Cross-Linked Cyanoacrylate Adhesive Composition

United States Patent [191 Overhults 154] CROSS-LINKED CYANOACRYLATE ADHESIVE COMPOSITIONS [75] Inventor: Wendell C. Overhults, East Brunswick, N.J. [73] Assignee: Johnson & Johnson, East Brunswick, N.J. [22] Filed: May 25, 1972 [21] Appl. No.: 257,036 [52] U.S. Cl. ..... .. 260/42.16; 260/42.29; 260/42.52; 260/85.5 A; 260/85.5 ES; 260/86.1 N [51] Int. Cl.” C08F 236/12; C08K 3/20; COSK 3/36; COSL 35/04 [58] Field of Search .... .. 260/41 A, 41 B, 87.7, 92.1, 260/998.11, 85.5 A, 85.5 ES, 86.1 N, 42.16, 42.29, 42.52 [56] References Cited UNITED STATES PATENTS 2,558,139 7/1951 Knock .............................. .. 260/45.5 2,833,753 4/1958 Lal ............................ .. 260/89.5 3,442,851 5/1969 McManimie . . . . . . . . . . . . . .3260/41 A 3,527,729 1/1971 Bingham et al.... .......... .. 260/37 3,539,533 11/1970 Lee .................................. .. 260/47 3,663,501 4/1972 Adams . . . . . . . . . . . . . . . . . . . . . .. 260/41 R FOREIGN PATENTS OR APPLICATIONS 1,122,439 7/1968 United Kingdom [11] 3,940,362 [45] Feb. 24, 1976 Primary Examiner—Allan Lieberman [57] ABSTRACT New polymerizable adhesive compositions comprising a monomeric ester of wcyanoacrylic acid and a di- functional monomeric cross—linking agent which is a diester of acrylic or methacrylic acid and an alcohol having at least two esterifiable hydroxyl group, are found to develop increased cohesive bond strength upon polymerization. The compositions, if desired, can contain a finely divided aggregate, preferred ag- gregates being alumina and quartz. In addition, the compositions can advantageously contain sodium fluoride. The monomeric compounds of these adhesive compositions are polymerized in a cross-linked mode by means of an amine activated free radical initiator. The compositions can be applied to either wet or dry surfaces of a variety of materials. They are suitable for application to animal tissue, e.g., bone and flesh, and are particularly suitable for the treatment of teeth, such as for use as temporary fillings, the preparation of dental restorations and especially for filling and sealing pits and fissures in prophylactic dentistry. 19 Claims, No Drawings 3,940,362 . 1 I CROSS-LINKED CYANOACRYLATE ADHESIVE * ' COMPOSITIONS FIELD OF THE INVENTION This invention relates to new and novel polymeriz- Vable adhesive compositions. In particular, this inven- tion relates to compositions comprising a monomeric ester of a-cyanoacrylic acid and a difunctional mono- meric cross-linking agent which is aldiester of acrylic or ' methacrylic acid and a polyfunctional alcohol having at least two esterifiable hydroxyl groups. These composi- ’ tions have been found to be particularly useful in the treatment of teeth. * r ‘ The compositions of this invention also include those which in addition comprise, either alone or in combina- ' tion, a finely divided aggregate or filler, such as alu- mina or quartz; and sodium fluoride as an adhesive bond enhancing material. H l While the compositions of this invention are in par- ticular described in connection with those embodi- ments that are primarily designed for use in the treat- ment ‘of teeth, it should be understood that the compo- sitions of this invention are not limited to such applica- tion. These compositions can be utilized for filling or bonding various other materials including, for example, animal tissue such as bone, flesh, skin and the like and also such porous and nonporous materials as ceramics, glass, metal, wood and plastics together with joining or _ filling other materials where the unique properties of the present composition can be advantageously em- ployed as will be apparent to those skilled in the art I upon reading thisdisclosure. DESCRIPTION OF THE PRIOR ART Monomeric ester of ‘ a—cyanoacrylic acid - are well known for use as adhesives. Upon polymerization, such ' compositions have been "utilized to join a variety of materials, and such compositions and uses therefor are described in U.S. Pat. No. 2,794,788. In addition, U.S. Pat. No. 3,663,501, describes the use of compositions comprising esters of oz—cyanoacrylic acid for use in the treatment of teeth. Many individuals have imperfections in the enamel layer of their teeth, which imperfections are a potential A site for the development of caries, especially if dental hygiene is less than complete. Such imperfections are most often found on the occlusive surfaces of the teeth. ' These imperfections are known as pits and fissures, and heretofore known compositions incorporating esters of 50. a—cyanoacrylic acid have‘ been utilized in dentistry to seal such pits and fissures. The pit and fissure sealant composition is applied in the fluid state to the occlusive surfaces of cleaned teeth. Upon curing in situ there is provided a protective layer which ‘seals the imperfec- tions and discontinuities in the enamel layer, which otherwise could permit bacteria to attack enamel and , initiate decay. Unless dental care is made available, such decay will ultimiately destroy the tooth structure. Unfortunately, these linearly polymerized alkyl 2- cyanoacrylates, while having‘ excellent adhesion to 'tooth surfaces do not develop an exceptionally high cohesive strength. Such“ cohesive strength is desirable to enable the cured sealant to withstand, over an ex- ‘ tended period, the grinding action and pressures expe- rienced during mastication. ” ’ ' Furthermore, composi , ons ‘heretofore utilized as dental restoratives, i.e., materials used to ‘fill prepared