては金属キレート化合物とチオ尿素との組
み合わせにより第２世代アクリル接着剤力接着速度を改
善している。(1) Metal chelate compound and/or vanadium chelate compound (2) 0-benzoic sulfimide and/or arylsulfonyl hydrazide An example of using a metal chelate compound as a component of a curing accelerator is given in Japanese Patent Publication No. 31830/1983. 49-21093
, 49-48678, JP-A-41-21786
However, the adhesion speed is insufficient. Furthermore, in Japanese Patent Publication No. 39-29195, the curing speed of unsaturated polyester resin is improved by using a curing accelerator consisting of a combination of a vanadium compound and mainly mercaptans, and Japanese Patent Publication No. 55-17041
In the publication, the adhesion speed of a second generation acrylic adhesive is improved by a combination of a metal chelate compound and thiourea.
これらの発明においては金属キレート化合物単独と比１
咬してかなり硬化速度の改善がみられるが、メルカプタ
ンやチオ尿素を用いた場合は臭気が大きく、作業環境上
問題があることや、被着材である金属の種類によっては
接着速度や接着強度が悪くなる傾向があり実用上充分な
性能を有しているとは言い戊１１い。In these inventions, the metal chelate compound alone has a ratio of 1
However, when using mercaptan or thiourea, there is a strong odor, which poses problems in the working environment, and the adhesion speed and strength may vary depending on the type of metal being adhered. However, it cannot be said that the performance is sufficient for practical use.
一方、０−ベンゾイックスルフィミドやアリールスルホ
ニルヒドラジドはそれぞれ特公昭４３−６５４５及び特
開昭５１−１１７７８９号公報に記載されている如く、
主として嫌気性接着剤に添加して一液での使用における
接着亢進剤として使用されているものである。On the other hand, 0-benzoic sulfimide and arylsulfonyl hydrazide are as described in Japanese Patent Publication No. 43-6545 and Japanese Patent Application Laid-Open No. 51-117789, respectively.
It is mainly used as an adhesion promoter when added to anaerobic adhesives in one-component use.
本発明者等は嫌気性接着剤の添加剤として用いられてい
るＯ−ベンゾイックスルフィミドやアリールスルホニル
ヒドラジドと金属キレート化合物のうち銅またはバナジ
ウムのキレート化合物の有機溶剤溶液が両者の相乗効果
により非常に優れた硬化促進能を発揮することを見出し
た。即ち、〇−ベンゾイックスルフィミドやアリールス
ルホニルヒドラジドは単独では硬化促進能は非常に弱く
、また、銅またはバナジウムのキレート化合物単独でも
促進効果はあるが充分ではない。しかしながら両者を混
合した場合にはそれぞれ単独の場合と比較して著しく優
れた硬化促進効果を発揮するのである。The present inventors have discovered that organic solvent solutions of O-benzoic sulfimide and arylsulfonyl hydrazide, which are used as additives in anaerobic adhesives, and copper or vanadium chelate compounds among metal chelate compounds are extremely effective due to the synergistic effect of the two. It has been found that this material exhibits excellent curing accelerating ability. That is, 0-benzoic sulfimide and arylsulfonyl hydrazide alone have a very weak curing accelerating ability, and copper or vanadium chelate compounds alone have an accelerating effect, but it is not sufficient. However, when both are mixed together, they exhibit a significantly superior curing accelerating effect compared to when either is used alone.
銅またはバナジウムのキレート化合物としては、β−ジ
ケトンまたはケトエステルのキレート化合物が適当であ
り、銅アセチルアセトネート、バナジウムアセチルアセ
トネート等があけられる。使用量は硬化促進剤溶液中０
０１〜５重量％好ましくは０１〜２重量％である。As the chelate compound of copper or vanadium, a chelate compound of β-diketone or ketoester is suitable, including copper acetylacetonate, vanadium acetylacetonate, and the like. The amount used is 0 in the curing accelerator solution.
01-5% by weight, preferably 01-2% by weight.
アリールスルホニルヒドラジドとしてはベンゼンスルホ
ニルヒトラシトオヨヒトルエンスルホニルヒドラジドが
あげられる。０−ベンゾイックスルフィミドおよびアリ
ールスルホニルヒドラジドの使用量は硬化促進剤溶液中
０．０１〜７重量係好ましくは０２〜３重量％である。Examples of the arylsulfonyl hydrazide include benzenesulfonyl hydrazine and toluenesulfonyl hydrazide. The amount of 0-benzoic sulfimide and arylsulfonyl hydrazide used is 0.01 to 7% by weight, preferably 0.2 to 3% by weight in the curing accelerator solution.
これらの硬化促進剤を溶解する溶剤としてはトリクロル
エタン、トリクロルエチレン、クロロホルム、メタノー
ル、エタノール、イソプロパツール等の低沸点有機溶剤
や重合性（メタ）アクリレート単量体が適当である。Suitable solvents for dissolving these curing accelerators include low-boiling organic solvents such as trichloroethane, trichloroethylene, chloroform, methanol, ethanol, and isopropanol, and polymerizable (meth)acrylate monomers.
以上の如き本発明の硬化促進剤溶液によって硬化を促進
される（メタ）アクリル系の硬化性組成物はラジカル重
合開始剤と（メタ）アクリル基を含有する単量体からな
るものであれば特に差仕えはない。ラジカル重合の開始
剤としては０−ベンゾイックスルフィミドのアミン塩や
有機過酸化物が友げられる。０−ベンゾイックスルフィ
ミドのアミン塩は本・ツト明者等が特公昭５３−４７２
６６号公報等において嫌気性接着剤の硬化剤として示し
たものであり、有機過酸化物とは異なるためこのアミン
塩を硬化剤とする接着剤は従来のレドックス系では硬化
を促進することが困姉であったが、本発明の硬化促進剤
溶液の使用により可能となった。The (meth)acrylic curable composition whose curing is promoted by the curing accelerator solution of the present invention as described above is particularly suitable if it is composed of a radical polymerization initiator and a monomer containing a (meth)acrylic group. There is no difference. Examples of initiators for radical polymerization include amine salts of 0-benzoic sulfimide and organic peroxides. The amine salt of 0-benzoic sulfimide was published by Hon.
It is shown as a curing agent for anaerobic adhesives in publications such as No. 66, and because it is different from organic peroxides, it is difficult to accelerate the curing of adhesives using this amine salt as a curing agent with conventional redox systems. However, this was made possible by using the curing accelerator solution of the present invention.
有機過酸化物としてはハイドロパーオキサイド、パーオ
キシエステル、ケトンパーオキサイド等があげら」する
。Examples of organic peroxides include hydroperoxide, peroxy ester, ketone peroxide, and the like.
また、（メタ）アクリル基を含有する単量体としては、
メチル（メタ）アクリレート、シクロヘキシルＣメタ）
アクリレート、ヒドロキソエチル（メタ）アクリレート
、ヒドロキシプロピル（メタ）アクリレート、２−ヒド
ロキシ−３−フェニルオキシブロビル（メタ）アクリレ
ート等のモノ（メタ）アクリレート類、エチレングリコ
ールジ（メタ）アクリレート、トリメチロールプロパン
トリ（メタ）アクリレート、ポリエチレングリコールジ
（メタ）アクリレート、ビスフェノールＡアルキレンオ
キサイド付加物のジ（メタ）アクリレート、液状ゴム末
端（メタ）アクリレート、エポキシ（メタ）アクリレー
ト、ウレタンポリ（メタ）アクリレート等の多価（メタ
）アクリレート類等があげられる。In addition, as a monomer containing a (meth)acrylic group,
Methyl (meth)acrylate, cyclohexyl C meth)
Acrylate, mono(meth)acrylates such as hydroxoethyl(meth)acrylate, hydroxypropyl(meth)acrylate, 2-hydroxy-3-phenyloxybrobyl(meth)acrylate, ethylene glycol di(meth)acrylate, trimethylolpropane Tri(meth)acrylate, polyethylene glycol di(meth)acrylate, bisphenol A alkylene oxide adduct di(meth)acrylate, liquid rubber-terminated (meth)acrylate, epoxy(meth)acrylate, urethane poly(meth)acrylate, etc. (meth)acrylates, etc.
以上が本発明の構成であるが、目的に応じて粘性な調節
するだめの可溶性ポリマーやチクソトロピック剤、硬化
生成物に強靭性を付与するためのエラストマー、接着強
度を高める目的で重合性酸性リン酸エステルやポリリン
酸等を適肝添加＋ルことも可能である。The above is the structure of the present invention, and depending on the purpose, soluble polymers and thixotropic agents to adjust viscosity, elastomers to impart toughness to the cured product, polymerizable acid phosphorus to increase adhesive strength, etc. It is also possible to add suitable acid esters, polyphosphoric acid, etc.
次に本発明を実施例および比較例によって更に詳細に説
明する。但し、部は全て重量部を示す。Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples. However, all parts indicate parts by weight.
〔実施例１−１．比較例１−１〕
ビスフェノールＡのエチレンオキサイド３モル付加物の
ジメタクリレート５０部とヒドロキシプロビルメタクリ
レート５０部にクメンハイドロパーオキサイド０５部添
加して嫌気性接着剤を調製した。また、トリクロルエタ
ン９９部とヒドロキシプロピルメタクリレート１部から
なる混合６媒に表１に示す各種硬化促進剤を所定＠み加
溶解して硬化促進剤溶液を調製した。次に、難接着材料
であるクロメートボルト（Ｍｌ Ｏ）のネジ−ｔ−ＵＫ
得られた硬化促進剤溶液を塗布乾燥後、前記嫌気性接着
剤を数滴塗布し同種のナンドをねじ込んだ後２３°Ｃで
セットタイムと２４時間後の戻しトルクを測定した。測
定方法は次の通りである。[Example 1-1. Comparative Example 1-1] An anaerobic adhesive was prepared by adding 05 parts of cumene hydroperoxide to 50 parts of dimethacrylate, which is a 3 mole adduct of bisphenol A with ethylene oxide, and 50 parts of hydroxypropyl methacrylate. In addition, a curing accelerator solution was prepared by adding and dissolving various curing accelerators shown in Table 1 in predetermined amounts in a mixed medium consisting of 99 parts of trichloroethane and 1 part of hydroxypropyl methacrylate. Next, the screws of chromate bolt (MlO), which is a difficult-to-adhesive material, are
After applying and drying the resulting curing accelerator solution, several drops of the anaerobic adhesive were applied and a similar type of nand was screwed in, and the set time and return torque after 24 hours were measured at 23°C. The measurement method is as follows.
セットタイム：ナツトをねじこんだ後硬化の開始によっ
てナンドを指でゆるめるこ
とができなくなるまでの時間を測
定しセントタイムとした。Set time: After the nut was screwed in, the time until the nut could no longer be loosened with fingers due to the onset of hardening was measured and was defined as the cent time.
戻しトルク ：接着したボルト・ナンドを２４時間放置
後トルクレンチでゆるめ、
１／４．１／２．３／４．１回転時の各トルクの平均値
を戻しトルクとした。Returning torque: After leaving the bonded bolt/nand for 24 hours, it was loosened with a torque wrench, and the average value of each torque at 1/4.1/2.3/4.1 rotations was taken as the return torque.
尚、比較の為に嫌気性接着剤単独で接着した場合および
硬化促進剤成分がそれぞれ単一である硬化促進剤溶液を
使用した場合についても行った。In addition, for comparison, the case where bonding was performed using an anaerobic adhesive alone and the case where a curing accelerator solution having a single curing accelerator component was used were also conducted.
Ｃ以下余白）
表１
グ
於
伊
汁
較
例
〔実施例１−２．比較例１−２〕
実施例１−１で得られた嫌気性接着剤と実施例１−１．
４３の硬化促進剤溶液を用いてクロメート以外の各種材
質のＭＩＯボルト・ナツトを接着した結果を表２に示す
。比較の為に比較例１−１゜Ａ５の硬化促進剤溶液を用
いた場合についても比較例として表２に示す。(Margin below C) Table 1 Comparative example of soup [Example 1-2. Comparative Example 1-2] Anaerobic adhesive obtained in Example 1-1 and Example 1-1.
Table 2 shows the results of bonding MIO bolts and nuts made of various materials other than chromate using the hardening accelerator solution No. 43. For comparison, Table 2 also shows a case where the curing accelerator solution of Comparative Example 1-1°A5 was used as a comparative example.
表２
〔実施例１−３．比較例１−３〕
ヒドロキシプロピルメタクリレートと２．４−）リレン
ジイソソアネートを常法に従って２対１のモル比で付加
反応させて得られたウレタンポリメタクリレート５０部
、ヒドロキシプロピルメタクリレート５０部、ラジカル
重合開始剤としてＯ−ベンゾイツクスルフイミドの表３
に示す各種アミン塩１．５部およびポＩＪ リン酸００
２部を混合溶解して有機過酸化物を含有しない鎌気性接
着剤を調製した。次いでこれを実施例１−１．Ａ３の硬
化促進剤溶液を用いて実〃１１Ｉ例１−１と同様にクロ
メートボルトを接着し、物性を測定した。結果を表３に
示す。尚、比較の為に硬化促進剤溶液を開用しない場合
についても比較例としてそれぞれ示す。有機過酸化物を
含有していない姥気性接着剤であるが、本発明の硬化促
進剤溶液の使用によって著しく速硬性になることが明ら
かである。Table 2 [Example 1-3. Comparative Example 1-3] 50 parts of urethane polymethacrylate, 50 parts of hydroxypropyl methacrylate, obtained by addition-reacting hydroxypropyl methacrylate and 2.4-)lylene diisocyanate at a molar ratio of 2:1 according to a conventional method. Table 3 of O-benzoic sulfimide as a radical polymerization initiator
1.5 parts of various amine salts shown in and PoIJ phosphoric acid 00
Two parts were mixed and dissolved to prepare an organic peroxide-free sickling adhesive. Next, this was prepared in Example 1-1. A chromate bolt was adhered using the A3 curing accelerator solution in the same manner as in Example 11I, and the physical properties were measured. The results are shown in Table 3. For comparison, cases in which no curing accelerator solution was used are also shown as comparative examples. It is clear that the use of the curing accelerator solution of the present invention makes the gas-permeable adhesive, which does not contain organic peroxides, harden significantly faster.
Ｃ以下余白）
表３
〔実施例１−４．比較例１−４〕
メチルメタクリレート４５部、２−ヒドロキシ−３−フ
ェニルオキシプロピルアクリレート３５部、ニトリルゴ
ム（日本ゼオン製二ポール１０７２）１５部、ポリリン
酸０．１部およびクメンハイドロパーオキサイド５部よ
り第２世代アクリル接着剤のＡ液を調製した。次いでＡ
ＳＴＭ、Ｄ９５０−５４に従って衝撃剥離強度を測定し
た。即ち、２３℃において５Ｓ−４１−膜構造用鋼材で
製造した衝撃剥離試験片の一方に実施例１１．Ａ３の硬
化促進剤溶液を塗布後乾燥し、他方の試験片には前記で
得られた第２世代アクリル接着剤を塗布した。次いで両
者をこすり合わせるようにして貼り合わせ、両者をもは
や手ではがすことができなくなるまでの時間ｃセットタ
イム）と２４時間後の衝撃剥離強度を測定した。尚、比
較の為に比較例１−１．Ａ５の硬化促進剤溶液を用いた
系についても行った。結果を表４ＦＣ示す。(Blank below C) Table 3 [Example 1-4. Comparative Example 1-4] 45 parts of methyl methacrylate, 35 parts of 2-hydroxy-3-phenyloxypropyl acrylate, 15 parts of nitrile rubber (Dipole 1072 manufactured by Nippon Zeon), 0.1 part of polyphosphoric acid, and 5 parts of cumene hydroperoxide. A liquid A of a second generation acrylic adhesive was prepared. Then A
Impact peel strength was measured according to STM, D950-54. That is, Example 11. The A3 curing accelerator solution was applied and dried, and the second generation acrylic adhesive obtained above was applied to the other test piece. Next, the two were bonded together by rubbing them together, and the time (c set time) until both could no longer be peeled off by hand was measured, and the impact peel strength after 24 hours was measured. For comparison, Comparative Example 1-1. A system using a curing accelerator solution of A5 was also tested. The results are shown in Table 4FC.
表４
〔実Ｍｕ例２．比較例２〕
メタノール１００部、ポリリン２０．０２部からなる溶
液を溶剤とし、バナジウムアセチルアセトネートとトル
エンスルホニルヒドラジドの添加量を変化させ、実施例
１−１の嫌気性接着剤に対する接着物性を実施例１−１
と同様忙測定した結果を表５ＦＣ示す。表５で明らかな
ように両者が共存した時にセットタイムが短かくなり、
接着強度も著しく増大している。Table 4 [Actual Mu example 2. Comparative Example 2 Using a solution consisting of 100 parts of methanol and 20.02 parts of polyphosphorus as a solvent, the adhesion properties of the anaerobic adhesive of Example 1-1 were tested by varying the amounts of vanadium acetylacetonate and toluenesulfonyl hydrazide. Example 1-1
Table 5FC shows the results of the same busy measurement. As is clear from Table 5, when both coexist, the set time becomes shorter,
Adhesive strength is also significantly increased.
表５Table 5
Claims (1)
（メタ）アクリル系硬化性組成物用の硬化促進剤溶液。 （１） 銅および／またはバナジウムのキレート化合物 （２）０−ベンゾイックスルフィミドおよび／またはア
リールスルホニルヒドラジド[Scope of Claims] A curing accelerator solution for a (meth)acrylic curable composition obtained by dissolving the following (1) and (2) in an organic solvent. (1) Copper and/or vanadium chelate compound (2) 0-benzoic sulfimide and/or arylsulfonyl hydrazide
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3433784A JPS60179407A (en) | 1984-02-27 | 1984-02-27 | Cure accelerator solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3433784A JPS60179407A (en) | 1984-02-27 | 1984-02-27 | Cure accelerator solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60179407A true JPS60179407A (en) | 1985-09-13 |
| JPH0133483B2 JPH0133483B2 (en) | 1989-07-13 |
Family
ID=12411325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3433784A Granted JPS60179407A (en) | 1984-02-27 | 1984-02-27 | Cure accelerator solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60179407A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03190907A (en) * | 1989-12-19 | 1991-08-20 | Toagosei Chem Ind Co Ltd | Modified redox catalyst |
| JP2009144054A (en) * | 2007-12-14 | 2009-07-02 | Gc Corp | Polymerizable composition |
| JP2013117011A (en) * | 2011-11-02 | 2013-06-13 | Okura Ind Co Ltd | Two-liquid curable acrylic composition |
-
1984
- 1984-02-27 JP JP3433784A patent/JPS60179407A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03190907A (en) * | 1989-12-19 | 1991-08-20 | Toagosei Chem Ind Co Ltd | Modified redox catalyst |
| JP2009144054A (en) * | 2007-12-14 | 2009-07-02 | Gc Corp | Polymerizable composition |
| JP2013117011A (en) * | 2011-11-02 | 2013-06-13 | Okura Ind Co Ltd | Two-liquid curable acrylic composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0133483B2 (en) | 1989-07-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4574142A (en) | Curable adhesive composition toughened with styrene-butadiene block copolymer rubbers | |
| US3836377A (en) | Cyanoacrylate adhesive composition | |
| US5003016A (en) | Surface activator for redox-initiated adhesives | |
| US3625930A (en) | Anaerobic composition and process for bonding nonporous surfaces, said composition comprising an acrylic monomer a peroxy initiator and a bonding accelerator | |
| US4182644A (en) | Polymer in monomer adhesive composition and method employing same | |
| KR101174195B1 (en) | Curable composition, bonding method and bonded body | |
| JPS6339031B2 (en) | ||
| KR102390137B1 (en) | Anaerobic curable (meth)acrylate composition | |
| JPH0138148B2 (en) | ||
| EP0379305B1 (en) | Low odor adhesive compositions | |
| US4373077A (en) | Anaerobically curing compositions | |
| EP0034046B2 (en) | Heat resistant toughened adhesive composition | |
| IE50787B1 (en) | Polyisoprene toughened adhesive composition | |
| US5106808A (en) | Surface activator for redox-initiated adhesives | |
| JPH01168777A (en) | Adhesive composition | |
| US4528059A (en) | Anaerobically-cuting compositions | |
| JPS60179407A (en) | Cure accelerator solution | |
| TW201922906A (en) | Cure accelerators for anaerobic curable compositions | |
| JP2019065082A (en) | Composition | |
| JP2019065083A (en) | Composition | |
| JP2757217B2 (en) | Adhesive composition | |
| JPS6117873B2 (en) | ||
| JPS6134082A (en) | Lowly odorous two-pack acrylic adhesive having excellent adhesion | |
| JP2769232B2 (en) | Acrylic adhesive composition | |
| EP0051386B1 (en) | Anaerobically-curing compositions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |