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(12) United States Patent (10) Patent No.: US 6,204,309 B1 Misiak Et Al

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(12) United States Patent (10) Patent No.: US 6,204,309 B1 Misiak Et Al USOO6204309B1 (12) United States Patent (10) Patent No.: US 6,204,309 B1 Misiak et al. (45) Date of Patent: Mar. 20, 2001 (54) FLUORESCENT CYANOACRYLATE 3,654,340 4/1972 Banitt ................................ 260/465.4 ADHESIVE 4,556,700 12/1985 Harris et al. ......................... 526/209 4,751,020 6/1988 Marten et al. .................. 252/301.21 (75) Inventors: Hanns R. Misiak, Wenningen; Heinz C. Nicolaisen, Ronnenberg; Annette FOREIGN PATENT DOCUMENTS Schroeter, Nordstemmen; Dagmar Behn, Hannover, all of (DE) O 105 062 4/1984 (EP). O 213 893 3/1987 (EP). (73) Assignee: Henkel Kommanditgesellschaft auf O 222333 5/1987 (EP). Aktien, Duesseldorf (DE) 2 228943 9/1990 (GB). 59-122567 7/1984 (JP). (*) Notice: Subject to any disclaimer, the term of this WO95/33708 12/1995 (WO). patent is extended or adjusted under 35 U.S.C. 154(b) by 0 days. OTHER PUBLICATIONS (21) Appl. No.: 09/297,190 Patent Abstracts of Japan, vol. 008, No. 241 (1984). (22) PCT Filed: Oct. 17, 1997 Database WPI, Derwent Publications, Class A81, (86) PCT No.: PCT/EP97/05753 AN84-201532. S371 Date: Apr. 23, 1999 Ullmann's Encyclopedia of Industrial Chemistry, vol. A1, S 102(e) Date: Apr. 23, 1999 (1985) p. 240. (87) PCT Pub. No.: WO98/18876 * cited by examiner PCT Pub. Date: May 7, 1998 (30) Foreign Application Priority Data Primary Examiner Kriellion Sanders (74) Attorney, Agent, or Firm Wayne C. Jaeschke; Oct. 25, 1996 (DE) .............................................. 196 44 332 Stephen D. Harper (51) Int. Cl." .............................. C08J 3/28; B32B 27/36; (57) ABSTRACT B32B 27/30 (52) U.S. Cl. .................... 523/300; 252/182.15; 428/412; Cyanoacrylate adhesive containing a pyrylium Salt as a 428/500; 428/522; 522/79 fluorescent dye are useful for bonding various Substrates, (58) Field of Search ....................... 252/182.15; 428/412, particularly transparent plastics. The pyrylium Salt may be 428/500, 522; 522/79; 523/300 present in relatively large quantities in the adhesive without any adverse effect on the Storage Stability and adhesive (56) References Cited properties, yet shows very little inherent coloration in Visible light. U.S. PATENT DOCUMENTS 3,254,111 5/1966 Hawkins et al. .................. 260/465.4 25 Claims, No Drawings US 6,204,309 B1 1 2 FLUORESCENT CYANOACRYLATE DETAILED DESCRIPTION OF THE ADHESIVE INVENTION BACKGROUND OF THE INVENTION The dyes are present in the adhesive in concentrations of 5 5 to 50,000 ppm and, more particularly, 20 to 10,000 ppm. 1. Field of the Invention The adhesive is preferably free from solvents or solubi This invention relates to a cyanoacrylate adhesive con lizers for the dyes and the monomers. Solvents are prefer taining a pyrylium Salt as a fluorescent dye and to its use. ably used where a concentration of more than 0.3% by 2. Discussion of Related Art weight of dye is to be dissolved. Adhesives of this type are already known. Thus, EPO 105 The following example illustrates the high solubility of 062 B1 describes a cyanoacrylate adhesive containing at the dyes used in accordance with the invention: least one dye from the group consisting of C.I. Solvent 2,4,6-triphenyl pyrylium tetrafluoroborate Green 5, C.I. Acid Red 50 and C.I. Acid Red 52 in a quantity of 5 to 1000 ppm, based on the monomers. The disadvantage 15 of these dyes lies in their bright, clearly visible color, particularly where the parts to be joined are transparent. In addition, the dyes are poorly Soluble in the monomers. Accordingly, it is not possible to prepare a master batch of cyanoacrylates and the dye, i.e. a Stock mixture of BF cyanoacrylates with a high concentration of dye which the user himself is then able to dilute to the extent required by the particular situation. Against the background of this prior art, the problem 25 addressed by the present invention was to provide a cyanoacrylate adhesive containing a fluorescent dye, the dye can be introduced into ethylcyanoacrylate at room tempera showing very little, if any, inherent coloration in Visible light ture in a quantity of up to about 2.5%. By contrast, other and lending itself to use in relatively large quantities without dyes, such as for example Acid Red 50 and Acid Red 52, any adverse effect on the Storage Stability and adhesive only dissolve in concentrations of up to a few hundred ppm properties of the adhesive. at room temperature. This high concentration enables the master batch process SUMMARY OF THE INVENTION to be applied. If, for example, the Stock Solution has a The solution provided by the invention is defined in the 35 concentration of 2.5% by weight, the user can easily dilute claims and consists in a highly specific choice of the it to the required concentration without encountering dosage pyrylium Salt. The cyanoacrylate adhesives according to the or homogeneity problems. The Stock Solution preferably has invention are characterized by an effective concentration of a concentration of 0.1 to 5% by weight of pyrylium salt (the at least one pyrylium Salt corresponding to the following upper limit being determined by the solubility factor). general formula: 40 Another unexpected advantage of the dyes used in accor dance with the invention is their fastness to light. In the (I) liquid State, a cyanoacrylate adhesive colored with the R3 pyrylium Salts mentioned above shows no reduction in R2 R4 45 fluorescence intensity, even after Several minutes exposure 21 to UV light (254 and 365 nm). A In addition, the relatively low inherent coloration of the N+ R O R5 dyes used in accordance with the invention in Visible light enables them to be universally used because bonds estab 50 lished with the correspondingly colored adhesives do not in which R to Rs represent hydrogen, alkyl and aryl groups or a fused aromatic radical at two vicinal positions. The show any visible inherent coloration in the adhesive joint, Substituents may in turn bear alkyl, aryl, alkoxy, aryloxy even where the joined parts are transparent. They fluoresce groups, halogen or pseudohalogen atoms. The total number on exposure to Short-wave light. The fluorescence Signal of carbon atoms in the Substituents should be from 1 to 18 55 reflected by the adhesive present on the Substrate enables the and, more particularly, from 6 to 10. The substituents may be application of the adhesive to be controlled with the assis the same or different. The counterion A may be selected tance of a luminescence probe. from non-nucleophilic anions Such as, for example, In the context of the invention, “C-cyanoacrylates are he Xafluorophosphate, he X a fluoro antimo nate, understood to be both typical monocyanoacrylates and also tetrafluoroborate, perchlorate and tetrachloroferrate. Dyes 60 biscyanoacrylates. used in accordance with the invention include 2,4,6- “Typical monocyanoacrylates' encompass compounds triphenyl pyrylium tetrafluoroborate, 2,4,6-triphenyl pyry corresponding to the following general formula: lium trifluoromethane sulfonate, 2,4-ditert-butyl-6-(2- methoxyphenyl)-pyrylium tetrafluoroborate, 1,4-phenylene HC=C(CN)-CO-O-R (II) 4.4"-bis-(2,6-diphenyl-4-pyrylium tetrafluoroborate), 2,4- 65 diphenyl-6-(4-methoxyphenyl)pyrylium perchlorate; 2,4- in which R is an alkyl, alkenyl, cycloalkyl, aryl, alkoxyalkyl, diphenyl-6-(p-tolyl)-pyrylium tetrachloroferrate. aralkyl or haloalkyl group containing 1 to 24 carbon atoms US 6,204,309 B1 3 4 and, more particularly, 1 to 12 carbon atoms, more espe Besides these two key components, the cyanoacrylate cially a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, adhesive also contains typical Stabilizers, for example pentyl, hexyl, allyl, methallyl, crotyl, propargyl, cyclohexyl, hydroquinone, Sulfur dioxide, boron trifluoride and methane benzyl, phenyl, creSyl, 2-chloroethyl, 3-chloropropyl, Sulfonic acid, in the usual quantities. 2-chlorobutyl, trifluoroethyl, 2-methoxyethyl, In addition, the adhesive according to the invention may 3-methoxybutyl, 2-methoxyisopropyl and 2-ethoxyethyl contain other additives, for example plasticizers, activators group. The cyanoacrylates mentioned above are known to or accelerators, thickeners and/or elasticizers, coupling the expert on adhesives, cf. Ullmann's Encyclopaedia of agents and other dyes. Industrial Chemistry, Vol. A1, page 240, Verlag Chemie The adhesives according to the invention are prepared in Weinheim (1985) and U.S. Pat. No. 3,254,111 and U.S. Pat. the usual way by mixing the components. No. 3,654,340. Preferred monomers are the allyl, The adhesives according to the invention may be used for methoxyethyl, ethoxyethyl, methyl, ethyl, propyl, isopropyl bonding typical Substrates, more particularly Substrates of or butyl esters of 2-cyanoacrylic acid. the same material or of different materials, for example “Bis(cyanoacrylates)” are understood to be compounds metal, elastomers and plastics, and above all for bonding corresponding to the following general formula: 15 transparent Substrates of polystyrene, polymethyl methacry late and polycarbonate. HC=C(CN)-CO-OR (III) The invention is illustrated by the following Examples. in which R is a branched or unbranched difunctional alkane EXAMPLES radical containing 2 to 18 and, more particularly, 6 to 12 1. Reactivity and Stability in Storage carbon atoms which may additionally contain hetero atoms, The substances 2,4,6-triphenyl pyrylium tetrafluoroborate Such as halogens and oxygen, or aliphatic or aromatic rings. and 2,4,6-triphenyl pyrylium trifluoromethane Sulfonate However, R is preferably a pure hydrocarbon. were added in concentrations of 50 ppm to 1,000 ppm (see It is important that the bis(cyanoacrylates) should be Table 1) to ethyl C-cyanoacrylate stabilized with 500 ppm of particularly pure. This requirement is Satisfied, for example, 25 hydroquinone and 10 ppm of SO. The additions readily by the following methods of production and purification. dissolved in the ethyl cyanoacrylate by brief Shaking.
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