Process of Applying a Cyanoadhesive Composition

111111111111111111111111111111111111111111111111111111111111111111111111111 US006660327B2 (54) United States Patent (10) Cordova (12) (45) 4,016,327 4,364,876 5,623,010 5,994,464 PROCESS OF APPLYING A CYANOADHESIVE COMPOSITION (75) Inventor: (73) Notice: A A A A * 4/1977 Fumei et al. 12/1982 Kimura et al. 4/1997 Groves 11/1999 Ohsawa et al. 428/314 260/465.4 524/174 525/85 Assignee: MatteI, Inc., EI Segundo, CA (US) ( *) Patent No.: US 6,660,327 B2 Date of Patent: Dec. 9,2003 Abimael Cordova, Whittier, CA (US) * cited by examiner Subject to any disclaimer, the term of this patent is extended or adjusted under 35 U.S.c. 154(b) by 42 days. (21) Appl. No.: 10/034,416 (22) Filed: Primary Examiner-Bernard Pianalto (74) Attorney, Agent, or Firm-Robert W. Mulcahy (57) ABSTRACT Dec. 28, 2001 Prior Publication Data (65) us 2003/0125443 A1 Jul. (51) (52) Int. CI? U.S. CI. (58) Field of Search (56) 3, 2003 B05D 5/10 427/207.1; 427/385.5; 427/393.5; 446/268 427/207.1, 385.5, 427/393.5; 446/268 References Cited The present invention provides a cyanoacrylate adhesive composition having high shear bond strength, peeling bond strength, tensile strength and impact bond strength and superior wear characteristics particularly in toy applications where hostile play environments demand hot-cold cycle resistance. The cyanoacrylate adhesive composition contains (a) up to 20% by weight of a cyanoacrylate monomer, (b) a styrene-based elastomeric block copolymer, and (c) a specifc solvent which is selected to effect the solution of both components. The invention is also directed to a method of applying the instant adhesives to substrate surfaces. U.S. PATENT DOCUMENTS 3,264,249 A * 8/1966 Araki et al. 260/32.4 12 Claims, No Drawings US 6,660,327 B2 1 2 generally remedied by modifying the cyanoacrylate adhesive compositions with various elastomers, core-shell polymers, adhesives and reinforcing agents. The present invention carries this modification concept one step further BACKGROUND OF THE INVENTION 5 in employing styrene block co-polymers in adhesive applications for toy manufacturing. 1. Field of the Invention As indicated above, the class of the styrenic elastomeric The present invention relates to a novel adhesive compomaterials commonly used as the molding material for toy sition and process for applying a styrenic based adhesive and doll faces and the harder structural portions of toy articles cement coatings to thermoplastic polymer surfaces, particularly to toy articles formed of resin materials. Specifically, 10 are A-B-A type block polymers such as styrene-butadienebutylene copolymer-styrene or styrene-butadiene-styrene, the present invention relates to a cyanoacrylate adhesive manufactured by Shell and sold under the trademark Kraton. composition having superior bonding and hot-cold cycle In the case of a toy having a hard surface comprised of a resistance characteristics, particularly suited for unfriendly rigid or semirigid A- B-A styrene based block copolymer, a toy play environments. 15 compatible elastomeric A-B-A styrene copolymer in the 2. Description of the Related Art form of styrene-ethylene-butylene-styrene, (SEBS, sold Children's toys and dolls, in particular, have a history under the trademark Kraton-G) has been found to be an dating back into antiquity. Generally, the technology surexceptional modifier of the alpha-cyanoacrylate adhesives to rounding the manufacture of dolls centers on creation of an render them useful as glues, cements, or sealants to bond attractive doll face, miniturized application of conventional 20 mechanical parts in in toy items. clothes, manufacture of a doll body using plush or other For adhesives used to bond toy mechanical parts and like sculptural techniques, and the simulation of the hair with structures which are used in rugged or otherwise unfriendly sculptural elements, fibers, or other techniques. In the case environments it is considered necessary to have not only a of doll faces, the doll maker has a wide panoply of possible high bond strength in the normal state of use but also a high constructions and manufacturing techniques at his disposal. Traditional techniques involve the use of plaster-like or hard 25 adhesive force to endure the heavy handling of child's play. Moreover, the bonded mechanical parts must even be plastics material to cast a doll face. In time, however, soft capable of withstanding extreme or sudden changes in rubber materials such as styrene-butadiene rubber (SBR) temperature caused by leaving the toy item outdoors or and styrene-butadiene-styrene block copolymer (Kraton) immersing the toy item in hot and cold water, e.g. a child elastomers have come to replace plaster and hard plastics in the production of doll heads because of their realistic look 30 subjecting a doll to a sink bath. Conventional cyanoacrylate adhesive compositions are not generally satisfactory in and feel. meeting these demands as adhesives in toy items. The soft rubber doll faces include all the normal features It has been found that a cyanoacrylate adhesive compoof a human figure simulated by the doll including the entire 35 sition containing certain styrenic block copolymers and head, including well formed lips, teeth, cheeks, nose, chin, certain solvents results in an adhesive which not only ears, and forehead. After the injection molding of an elaspossesses high shear adhesive force, peeling bond strength tome ric doll face, it is finished by applying a dye or other and impact adhesive force but also exhibits an outstanding similar material to give the face a natural skin color. Therehot-cold cycle resistance and heat resistance. after the soft rubbery doll's head must be joined to a body portion comprised of a torso and limbs to complete a full 40 SUMMARY OF THE INVENTION bodied toy doll item. This is generally accomplished by In accordance with the present invention, there is progluing, sealing or cementing the soft eleastomeric head vided an improved cyanoacrylate adhesive composition parpotion to the headless body section generally composed of a hard or firm plastic. In selecting an adhesive for the ticularly useful for toy article applications comprising (1) a purpose of affixing the dolls'head two considerations are 45 styrenic elastomeric block copolymer, (2) a cyanoacrylate monomer, and (3) a solvent composition comprised of important: (1) that the adhesive form a firm and effective bond and seal between the soft elastomer and the harder certain high evaporation rate organic solvents. More resin substrate surface and (2) that the adhesive composition particularly, the cyanoacrylate adhesive composition is charbe relatively quick drying so as to accommodate expeditious acterized by containing (a) up to 20% by weight of an alpha doll manufacturing processes. The principle outlined here 50 cyanoacrylate monomer, (b) a styrenic elastomeric block copolymer miscible or compatible with the cyanoacrylate can be applied to any toy parts requiring laminating or monomer, and (c) an organic co-solvent mixture having bonding affixation of parts. The present invention provides solubility parameters compatible with the solubility parama cyanoacrylate adhesive which provides superior bonding eter of the elastomeric phase of the block copolymer. and rapid curing or drying. Specifically provided herein as a preferred embodiment is It is well known that alpha.-cyanoacrylate (also known as 55 a cyanoacrylate adhesive comprises from about 2% up to 2-cyanoacrylate) adhesives polymerize and cure rapidly in 10% by weight of an alpha alkyl cyanoacrylate, a high the presence of trace water absorbed on the surface of a molecular weight styrene-ethylene-butylene-styrene block material to be bonded, affording an extremely strong bond in copolymer, and an organic solvent having a solubility coma short time for almost all materials except some inert materials such as polyethylene and Teflon. Because of such 60 patibility with both components. The solvents are certain organic liguids which (1) have relatively high evaporation a superior property, alpha-cyanoacrylate adhesives are rates, (2) are capable of solubilizing the cyanoacrylate, and widely used as instantaneous adhesives for a room tempera(3) offer stability to the styrenic copolymer partner in the ture setting as one-part type adhesives for the bonding of coating composition and in the elastomeric substrates to metals, plastics, rubber, wood, etc. However, since the cyanoacrylate polymer is a brittle polymer, cyanoacrylate 65 which they are applied in that the co-solvent is non-reactive with and non-destructive to the respective component mateadhesives have the drawback that they are inferior in peeling rials. bond strength and impact resistance. This problem has been PROCESS OF APPLYING A CYANOADHESIVE COMPOSITION US 6,660,327 B2 3 4 effective in solubilizing the copolymer and cyanoacrylate High evaporation rate organic solvents and co-solvents within the purview of the present invention include isoprene, and the styrene-based copolymer molecules of the substrate hexane, heptane, styrene liquid, xylene, toluene, surface thereby takifying the elastomeric surface to generate methylcyclohexane, cyclohexane, 2,2-dichloropropane, a miscible interface with the applied film of adhesive, methylene chloride, diisobutyl ketone, diisopropylketone, 5 resulting in a very strong amalgam like bonding of the methyl isobutyl ketone, methyl isopropyl ketone, methyl adhesive film to the substrate upon drying. When the adhecyclohexanone, cyclohexanone, isobutyl acetate, isopropyl sive is used to laminate two substrate surfaces an amagam of acetate, butyl acetate, propyl acetate, ethyl acetate, diethyl the two surfaces occurs resulting in a strong high peel ether, dimethyl ether, diethylene glycol, 2-ethylhexanol, and strength bonding between the two surfaces. The adhesive mixtures thereof. Anyone or more of these solvents that is 10 composiitons herein have particular advantage and applicacapable of solubilizing both the styrene phase and the tion to children's toys because of the pervasive use of elastomeric rubber portions of the styrenic block copolymer styrenic block soft and hard elastomeric material substrates of the present cyanoacrylate adhesive composition will in toy manufacturing and are particularly useful in applicafunction effectively in the instant invention. In the case of tions to the soft elastomeric materials used in doll facial the high molecular weight styrenic block SEBS, the solu- 15 structures where the adhesion of these rubber facial strucbility parameter (to be explained below) is about 7.9 from tures to a hard resin torso and limb structure is expected to which it can be calculated that a solvent combination or withstand the rigorous and hostile environment of child use. blend having a solubility parameter of between 7.4 to 9.4 In a further embodiment, the present invention is even will be effective within the purview of the instant invention. more particularly directed to a cyanoacrylate adhesive coatThe high evaporation rates of the instant solvents causes 20 ing composition for elastomeric substrates comprising from enhancement of evaporation of any water adsorbed on the about (1) 1.0% to 20% by weight of an alkyl cyanoacrylate, surface of the resin substrate surface to which the present (2) styrenic elatomeric copolymer resin selected from the adhesive to be applied with the result that the water is group comprising styrene butadiene rubber (SBR), styrenecompletely driven off in an adhesive coating drying step. butadiene-styrene (S-B-S), and styrene-ethylene-butylene The present invention utilizes styrene block copolymers 25 styrene (SEBS) elastomeric block copolymers, and (3) an sold generally under the trademark Kraton by the Shell organic solvent having a specific Solubility Parameter of Chemical Company. Kraton polymers can be dissolved in from about 7.4 to about 9.4. An even more preferred many single solvents, such as toluene, and in many solvent adhesive composition comprises (1) from about 2.0% to blends, such as hexane/MEK. In contrast to the usual 10% of an alkyl cyanoacrylate selected from group complastics and rubbers which have only a single phase, a 30 prising methyl, ethyl, or propyl cyanoacrylate, (2) a styreneKraton polymer has two phases. In order to form a true ethylene-butylene styrene (SEBS) elastomeric block copolysolution, the solvent system must be capable of dissolving mer and (3) an organic solvent selected from the group both of these phases. If blends of solvents are used, and even consisting of toluene, xylene, heptane, t-butyl acetate and wider variety of solvent systems may be considered. A mixtures thereof. As already indicated, this coating compopolymer will generally dissolve in those solvents with 35 sition has been found especially effective in application to Solubility Parameters close to that of the polymer itself. styrenic surface subtrates and, particularly, the group comSince Kraton polymers have two different polymers in each prising styrene butadiene rubber (SBR), styrene butadiene molecule, a good solvent must have a Solubility Parameter styrene, and styrene-ethylene-butylene-styrene elastomeric for both. copolymer surfaces. The Solubility Parameter is the Hilderbrand solubility 40 DETAILED DESCRIPTION OF THE parameter which is a measure of the total forces holding the INVENTION molecules of a solid or liquid together. This measurement and its application to Kraton type copolymers (styrenic The cyanoacrylate monomer as the first ingredient of the elastomeric block copolymers) is explained in the publicacyanoacrylate adhesive composition according to the tion "Solution Processing of Kraton Polymer Coatings" 45 present invention is a compound known well as an alphapublished by the Shell Chemical Company (Dec. 30, 1998) cyanoacrylate and represented by the following general and hereby incorporated by reference in its entirety. formula: The styrenic copolymer/co-solvent adhesive composiCN tions made in accordance with the present invention dry in / a rapid manner to enable a strong bond of the copolymer 50 CH2=C with polymeric substrate surfaces thereby engendering firm \ COOR bonding of an applied surface with a substrate surface; that is, a sandwiched film of adhesive between an applied blanket cover to a substrate will afford an extremely strong bond where R is an ester residue such as alkyl, cycloalkyl, between the two surfaces. 55 alkenyl, cycloalkenyl, alkynyl, phenyl, or aryl. The number The discovery of the present invention is that one may of carbon atom of the ester residue is not specially limited, but there usually is employed a hydrocarbon group having 1 formulate a superior adhesive, cement, or glue composition to 8 carbon atoms. A substituted hydrocarbon group such as by combining a cyanoacrylate, a styrenic elastomeric alkoxyalkyl or trialkylsilylalkyl is also employable as the copolymer and a solvent in certain amounts to form an adhesive composition of exceptional character when applied 60 ester residue. to elastomeric substrate surfaces. While the adhesive comAs examples of the cyanoacrylate monomer are mentioned alkyl and cycloalkyl alpha-cyanoacrylates such as position can be applied to any thermoplastic resin surface, the instant compositions are especially effective as an adhemethyl alpha-cyanoacrylate, ethyl alpha-cyanoacrylate, propyl alpha-cyanoacrylate, butyl alpha-cyanoacrylate, and sive for substrates comprised of styrene based elastomers, those copolymers with a linear A-B-A configuration in 65 cyclohexyl alpha-cyanoacrylate, alkenyl and cycloalkenyl alpha-cyanoacrylates such as allyl alpha-cyanoacrylate, which A is a polystyrene endblock. It is believed that the methallyl alpha-cyanoacrylate, and cyclohexenyl alphasolvent selection or mixture of same herein is particularly US 6,660,327 B2 5 6 cyanoacrylate, alkynyl alpha-cyanoacrylates such as propstyrene-ethylene-butylene-styrene (SEBS sold commerargyl alpha-cyanoacrylate, aryl alpha-cyanoacrylates such as cially as Kraton G by The Shell Chemical Company). It has phenyl alpha-cyanoacrylate and toluyl alpha-cyanoacrylate, been found that Solubility Parameters of from 7.4 to 9.4 are hetero atom-containing methoxyethyl alpha-cyanoacrylate, required for solubilization of both the elastomeric mid-block ethoxyethyl alpha-cyanoacrylate, furfuryl alpha- 5 and styrenic portions of SEBS. Accordingly, solvents having cyanoacrylate, silicon atom-containing trimethylsilylmethyl this solubility characteristic for the I-cyanoacrylate and SEBS in the most preferred embodiments of the present alpha-cyanoacrylate, trimethylsilylethyl alphacyanoacrylate, trimethylsilylpropyl alpha-cyanoacrylate and adhesive composition comprise t-butyl acetate, dimethylvinylsilylmethyl alpha-cyanoacrylate. cyclohexanone, heptane, toluene, xylene and mixtures While any and all the alpha cyanoacrylates operate within 10 thereof. Optimum solvents are solvent blends of heptane/tthe purview of the present invention, the preferred butyl acetate, toluene/cyclohexanone, and xylene/t-butyl acetate. These preferred solvents have very high evaporation cyanoacrylates are alkyl alpha cyanoacrylates having alkyl rates and maximum compatibility with the high molecular groups of from 1-8 carbon atoms and most preferred alkyl weight SEBS copolymer and the I-cyanoacrylate in the alpha cyanoacrylates are selected from the group comprising methyl, ethyl, propyl, and butyl alpha cyanoacrylate (also 15 instant adhesive composition. known as methyl 2-cyanoacrylate, ethyl 2-cyanoacrylate The styrene based resinous component of the present etc.) adhesive composition includes blends prepared by the copoThe second ingredient of the 2-cyanoacrylate adhesive lymerization of one or more conjugated dienes, such as compositions according to the present invention is an elasbutadiene, isoprene, and chloroprene with styrene. Useful tomer which is miscible or compatible with the cyanoacry- 20 blends in the preparation of the instant adhesive composilate monomer. The terms "miscible" or "miscibility" and tions include styrene butadiene rubber (SBR) and styrene"compatible" or "compatibility" are commonly used in the butadiene-styrene block copolymer. Styrene-based thermopolymer alloy field. The former represents a state wherein plastic elastomers comprise blocks of hard segments, e.g., the elastomer and the cyanoacrylate monomer are mixed polystyrene, and blocks of soft segments, e.g., polyisoprene, microscopically, namely, on a molecular level, while the 25 polybutadiene, poly(ethylene-propylene), poly(ethylenelatter represents a state wherein the elastomer is dispersed butylene), and polypropylene. Thus, useful styrene-based macroscopically in the cyanoacrylate monomer in a stable elastomers may comprise, for example, blocks of polystymanner [see, for example, "Polymer Alloy-Basis and rene and blocks of polyisoprene, or blocks of polystyrene and blocks of polybutadiene, or blocks of polystyrene and Application", edited by Kobunshi Gakkai, published by Tokyo Kagaku Dojinsha, (2nd Edition, Apr. 16, 1993)]. 30 blocks of poly(ethylene-butylene). Examples of the most The present adhesive composition is the combination of preferred styrene based thermoelastic elastomers useful in three key ingredients: the I-cyanoacrylate, the elastomeric the present adhesive composition, include high molecular styrene block copolymer, and the solvent comprised of a a weight styrene-ethylene-butylene-styrene (SEBS) block high evaporation rate organic solvent or co-solvent having coplymers (e.g. KRATON G-1650, G-1651, G-1652, and specific solubility parameters tailored to the solubility of the 35 G-1657). Other styrenic copolymers operable within the elastomeric copolymer, which combination of characterispurview of the instant invention include styrene-ethylenetics provides for the desirable properties of the instant propylene-styrene block copolymers (e.g. KRATON invention recited above. The advantages of the instant G-1701, G-1702 and G-1762X), all commercially available composition are generated by the use of particular organic from Shell Chemical Company as well as combinations of polymer solvents in combination to enhance the application 40 these block copolymers with SEBS can also be included. of alphacyanoacrylate/polymer/organic solvent based coatOther styrenic block copolymers include styrene-isopreneing compositions. In particular, the organic solvent or styrene (S-I-S), natural butyl rubber (NBR), and styreneco-solvent used in the present adhesive composition must ethylene-styrene (S-E-S). Styrene-ethylene-butylenepossess (1) a high evaporation rate, (2) polymer solubilizastyrene (SEBS) copolymers are particularly effective tion charateristics, i.e. it must be capable of dissolving 45 because they have superior physical properties manifested in styrene based polymers and copolymers, and (3) styrene the cyanoacrylate adhesives of the present invention, includbased stability, i.e. the solvent must be non-reactive with ing durability in that the instant adhesives can withstand styrene based polymers so as to not chemically degrade prolonged wear and tear in the form of impact resistance and them in solution or on a substrate containing styrene based flexibility. Since the cyanoacrylate is present in a minimum polymers upon which the coating is to be applied. Solvents 50 of up to 20% by weight, the amount of thermoplastic block possessing these characteristics include isoprene, hexane, copolymer elastomer useful in the present adhesive compoheptane, styrene liquid, xylene, toluene, methylcyclohexane, sitions is not critical in achieving the desired characteristics; cyclohexane, 2,2-dichloropropane, methylene chloride, that is, the block copolymer can be present in any amounts of between 80 to 99 wt %. diisobutyl ketone, diisopropylketone, methyl isobutyl The compositional weights recited herein are based on the ketone, methyl isopropyl ketone, methyl cyclohexanone, 55 resin/Lcyanoacrylate composition and inclusion of any cyclohexanone, isobutyl acetate, isopropyl acetate, butyl additives will accordingly affect the overall compositional acetate, propyl acetate, ethyl acetate, diethyl ether, dimethyl weight but the ratio of styrenic resin to the alpha cyanoacryether, diethylene glycol, 2-ethylhexanol and mixtures late will remain the same as initially formulated; that is, a thereof. Other solvents within the purview of the present invention include terpenes such as limonene, d-limonene, 60 5% by weight cyanoacrylate in 95 wt % of a styrenic l-limonene, all taught in common assignee owned U.S. copolymer blend will remain in the same ratio to one another patent application Ser. No. 09/921,116 filed on Aug. 2, 2001, even with the addition of dye or pigment. which solvents may be used in combination with the high It is to be emphasized that the purview of the composievaporation rate solvents but not preferably because the tional invention herein is the combination of a styrene based terpenes have inherently lower evaporation rates. 65 thermoplastic polymer and a I-cyanoacrylate mixture in As indicated above, a preferred elastomeric styrenic block certain amounts for adhesion application to elastomeric copolymer in the instant invention is high molecular weight substrate surfaces. As indicated above, especially effective US 6,660,327 B2 7 8 elastomers are styrene-ethylene-butylene-styrene (SEES) copolymers which are solvated very effectively with the solvents recited, the compatibility between the polymer and the solvents being speculated as being due to the mutual unsaturation in the solvents and the ethylene-butylene segment of the styrenic polymer. The particular compatibility of the solvent and the SEES polymer in the coating composition follows on through application to a solid molded or otherwise formed SEES or other styrenic block copolymer substrate surface, which acts as an optimal substrate surface for application of the SEES/cyanoacrylate/solvent adhesive composition. Accordingly, the most preferred embodiment of this invention is an application of an SEES/alpha cyanoacrylate/solvent mixture adhesive coating to a solid molded SEES substrate surface. It is apparent that the adheive coating solution may contain the same styrenic co-polymer as that material co-polymer in the substrate to be coated. In fact the solubilizing effects of the instant specialized solvents on the styrenic copolymer in the instant adhesive coating composition encourages application of the coating to a similar or identical co-polymer substrate surface so that compatible adhesion takes place between the solubilized co-polymer in the adhesive coating solution and that similar or identical co-polymer material in the substrate to which the coating is to be applied. An application of the subject adhesive coating include the steps of (i) providing an elastomeric resin substrate; (ii) applying a composition comprising from about 1.0% to 20.0% by weight of a cyanoacrylate, from 80% to 99.0% by weight of a styrenic block copolymer resin in a solvent mixture to the elastomeric substrate; and (iii) curing the applied composition to form a layer of adhesive on the elastomeric substrate. The coatings and adhesive compositions herein are characterized by viscosities approaching that of ordinary viscous glue formulations. A dried coat of the instant formulations have elongation values and adhesion characteristics conforming to the quality and safety standards necessary for application to toy products. In addition, these adhesives have ultimate tensile values of greater than about 500 psi indi eating that toughness is not being sacrificed to flexibility in the use of these coating compositions. It is important that coatings or adhesives used for application to toy articles, such as a soft elastomeric doll facial element, have high tensile strength so that the coated or painted article have child use durability especially as to stretchability. The instant adhesive compositions have flexibility at both ambient and cold temperatures. The instant coating may contain a pigment, dye, or colorant in amounts of up to 3% by weight in addition to the thermoplastic elastomeric resin, the cyanoacrylate, and organic solvent. The pigment used herein is not particularly limited and various inorganic or organic pigments can be employed. Concrete examples of pigments and colorants are: synthetic organic colorants sold as the T-series by the Day Glow Corporation of South Gate City, Calif. Other pigments which can be used include sodium aluminum sulpho silicate sold as MR 582 by the Cleveland Pigment Corp. of Cleveland, Ohio; polyamide condensates with organic dyes with less than 2% phthalocyanine; and tetrachloro-zincate sold by the Day Glow Corporation. In addition to the additives mentioned above, compositions made in accordance with the present invention may additionally employ small amounts of agents such as ethylene glycol and clay mixtures to provide the desired texture and body for ease of application of the instant adhesive coating compositions. In certain adhesive applications, fill- ers and stabilizers such as organic and inorganic fibers, sand, talc and mixtures thereof may also be included as part of the coating composition. Compositions of the present invention can be applied by any means such as with a spatula, brush, a cloth, or a spray applicator. The surface of a polymeric substrate surface should be clean and dry before application of the instant adhesive coating. Once applied the compositions should be allowed a sufficient period to allow curing of the composition by drying of the solvent. Having generally described the present invention, the following examples are set for the below to further demonstrate compositions embodying the present invention. The compositions of the present invention are prepared by adding a specified amount of cyanoacrylate to styrenic block copolymer resins in a particular solvent mixture under agitaiton. Specified amounts of other ingredients are added where indicated. In the following Example 1, the applied composition is subjected to a Surface Coating Adhesion (Tape Pull) Test, and a Shear and Stretch Tests to determine the adhesion and stretch characteristics of the present cyanoacrylate/styrenic elastomeric block copolymer/organic solvent adhesive coating composition. These tests are carried out employing standard Quality and Safety Operating Procedures of the Assignee of the present application, MatteI, Inc. The shear strength test is a measure of the cohesiveness or internal strength of an adhesive. It is based upon the amount of force required to pull an adhesive strip from a standard flat surface in a direction parallel to the surface to which it has been affixed with a definite pressure. It is measured in terms of time (in minutes) required to pull a standard area of adhesive coated sheet material for a stainless steel test panel under stress or a constant, standard load. 5 10 15 20 25 30 35 40 45 50 55 60 65 EXAMPLE 1 4 percent by weight of I-methyl cyanoacrylate is added to 96 percent by weight of a high molecular weight styreneethylene-butylene-styrene (SEES) copolymer elastomer known as Kraton 1650 and dissolved in 200 mls of at-butyl acetate/heptane/cyclohexanone cosolvent mixture (in a 20/30/50 volume ratio) in a flask. After complete disolution of measured quantities of the styrenic elastomer and cyanoacrylate, a viscous solution is achieved significantly greater than water. A molded soft elastomeric rubbery doll face comprised of a solid molded SEES elastomeric copolymer is provided and the cyanoacrylate adhesive composition applied to the back surface of the molded doll face for intended adhesion and affixation to a doll torso body structure comprised of a hard elastomeric styrenic copolymer surface. The rubbery doll facial item was fitted to the torso by applying the adhesive coated back surface to and affixing the face to the doll body. The constructed item was allowed to dry for 3 minutes. Thereafter the rubbery doll face and body structure were subjected to 1600% Elongation Test, a Shear Test, and a Peel Test to stress the adhesive laminate. The tests revealed that the adhesive laminate did not split, peel, or abrade under the tests, the doll's head remaining firmly on the torso body. The surface bonding between the adhesive coating on the backside of the doll's face and the surface substrate of the torso was so strong and uniform so as cause complete adhesion between the styrenic coating and the elastomeric substrate surface of the doll body. EXAMPLE 2 100 grams of the same styrenic thermoplastic elastomer of Example 1 (Kraton 1650) and 10 grams of US 6,660,327 B2 9 10 2-ethylcyanoacrylate were dissolved in a 100 mls volume of a heptane/xylene/toluene solvent mixture in a wide mouth beaker. After complete disolution of the styrenic thermoplastic elastomer with difficult stirring, the viscosity of the solution was approximate that of a thick glue. Thereafter a hard thermoplastic styrenic copolymer substrate surface is provided and a dab of the viscous glue is applied to the hard surface and as separate piece of rubbery material, comprised of Kraton G material, is patched onto the dabbed viscous area. After drying for an hour the patched rubber item was found glued tenaciously to the hard thermoplastic elastomeric substrate surface without any damage to the surface. Attempts at removal of the patch results in damage to the hard elastomeric substrate surface because of the tearing action. The adhesive compositions of the present invention possess unique combinations of properties, including both a high degree of elastic durability under suddenly applied stresses, and a high degree of plasticity when the stress is applied more slowly. The miscible character of the styrenic polymer/cyanoacrylate/solvent composition when applied to a molded polystyrene endblocked polymer substrate surfaces causes an anneal like bonding with that substrate surface so as to form a physically indistinguishable layer with that surface. Accordingly the well bonded compositionallayer reacts to the physical stresses applied to the body of the substrate in exactly the same manner as the underlying substrate. Therefore the bond created by the adhesives herein will stretch, strain, and impact as its substrate underlayer and shoe no splitting or peeling. Other properties include excellent stability throughout a very wide temperature range. Having thus described the principals of the invention, together with illustrative embodiments thereof, it is to be understood that although specific terms are employed, they are used in a generic and descriptive sense and not for the purpose of limitation, the scope of the invention being set forth in the following claims. What is claimed: 1. A process for applying a coating to a surface comprising the steps of: (i) providing a thermoplastic elastomeric resin substrate; (ii) contacting the elastomeric substrate surface with an adhesive composition comprising a styrenic copolymer resin, an alpha cyanoacrylate, and a high evaporation rate solvent, the alpha cyanoacrylate being present in an amount of 2.0 to 10 weight percent based on the weight of the styrenic copolymer resin; and (iii) curing the applied composition to form an adhesive layer on the elastomeric substrate. 2. The process of claim 1 wherein the high evaporation rate solvent is selected from the group comprising isoprene, hexane, heptane, styrene liquid, xylene, toluene, methylcyclohexane, cyclohexane, 2,2-dichloropropane, methylene chloride, diisobutyl ketone, diisopropylketone, methyl isobutyl ketone, methyl isopropyl ketone, methyl cyclohexanone, cyclohexanone, isobutyl acetate, isopropyl acetate, butyl acetate, propyl acetate, ethyl acetate, diethyl ether, dimethyl ether, diethylene glycol, 2-ethylhexanol and mixtures thereof. 3. The process of claim 2 wherein the high evaporation rate solvent is selected from the group consisting essentially of t-butyl acetate, cyclohexanone, heptane, toluene, xylene and mixtures thereof. 4. The process of claim 1 wherein styrenic copolymer resin is selected from the group consisting essentially of styrene butadiene rubber (SBR), styrene butadiene styrene (SBS), styrene-isoprene-styrene (S-I-S), natural butyl rubber (NBR), styrene-ethylene-propylene-styrene (SEPS), styrene-ethylene-styrene (SES), and styrene-ethylenebutylene-styrene (SEBS) copolymer. 5. The process of claim 1 wherein the alphacyanoacrylate is I-alkyl cyanoacrylate and the alkyl group contains from 1 to 8 carbon atoms. 6. The process of claim 1 wherein the I-alkyl cyanoacrylate is selected from the group consisting essentially of methyl, ethyl, and propyl cyanoacrylate or mixtures thereof. 7. A process for applying an adhesive to a surface of a toy item comprising the steps of: (i) providing an elastomeric resin substrate comprised of a high molecular weight styrene-ethylene-butylenestyrene block copolymer in the form of a facial doll element; (ii) contacting the elastomeric substrate surface with of an adhesive composition comprising a styrenic copolymer resin, an alpha cyanoacrylate, and a high evapoation rate solvent to a surface of the facial doll element; and (iii) curing the applied composition to form an adhesive layer on the selected surface of the doll face item. 8. The process of claim 7 wherein the composition comprises comprising from about 2.0 to 10.0 weight % of the alpha cyanoacrylate based on the weight of the styrenic copolymer resin in the composition. 9. The process of claim 7 wherein the cyanoacrylate is I-alkyl cyanoacrylate and the alkyl group contains from 1 to 8 carbon atoms. 10. The process of claim 9 wherein the solvent has a solubility parameter of from 7.4 to 9.4. 11. The process of claim 10 wherein the high evaporation rate solvent is selected from the group consisting essentially of t-butyl acetate, cyclohexanone, heptane, toluene, xylene and mixtures thereof. 12. The process of claim 10 wherein the solvent is a co-solvent mixture and the styrenic copolymer resin in the coating composition is selected from the group of copolymers consisting essentially of styrene butadiene rubber (SBR), styrene butadiene styrene (SBS), styrene-isoprenestyrene (S-I-S), natural butyl rubber (NBR), styreneethylene-propylene-styrene (SEPS), styrene-ethylenestyrene (SES), and styrene-ethylene-butylene-styrene (SEBS) copolymer. 5 10 15 20 25 30 35 40 45 50 55 * * * * *