Abstract:
This invention is a method of using a heat activatable adhesive for laminating vinyl sheet to wood. The organic solvent-free adhesive combines a reactive styrene-acrylic latex emulsion, an ethylene vinyl acetate copolymer emulsion, and a wax. After application to the vinyl substrate the adhesive is heat activated at temperatures as low as 160° F. (71° C.) and the laminate resists delamination at 190° F. (88° C.).

Description:
This application is a continuation-in-part of application No. 08/442,087, filed on May 16, 1995, now abandoned, which is a continuation of No. 08/180,937, filed Jan. 12, 1994, now abandoned. 
    
    
     This invention relates to water-based adhesives for bladder pressing, vacuum pressing and laminating vinyl to wood substrates. 
     BACKGROUND OF THE INVENTION 
     A variety of adhesives have been developed for use in laminating wood substrates and in laminating wood substrates to vinyl substrates. 
     Among the wood laminating adhesives is that described in U.S. Pat. No. 3,931,088 Kuraray which combines an isocyanate polymer in solvent with aqueous polyvinyl alcohol, aqueous vinyl acetate, or aqueous butadiene polymer. This adhesive provides excellent bonding in wood-to-wood applications. However, in specialty applications where a flexible substrate such as plastic sheeting or film is bonded to wood, the degree of adhesiveness at the plastic interface exhibited by such compositions is less than desired. 
     U.S. Pat. No. 4,396,738 Ashland describes a wood-to-wood adhesive made with a vinyl polymer and a partially reacted polyisocyanate. 
     U.S. Pat. No. 4,433,095 Bayer describes a wood-to-wood adhesive made from aromatic isocyanate and an emulsifier made from isocyanate and alcohol. 
     U.S. Pat. No. 4,491,646 Ashland describes a wood-to-wood adhesive which combines an aqueous hydroxyl functional acrylic latex containing hydroxyl groups as its only isocyanate reactive functionality and a multi-isocyanate crosslinking agent. 
     U.S. Pat. No. 4,609,690 Ashland describes a wood laminating adhesive curable at room temperature which combines an aqueous hydroxyl-functional acrylic latex with emulsified multi-isocyanate crosslinking agent. 
     None of these wood-to-wood adhesives makes very strong bonds when used to adhere vinyl substrates to wood substrates. They also suffer from the drawback of having very short pot-lives. Various adhesives especially designed for adhering wood to vinyl have been developed. Because vinyl softens at temperatures around 200° F., these vinyl to wood adhesives must activate or cure below 200° F., they must however be able to withstand high temperatures because the adhered substrates are used in hot kitchens, mobile homes, and automobile interiors where temperatures may climb above 200° F. for short time periods. 
     European Patent Application 367120 Air Products describes a water-based adhesive for laminating vinyl substrates to wood which consists essentially of vinyl acetate-ethylene emulsion copolymer and water dispersible polyisocyanate, has a pot life of 6 hours and passes a heat and creep resistant test at 170° F. 
     European Patent Application 444259 Bayer describes a laminating adhesive for PVC or PVC foam and ABS made of polyurethane dispersions forming films below 70° C., copolymers of a,b-unsaturated monomers such as styrene having a softening point above 70° C., and, optionally, dispersible reactive aliphatic polyisocyanate. 
     U.S. Pat. No. 4,618,390 Ashland describes an adhesive for bonding a vinyl substrate to a rigid wood substrate. The adhesive is an aqueous emulsion of butylacrylate-methylmethacrylate-2 hydroxyethyl acrylate terpolymer, polypropylene glycol and polyisocyanate having a pot life of at least one hour. This adhesive is applied by roll coater to one substrate, the second vinyl substrate is applied immediately. The manufacturer of wood-vinyl laminates uses the bonding adhesive directly and must see that coating equipment spreads the liquid adhesive evenly and completely. 
     It would be desirable to have an adhesive which is applied, not at the facility where the vinyl is laminated to the wood substrate, but at another location where the adhesive is applied to the vinyl substrate, dried, and then at a convenient later date, is heat activated. The laminator would then simply apply the coated vinyl to the wood using heat and pressure to activate the adhesive and avoid all complications of applying liquid adhesive. The laminated vinyl-adhesive-wood product should withstand environments hotter than 200° F. 
     OBJECT OF THE INVENTION 
     It is therefore an object of this invention to develop a strong water-based adhesive which is applied to vinyl substrate, dried, then heat activated at temperatures as low as 150° F. to join vinyl to wood substrates forming a strong bond which will withstand exposure to temperatures as high as 250° F. 
     SUMMARY OF THE INVENTION 
     This invention is a method of using a heat-activatable adhesive for laminating vinyl sheet to wood substrates. This solvent-free adhesive combines a reactive styrene-acrylic latex emulsion and a vinyl acetate-ethylenecopolymer emulsion, vinyl acetate-butyl acrylate copolymer emulsion, or vinyl acetate-butyl acrylate-2 ethylhexyl acrylate terpolymer emulsion, having certain glass transition temperatures (Tg) as measured by ASTME 1356. Optionally, one or more of itaconic acid, glyoxal, zinc acetyl acetonate catalyst, and a stable nonreactive aliphatic water-based polyurethane dispersion, also having a specific Tg, may be added. After applying the adhesive on the vinyl, the adhesive is dried, the coated vinyl is rolled and shipped to the customer. The customer forms or laminates the adhesive coated vinyl on to the customer&#39;s wood substrate and the adhesive is heat activated at temperatures of 160° F. or 170° F. depending on the combination of ingredients in the adhesive. After lamination to a wood substrate the laminate resists temperatures greater than 200° F. 
     DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     Vinyl films which can be used in the present invention include cast, calendered and extruded vinyl films. Suitable vinyl films, include polyvinyl chloride, copolymers of vinyl chloride, such as vinyl chloride-vinyl acetate copolymers, polyvinyl fluoride, polyvinyl formal, polyvinylidene chloride, polyvinyl butyral, polyvinylidene fluoride, and the like. The preferred vinyl film for use in the present invention is a polyvinyl chloride film. Vinyl films of any thickness between 4 and 30 mils may be used in the present invention. It is not necessary to use a primer on vinyl substrates when the &#34;primerless&#34; adhesive of this invention is used. Among other useful flexible substrates are paper and cloth. Suitable substrates for lamination with the adhesive of this invention may be fibrous, non-fibrous, porous and non-porous, metallic and non-metallic, polymeric, leather, cork, wood and glass. The preferred rigid substrate in the practice of this invention is particle board. 
     The first ingredient of the adhesive of this invention is a reactive styrene-acrylic latex emulsion. This emulsion can be made from acrylic acid, methyl methacrylate, styrene, hydroxy ethyl acrylate, butyl acrylate polymer, water and ethyl acrylate. The pH may be 6.5 to 8. Useful reactive styrene-acrylic latex emulsions include: 
     Rohm &amp; Haas 76 RES 1026 styrene-butyl acrylate emulsion -32° C. Tg±6° C. 
     Rohm &amp; Haas Rhoplex P-376 styrene-butyl acrylate emulsion +21° C. Tg±6° C. 
     Rohm &amp; Haas 76 RES 1018 styrene-butyl acrylate emulsion +22° C. Tg±6° C. 
     Rohm &amp; Haas HSB6 styrene-butyl acrylate-ethyl acrylate-methyl methacrylate emulsion 12° C. Tg±10° C. and 48°±10° C. (bimodal) 
     Rohm &amp; Haas 76 RES 1019 styrene-butyl acrylate emulsion -15° C. Tg±6° C. 
     Rohm &amp; Haas 76 RES 1026 styrene-butyl acrylate emulsion -32° C. Tg±6° C. 
     Union Carbide UCAR 462 styrene-butyl acrylate-methyl methacrylate-hydroxyethyl acrylate emulsion 45°±6° C. Tg 
     Union Carbide UCAR 451 styrene-ethyl acrylate-hydroxyethylacrylate-acrylic acid emulsion 42°±5° C. Tg 
     Composition analysis as determined from the NMR spectrum is presented below: 
     
         ______________________________________  RES 1018  RES 1019    RES 1026    Mole %  Wt. %   Mole %                          Wt. % Mole %                                      Wt. %______________________________________Styrene  54      49      33    29    16    13Butyl Acrylate    46      51      67    71    84    87______________________________________  RHOPLEX P-376         HSB6    Mole %  Wt. %             Mole %                                    Wt. %______________________________________Styrene  49      44      Styrene   46.4  42.2Butyl Acrylate    51      56      Butyl Acrylate                              44.7  50.0                    Ethyl Acrylate                              4.3   3.7                    Methyl    4.6   4.1                    Methacrylate______________________________________  UCAR 451              UCAR 462    Mole %  Wt. %             Mole %                                    Wt. %______________________________________Styrene  39.6    44.1    Styrene   22.5  20.7Ethyl Acrylate    44.6    41.1    Butyl Acrylate                              41.8  47.2Hydroxyethyl     5.5     6.9    Methyl    31.9  28.2Acrylate                 MethacrylateAcrylic Acid    10.3     7.9    Hydroxyethyl                               3.8   3.9                    Acrylate______________________________________ 
    
     The most preferred reactive styrene-acrylic latex emulsion is styrene-butyl acrylate-methyl methacrylate-hydroxy ethyl acrylate having a Tg of 45°±6° C. for making laminates having the best strength at room temperature. For making laminates having the best strength when tested at temperatures as high as 200° F. (93° C.) the most preferred styrene acrylic is styrene-butyl acrylate-ethyl acrylate-methyl methacrylate emulsion having a bimodal Tg distribution of 12°±6° C. and 48°±6° C. 
     From 30 to 70 weight percent reactive styrene acrylic emulsion is used in the heat activated vinyl to wood laminating adhesive of this invention. 
     The second ingredient of the adhesive of this invention is a vinyl acetate-copolymer emulsion having a Tg between -5° C. and 10° C. This vinyl acetate-copolymer emulsion can be either a vinyl acetate-ethylene copolymer emulsion, vinyl acetate-butyl acrylate copolymer emulsion, or vinyl acetate-butyl acrylate-2 ethyl hexyl acrylate copolymer emulsion. Useful vinyl acetate-acrylic copolymer emulsions include LAM2 vinyl acetate-butyl acrylate copolymer emulsion having a Tg of 10°±10° C. available from Rohm &amp; Haas, Philadelphia, Pa.* Useful vinyl acetate-ethylene copolymer emulsions include Airflex 465 vinyl acetate-ethylene copolymer emulsion having a Tg of -5°±3° C. available from Air Products, Allentown, Pa. From 30 to 70 weight percent vinyl acetate-ethylene copolymer emulsion, vinyl acetate-butyl acrylate copolymer emulsion, or vinyl acetate-butyl acrylate-2 ethylhexyl acrylate terpolymer emulsion is used in the adhesive of this invention. 
     The third ingredient of the organic solvent free adhesive used in the method and composition of this invention is a wax selected from carnauba wax, paraffin wax, polyethylene wax or mixtures thereof. Carnauba wax is available from Drew Industrial Division of Ashland Chemical Company, Boonton, N.J. Paraffin wax is available from Daniel Products, Jersey City, N.J. as SL 145E paraffin in a 45 percent emulsion in water. A polyethylene/paraffin wax is available from Drew Industrial Division, Ashland Chemical, Boonton, N.J., as Drewax E-9040 40 percent solids emulsion. The polyethylene/paraffin wax is preferred in the invention. 
     A non-ionic dissociative thickener available from Henkel Corporation, Ambler, Pa. as DSX-1550 clear thickener may also be added to the adhesive of this invention. 
     Optional ingredients for addition to the adhesive of this invention include a stable non-reactive aliphatic water based urethane having an ionic charge such as Q-Thane QW-16 urethane available from K. J. Quinn, Seabrook, N.H., having a Tg -26° C.±11° C., a polyether based aliphatic polyurethane. From 16 to 35 weight percent aliphatic water based urethane may be used in the adhesive of this invention. 
     Glyoxal is another optional ingredient. Glyoxal is available from Aldrich Chemical, Milwaukee, Wis. Up to 6 weight percent glyoxal may be used. 
     Itaconic acid, acrylic acid and methacrylic acid are other optional ingredients and are available from Aldrich Chemical. Up to 6 weight percent acid may be used in the adhesive of this invention. 
     Zinc acetyl acetonate catalyst is a further optional ingredient, 0.01 to 0.5 weight percent may be used in the adhesive of this invention. 
     In one embodiment this invention is a method of making a heat stable laminate of a flexible substrate and a solid substrate adhered together by the dried residue of a heat activatable 55 to 65 weight percent reactive styrene-acrylic emulsion, 35 to 45 weight percent ethylene-vinyl acetate emulsion and 1 to 3 percent itaconic acid. 
     The adhesive of this invention is prepared by first admixing the urethane and other optional ingredients with the vinyl acetate copolymer emulsion. To this mixture the styrene-acrylic copolymer is added. These are mixed for 30 minutes. The adhesive can then be used immediately or stored for at least two months without detrimental effects on its bonding capability. If a higher viscosity product is desired, cellulosic and urethane based thickening agents can be added. Silica based products, defoamers, coalescing aids, and extenders can also be added at this point. 
     The adhesive of this invention is used by coating the adhesive by any of a variety of common coating methods onto a vinyl or paper substrate and drying. The coated substrate is then heat reactivated at temperatures greater than 150° F. (65° C.) and pressed onto the second substrate of choice, which may be wood, steel, glass or foam. Bladder pressing, nip rolling, and vacuum pressing are common methods for accomplishing this. Match metal presses, roller presses and platen presses may also be used. 
     All references cited herein are hereby expressly incorporated by reference. In order to further illustrate the manner in which the present invention can be implemented, the following working examples are given. All parts and percentages referred to therein are by weight unless otherwise indicated. 
     The following examples show adhesives of this invention which are activated at 170° F. (77° C.) and 150 (65° C.) or 155° F. (68° C.). 
    
    
     EXAMPLE 1 170° F. ACTIVATION 
     Reported in Table 1 are peel strengths (&#34;PLI&#34; means pounds per linear inch) at room temperature and at 180° F. (82° C.) of vinyl-wood laminates. 
     
                       TABLE 1______________________________________PRELAM 17077° C., 2 BAR, 3 MINUTES             PEEL             STRENGTH             (PLI)             PRE-ADHESIVE          RT        82° C.                               HEATED______________________________________HSB6 styrene-acrylic             2.11      4.68    1.71LAM2 vinyl acetate-butyl acrylate             2.25      1.19    3.28LAM2/HSB6.sup.1   2.35      6.01    1.88PRELAM 170, NO CATALYST.sup.2             4.05      5.87    1.7PRELAM 170, NO GLYOXAL.sup.3             5.05      6.81    2PRELAM 170, NO ITACONIC             3.33      7.87    1.5ACID.sup.4PRELAM 170.sup.5  4.81      6.63    1.28PRELAM 170, NO ITACONIC             4.34      7.15    1.32ACID OR CATALYST.sup.6PRELAM 170, NO GLYOXAL OR             3.44      5.81    1.49CATALYST.sup.7______________________________________ &#34;Preheated&#34; means heated to 71° C. for 3 minutes, cooled, then applied to wood substrate RT is room temperature 
    
     
                       TABLE 2______________________________________160° F. Activation (71° C.)2 BAR; 3 MINUTES             PEEL             STRENGTH          PRE-             (PLI)             HEATED.sup.aADHESIVE          RT        180° C.                               RT______________________________________UCAR 462 styrene-acrylic             0.61      3.28*   1.38HSB6 styrene-acrylic             0.46      4.68*   1.71LAM2 vinyl acetate-butyl acrylate             0         1.19*   3.28QW16 aliphatic water based             1.77      2.95    5.59urethaneLAM2/QW16.sub.1   1.82      4.18    4.28UCAR 462/LAM2.sup.2             1.65      2.88*   1.72UCAR 462/QW16.sup.3             1.79      5.47    1.69LAM2/HSB6.sup.2   1.67      6.01*   1.88PRELAM 160.sup.4  5.91      6.04    1.61PRELAM 160.sup.5  4.34      7.25HSB6/QW16.sup.6   1.42      9.88    2.37______________________________________ .sup.a Heated to 160° F. (71° C.) in the press at 0.531 A atmospheres, cooled, then laminated at 77° C. 
    
     Example 2 and Table 2 show that a laminating adhesive activatable at 160° F. (71° C.) can be prepared by combining vinyl acetate-butyl acrylate copolymer, styrene-acrylic with Tg 35° C.-48° C. and aliphatic water based urethane (footnote 4). An adhesive activatable at 160° F. (71° C.) can also be prepared by combining vinyl acetate-butyl acrylate copolymer, styrene acrylic with Tg of 42°±5° C., and aliphatic water based urethane. (footnote 5). Both adhesives are strong at room temperature and when tested at 180° F. for heat resistance. 
     EXAMPLE 3 
     Example 3 compares peel strength and substrate fiber tear of laminating adhesives of this invention made with RES 1026 styrene-acrylic having a Tg of -32° C., vinyl acetate-ethylene copolymer having Tg -5°±3° C. (AP 465) and vinyl acetate-butyl acrylate copolymer having a Tg 10° C.±10° C. (LAM 2) at different levels of water based urethane. The vinyl to particle board laminates were made at 160° F. (71° C.), using 2 atmospheres pressure for 3 minutes. Fiber tear was tested at room temperature. 
     
                                           TABLE 3__________________________________________________________________________      1  2  3  4  5  6* 7  8  9  10 11__________________________________________________________________________Styrene acrylic      60 60 60 60 60 60 60 60 60 60 60RES 1026Tg -32° C.vinyl acetate-butyl      40 40 40 40 40 40acrylateLAM 2 Tg 10° ± 10° C.vinyl acetate-ethylene       40 40 40 40 40AP 465 Tg -5 ± 3° C.Urethane % 16.7         21 25 28.6                  0  0  16.7                           21 25 28.6                                    0Peel Strength      6.8         8.4            8.6               10.2                  3.1                     5.9                        3.6                           4.8                              7.4                                 5.0                                    2.1% Fiber Tear      10 10 10 5  0  10 50 50 65 50 0__________________________________________________________________________ *6 also contains glycoxal, itaconic acid and catalyst 
    
     Table 3 shows that optimum levels of water based urethane are 25 to 30 percent and that vinyl acetate copolymers having Tg of -5°±3° C. and 10° C.±10° C. are effective in the laminating adhesive of this invention. 
     EXAMPLE 4 
     Tables 4, 5, 6, 7, 8 and 9 report peel strength and fiber tear of laminating adhesives used with vinyl and wood. Styrene-acrylic copolymer emulsions having various glass transition temperatures are combined with vinyl acetate copolymers and different levels of aliphatic water based urethane. 
     
                                           TABLE 4__________________________________________________________________________       12 13            14 15 16 17 18 19 20 21__________________________________________________________________________Styrene-acrylic UCAR 462.sup.1       60 60            60 60 60 60 60 60 60 60LAM2.sup.2  40 40            40 40 40AP 465.sup.3              40 40 40 40 40% urethane.sup.4       16.7          21            25 28.6                  0  16.7                        21 25 28.6                                 0peel strength       2.2           4            5.91               4.3                  1.65                     1.9                        2.9                           3.5                              2.2                                 1.8% fiber tear       90 97            100               100                  80 90 100                           95 95 80__________________________________________________________________________ .sup.1 Tg 45 ± 5 .sup.2 vinyl acetatebutyl acrylate copolymer emulsion Tg 10° C. ± 10° C. .sup.3 vinyl acetateethylene copolymer emulsion Tg -5° C. ± 3 .sup.4 aliphatic water based urethane 
    
     
                                           TABLE 5__________________________________________________________________________  22 23 24 25 26 27 28 29 30 31 32__________________________________________________________________________Styrene-acrylic  60 60 60 60 60 60 60 60 60 60 60RES 1019.sup.5LAM2.sup.6  40 40 40 40 40 40AP465.sup.7              40 40 40 40 40% urethane.sup.8  16.7     21 25 28.6              0  0  16.7                       21 25 28.6                                0peel strength  3.7     6.1        5.8           3.1              3.1                 5.2                    2.1                       2.6                          4.7                             5.1                                1.8% fiber tear  2  5  2  2  0  2  90 95 100                             99 85__________________________________________________________________________ .sup.5 Tg -15° C. .sup.6 vinyl acetatebutyl acrylate copolymer emulsion Tg 10° ± 10° C. .sup.7 vinyl acetateethylene copolymer emulsion TG -5° ± 6° C. .sup.8 aliphatic water based urethane 
    
     
                                           TABLE 6__________________________________________________________________________     33 34 35 36 37 38 39 40 41 42__________________________________________________________________________Styrene-acrylic HSB6.sup.9     60 60 60 60 60 60 60 60 60 60LAM2.sup.10     40 40 40 40 40AP465.sup.11             40 40 40 40 40% urethane.sup.12     16.7        21 25 28.6                 0  16.7                       21 25 28.6                                0peel strength     2.8        3.4           4.3              3.3                 1.7                    2.8                       3.4                          6  3.8                                2.6% fiber tear     85 90 100              90 50 90 95 98 100                                95__________________________________________________________________________ .sup.9 Tg 12 ± 6° C. and 48 ± 6° C. .sup.10 vinyl acetatebutyl acrylate copolymer emulsion Tg 10° C. ± 10° C. .sup.11 vinyl acetateethylene copolymer emulsion Tg -5° C. ± 3° C. .sup.12 aliphatic urethane 
    
     
                       TABLE 7______________________________________     43     44     45       46   47______________________________________Styrene-acrylic       60       60     60     60   60UCAR451.sup.13LAM2.sup.14 40       40     40     40   40% urethane.sup.15       16.7     21     25     28.6 0peel strength       2.9      2.2    2.4    3.3  3% fiber tear       90       80     85     90   10______________________________________ .sup.13 Tg 42° C. ± 5 .sup.14 vinyl acetatebutyl acrylate copolymer emulsion Tg 10° C. ± 10 .sup.15 aliphatic water based urethane 
    
     
                       TABLE 8______________________________________     48     49     50       51   52______________________________________Styrene-acrylic P376.sup.16       48       49     50     51   52LAM2.sup.17 40       40     40     40   40% urethane.sup.18       16.7     21     25     28.6 0peel strength       1.9      3.3    3.3    3.1  3.8% fiber tear       60       90     90     90   80______________________________________ .sup.16 Tg -32° C. .sup.17 vinyl acetatebutyl acrylate copolymer emulsion Tg 10° ± 10° C. .sup.18 aliphatic water based urethane 
    
     
                       TABLE 9______________________________________       53   54     55       56   57______________________________________Styrene-acrylic RES 1018.sup.19         60     60     60     60   60LAM2.sup.20   40     40     40     40   40% urethane.sup.21         16.7   21     25     0    0peel strength 1.9    2.1    3.2    2.2  2.1% fiber tear  50     65     30     35   60______________________________________ .sup.19 +22° Tg .sup.20 vinyl acetatebutyl acrylate copolymer emulsion Tg 10° ± 10° C. .sup.21 aliphatic water based urethane 
    
     Review of Tables 4 through 9 shows that optimum levels of water based urethane are 35 to 30 percent and that styrene-acrylic copolymer emulsions having Tg from -32° C. to +50° C. are effective in the laminating adhesive of this invention. 
     The most preferred laminating adhesive for strong bonds between vinyl and wood when tested at room temperature is a mixture of a styrene acrylic latex emulsion having a Tg of 45°±6° C., a vinyl acetate-butyl acrylate copolymer having a Tg of 10°±10° C. and a stable non-reactive aliphatic water based urethane. 
     The most preferred laminating adhesive for strong bonds between vinyl and wood when tested at higher temperatures such as 180° F. (82° C.) is a mixture of a styrene acrylic latex emulsion having a bimodal glass transition temperature distribution of 12°±6° C. and 48°±6° C., a vinyl acetate-butyl acrylate copolymer having a Tg of 10°±10° C., glyoxal, itaconic acid, and, optionally, zinc acetyl acetonate catalyst. 
     EXAMPLE 5 
     A formulation was sought that allowed coating an adhesive onto vinyl, then rolling it up without the use of a release liner. This formulation would necessarily then need to withstand the forces of a wound roll of vinyl being shipped in a truck at temperatures up to 150F. The resultant changes would also allow the adhesive to slide on the pressing table on which the final parts are made, at least initially. This would allow parts to be made with less stress inherent in the final vinyl parts. It was hoped that this would allow the final part to have at least equivalent heat resistance to that of parts made with the adhesive that did not contain a wax. The other benefits would be resistance to mechanical marring and lack of dust and dirt pickup by the slight tack inherent in the base adhesive. This would allow parts to made with better esthetics and fewer rejects due to dirt in the bondline telegraphing through the vinyl. 
     To 400 grams of Airflex 465 ethylene-vinyl acetate copolymer emulsion was added 1600 grams of UCAR 462 styrene-acrylic copolymer emulsion. These were mixed thoroughly for 30 minutes. Next was added slowly with stirring 20 grams of the wax emulsion. This mixture was again mixed thoroughly for 30 minutes. The mixture was ready for use immediately thereafter. Additional additives may be necessary for improving coatability such as defoamers, surfactants, thickening agents, and coalescing aids. Extenders may also be added as desired. 
     Table 10 shows the benefits of adding different waxes to the adhesive. Although the adhesive lacking wax made a laminate with 170° F. heat resistance, that adhesive stuck to the adjacent rolled-up surface or &#34;blocked&#34; and was not mar resistant. Adhesives containing as little as 2% carnauba wax, paraffin wax, or polyethylene/paraffin wax were anti-blocking and mar-resistant. 
     
                       TABLE 10______________________________________170F BondlineEffect of Wax on Blocking and Adhesion        Anti-      Heat  MarAdhesive  %     Blocking   Resist.                         Resist.                                Wax______________________________________Blank  0     POOR       170   POORE7920  1     V. GOOD    170   GOOD   CARNAUBAE7920  2     V. GOOD    170   GOOD   CARNAUBAE7920  4     V. GOOD    170   V. GOOD                                CARNAUBAE7030  1     V. GOOD    170   GOOD   CARNAUBAE7030  2     V. GOOD    170   GOOD   CARNAUBAE7030  4     EXCELLENT  170   V. GOOD                                CARNAUBAE9040  1     EXCELLENT  170   GOOD   PE/PARAFFINE9040  2     EXCELLENT  170   V. GOOD                                PE/PARAFFINE9040  4     EXCELLENT  170   V. GOOD                                PE/PARAFFINSL535  1     V. GOOD    170   GOOD   CARNAUBASL535  2     EXCELLENT  170   V. GOOD                                CARNAUBASL145  1     V. GOOD    170   GOOD   PARAFFINSL145  2     EXCELLENT  170   V. GOOD                                PARAFFINSL145  4     EXCELLENT  170   V. GOOD                                PARAFFIN______________________________________ 
    
     The preferred non-blocking formulation of the adhesive of the method and composition of this invention is: 20 parts by weight Airflex 465 ethylene-vinyl acetate, 80 party by weight UCAR 462 styrene/butyl acrylate/methyl methacrylate/ hydroxyethyl acrylate, 0.26 parts by weight Henkel DSX-1550 clear thickener, 5.1 parts by weight deionized water, and 2 to 4 parts by weight Drewax 9094 polyethylene/paraffin 40% wax emulsion.