2-Cyanoacrylate Adhesive Composition

United States Patent [191 Dombroski et al. [54] [75] [73] [21] [22] [51] [521 [581 2-CYANOACRYLATE ADHESIVE COMPOSITION Inventors: John R. Dombroski, Kingsport; Doyle A. Weemes, Greeneville, both of Tenn. Assignee: Eastman Kodak Company, Rochester, N.Y. App1.No.: 745,757 Filed: Nov. 29, 1976 Int. CL? .............................................. .. B32B 7/00 U.S. C]. .................................. .. 156/310; 156/314; 156/331; 260/881; 260/885; 427/302; 428/522; 526/298 Field of Search ..................... .. 156/331, 314, 310; 427/302; 428/463, 522; 526/298; 260/881, 256, 885 [11] 4,042,442 [45] Aug. 16, 197 7 [56] References Cited U.S. PATENT DOCUMENTS 2,765,332 10/1956 Coover et al. ..................... .. 526/298 2,784,127 3/1957 Joyner et‘a1. .................. .. 428/463 3,178,379 4/1965 Wicker et a1. ............ .. 3,260,637 _ 7/1966 Von Bramer ..... .. 3,970,505 7/1976 Hauser et a1. ...................... .. 156/310 ‘ FOREIGN PATENT DOCUMENTS 938,742 10/1963 United Kingdom ............... .. 156/331 1,000,665 8/1965 United Kingdom ............... .. 156/310 Primary Examiner—Char1es E. Van Horn Assistant Examiner——J. J. Gallagher Attorney, Agent, or Fz'rm—E11iott Stern; Daniel B. Reece, III [57] ABSTRACI‘ Adhesive composition comprising A. at least one monomeric ester of 2-cyanoacrylic acid, and B. at least one polymerization initiator selected fro caffeine and theobromine. - 18 Claims, No Drawings 4,042,442 1 2-CYANOACRYLATE ADHESIVE COMPOSITION This invention relates to the use of initiators with alphacyanoacrylate adhesive compositions. It is particu- larly concerned with the use of caffeine or theobromine as an initiator for promoting the polymerization of 2- cyanoacrylate adhesive compositions in thick, gapfill- ing layers. The initiators of this invention can be applied to the substrate prior to bonding or can be conveniently added to the 2-cyanoacrylate adhesive just prior to use. The initiators of this invention impart an unusual and unexpected polymerizing capability to the thickened 2-cyanoacrylate adhesive composition which give thick, gap-filled bonds with excellent lap shear strengths. The initiators of this invention also exhibit highly advantageous physical properties when used in conjunction with unthickened 2-cyanoacrylate adhe- sives. An important property of 2-cyanoacrylate adhesive compositions is their ability to rapidly polymerize in the presence of weakly basic catalysts such as water, alco- hols, and amines. See for example U.S. Pat. Nos. 3,260,637 and 2,768,109. In most cases, the absorbed moisture on surfaces is sufficient to rapidly initiate the 2-cyanoacrylate polymerization as the substrates are pressed together. Bonds formed by this technique in- volve only a thin layer of adhesive. For many other applications, however, it is desirable to increase the overall thickness of the adhesive layer to insure ade- quate bond formation of substrates separated by, for example, a shim spacer, void or gap. It is desirable for these thicker adhesive layers to polymerize rapidly and form a strong bond. In some cases, the polymerization of the adhesive composition has been accelerated by either treating the surface to be bonded with a basic material or by adding a small amount of a basic catalyst to the adhesive just prior to use. Treatment of substrates with basic materials such as alcohols, ammonia, pyri- dine, dimethylaniline, sodium hydroxide, and the like, however, causes the bonding to occur with such ex- treme rapidity that weak bonds are formed. Further- more, it is difficult to incorporate the basic substance into the adhesive just prior to use, since this often results in either encapsulation of the activator droplets with no further reaction or an instantaneous polymerization of the monomer mass. The problems associated with the prior art have been overcome by the use of an adhesive composition com- prising A. at least one monomeric ester of 2-cyanoacrylic acid, and B. at least one polymerization initiator selected from caffeine and theobromine. In a preferred embodiment of the invention the initia- tor utilized is caffeine because of its availability, low cost and desirable performance characteristics. In an especially preferred embodiment the ester of 2-cyanoa- crylic acid has been modified with from 0.1 to about 25 parts by weight of a thickening agent. The amount of initiator utilized in the practice of the invention is from 0.01 to about 10 parts by weight, based on the weight of the adhesive. Preferably the amount is 0.1 to about 3 parts by weight. Suitable adhesive compositions for practicing this invention comprise one or more 2- cyanoacrylate monomers represented by the formula: 5 10 15 20 25 30 35 45 50 55 60 65 2 CH2=(|:'—CO2R. CN wherein R represents alkenyl having 2 to 6 carbon atoms, cyclohexyl, phenyl, and alkyl having 1 to 16 carbon atoms. Examples of the monomers utilizable and included in this invention are for example, allyl, methyl- allyl, butyryl, cyclohexyl, phenyl, methyl, butyl, ethyl, isobutyl, hexyl, decyl, pentadecyl and the like. Of these 2-cyanoacrylates the preferred are methyl 2-cyanoacry- late, allyl 2-cyanoacrylate, butyl 2-cyanoacrylate, iso- butyl 2-cyanoacrylate and ethyl 2-cyanoacrylate. Of these adhesives the allyl 2-cyanoacrylate is the most preferred. The thickening agents utilizable in the prac- tice of this invention are any of the well-known thicken- ing agents which have been found to be useful with 2-cyanoacrylate adhesives. Examples of these thicken- ing agents are the polyacrylates, poly(methyl methacry- lates), copolymers thereof, and the poly(2-cyanoacry- lates). Specific examples of these thickening agents are poly(methyl methacrylate), poly(methylacrylate), cel- lulose acetate,’ and the like. The‘preferred thickening agent is poly(methyl methacrylate). Typically, the amount of thickening agent useful in the practice of this invention is an amount sufficient to -render the composi- tion sufficiently viscous to remain in the locus of the intended bond. Generally, it has been found that any- where from 5 to 25% based on the weight of the cyano- acrylate adhesive composition of thickner will give the composition the desired viscosity. Preferably, around 5 to 15% thickening agent is utilized, about 10% being especially preferred. ’ The initiation of the 2-cyanoacrylate polymerization with either caffeine or theobromine in thick layers can be accomplished by several different techniques. In the most direct method, the initiator can be added directly to a small quantity of the thickened 2-cyanoacrylate monomer just prior to application, stirred and then applied to the gap or void area of the substrate or sub- strates. Polymerization of the adhesive occurs within several minutes and results in a thick, clear film with strong adhesion to the substrate or substrates. The amount of initiator utilized is from 0.01 to about 10, based on the weight of the adhesive. Preferably the amount is 0.1 to 3. In a preferred method the initiator can be first dissolved in an appropriate volatile solvent, and this solution is then applied to the substrate or sub- strates. After a brief time, sufficient to allow the solvent to evaporate, the desired amount of thickened 2- cyanoacrylate adhesive composition is applied to the substrate surface. Polymerization of the 2-cyanoacry- late adhesive occurs within a few minutes and forms a thick, clear film strongly bonded to the substrate or substrates. Volatile solvents useful in this process are thosehaving a boiling point of 100° C. or below and in which the initiators are soluble. Specific examples of suitable solvents are water, saturated monohydroxy aliphatic alcohols containing from 1 to 4 carbon atoms such as methanol, ethanol, propanol, isopropanol, buta- nol, an ester of these alcohols with a saturated monoba- sic fatty acid containing from 1 to 3 carbon atoms such as methyl acetate, ethyl acetate, acetone, methyl ethyl ketone, methylene chloride, chloroform, diethyl ether, dimethyl ether, methyl chloroform, and mixtures of these solvents. Generally, the amount of initiator used in this process is 0.1 to about 10, and preferably 2 to 5 4,042,442 3 parts by weight, based on the weight of the volatile solvent. If desired, a plasticizer may also be advantageously added to the composition such as alkyl esters of ali- phatic monocarboxylic acids, e.g., methylcyanoacetate, ethylcyanoacetate, etc. These plasticizers are well known in the art and further illustrated in U.S. Pat. No. 2,784,127. Additionally, the adhesive compositions may be protected against premature polymerization of the monomer by the addition thereto of polymerization inhibitors such as hydroquinone, t-butyl catechol, sulfur dioxide, nitric oxide, hydrogen fluoride, and the like. The following examples illustrate further the manner of practicing the invention. EXAMPLE 1 This example illustrates the overall gap-filling capa- bility of a 2-cyanoacrylate adhesive initiated with caf- feine. a. Into a three-inch-diameter aluminum cup was added 0.5 gram of allyl 2-cyanoacrylate thickened with 10% poly(methyl methacrylate). Three milli- grams (3 mg.) of caffeine are then added to the cyanoacrylate composition and stirred for 30 sec- onds. A portion of this solution was then added by means of a glass dropper to fill the cavity of a 3/16- inch diameter hole previously drilled in an alumi- num block. Within 3 minutes, the composition poly- merized and filled the entire gap with a clear hard plug of adhesive. b. Experiment (a) was repeated with the exception that caffeine was not added to the 2-cyanoacrylate composition. After several hours, the liquid adhe- sive composition had not yet polymerized within the gap. The above results illustrate the fast-setting, gap-filling 10 15 20 25 30 35 4 by spraying the area with a caffeine/ethyl alcohol solution and allowing the alcohol to evaporate. Allyl 2-cyanoacrylate, thickened with 10% poly(- methyl methacrylate), was deposited within the gap area and the other piece of steel was placed over the ‘ adhesive in such a manner as to form a lap shear specimen. The lap shear strength was determined after 10 minutes, 30 minutes, one hour, and 24 hours of bonding time. The results are listed in Table 1 below. b. The above experiments were repeated using methyl 2-cyanoacrylate, thickened with 5.5% poly(methyl methacrylate). No caffeine initiator was used. The results are listed in Table 1 below. Table 1 Age 15 Mil Adhesive of ‘ Cap Lap Shear‘ Adhesive Bond Strength (psi) Per Example la 10 min 1419 .90% Allyl 2-cyanoacrylate 30 min 1471 10% Polymethyl methacrylate 1 hr 1870 Caffeine Initiator 24 hr 2600 Per Example lb 10 min 19 94.5% Methyl 2-cyanoacrylate 30 min 27 5.5% Polymethyl methacrylate 1 hr 26 No Initiator 24 hr 1048 ‘ASTM D-1002-64 EXAMPLE 3 This example illustrates the unexpected capability of the 2-cyanoacrylate adhesive/caffeine initiator system in forming strong, gapfilled bonds even on oily sub- strates. Lap shear specimens with 15 mil gap thickness were prepared as in Example la. However, the gap area was intentionally coated with various oils and the effect on the lap shear strength is noted in Table 2. Table 2 15 Mil‘ Adhesive Gap Oil on Caffeine Lap Shear Adhesive Substrate Initiator Strength (psi) None None 1515 None Yes 2289 90% Allyl 2-cyanoacrylate Cutting oil None 2001 10% Polymethyl methacrylate Cutting oil Yes 2249 30w motor oil None 1715 30w motor oil Yes 2523 ‘Time before testing 24 hrs. - Procedure ASTM D-[(1)2-64 ca abilit im arted b the caffeine initiator. Similar . P Y P 3' EXAMPLE 4 results can be obtained using theobromine. EXAMPLE 2 This example illustrates the effectiveness of caffeine in promoting strong; gap-filling bonding of steel sub- strates. . a. Cold rolled steel specimens 1/16 inch X 1 inch X 4 inches were cleaned with trichloroethane and then wiped with acetone. A five mil thick piece of adhesive tape was applied to one of the substrates and a 0.5 square inch area was cut from the tape with a sharp blade. Three successive layers of tape were applied in this manner to form a gap thickness of 15 mils. The gap area was coated with caffeine 55 60 65 The objective of this example was to measure the set time and lap shear strength of a 2-cyanoacrylate-based gap ‘filling adhesive on selected substrates. The gap filling adhesive is allyl 2-cyanoacrylate thickened with 10 weight percent Elvacite 2041 (polymethyl metha- crylate) a trademark of E. I. du Pont de Nemours and polmerized with the surface activator, caffeine. The results (Table 3) show the gap filling adhesive gives -fast-setting, high lap shear strength bonds across 2, 5 and 15 mil gaps on metal-to-metal, plastic-to-plastic and plastic—to-metal substrates. It was concluded that the gap filling adhesive gives excellent fast-setting adhesive performance across gaps up to 15 mils. 4,042,442 5 Table 3 Set Time and Lap Shear Strength of Gap Filling Cyanoacrylate Adhesive on Selected "Substrates ._ Lap Shear“ (1) " MCAO) V Gap Set“‘ Lap Shear" ’ Set‘” ~ Substrates Thickness Strength (PSI) Time (Min.) Strength (PSI). Time (Min.) Steel-to-Steel 2 Mil 2777 ' 30 5 Mil 2719 30 15 Mi] 2801 2 V ' 75.1 >60 Aluminum-to-Aluminum 2 Mil 1211 30 5 Mil 1307 60 Steel-to-Aluminum 2 Mil 1272 ' 30 5 Mil 1639 30 15 Mil 1502 2 . 70 >60 Fiberglass Reinforced 2 Mil 627 30 Plastic (FRP)-to-FRP 5 Mil 778 30 . 15 Mil 692 2 - 1145, >60 Phenolic-to-Phenolic 2 Mil 1002‘ 30 5 Mil 993‘ 30 15 Mil 1048' 2 . 922‘ >60 Polycarbonate-to—Aluminum 2 Mil 575‘ 30 5 Mil 452‘ 30 15 Mil 600‘ 1.5 853" ' >60 .__T. "’Allyl 2-cyanoacrylate thickened with 10 weight percent poly(methyl methacrylate) I.V. 1.72. Polymerization on substrate initiated with caffeine as in Example 1. The set time and lap shear strength of this gap-filling adhesive on steel-to-steel without the caffeine initiation is as follows: Gap-Filling Adhesive Without Caffeine Gap Lap Shear Set Substrates Thickness Strength (PSI) Time (Min.) Steel-to-Steel 2 Mil 2693 60 5 Mil 2516 >90 15 M11 1548 >120 "’Methy| Zcyanoacrylate thickened with 10 weight percent poly(methyl methacrylate), IV. 1.72. ‘Substrates broke during testing. "Determined after 24 hours. ASTM D-1002-64. "‘Time for adhesive to fully polymerize within the gap. The invention has been described in detail with par- ticular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention. We claim: 1. Adhesive composition comprising A. at least one monomeric ester of 2-cyanoacrylic acid, and B. at least one polymerization initiator selected from caffeine and theobromine. 2. The composition of claim 1 wherein the mono- meric ester of 2-cyanoacrylic acid has been modified with from about 0.1 to about 25 parts by weight of a thickening agent. 3. The composition of claim 2 wherein the 2-cyanoa- crylate has the formula CH2=?-COZR CN wherein R is selected from alkyl of l to 16 carbon atoms, alkenyl of 2 to 6 carbon atoms, phenyl and cyclo- hexyl. 4. The composition of claim 3 wherein the mono- meric ester of 2-cyanoacrylic acid is selected from the methyl 2-cyanoacrylate, ethyl 2-cyanoacrylate, butyl 2-cyanoacrylate, isobutyl 2-cyanoacrylate, allyl 2- cyanoacrylate, and the initiator is caffeine. 5. The composition of claim 4 wherein the mono- meric 2-cyanoacrylate is allyl 2-cyanoacrylate. , 6. The composition of claim 5 wherein the thickening agent is poly(methyl methacrylate). 7. A process for bonding surfaces with a monomeric ester of 2-cyanoacrylic acid adhesive comprising 35 45 50 55 65 A. uniformly distributing in said adhesive or on at least one of surfaces surface to be bonded an amount sufficient to initiate polymerization of the adhesive of a compound selected from caffeine and theobromine, B. applying said adhesive to at least one of said sur- faces, and C. placing said surfaces in contact until said adhesive cures. . 8. The process of claim 7 wherein the adhesive is modified with from about 0.1 to about 25 parts by weight of a thickening agent. 9. The process of claim 8 wherein the monomeric ester of 2-cyanoacrylic acid corresponds to the formula CH,=('2—C01R CN wherein R is selected from the group consisting of alkyl of 1 to 16 carbon atoms, alkenyl of 2 to 6 carbon atoms, phenyl and cyclohexyl. 10. The process of claim 9 wherein the monomeric ester of 2-cyanoacrylic acid is selected from the methyl 2-cyanoacrylate, ethyl 2-cyanoacrylate, butyl 2-cyanoa- crylate, isobutyl 2-cyanoacrylate and allyl 2-cyanoacry- late, and the initiator is caffeine. 11. The process of claim 10 wherein the monomeric ester of 2-cyanoacrylic acid is allyl 2-cyanoacrylate. 12. The process of claim 11 wherein the thickening agent is poly(methyl methacrylate). 13. A method of bonding the surfaces of articles to- gether by the use of a monomeric ester of 2-cyanoacry- lic acid adhesive composition, comprising moistening at least one of the surfaces to be bonded with a solution 4,042,442 7 consisting of from 0.1 to 10 parts weight of a com- pound selected from caffeine and theobromine and from_ 90 to about 99.9 parts by weight of a solvent having a » boiling point of 100' C. or below‘ selected from the group consisting of water, saturated lmonohydroxy ali- , .. phatic alcohols containing from 1 to 4 carbon atoms, an ester of said alcohol with a saturated rnonobasic fatty acid containing from 1 to 3 carbon atoms, acetone, methyl ethyl ketone, methylene chloride, chloroform, diethyl ether, dimethyl ether, methyl chloroform, and mixtures thereof, and thereafter applying to the surface of at least one of the surfaces to be bonded a film of an adhesive composition comprising a monomeric ester of 2-cyanoacrylic acid and maintaining said surfaces in contact. - ' 14. The process of claim 13 wherein the adhesive contains from 0.1 to about 25 parts by weight of a thick- ening agent. 10 8 15, The method of claim 14 in which the monomeric ester of 2-cyanoacrylic acid has the general formula cH,=