Instant-Setting Adhesive Composition

,UnitedAStates Patent [19] * . [11] 4,313,865 Teramoto et al. . [45] Feb- 2, 1932 [54] INSTANT-SE"I'l'ING ADHESIVE [56] COMPOSITION ' References Cited [75] Inventors: Toshio Teramoto, Yokohama; Noriaki Ijuin, Kawasaki; Teizo Kotani, Yokohama, all of Japan Japan Synthetic Rubber Co., Ltd., Tokyo, Japan ~ ‘ [21] Appl. No.: 189,909 [22] Filed: Sep. 23, 1980 [30] Foreign Application Priority Data sep; 28, 1979 [JP] [51] Int. Cl.3 .............................................. .. C08K 5/10 [52] U.S. Cl. ....................... .. 260/31.4 R; 260/32.8 N; 260/33.2 R; 260/33.4 R; 526/278; 526/286; 526/312 [58] Field of Search ............. .. 526/278, 286, 303, 312; 260/31.4 R, 32.8 N, 33.2 R, 33.4 R [73] Assignee: Japan ...................... ., ...... .. 54- 125070 ’ U.S. PATENT DOCUMENTS 3,316,227 4/1967 Gerber ................................ .. 526/75 Primary Examiner—Joseph L. Scliofer Assistant Examiner—-—Bernard Lipman Attorney, Agent, or Firm—Oblon, Fisher, Spivak, McClelland & Mpaier 5 [5 7] ABSTRACT An instant-setting adhesive composition comprising a 2-cyanoacrylate and at least one 1,1-disubstituted diene, the amount of said‘l,1-disubstituted diene exceeding 50% by weight based on the total weight of both com- ponents. This composition is useful in the same fields as those where conventional 2-cyanoacrylate adhesives have been used, and is excellent in impact resistance, peel resistance, heat resistance and water resistance. 19 Claims, 4 Drawing Figures U.S. Patent Feb. 2, 1982 Sheet 1 of3 4,313,865 FIG 2 F I 9 i- PrCCB/ CA=3/ 7 3 20,000 U.S. Patent Feb. 2, 1982 Sheet 2 of3 . 4,313,865 FIG. 3 PEEL STRENGTH :- DISTANCE OF TRANSFER OF JAW U.S. Patent Feb. 2, 1982 Sheet 3 of3 4,313,865 FIG. 4 PEEL STRENGTH —-- DISTANCE OF TRANSFER OF JAW -——* 1 » INSTANT-SVETTING ADHESIVE COMPOSITION This invention . relates to instant-setting. adhesive compositions which are improved in impact resistance, peel resistance, heat resistance and :water‘ resistance. . 2-Cyanoacrylate adhesives xhave [heretofore been known as instant-setting adhesives. These adhesives are utilized in various’ fields,‘because they are single-com- ponent liquid adhesives ofthe‘ nonsolvent type having the specific property that they polymerize instanta- neously at room temperature in the presence of a minute amount of moisture existing on the surface of adherends or in the air to bond metals, plastics, rubbers, and the like. 1 A - t i ’ ’ ' The 2-cyanoacrylate adhesives, however, are unsatis- factory in impact resistance, peelpresistance, flexibility, heat resistance or water resistance, and hence, are lim- ited in their use range. For instance,’ because of their’ low‘imp‘act‘strength,"they cannot be used, except for . tentative bonding, in metal-to-metal bonding where the resulting bonds are required, to have a" high impact, strength. A problem whichiarises in" bonding rubbers to themselves with the" 2-cyanoacrylate adhesive i_s,th'at owing to lack of flexibility and peel resistancethe adhe- sive layer is unable to follow closely the deformation of rubber, resulting in, delarninationf _ ' V _, H _ Further, the maximum « temperature at- p which the 4-,3.—1:3,8,65' 10 15 20 25 bond strength of conventional 2-cyanoacrylate adhe- 30 sives is practically acceptable is 80° C. and this does not meet the heat resistance required especially for electri- cal and mechanical parts. _ V g . To overcome the above.defects,_..a large number of studies and proposals have been made in the past. For instance, for the purpose of improving the impact resis- tance, incorporation. of various additives into a 2- cyanoacrylate has been proposed asdescribed in Japa- nese Patent Application Kokai (Laid-Open) Nos. 146,445/77 and 35,743/ 78. These attempts, however, have not yet succeeded in imparting sufficient perfor-' mance characteristics to the resulting adhesives. For the improvement in heat resistance, there‘ havebeen known those methods which employ crosslinking monomers as disclosed in Japanese Patent Application Kokai (Laid- Open) Nos. 22,432/-74, 22,433/74 and 94,722/74’or use hydroxyacrylates as disclosed=in Japanese Patent Appli-‘ cation Kokai (Laid-Open) No. 110,635/78. Although these methods result in an appreciable_improvementof ' the adhesive performance,'they are not yet s'ucces'sful’in’ improving atthe same‘ time the impact resistanceito a satisfactory degree. ' ' ‘ ‘ " The present inventors" have conducted ,extensiv__e studies to‘ solve theabove problems and, asia result, have found that it is possible toobtain an adhesive com- position, in which the impact resistance, peel resistance, heat resistance ‘and water resistance are markedly'im- proved and the instant-setting property characteristic of A35 40 45 50. 55 the 2-cyanoacrylates remain unimpaired, by the addi— 50 tion of a specified 1,1-disubstituted diene toga 2—_cyan’oa—‘ crylate. ' ‘ i ' This invention provides an instant-setting adhesive compositionicomprising_a 2-cyanoacrylate and at. least one 1,1-disubstituted dieneirepresented by the following 65 general formula, the amount of said‘1,1-disbustituted, diene being more than 50% by weight based on the total amount of said twocomponents: 1 V x / \ Y I 'CH2=e—(I:=c: R1 R2 wherein R1 is hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group,‘an aralkyl group or a halogen atom, R2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and ‘X and Y, which may be the same or ‘different, are selected from the group con- sisting of cyano group, carboxylate group, ethylsulfone group, phenylsulfone group, formyl group, acetyl group, benzoyl group, diethylphosphonyl group, amide group and phenylgroup. _ The 2-cyanoacrylates used in this invention include all ofthe common esters of 2-cyanoacrylic acid. The specific examples,‘of‘such'esters: are methyl, ethyl, n- propyl, isopropyl, "n-butyl, isobutyl,‘ tertbutyl, amyl, n-hexyl, cyclohexyl, heptyl, n-octyl, 2-ethylhexyl, do- decyl,‘ allyl, propargyl, benzyl, phenyl, 2-methoxyethyl, 2-ethoxyethyl, 2-chloroethyl, hexafluoroisopropyl, tri- fluoroethyl, and 2-cyanoethyl ‘2—c‘yanoacrylates. These may -be used alone or in admixture. ' The 1,1-disubstituted dienes used in this invention are represented by the general formula: _ . X / 1. CI-I2=C-C=C \ , I I R] R2 Y wherein R1, R2, X and Y are as defined above. It is preferably that R1 be a hydrogen atom or an alkyl group of *1 or 2 carbon atoms, R2 be a hydrogen atom, X be a cyano group, and Y be a carboxylate group, ethylsul- fone group, benzoyl group, diethylphosphonyl group, amide group or phenyl group. Specific examples are ‘l-cyano-l-carbomethoxybutadiene- 1,3, 1~cyano-1-car- L bethoxybutadiene-1,3, l-cyano-l-carbo-n-propox- ybutadiene-“1,3, _1-cyano-1-carboisopropoxybutadiene- 1,3, l-cyano-1~carbon-butoxybutadiene-1,3, 1-cyano-1- carboisobutoxybutadiene-1,3, 1—cyano-l-carbo-tert- butoxybutadiene-1,3, l_,l-dicyanobutadiene-1,3, 1,1- dicarbomethoxybutadiene-1,3, 1,1-dicarbethoxybutadi- ene-1,3, l-cyano-1-ethylsulfonylbutadiene-1,3, 1-acetyl- 1-phenylbutadiene-1,3, 1-cyano-1-acetamidobutadiene- 1, 3, 1-formy1-l-phenylbutadiene-1,3, 1-cyano-1-pheny1- butadiene-1,3, 1-cyano-1-benzenesulfonylbutadiene-1,3, l-cyano-1-diethylphosphonobuta»diene-1,3, 1-benzoyl- 1-cyanobutadiene-1,3, am,yl)butad_iene-1,3, V 1-cyano-l—carbethoxy-2-methyl- butadiene-1,3, V - 1-cyano—l-carbethoxy-3-phenylbutadi- ene-1,3, 1,1-dicarbethoxy-3-methylbutadiene-1,3, and l-cyano-1—carbethoxy-3-chlorobutadiene-1,3. These are used alone or in admixture. Preferable 1,1-disubstituted dienes are l-cyano-l-carbometIhoxybutadiene-1,3, l- cyano-1-carbethoxybutadiene-1,3», l-cyano-1-carbo-n- propoxybutadiene-1,3, 1-cyano-1-carbo-n-propox- ybutadiene- 1 , 3, l-cyano- l -carboisopropoxybutadiene- 1,3, 1—cyano-1-carbo-n-butoxybutadiene-1,3, 1-cyano-1- car_boisobutoxybutadiene— 1 , 3, 1-cyano-1—carbo-tert- butoxybu,tadiene_-1,3, l-cyano-1-ethylsulfonylbutadiene- 1,3, l-cyano-1-acetamidobutad.iene-1,3, l-cyano-1- phenylbutadiene- 1 , 3, ll-cyano-1—diethylphos- phonqbutadiene-1,3, 1-benzoyl-1-cyanobutadiene-1,3, 1-cyano—1.-carbethoxy-2-methylbutadiene-1,3, and mix- l-cyano-1-carbethoxy-3-(n-. 4,313,865 3 tures thereof. These compounds can be synthesized, as described in U.S. Pat. No. 3,316,227, by the reaction between an a,B-unsaturated carbonyl compound (e.g. acrolein) and an active methylene compound (e. g. ethyl cyanoacetate) in the presence of a metal salt as catalyst. The amount of l,l-disubstituted diene added is more than 50%, preferably at least 60%, most preferably 65 to 85%, by weight based on the total amount of the 2-cyanoacrylate .and the 1,1-disubstituted diene. The addition of 1,1-disubstituted diene in an amount of not more than 50% by weight results in low impact resis- tance in some cases, an insufficient increase in water resistance or in heat resistance, and a marked low peel strength, as compared ‘with the case of addition of more than 50% by weight of l,l-disubstituted diene.— When the amount of 1,1-disubstituted diene added exceeds 50% by weight based on the total amount of the 2- cyanoacrylate and the 1,1-disubstituted diene, as it were a borderline, a rapid increase in peel strength is ob- served, though the reason therefor has not been clari- tied. In order to examine such a phenomenon more closely, a mixture of ethyl 2-cyanoacrylate and 1-cyano- 1-carboisopropoxyb.utadiene-1,3 (i-PrccB) as a selected example of the 1,1-disubstituted diene, was allowed to polymerize autogenously into a hardened product and the latter was observed under an electron microscope. As is seen from FIGS. 1 and 2 of the accompanying drawings, there was observed the formation of polymer presumably not by random polymerization but by unex- pected block copolymerization. By comparison of FIG. 1, wherein the weight ratio of diene to 2-cyanoacrylate is 70:30, with FIG. 2, wherein said ratio is 30:70, the occurrence of phase transition between the diene phase dyed black with OsO4 and the white, undyed 2-cyanoa- crylate phate is evident. From the observation it is pre- sumable that the critical concentration for the phase transition is just over 50% by weight of 1,1-disub- stituted diene based on the total amount of the 2- cyanoacrylate and the 1,1-disubstituted diene and that when the diene phase becomes the matrix, the adhesive layer is placed under the control of the diene phase,’ resulting in a rapid increase in peel strength. As a conse- quence, the peel strength becomes maximum at a diene concentration of just over 50% by weight and thence decreases with the further increase in diene concentra- tion. The upper limit of the preferable diene concentra- tion is 95% by weight. The instant-setting adhesive composition of this in- vention is further improved in peel strength and tensile shear strength by the addition of a certain type of lac- tone compound. Preferable lactone compounds are monocyclic, bicyclic or condensed ring lactones having a 4- to 7-membered lactone ring. These are saturated or unsaturated compounds having preferably 3 to 20, most preferably 3 to 10, carbon atoms and may have substitu- ents such as alkyl groups, aryl groups, aralkyl groups, cycloalkyl groups or carboxylate groups. Specific ex- amples thereof include ,B—propiolactone, ,8—pivalolac- tone, 'y-butyrolactone, 3-carbethoxy-‘y-butyrolactone, 5-ethyl-'y-butyrolactone, phthalide, 8-valerolactone, coumarin, dihydrocoumarin, e-caprolactone, hep- todilactone, and dimethylheptodilactone. These lac- tones are added alone or in admixture to the mixture of 2-cyanoacrylate and 1,1-disubstituted diene. The amount of lactone added is preferably 0.1 to 30 parts by weight, most preferably 0.5 to 10 parts by weight per 100 parts by weight of the mixture of 2-cyanoacrylate and 1,1-disubstituted diene. If the amount exceeds 30 10 15 20 25 30 35 45 50 55 60 65 4 parts by weight, the tensile shear strength will some- times be decreased. The conventional 2-cyanoacrylate adhesives are gen- erally incorporated with stabilizers, thickeners, plasti- cizers, coloring agents, perfumes, hardening promoters and the like. These may be added also to the instant—set- ting adhesive composition of this invention. Stabilizers such as sulfur dioxide, sulfonic acids, sultones, lactone- boron trifluoride, hydroquinone, hydroquinone mono- methyl ether, catechol, pyrogallol and the like may be added in a proportion of 1 to 1,000 ppm. It is also possi- ble to incorporate, as a thickener, such polymers as methyl methacrylate polymer, 2-cyanoacrylate poly- mer, acryl rubber and polymers of those 1,1-disub- stituted dienes which are used in the instant-setting adhesive composition of this invention, in a proportion of 50 parts by weight per 100 parts by weight of the total amount of both the 2-cyanoacrylate and 1,1-disub- stituted diene. If necessary, plasticizers such as dioctyl phthalate, sebacates, phosphoric esters, and the like may be added to further improve the flexibility. Although the instant-setting adhesive composition of this invention exhibits sufficiently good heat resistance in the absence of a radical generating agent, the latter may be added in an amount of up to 10% by weight for the purpose of promoting the formation of a three-di- mensional structure of the hardened polymer in the adhesive layer, leading to a further improvement in heat resistance. Effective radical generating’ agents are chiefly organic peroxides, typical examples of which’ are benzoyl peroxide, dibutyl peroxide, dicumyl perox- ide, tert-butylcumyl peroxide, 1,1-bis(tert-butylperoxy)- cyclohexane, and 2,2-bis(tert-butylperoxy)butane. Other compounds such as azo compounds, ammonium persulfate, and sulfur may also be used. The hardening promoters for use in the instant-setting adhesive composition of this invention are alcohols, alcohol ethers, alcohol esters‘ or crown ether com- pounds. Specific examples of the alcohols, alcohol ethers, and alcohol esters are as follows: Monohydric alcohols: methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, n-amyl alcohol, etc. Dihydric alcohols: ethylene glycol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexa- methylene glycol, heptamethylene glycol, octamethy- lene glycol, decamethylene glycol, polybutadienediol, chloropropylene glycol, 3-methylpentanediol, 2,2-die- thylpropanediol, 2-ethyl-1,4-butanediol, diethylene gly- col, triethylene glycol, polyethylene glycol, dipropyl- ene glycol, polypropylene glycol, etc. Polyhydric alcohols: glycerol, trimethylolmethane, trimethylolethane, trimethylolpropane, 1,2,6-hexane- triol, etc. 0 Alcohol ethers: propylene glycol methyl ether, di- propylene glycol methyl ether, tripropylene glycol methyl ether, ethylene glycol ethyl ether, ethylene gly- col n-butyl ether, diethylene glycol methyl ether, dieth- ylene glycol ethyl ether, diethylene glycol n-butyl ether, ethylene glycol phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, etc. Alcohol esters: polyethylene glycol monolaurate, polyethylene glycol monostearate, glycerol monolau- rate, glycerol monostearate, sorbitan monolaurate, polyoxyethylene sorbitan monolaurate, etc. The above alcohols, alcohol ethers and alcohol esters may be added alone or in admixture to the mixture of 4,313,865‘ 2-cyanoacrylate ' ‘and’ ' l,l-disubstituted diene.“ The amount of the alcohol, alcohol ether or. alcohol ester added is preferably 0.001 to Sparts by weight, most preferably 0.05,to 2 parts by’ weight, 100 parts by weight of thetotal amount of the 2-cyanoacrylate and the 1,1- disubstituted diene. If the amount is less than 0.001 part by weight, the promoting effect on the hardening will be insignificant, ‘while if it exceeds 5 parts by weight, the storage stability of the’ adhesive will somet_imes become worse. -' v : ' The nomenclature of crown ethers is based on the form of their structural formulas. The”most typical Acyclicghexamer of ethylene oxide is called l8-crown-6. The numeral 18 denotes the number of ring ‘members and the numeral 6 denotes the number of oxygen atoms. ’ The oxygen atoms-of a crown ether are arranged inside the ring and take hold of metal ions or organic ions in the molecule by coordinate bonds, whereby the com- pound has the specific properties. : . , . Crown etheranalogs in which the oxygen atoms of crown ethers are partially or wholly replaced. with nitrogen, sulfur, phosphorus or boron atoms, such as, for example, dithia-15-crown‘ may’ also be used. Also usable are those analogsin which the ethylenesegments of crown ethers are partially replaced with benzo, cy- clohexyl, decalyl, naphtho, methylbenzo, tbutylbenzo, vinylbenzo, butylcyclohexyl, oxocyclohexane, methy- lene, trimethylene; tetramethylene, and pentamethylene radicals and those analogs in which a part of the hydro- genatoms of the.ethylene segment is substituted by methyl, ethyl, propyl, butyl, ‘acetyl, _phenyl, oxygen, or fluoro. ‘ Typical-examples "of the crown ether compounds used as hardening promoters include the following: (1'). 18-Crown-6 ‘ * * ‘ (2) Dithia-15-crown (3) 15-Crown-5 ‘ (4) ' 18-Crown-5 (5) Dibenzo-18-crown-6 (6) Dibenzo-24-crown-8 .' . : (7) Dicyclohexyl-18-crown-6 (8) l,2—Vinylben_zo—15-crown—5 The above crown ether compounds are added alone or in admixture 'to.the mixture of 2-cyanoacrylate and 1,1-disubstituted diene.‘ The amount of thecompound added is preferably 0.001 to. 5 parts by weight, most preferably 0.05 to 2 parts'by weight‘ per 100 parts by weight of the total ='of the 2-cyanoacrylate and the -1,l- disubstituted diene. If the amount is.less.than. 0.001 part by weight, the promoting effect on the hardening will be small, while if it exceeds 5% by weight, the storage stability’ of the adhesive will sometimes be impaired. The conditions for the application and subsequent hardening of the instant-setting adhesive composition of this invention are similar to those for the conventional 10 15 20 25 30 35 " 40 45 50 55 cyanoacrylate adhesives. As a-generalvrule, the instant- - setting adhesive composition of this invention is coated on one side of one of -the adherend members, The coated side is brought into contact with uncoated side of the other member to allow the adhesive to spread into a thin layer and both members are firmly held to- gether by the finger or by means of a suitable jig for several seconds to several minutes to set the adhesive. If necessary, both uncoated adherend members are held together in a bonding position and the instant-setting adhesive composition of this invention is allowed to 6 tive to rub the bonding surfaces-of the uncoated adher- ends with a cloth or the like moistened with ,a weak- anionic polymerization initiator such. as an aqueous solution of sodiumhydroxide orca weak amine base and then to apply the adhesive.composi_tion followed by the same bonding procedure as described above. It is also effective to preheat the uncoated adherend materials at about 40? to 60° C. The former procedure of pretreating the adherend surfaces is, particularly effective in bond- ing porous materials such as wood and cardboards. Some of . the instant-setting adhesive compositions of this invention may crystallize at low temperatures. In such a case, the adhesive composition should be heated beforeuse to melt away the crystals or should be ap- plied:to the adherend materials-which have been kept‘ at a temperature at which the crystals will melt upon ap- plication of the-‘adhesive composition. Upon hardening, the instant-setting adhesive compo- sition of this invention seems to be converted, into a mixture .of a copolymer of a 2-cyanoacrylate. with a l,l-disubstituted diene and homopolymers of the re- spective components; the diene u.nit in the polymerizate seems to. afford the crosslinking site, thus contributing to the improvement in heat resistance of the adhesive bond. , . . . The instant-setting adhesive composition of this in- vention is able to bond firmly metals, glass, plastics, rubbers andzother materials within a period of several seconds to several minutes similarly to the conventional 2-cyanoacrylate adhesives. The bond which is formed manifests a peel strength as high as 5 to 20 times that of the bond formed by the conventional 2-cyanoacrylate adhesives. ‘As compared with the -conventional 2_- cyanoacrylate adhesives, the present adhesive composi- tion provides a bond which is markedly improved in heat resistance and chemical resistance. Accordingly, the instant-setting adhesive compositionof this inven- tion is able to meet the requirements .for the structural instant-setting adhesive. - ’ - The invention is illustrated below with reference to Examples and accompanying drawings. The Examples, however,» are merely. illustrative and not limitative. In the drawings,‘ » FIG. 1 is an electron micrograph of the hardened adhesive composition of this invention; FIG. 2 is an electron micrograph of the hardened product of anadhesivecomposition not covered by the presentinvention; FIG. 3 represents a peel strength curve of the present adhesive composition; and » ~. FIG. 4 represents a peel strength curve of aluminum plates adhered to each other with the present adhesive composition. . ’ The l,l-disubstituted diene was synthesized in the following manner: ‘ I Zinc chloride (87.7 g) was heated with stirring in 351 ml of dioxane. To the mixture, after having been cooled to roomtemperature, were added ll4 ml of ethyl cya- gnoacetate and 98 ml of acrolein. The mixture was al- 60 65 penetrate into the interface to be bonded. For the pur-‘ . _ pose of further promotion of the hardening, it is effec- lowed to react at room temperature for 3 hours. The reaction mixture was mixed with about 800 ml of petro- leum ether and washed three times with one-liter por- tions ,of cold dilute hydrochloric acid. The organic layer was separated and dried. On removal of the sol- vent, there wasobtained 116 g (73% yield) of l-cyano- l-carbethoxybutadiene-1,3. The product was purified by adding thereto" small amount:s of p-toluenesulfonic acid and p-tert-butylcatechol and distilling the mixture 4,313,865 7 under reduced pressure (boiling point 66.5° C./2 mmHg). In the same manner as above, l-cyano-l-carbome- thoxybutadiene- 1,3, l, l -dicarbethoxybutadiene- l ,3,- 1- cyano-l-carboisopropoxybutadiene- 1,3, l-cyano-1-car- boisobutoxybutadiene-1,3 and 1,1-dicyanobutadiene-1,3 were synthesized. EXAMPLES 1 TO ll AND COMPARATIVE EXAMPLES 1 TO 10 Adhesive compositions were prepared by mixing commercial ethyl 2-cyanoacrylate with l,l-disub- stituted dienes in varying proportions as shown in Table 1. Each one drop of the dienes was placed on the test piece prepared as specified in J IS or ASTM (described later). Another test piece was laid over the test piece carrying a drop of the adhesive and both pieces were pressed together under an applied force of 2 kg f. After standing for 24 hours, each test specimen was subjected to bonding tests. The results obtained were as shown in Table 1. Peel strength of adhesive bond: The peel strength was determined in accordance with JIS K 6854. The test piece was aluminum sheet, 0.1 mm in thickness, and the T-peel test was performed. Impact strength of adhesive bond: The impact strength was determined in accordance with ASTM D 950-78. The test piece material was aluminum. Heat resistance of adhesive bond: The test pieces were bonded together in the same manner as in the tensile test and cured at room temperature for 24 hours to prepare test specimens. After being allowed to stand in a Geer oven at 150° C. for 3 hours, the test specimen was tested for the bond strength on a Schopper tensile tester provided with a thermostat maintained at 150° C., at a tensile rate of 50 mm/min. As is seen from the test results shown in Table 1, as compared with the conventional 2-cyanoacrylate adhe- sive, the instant-setting adhesive composition of this invention is greatly improved in heat resistance and peel strength. It is also seenthat if the amount of the 1,1- disubstituted diene is below 50% by weight, the in- crease in heat resistance is small and the peel strength is decreased. . - EXAMPLE 12 Various materials were bonded with the same adhe- sive composition as used in Example 1. The results of tests for the setting time and the tensile strength of adhesive bond were as shown in Table 2. l0 15 20 25 30 35 45 50 8 The test for the setting time was performed in accor- dance with JIS K 6861 and the test for the tensile strength in accordance with JIS K 6861 and JIS K 6849. The aptitude of the instant-setting adhesive composi- tion of this invention for instantaneous bonding is evi- dent from Table 2. EXAMPLES l3 AND 14 AND COMPARATIVE EXAMPLES 11 AND 12 The peel strength of the adhesive bond was deter- mined in accordance with JIS K 6854 on theadhesive bonds formed by use of the adhesive compositions shown in Table 3. The test piece was a steel plate, 1.6 mm in thickness, and the T-peel test was conducted. The peel strength-curve of an adhesive composition was as shown in FIG. 3. The peel strength was deter- mined from the load value at B of the curve. In FIG. 3, the abnormal peak load at A seemed to be due to the cleavage force when the test specimen was subjected to tension. The ordinate corresponds to the peel strength. When a thin aluminum sheet, 0.1 mm in thickness, was used as test piece material, a peel strength-curve shown in FIG. 4 was obtained. The peel strength was calculated by averaging all load values at crests and troughs (C in FIG. 4). When the adherend material was sufficiently thick, a peel strength-curve as shown in FIG. 3 was obtained. In this case, the peel-strength was determined from the load value at B. The test results were as shown in Table 3. EXAMPLES 15 AND 16 AND COMPARATIVE EXAMPLES 13 AND 14 Test specimens prepared in a manner similar to that in Example 1 by using adhesive compositionsshown in Table 4 were immersed in water at 25° C. for 7 days. Upon removal of each test specimen from the water, the tensile shear strength of the adhesive bond was immedi- ately determined in accordance with JIS K 6850. The test results were as shown in Table 4. It is seen from Table 4 that the instant-setting adhesive composition of this invention is excellent in water resistance. EXAMPLES 17 TO 24 By using the adhesive compositions shown in Table 5, various bonding tests were performed similarly to Ex- amples 1 to 11. The setting time for the steel-to-steel bond was determined similarly to Example 12. The test results were as shown in Table 5. The effects of various additives on the performance characteristics of the in- stant-setting adhesive compositions of this invention are apparent from Table 5. TABLE 1 1,1-Disubstituted diene Peel Impact Heat (l,l-disubstituted diene/ethyl strength strength resistance 2-cyanoacrylate weight ratio) (kg/cm) (kg . cm/inz) (kg/cmz) Example l-Cyano—l-carbomethoxy— (80/20) 2.05 150§ 103 l butadiene-1,3 Example l-Cyano-l-carbomethoxy- (70/30) 2.00 ” 96 2 butadiene-1,3 Example l-Cyano-l-carbomethoxy- (55/45) l.93 " 84 3 butadiene-1,3 Comparative Example l-Cyano-l-carbomethoxy- (40/60) 0.71 74 l butadiene-1,3 Comparative Example l-Cyano-l-carbomethoxy- (20/80) 0.20 " 68 2 butadiene-1,3 Comparative Example l—Cyano- l -carbomethoxy- (100/0) 0.10 ” 108 3 butadiene-1,3 4,313,865 9 .10 TABLE 1-continued 1,1-Disubstituted diene ' V 1‘ Peel Impact Heat ( 1,1-disubstituted diene/ethyl strength strength resistance 2-cyanoacrylate weight ratio) (kg/cm) (kg . cm/inz) (kg/cmz)‘ Example 1-Cyano-1-carboiso- (90/10) 1.24 ” 98 4 propoxybutadiene-1,3 - Example l-Cyano—l—carboiso- (70/30) 1.46 " 95 ‘ 5 propoxybutadiene-1,3 . Example l—Cyano-l-carboiso- ‘ (55/45) 1.02 ” 91 6 propoxybutadiene—l,3 Comparative . 1 - Example 1-Cyano- l-carboiso- (30/70) 0.28 " 80 4 propoxybutadiene-1,3 A ‘ Comparative 1 Example ‘1-Cyano-1-carboiso- (10/90) 0.22 ” 34 5 propoxybutadiene-1,3 Comparative ~ Example l-Cyano—1-carboiso- (100/O) 0.46 " 105 6 propoxybutadiene-1,3 Example l—Cyano-1-carbethoxy- (80/ 20) 2.31 l50§ 92 7 butadiene-1,3 . ’ Example 1—Cyano-1-carbethoxy- (55/45) 1.80 " 85 8 butacliene-1,3 Example l,l-Dicarbetho'xy- (60/40) 2.32 ” 86 9 butadiene-1,3 Comparative Example 7 1,1-Dicyanobutadiene-1,3 (40/60) 1.32 150: 86 Comparative Example 1-Cyano-1-carbethoxy- (20/80) _0.73 " 76 8 butadiene-1,3 Comparative . V Example l-Cyano-1-carbethoxy- (5/95) 0.22 46 21 9 butadiene-1,3 Comparative Example Ethyl 2-cyanoacrylate (0/ 100) 0.14 42 10 10 alone Example 1-Cyano-l-carbomethoxy- 10 butadiene-l,3/ 1-Cyano-l-carboisopropoxy- 2.51 150§ 168 butadiene-1,3/ Ethyl 2-cyanoacrylate (30/40/30) Comparative l-Cyano-l-carbomethoxy- Example butadiene-l,3/ 11 l-Cyano-1-carboethoxy- ‘ 2.60 ” - 160 butadiene-l,3/ ethyl 2-cyanoacrylate (40/40/20) TABLE 2 TABLE 2-continued Setting time Tensile strength Setting time Tensile strength Adherend material (second) (kg/cmz) Adherend material (second) (kg/cm?) Same material 45 Aluminum/stainless steel 30-60 155 Natural rubber 3-5 ‘33 Steel/81355 3-20 *- Nllrlle rubber 3'5 142 ‘Cohesive failure in adherend material. Rigid polyvinyl chloride 5-10 *2OO Polymethyl methacrylate 30-90 ‘150 Bakelite 20-40 *100 50 TABLE 3 Polystyrol 40-60 *40 ABS resin 15-30 *1oo . . , Pee‘ Steel 2040 160 1,1-Disubstituted diene strength Copper 2o_3O 87 (1,1-disubstituted diene/ethyl (kg/25 Stainless Steel 2O_40 140 2-cyanoacrylate weight ratio) mm) Aluminum 30-60 142 55 Example 13 1-Cyano-1-carbomethoxybu.tadiene-1,3/ Brass .20-30 150 ethyl 2-cyanoacrylate (70/30) 19.5 Glass 3-5 *— Example 14 1-Cyano—I-carbomethoxybutadiene—l,3/ 131 Wood 60-120 ‘I20 ethyl 2-cyanoacrylate (55/415) Different material Comparative 1-Cyano-1-carbomethoxybutadiene-1,3/ 5.0 ABS resin/aluminum 15.40 *70 Example 11 ethyl 2-cyanoacrylate (40/60) PVC/stainless steel 5-20 ‘I40 Comparative Ethyl 2-cyanoacrylate alone (0/100) 0.1: Nitrile rubber/copper 3-20 *38 60 Example 12 TABLE 4 Tensile shear 1,1-Disubstituted Diene Tensile strength after (1,l-disubstituted diene/ethyl shear strength immersion in 2-cyanoacrylate weight ratio) (kg/cmz) water (kg/cmz) Example 15 l—Cyano-1-carboisopropoxybutadiene- 249 220 4,313,865 11 TABLE 4-continued 12 Tensile shear 1,1-Disubstituted Diene Tensile strength after (l,l-disubstituted diene/ethyl shear strength immersion in 2-cyanoacryl-ate weight ratio) (kg/cmz) water (kg/cmz) 1,3/ethyl 2-cyanoacrylate (70/30) Example 16 l-Cyano-l—carbomethoxybutadiene- 240 210 1,3/ethyl 2-cyanoacrylate (70/30) Comparative l-Cyano-l-carbomethoxybutadiene-l,3/ 187 62 Example 13 ethyl 2-cyanoacrylate (40/60) Comparative Ethyl 2-cyanoacrylate alone (O/100) 132 24 Example 14 TABLE 5 1,1-Disubstituted diene Additive Tensile Impact (l,l-disubstituted (added shear Peel strength Setting Example diene/ethyl 2-cyano- amount, % strength strength (kg . cm/ time No. acrylate weight ratio) by weight) (kg/cmz) (kg/cm) inz) (second) 17 l-Cyano-l-carbethoxy- Methyl 178 2.48 l50§ 3-5 17 butadiene-1,3/ethyl alcohol 2-cyanoacrylate (70/30) (0.1) 18 I-Cyano-l —carbethoxy- Ethylene 180 2.50 " 8-10 butadiene-1,3/ethyl glycol (0.1) 2—cyanoacrylate 19 1—Cyano-carbethoxy- 18-Crown-6- 165 2.50 " 5-10 ' butadiene-1,3/ethyl (70/30) ether (0.1) 2-cyanoacrylate 20 1-Cyano-l-carbethoxy l5-Crown-5- 198 2.52 " 3-S butadiene-1,3/ethyl (70/30) ether (0.1) 2-cyanoacrylate 21 1-Cyano—1-earbethoxy- l5-Crown-5- 180 2.38 ” 5-10 2-cyanoacrylate 22 ,1-Cyano-l-carbethoxy- 'y-Butyrolac— 270 2.60 ” 20-40 butadiene-1,3/ethyl (70/30) tone 5 2-cyanoacrylate 24 1-cyano-carbethoxy — 180 2.20 " 20-40 2-cyanoacrylate What is claimed is: 35 1. An instant-setting adhesive composition compris- ing a 2-cyanoacrylate and at least one 1,1-disubstituted diene represented by the following general formula (A), the amount of said 1,1-disubstituted diene being more than 50% by weight but not more than 90% by weight based on the total amount of both components: X / CH2=C—C=C \ I I R]R2 Y (A) wherein R1 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group, an aralkyl group or a halogen atom, R2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and X and Y, which may be the same or different, are selected from the group con- sisting of cyano group, carboxylate group, ethylsulfone group, phenylsulfone group, formyl group, acetyl group, benzoyl group, diethylphosphonyl group, amido group and phenyl group. 2. An instant-setting adhesive composition according to claim 1, wherein in the general formula (A), R1 is a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, R; is a hydrogen atom, X is a cyano group, and Y is a carboxylate group, an ethylsulfone group, a ben- zoyl group, a diethylphosphonyl group, an amide group, or a phenyl group. 3. An instant-setting adhesive composition according to claim 1, wherein the 1,1-disubstituted diene repre- sented by the general formula (A) is one or more com- pound selected from the group consisting of 1-cyano-1- carbomethoxybutadiene-1,3, l-cyano- l -carbethox- 40 45 50 55 60 65 ybutadiene- 1 , 3, 1-cyano-1-carbo-n-propoxybutadiene- 1,3, 1-cyano-1-carboisopropoxybutadiene-1,3, 1-cyano- l-carbo-n-butoxybutadiene-1,3, 1-cyano-1-car- boisobutoxybutadiene- 1 , 3, 1-cyano-1-carbo-tert-butox- ybutadiene-1,3, 1,l-dicyanobutadiene-1,3, 1,1-dicar- bomethoxybutadiene- 1 , 3, 1, 1-dicarbethoxybutadiene- 1,3, 1-cyano-1-ethylsulfonylbutadiene-1,3, 1-acetyl-1- phenylbutadiene-1,3, 1-cyano-l-acetamidobutadiene- 1,3, 1-formyl-1-phenylbutadiene-1,3, 1-cyano-l—phenyl- butadiene-1,3, 1-cyano-1-benzenesulfonylbutadiene-1,3, 1-cyano-1—diethylphosphonobutadiene-1,3, l-benzoyl- l-cyanobutadiene1,3, 1-cyano-1-carbethoxy-3-(n-amyl)- butadiene-1,3, 1-cyano-1-carbethoxy-2-methylbutadi- ene-1,3, l-cyano-1-carbethoxy-3-phenylbutadiene-1,3, 1,1-dicarbethoxy-3-methylbutadiene-1,3, and 1-cyano- l-carbethoxy-3-chlorobutadiene- l , 3. 4. An instant-setting adhesive composition according to claim 2, wherein the 1,1-disubstituted diene repre- sented by the general formula (A) in one or more com- pound selected from the group consisting of 1-cyano-1- carbomethoxybutadiene—1,3, 1 -cyano- 1-carbethox- ybutadiene-1,3, 1-cyano-1-carbo-n-propoxybutadiene- 1,3, 1-cyano-1-carboisopropoxybutadiene-1,3, l-cyano- 1-carbo-n-butoxybutadiene-1,3, 1-cyano-1-car- boisobutoxybutadiene-1,3, 1-cyano-1-carbo-tert-butox- ybutadiene-1,3, 1-cyano-1-ethylsulfonylbutadiene-l,3, 1-cyano-l—acetamidobutadiene-1,3, l-cyano-l-phenyl- butadiene-1,3, 1-cyano-l-diethylphosphonobutadiene- 1,3, l-benzoyl-1-cyanobutadiene-1,3, and 1-cyano-1- carbethoxy-2-methylbutadiene-1,3. 5. An instant-setting adhesive composition according to claims 1, 2, 3 or 4, wherein the 2-cyanoacrylate is one or more compound selected from the group consisting -4,313,865 13 of methyl 2-cyanoacrylate, ethyl 2-cyanoacrylate, n- propyl 2-cyanoacrylate, isopropyl 2-cyanoacrylate, n-butyl 2-cyanoacrylate, isobutyl 2-cyanoacrylate, tert- butyl 2-cyanoacrylate, amyl 2-cyanoacrylate, n-hexyl 2-cyanoacrylate, cyclohexyl. 2-cyanoacrylate, heptyl 5 2-cyanoacrylate, n-octyl 2-cyanoacrylate, 2-ethylhexyl 2-cyanoacrylate, dodecyl 2-cyanoacrylate, allyl 2- ’ cyanoacrylate, propargyl 2-cyanoacrylate, benzyl 2- cyanoacrylate, phenyl 2-cyanoacrylate, 2-methoxyethyl 2-cyanoacrylate, 2-ethoxyethyl 2-cyanoacrylate, 2- chloroethyl 2-cyanoacrylate, hexafluoroisopropyl 2- cyanoacrylate, tritluoroethyl 2-cyanoacrylate, and 2- cyanoethyl 2-cyanoacrylate. 6. An instant-setting adhesive composition according to claims 1, 2, 3 or 4, wherein the amount of one or more l,l-disubstituted dienes is 60 to 90% by weight per 40 to 10% by weight of the 2-cyanoacrylate. 7. An instant-setting adhesive composition according to claims 1, 2, 3 or 4, wherein the amount of one or more l,l-disubstituted dienes is 65 to 85% by weight per 35 to 15% by weight of the 2-cyanoacrylate. 8. An instant-setting adhesive composition according to claims 1, 2, 3 or 4, which further contains one or more members selected from the group consisting of lactone compounds, alcohols, alcohol ethers, alcohol 25 esters, and crown ether compounds. - 9. An instant-setting adhesive composition according to claim 8, wherein the lactone compound is one or more members selected from the group consisting of B-propiolactone, B-pivalolactone, 'y-butyrolactone, 3- 30 carbethoxy-7-butyrolactone, 5-ethyl-'y.-butyrolactone, phthalide, 6-valerolactone, coumarin, dihydrocouma- rin, e-caprolactone, heptodilactone, and dimethylhep- todilactone. 10. An instant-setting adhesive composition accord- 35 ing to claim 8, wherein the alcohol is one or more mem- bers selected from the group consisting of methyl alco- hol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, n-amyl alcohol, ethylene glycol, propylene glycol, tet- ramethylene glycol, pentamethylene glycol, hexameth- ylene glycol, heptamethylene glycol, octarnethylene glycol, decamethylene glycol, polybutadienediol, chlo- ropropylene glycol, 3-methylpentanediol, 2,2-diethyl- propanediol, 2-ethyl-1,4-butanediol, diethylene glycol, triethylane glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, glycerol, trimethylolme- thane, trimethylolethane, trimethylolpropane, and 1,2,6-hexanetriol. 11. An instant-setting adhesive composition accord- 50 ing to claim 8, wherein the alcohol ether is one or more members selected from the group consisting of propy- lene glycol methyl ether, dipropylene glycol methyl l0 l5 20 40 45 55 60 65 14 ether, tripropylene glycolmethyl ether, ethylene glycol ethyl ether, ethylene glycol n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, di- ethylene glycol n-butyl ether, ethylene glycol phenyl ether, polyoxyethylene lauryl ether, and polyoxyethyl- ene nonylphenyl ether. 12. An instant-setting adhesive composition accord- ing to claim 8, wherein the alcohol ester is one or more members selected from the group consisting of polyeth- ylene glycol monolaurate, polyethylene glycol mono- stearate, glycerol monolaurate, glycerol monostearate, sorbitan monolaurate, and polyoxyethylene sorbitan monolaurate. 13. An instant-setting adhesive composition accord- ing to claim 8, wherein the crown ether compound is one or more members selected from the group consist- ing of 18-crown-6, dithia-15-crown, 15-crown-5, 18- crown-5, dibenzo-18-crown-6, dibenzo-24-crown-8, dicyclohexyl-18-crown-6, and 1',2-vinylbenzo- l 5- crown-5. 14. An instant-setting adhesive composition accord- ing to claim 8, wherein the amount of the lactone com- pound is 0.1 to 30 parts by weight per 100 parts by weight of the total amount of the 2-cyanoacrylate and the l,l-disubstituted diene. 15. An instant-setting adhesive composition accord- ing to claim 8, wherein the amount of the lactone com- pound is 0.5 to 10 parts by weight per 100 parts by weight of the total amount of the 2-cyanoacrylate and the l,l-disubstituted diene. 16. An instant-setting adhesive composition accord- ing to claim 8, wherein the amount of at least one com- pound selected from the group consisting of alcohols, alcohol ethers and alcohol esters i.s 0.001 to 5 parts by weight per 100 parts by weight of the total amount of the 2-cyanoacrylate and the l,l-disubstituted diene. 17. An instant-setting adhesive composition accord- ing to claim 8, wherein the amount of at least one com- pound selected from the group consisting of alcohols, alcohol ethers and alcohol esters is 0.05 to 2 parts by weight per 100 parts by weight of the total amount of the 2-cyanoacrylate and the l,l-disubstituted diene. 18. An instant-setting adhesive composition accord- ing to claim 8, wherein the amount of the crown ether compound is 0.001 to 5 parts by weight per 100 parts by weight of the total amount of the 2-cyanoacrylate ester and the l,l-disubstituted diene. 19. An instant-setting adhesive composition accord- ing to claim 8 wherein the amount of the crown ether compound is 0.05 to 2 part by ‘weight per 100 parts by weight of the total amount of the 2-cyanoacrylate and the 1, l-disubstituted diene. * * * * *