Cyanoacrylate Adhesive Composition

 [Jiiited States Patent [191 [111 3,836,377 Belahnnty [451 Sept. 17, 1974 [54] CYANOACRYLATE ADHESIVE 3,260,637 7/1966 Bramer .................... .. 260/78.4 N X CQMPOSITIQN 3,640,972 2/1972 Bolger .......................... .. 260/78.4 N [76] [22] [21] [30] [52] [51] [58] [56] 2,765,332 Inventor: John .1. Deiahunty, 18 Chalfont Estate, Texas Ln., Malahide Co., Dublin, Ireland Filed: Dec. 7, 1972 Appl. No.2 313,061 Foreign Application Priority Data Dec. 14, 1971 Ireland .............................. .. 1584/71 US. Cl ........ .. 106/287, 260/33.4 R, 260/33.64, 260/78.4 N int. Cl. ............................................ .. C08[ 3/42 Field] of Search..... 260/78.4 N, 33.4 R, 33.6 U, 260/33.8 U; 106/287 References Cited UNITED STATES PATENTS 10/1956 Coover ............................. .. 260/464 Primary Examiner——-Morris Liebman Assistant Examiner«——Richard Zaitlen Attorney, Agent, or Firm—-J. Rodney Reck, Esquire; Jean B. Mavro, Esquire [57] This invention concerns polymerization accelerators or surface activators forincreasing the rate of cure of cyanoacrylate adhesive compositions. The active in- gredients of the activators are organic compounds ABSTRACT containing a \ I I I I N—C==S or a N=C—S— / group. 12 Claims, No Drawings 3,836,377 ll CYANOACRYILATE ADHESIVE COMPOSITION BACKGROUND OF THE INVENTION This invention relates to improved methods of form- ing adhesive bonds with adhesive compositions con- taining organic cyanoacrylates, and to compositions for 'use in such methods. Certain known organic com- pounds have been discovered to accelerate polymeriza- tion in such adhesive compositions, even when used as primers or surface activators, and thus to assist in rapid adhesive bond formation. Adhesive compositions comprising one or more es- ters of 2-cyanoacrylic acid (hereinafter “cyanoacrylate esters”) are known to have excellent utility in bonding pairs of juxtaposed surfaces or substrates. Rapid setting (e.g., within several minutes, and frequently within a matter of 15 seconds or less) to form adhesive bonds is a desirable, and frequently essential, property of such compositions. It is this ability to rapidly and depend- ably bond a wide variety of substrates that has rendered cyanoacrylate ester adhesives an extremely popular product in today’s homes and industries. Cyanoacrylate ester adhesive compositions, how- ever, are affected substantially by certain surfaces or by common contaminants in or on many surfaces, and the bonding speed or durability is frequently adversely af- fected thereby. As a result, it has become necessary in some cases, and a desirable precaution in other cases, to use polymerization accelerators in conjunction with the cyanoacrylate ester adhesives to accelerate bond formation. Some polymerization accelerators may be incorporated in cyanoacrylate adhesive compositions, but more commonly they are coated on one or both substrates as a primer or surface activator before appli- cation of the cyanoacrylate ester adhesive. See, for ex- ample, U.S. Pat. No. 3,640,972 of O’Sullivan and Bolger, issued Feb. 8, 1972. Some disadvantages of the polymerization accelera- tor techniques of the prior art have included unsatisfac- torily low ultimate bond strengths and failure to form firm bonds at all when one or both substrates is, e.g., wood (including plywood) or a phenolic resin. Many factors certainly contribute to the difficulties experi- enced with certain substrates, but one significant factor is thought to be the slightly acid nature of certain sur- faces since cyanoacrylate ester adhesive cure is anioni- cally initiated. Prior art polymerization accelerator techniques have had certain disadvantages, which has led to a continu- ing demand for a more fully acceptable accelerator product. Typical examples of prior art patents are U.S. Pat. No. 2,768,109 to Coover, issued Oct. 23, 1956, which discloses a method for improving the adhesive efficiency of cyanoacrylate ester adhesives by treating the substrate with an aliphatic monohydric alcohol prior to the application of the adhesive composition; and U.S. Pat. No. 3,259,534 to Wicker and Shearer, is- sued July 5, 1966, which describes the treatment of sur- faces to be bonded with a monomeric epoxide prior to application of the adhesive composition. Satisfactory results are not always obtainable with the use of these compositions and techniques. The ultimate strength of bonds formed with their use was often substantially lower than that of bondsformed between metallic or other non-acidic surfaces using cyanoacrylate ester ad- hesives without accelerator pretreatment. Further, even bonds between metal or other non-acidic sub- 5 10 15 20 25 30 35 40 45 50 55 60 65 2 strates frequently are noticeably lower in ultimate strength when the polymerization accelerator pretreat- ment is used, when compared to comparable bonds be- tween such substrates without pretreatment. THE INVENTION It is an object of the present invention to provide compositions and methods involving cyanoacrylate ester adhesives wherein rapid bonds of satisfactory ulti- mate strength are formed between a wide variety of substrates, as well as under a variety of bonding condi- tions. More specifically, the invention concerns adhesive compositions containing polymeri.zable cyanoacrylate esters and a polymerization accelerator for use there- with, such polymerization accelerator comprising an organic compound containing a I I I N—C=S or a N=C——— 8- group. The invention includes the incorporation of the above-described polymerization accelerator directly into the cyanoacrylate ester adhesive at the time of use but, more commonly, the polymerization accelerator is applied to one or both of the substrates to be bonded, followed by direct application to one or both of said substrates of the cyanoacrylate ester adhesive. Thereaf- ter, the substrates are placed in the juxtaposed relation- ship until the adhesive has hardened therebetween. In addition, the invention concerns the process for bonding substrates which involves the above-described compositions, wherein the polymerization accelerator is used as a direct additive to the cyanoacrylate ester adhesive, or, more commonly, as a surface primer as described above. DISCUSSION OF THE INVENTION AND ITS PREFERRED EMBODIMENTS The benefits of this invention are achievable with es- sentially all adhesive compositions. based upon cyano- acrylate esters. Most commonly, the esters have the formula ‘EN ' CHa§C——C 0 0 R wherein R represents a C,_16 alkyl, cycloalkyl, alkenyl, cycloalkenyl, phenyl or heterocyclic (such as furfuryl) radical. Naturally, the above R group can contain any linkages or substituents which do not adversely affect the monomer in the performance of its intended func- tion in the cyanoacrylate adhesive compositions, such as strongly basic substituents which may adversely af- fect the stability of the adhesive composition. For pur- poses of this invention, the preferred monomers are those wherein R is a cyclohexyl or a C, to C6 alkyl, or alkenyl radical. The esters may be used singly or in ad- mixture. The above monomeric esters of 2-cyanoacrylic acid can be prepared by methods known in the art, such as those described in U.S. Pat. Nos. 2,467,927 to Ardis, issued Apr. 9, 1949 and 3,254,111 to Hawkins et al., issued May 31, 1966. Cyanoacrylate ester adhesive compositions generally contain an anionic inhibitor, e.g., :an acidic substance, soluble in the ester of 2-cyanoacrylic acid, which inhib- its anionic polymerization. The specific inhibitor 3,836,377 3 chosen is not critical to this invention, and a number of suitable inhibitors of anionic polymerization are well known in the art. The best known are the soluble acidic gases such as sulfur dioxide, sulfur trioxide, nitric oxide, and hydro- gen fluoride. More recently, organic sultone inhibitors have been developed, the sultone being generally rep- resented by the formula in’ 9~—%=° yxg wherein X is an organic radical joining the —-S(O2)O— group in a 4, 5, or 6 member heterocyclic ring, prefera- bly a 5 member heterocyclic ring. Preferably, X is a hy- drocarbon group, although it can contain any substitu- ents or linkages which do not adversely affect the sul- tone for its intended use as a stabilizer of the adhesive composition. Another excellent class of stabilizers are the organic sulfonic acids, preferably having a molecu- lar weight less than about 400. To be optimally useful as a stabilizer in the adhesive compositions, the sulfonic acid should have a pKA value (dissociation constant in water) of less than about 2.8, and preferably less than about 1.5. While not essential, the cyanoacrylate adhesive com- positions of this invention generally also contain an in- hibitor of free radical polymerization. The most desir- able of these inhibitors are ofthe phenolic type, such as quinone, hydroquinone, t-butyl catechol, p—methoxy phenol, etc. The above inhibitors may be used within wide ranges, but the following general guidelines are representative of common practice, all figures being weight percent of the adhesive composition: acidic gases——from about 0.001% to about 0.06% by weight; sultones-from about 0.1% to about 10% by weight; sulfonic acids—— from about 0.0005% to about 0. 1% by weight; free rad- ical inhibitors—from about 0.001% to about 1%. Other common additives for cyanoacrylate adhesive compositions are plasticizers and thickeners. Plasticiz- ers serve to make the cured bonds less brittle and, therefore, more durable. The most common of these plasticizers are C, to Cm alkyl esters of dibasic acids such as sebasic acid and malonic acid. Other plasticiz- ers, such as diaryl ethers and polyurethanes, also may be used. . Thickeners increase the viscosity of the adhesives and render them capable of greater retention on parts to be bonded, and particularly to fill larger gaps be- tween such parts. A number of such thickeners are known for use in combination with cyanoacrylate adhe- sives, the most common of which are acrylate resins such as polymethylmethacrylate and polyethylmetha- crylate. Other suitable thickeners include polymeric alkylcyanoacrylates, cellulose esters such as cellulose acetate and cellulose butyrate, and polyvinyl ethers such as polyvinylmethyl ether. Compositions of this invention are prepared from the original starting materials by a conventional mixing op- eration, although moderate heating may be helpful to achieve solution of the ingredients within a reasonable time. 10 15 20 25 30 35 40 45 50 55 60 65 4 The polymerization accelerators which are used in the compositions and processes of this invention are or- ganic sulfur containing compounds containing a \ l I /N—C=S or a —N=C—S— group. The remainder of the molecule does not seem critical for purposes of this invention, although it should be free of reactive groups which could serve as Lewis acids, since such groups could tend to inhibit cure. Examples of three specific classes of compounds which have been found excellent for purposes of this invention are as follows. a. N-disubstituted metallic dithiocarbamates having the general formula R,R2N-C-(=S)-S ,,M,, where each of R, and R2, which may be the same or different, repre- sents a saturated or an ethylenically or aromatically un- saturated group, preferably a hydrocarbon group, hav- ing a maximum of 10 carbon atoms, and R, and R2 to- gether with the nitrogen atom to which they are at- tached, may additionally represent a heterocyclic group having a maximum of 10 carbon atoms; M is any metal which forms dithiocarbamates, which metal is commonly any of the transition metals; and x and y are integers which depend in well-known manner upon the valency of the metal, and generally are from 1 to about 4. . b. N-disubstituted benzothiazole-Zsulfenamides hav- ing the general formula S\ /R’ C— S——N N/ \ R: where R, is defined in (a), above, and R3 is either R, or hydrogen. (c) N,N-tetrasubstituted thiruam mono- and oligosul- fides having the general formula R,R2N'C(=S)‘S,,'C(=S)'NR,R2, where each of R, and R2, which may be the same or different, has the mean- ing given in (a) above; z is an integer not exceeding 5. The polymerization accelerator generally is used in a volatile organic solvent, and applied as a solution to the substrate. Any solvent capable of dissolving the poly- merization accelerator and which will evaporate from a thin film at standard conditions of temperature and pressure within about one minute can be used. Exam- ples of suitable solvents are halogenated hydrocarbons, such as methylene chloride, trichloroethylene, trichlo- roethane and methyl chloroform. Other solvents such as alcohols, hydrocarbons and laquer-type solvents also can be used. The polymerization accelerator may be used within broad ranges in the solvent, e.g., 0.01% to about 20% by weight. A preferred range is from about 0.1% to about 5.0% by weight of the total mixture, and most preferably 0.1% to about 1.0% by weight. The invention will be illustrated now by reference to the following specific examples which are not intended to limit the scope of the invention in any way. EXAMPLE I Two pieces of oakwood were bonded together with an adhesive composition comprising methyl 2- cyanoacrylate containing 0.5% propane sultone and 3,836,377 5 0.01% hydroquinone as stabilizers. The pieces were clamped together for 15 minutes, after which it was found that no effective bond had been formed. The above procedure was then repeated with the fol- lowing variation according to this invention. Both of 5 the wood surfaces to be bonded were moistened with a 0.1% by weight solution of bismuth dimethyldi- thiocarbamate in 1,1,1-trichloroethane/chloroform (a 50/50 mixture by volume). The solvent was allowed to evaporate. The adhesive was applied to one of the sur- faces, the pieces were joined and a firm bond resulted within one minute. The first part of the above example illustrates a disad- vantage of adhesive compositions of the prior art. The 10 second part illustrates the effectiveness of a solution of 15 bismuth dimethyldithiocarbamate in promoting the bonding of wood, when used according to the process of the present invention. EXAMPLE II Two pieces of oakwood were moistened with a 0.1% by weight solution of N—oxydiethylene benzothiazole 2-sulfenamide in 1,1,1-trichloroethane. The "solvent was allowed to evaporate, and the adhesive of Example I was applied to one of the surfaces. The pieces were then joined together and a firm bond became estab- lished within one minute. EXAMPLE lll Two pieces of grit blasted mild steel were bonded to- gether with an adhesive composition comprising methyl 2—cyanoacrylate and containing 0.5% by weight propane sultone and 0.01% hydroquinone as stabiliz- ers. After 1 minute the bond formed was found to have a tensile-shear strength of 1,200 lbs./in2, when tested according to ASTM Method D 1002-64. The above experiment was repeated with the excep- tion that the tensile-shear strength of the bond was ex- amined after full or ultimate cure had taken place (24 hours after assembly). The ultimate tensile-shear strength was found to be 3,600 lbs./inz. The above illustrates the normal behavior of cyano- acrylate adhesives with grit blasted mild steel. The fol- lowing experiment was then carried out and demon- strated by comparison that the practice of the present invention does not result in any weakening of the ulti- mate bond strength attainable with cyanoacrylate ad- hesives. Two pieces of grit blasted mild steel were moistened with a 0.1% by weight solution of N—oxydiethylene ben- zothiazole 2-sulfenamide. The solvent was allowed to evaporate, and the adhesive composition of Example I was applied to one of the surfaces. The pieces were joined and the tensile-shear strength, tested after 1 minute, was found to be 3,050 lbs./in? The immediately preceding experiment was repeated with the exception that the tensile-shear strength was tested after a curing time of 24 hours. The ultimate ten- sile-shear strength was 3,600 lbs./inz. We claim: 1. A cyanoacrylate adhesive composition comprising a monomeric ester of 2-cyanoacrylic acid and, as a po- lymerization accelerator, an organic compound con- taining a \ I 1 I 1 N—C:S or N==C—S / 20 25 30 35 40 45 50 55 60‘ 65 6 group. 2. The adhesive composition of claim 1 wherein the monomeric ester has the formula (IJN C H1=C—C O O R wherein R represents a C,’ ,6 alkyl, cycloalkyl, alkenyl, cycloalkenyl, phenyl or heterocyclic radical; and the polymerization accelerator is an organic compound se- lected from the class consisting of.: a. N-disubstituted metallic dithiuocarbamates having the general formula R,R2N'(C'(=S)-S,M,, where each of R, and R2 is a saturated or an ethylenically or aromatically unsaturated hydrocarbon group containing up to about 10 carbon atoms, or where R, and R2 together with the nitrogen atom to which they are attached form a heterocyclic group con- taining up to about 10 carbon atoms; M is a transi- tion metal; and x and y are integers; b. N-disubstituted benzothiazole-2—sulfenamides hav- ing the general formula /s\ /R‘ N/C-— S ——N\ R3 where R, is as defined above, and R3 is either R, or hy- drogen; and ‘ c. N,N-tetrasubstituted thiuram :mono- and oligosul- fides having the general formula R,R2N'C(=S)'Sz'C(=S)'NR,R2, where each of R, and R2 is as described above; and z is an integer. 3. The adhesive composition of claim 2 wherein the monomeric ester has the formula (EN CH2=C—C O 0 R wherein R is cyclohexyl or a C, to CS alkyl or alkenyl radical. 4. The adhesive composition of claim 2 wherein the polymerization accelerator is a dithiocarbamate. 5. A two part adhesive composition consisting of: a. an adhesive component comprising a monomeric ester of 2-cyanoacrylic acid having the formula $N CH2=C—C O O R wherein R represents a C,”,,; alkyl, cycloalkyl, alkenyl, cycloalkenyl, phenyl or heterocyclic radical; and b. an activator component comprising a polymeriza- tion accelerator selected from the class consisting of: a. N-disubstituted metallic dithiocarbamates hav- ing the general formula R,R2N'C,(=S)‘S,M,, where each of R, and R2 is a saturated or an eth- ylenically or aromatically unsaturated hydrocar- bon group containing up to about 10 carbon atoms, or where R, and R2 together with the ni- trogen atom to which they :are attached form a heterocyclic group containing up to about 10 carbon atoms; M is a transition metal; and x and y are integers; b. N-disubstituted benzothiazone-2-sulfenamides having the general formula 3,836,377 7 s / R, C—S——N/ \R N 3 5 where R, is as defined above, and R3 is either R, or hy- drogen; and c. N,N-tetrasubstituted thiuram mono- and oligosul- fides having the general formula 10 R,R2N-C(=S)-S,-C(=S)-NR,R2, where each of R, and R2 is as described above; and z is an integer. 6. The adhesive composition of claim 5 wherein the adhesive component additionally contains an inhibitor of anionic polymerization. . 15 7. The adhesive composition of claim 6 wherein the polymerization accelerator is dissolved in a volatile or- ganic solvent, and comprises from about 0.01% to about 20% by weight of the mixture of solvent and po- lymerization accelerator. 20 8. The process for bonding two substrates which comprises (a) applying to at least one of said substrates a solvent solution of a polymerization acceleration se- lected from the class consisting of: a. N-disubstituted metallic dithiocarbamates having 25 the general formula R,R2N~C-(=S)-S,m,, where each of R, and R2 is a saturated or an ethylenically or aromatically unsaturated hydrocarbon group containing up to about 10 carbon atoms, or where R, and R2 together with the nitrogen atom to which they are attached form a heterocyclic group con- taining up to about 10 carbon atoms; M is a transi- tion metal; and x and y are integers; b. N-disubstituted benzothiazole-2-sulfenamides hav- 30 ing the general formula 35 s \ RI / C—~S—N / \ R3 N 40 45 50 55 60 65 8 where R, is as defined above, and R3 is either R, or hy- drogen; and c. N,N-tetrasubstituted thiuram mono- and oligosul- fides having the general formula R,R2N-C(=S)'Sz‘C(=S)-NR,R2, where each of R, and R2 is as described above; and z is an integer; (b) applying to at least one of said substrates an ad- hesive comprising 21 monomeric ester having the formula S / R1 \c—s—N/ / \Rx N wherein R represents a C,“,,, alkyl, cycloalkyl, alkenyl, cycloalkenyl, phenyl or heterocyclic radical; and (c) placing the substrates of steps (a) and (b) in contacting relationship until the adhesive has hardened to form an adhesive bond therebetween. 9. The process of claim 8 wherein the polymerization accelerator comprises from about 0.1% to about 5.0% by weight of the solvent solution, and the adhesive comprises a monomeric ester having the formula CN CI-I;=d)-—-C 0 OR wherein R is cyclohexyl or a C’, td"c., alkyl or alkenyl radical. 10. The process of claim 9 wherein the adhesive addi- tionally contains an inhibitor of anionic polymeriza- tion. 11. The process of claim 8 wherein each of x and y are integers between 1 and about 4, and z is an integer _ not exceeding about 5; and the adhesive additionally contains an inhibitor of anionic polymerization. 12. The process of claim 11 wherein the inhibitor of anionic polymerization is selected from the class con- sisting of acidic gasses, organic sultones, and organic sulfonic acids. * * >l< * *