PRESSURE-SENSITIVE ADHESIVES BASED ON SIMILAR POLYMERS

Abstract: A pressure-sensitive adhesive is formed from a high-molecular-weight polymer and is plasticized by a low-molecular-weight polymer, which polymers have monomer contents which differ by no more than 3 percent by weight.

Description: PRESSURE-SENSITIVE ADHESIVES BASED ON SIMILAR POLYMERS Cross-Reference to Related Applications This is a Continuation-in-Part of Application Serial No. 06/711,500, filed March 14, 1985. Background of the Invention A pressure-sensitive adhesive should be soft so that it can develop sufficient interfacial contact area with a substrate on application of very light pressure. It must, however, also be strong enough to resist debonding failure. Conventionally, this rate-dependent viscoelastic property of pressure-sensitive adhesives was achieved by blending tackifying resins with a rubber. More recently, there has been an increased interest in using polyacrylates among other polymers as pressure-sensitive adhesives for their superior weathering and aging properties. There are, however, some disadvantages in the use of such acrylic pressure-sensitive adhesives. The materials cost of the acrylates is higher than the conventional rubber-based adhesive, and tack performance is normally lower. In addition, it is difficult to find good tackifiers that are commercially available for acrylic adhesives. When a porous material such as paper is used as the facestock, many compounded acrylic adhesives are prone to have certain components "bleed" out and stain the facestock. In 1964 Wetzel presented a model of a compoundable pressure-sensitive adhesive based on a resin " and a sticky low-molecular-weight rubber in which a sticky low-molecular- weight tackifier was dispersed in the bulk of the base resin. Solid tackifiers have since been conventionally employed to induce pressure-sensitive characteristics to a base polymer. The effect of tackifier addition is shown in FIG. 1, attached hereto. Summary of the Invention The present invention is directed to compatible mixtures of low- and high-molecular-weight polymers of similar molecular composition which may be combined to form novel products ranging from plasticized self-supporting films to pressure-sensitive adhesives. In particular, the compositions of the invention are comprised of at least one high-molecular-weight polymer having a molecular-weight of greater than at least 10 times the entanglement molecular-weight thereof and which is not a pressure-sensitive adhesive, with at least one lower molecular-weight polymer having a molecular-weight which is less than 2 times the entanglement molecular- weight thereof and may or may not have pressure-sensitive adhesive properties, and differs in comonomer content from the high-molecular-weight polymer by no more than about 30 percent by weight preferably no more than 10 percent by weight. When combined, the mixture at least forms a plasticized self-supporting film preferably the mixture forms apressure-sensitiveadhesivehavingaglass-transition temperature at least 10°C below use temperature preferably about 20*Cbelowusetemperature. Glass-transitiontemperature of the mixed polymers with additives is most preferably at least about 40 * C below use temperature. The presently preferred polymers are copolymers containing an alkyl acrylate and, while any copolymerizable comonomer can be used to modify the properties of the acrylate containing polymers, it is preferred to include styrene for cost reduction and at least a minor amount of an unsaturated carboxylic acid, preferably acrylic acid, to enable crosslinking and to enhance adhesive properties. The low-molecular-weight polymer is preferably present in a concentration of from about 30 percent to about 80 percent by weight, based on the mixture of high- and low- molecular-weight polymers. By combining the two polymers of highly similar chemical structure, one can obtain without loss of compati¬ bility a wide range of properties including pressure- sensitive adhesiveproperties cateredtoenduse applications. Alkali removability is feasible; for the formed pressure- sensitive adhesives having an unsaturated carboxylic acid content of from about 5 percent to about 30 or more percent by weight. Properties, particularly high-temperature physical properties, can be enhanced by exposure of the mixture to crosslinking reactions, particularly free radical reactions such as induced by actinic radiation, electron-beamradiation, andchemical crosslinkingreactions. Brief Description of the Drawings FIG. 1 is a plot of the log of the shear modulus (Log G) or the log of the ratio of shear stress over shear strain vs. frequency of deformation (Log ω ) for a base resin (solid line) modified by a tackifier system to form a pressure-sensitive adhesive of desired properties (dashed line) . FIG.2 shows, on the same scaleas FIG.1, the formulation of a pressure-sensitive adhesive by plasticizing a high- molecular-weightpolymerwithalow-molecular-weightpolymer. Detailed Description According to the present invention, there are provided pressure-sensitiveadhesivesbasedonamixture ofelastomeric, high-molecular-weight polymers and normally liquid, low- molecular-weightpolymersofidentical ordifferingcomonomeric content, which in combination, form novel products ranging from plasticized films to low-cost pressure-sensitive adhesives having a wide variety of properties including, when containing a copolymerized amount of unsaturated carboxylic acid, alkali removability. Independent of monomer content, the high molecular polymers have a molecular-weight of at least 10 times their entanglement molecular-weight. Stated another way, they have a weight-average molecular-weight (Mw) of at least 10 5 to about 5 x 10 6 . "Entanglement molecular- weight" as used herein, is defined inViscoelastic Properties of Polymers, 3rd Edition, John D. Ferry, John Wiley and Sons, 1981, incorporated herein by reference, which can be calculated using the formula: M e = 5.4 x 10 4 ∑M r ____ - 1.48 X 10~ 5 2 ΣN [_ ' ΣN where: M = molar weight of group N = number of main chain carbon atoms per group V = group contribution to molar volume The formula, M, N, and V are explained and supported indetail in ComputerAidedDesign ofPolymersandComposites. D. Kaeble, Marcel Dekker, Inc., 1985, pgs. 116 to 121, incorported herein by reference. The second component is a compatible, i.e. soluble low-molecular-weight, generally liquid polymer having essentially the same chemical constituency as the high- molecular-weightpolymer. The secondpolymerhas amolecular- weight which is less than 2 times the entanglement molecular- weight, and/or a weight-average molecular-weight of less than about 2 x 10 4 , or less than about 20,000. The high- and low-molecular-weight polymers should contain at least about 25 percent by weight of a common monomer preferably about 50 percent or more preferably 80 to 100 percent of a common monomer. While other comonomers may be present, the chemical difference of the high-molecular-weight polymers should not differ from the monomer content of the low- molecular-weight polymer by more than about 30 percent by weight preferably not more than 10 percent by weight. The degree of difference allowable depends, however, on mutual monomer solubility with a greater differential permitted for monomers of high mutual solubility. To this end, as used herein and in the claim, the words "molecular-weight" when referring to other than entanglementmolecular-weightmeans "weight-averagemolecular- weight". Any monomer can be employed in the practice of the inventionso longas itishomopolymerizableorcopolymerizable to meet the criteria specified for forming a pressure- sensitive adhesive. Illustrative, but nowise limiting of functional monomers, are the alkyl acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and the like; alkyl methacrylates such as methyl methacrylate ethyl methacrylate, butyl methacrylate, 2-ethylhexy methacrylate and the like; diesters of fumaric acid suc as dibutyl fumarate and the like; unsaturated carboxyli acids preferably containing from 2 to about 6 carbon atom such as acrylic acid, methacrylic acid, itaconic acid, fumari acid and the like; aromatic monomers such as styrene •<methylstyrene and the like; and other monomers such as viny acetate, vinyl proprionate, acrylonitrile, ethylene propylene, butadiene and the like. The presently preferre monomers are the alkyl acrylates, styrenic monomers an unsaturated carboxylic acids, the latter being limited t amounts of from about 2 to about 30 percent by weight of comonomer system. It is presently preferred that th high-molecular polymer have a glass-transition temperatur less than about 25 " C . It is presently preferred that a alkyl acrylate be present in an amount of at least abou 20 percent by weight based on the total weight of th monomers. There may be included in the mix of polymer other ingredients, such as anti-oxidant, colorants, U absorbents, and the like. The presently preferred pressure-sensitive adhesives ofthe invention comprise an alkyl acrylatepolymercontainin from about 50 percent to about 100 percent by weight polymerized acrylate in admixture with a low-molecular- weight alkyl acrylate polymer also containing at least about 50 percent by weight of the same alkyl acrylate in which the comonomer content of the high- and low-molecular- weight polymers differs by no more than about 10 percent by weight. In conventional pressure-sensitive-adhesive system, a tackifier system is employed to modify properties of the base resin, and acts to raise the glass-transition temperature and to lower the rubber-plateau modulus of the base resin. This is shown in FIG. 1, wherein the solid line is the base resin and the dashed line is the desired pressure- sensitive adhesive (PSA) . In the practice of the instant invention and with reference to FIG. 2, the low-molecular-weight polymer acts as aplasticizerwhichlowerstheglass-transitiontemperature and rubber plateau of the base resin (solid line) to adhere to the desired master curve (dashed line) for the pressure-sensitive adhesive. The amount of low-molecular-weight polyme (s) added will depend on the nature of the high-molecular-weight polymer(s) and properties desired. The total low-molecular- weight polymer content will be in an amount of from about 30 percent to about 80 percent by weight, based on the total weight of the polymers. Within the same or a different range, the low-molecular-weight polymer can serve to plasticize the high-molecular-weight polymer or render the mixture a pressure-sensitive adhesive. This results, in bothinstances, inastablenon-bloomingproductinconsequence to mutual compatibility due to substantial chemical identity of the polymers. The components of formulations provided in accordance with the instant invention may be formed by emulsion, solvent orbulkpolymerization. Emulsion polymerization is presently preferred. Filmoradhesiveproperties, especiallyhigh-temperature properties, may be enhanced by exposure of the mixture to the action of actinic radiation with or without the use of initiators as required, electron-beam radiation and/or chemical and/orthermal crosslinkingusingknowncrosslinking agents with or without the use of accelerators. Besides separate formulation of the pressure-sensitiv adhesives of this invention from individually polymerize high-molecular-weight polymers and low-molecular-weigh polymers, and the polymerization of a mixture of monomers polymerization can be conducted by initially polymerizin the polymer in the absence of a chain transfer agent to desired solids level; and then by the inclusion in th polymerization system of a chain transfer agent to induc limitations on the molecular-weight of the polymeric chai in continued polymerization, to form an in situ mixture o high-molecular-weight polymers and low-molecular-weigh polymers which, on deposition onto a face stock or release surface provide a pressure-sensitive adhesiv layer. The compositions of this invention uniquely enabl the adhesive coating of porous facestocks without bleed, may have wet-stick characteristics, namely the ability t adhere to surfaces on which moisture has condensed and whe containing carboxylic-acid moieties, have the ability t be readily removed from a substrate by alkaline cleanin solutions and caustic solutions. While nowise limiting, the following Examples are illustrative of the invention. "P" means panel failure; "C" means cohesive failure; "IPT" means immediate paper tear; "PS" means panel stain; "SPS" means slight panel stain; "ks" means kiloseconds; "F" means fail; and "PE" means polyethylene. Test methods utilized were as follows: molecular-weight distribution by ASTM D-3536-76, ASTM D- 3590-68 and ASTM E-682-79; shear by ASTM D-3654-78 and D-1000- 68 and PSTC (Pressure-Sensitive Tape Council) Test #7, 6th Edition; 90° peel by PSTC Test #2, 5th Edition; loop tack by PSTC Test #7, 6th Edition, mandrel by ASTM D-3654-78 and D-1000-68. Vellum 80 was used as a facestock because it is highly absorbant and amplifies bleed. Examples 1 to 10 Therewere formedbyemulsionpolymerization, homopolymers of ethyl acrylate to provide a feasibility evaluation of the ability to form pressure-sensitive adhesives from high- molecular-weight- and low-molecular-weight homopolymers of ethyl acrylate. Examples 1 to 3 disclose the formation of high-molecular-weight elastomeric resins, and Examples 5 to 7 disclose the formation of low-molecular-weight resins. Example 4 is a transitional example, showing the formation of a resin of reduced molecular-weight as a consequence of the introduction of a small quantity of n-dodecyl mercaptan (n-DDM) as a chain transfer agent. The polymerization conditions and polymer properties are shown in Table I. Solids content after polymerization was about 50 percent by weight. Table II shows the performance properties of mixtures of the polymers of Example 2 and Example 7. tn n o en o n TABLE I Examples 1 to 7 EXAMPLES Monomer, pts Ethyl Acrylate 100 100 100 100 100 Surfactant N-l l l 1 3.6 X-2U0 2 3.4 0O-4363 (60% solids ) 4.3 CO-730 (60% solids ) — — — 5.7 5.7 Buffer (NH 4 )2C0 3 .21 .14 .14 .14 .14 Initiator (NH 4 ) ->S2 0 8 .28 .28 .14 .57 .57 t-BHP 5 - .28 .28 .57 .57 AWC 6 .28 .28 .28 .29 .29 Fe 3 +£DTA Trace Trace Trace Trace Trace Chain Transfer n-DCM None None None .57 1.50 Monomer Pre- Pre- Pre- Pre- POLYMERIZATION CONDITIONS Feed Drulsion Biulsion Biulsion Bmulsion Reactor Temperature, *K 308-318 333 333 308-313 308-313 Jacket Ter erature, *K 293-298 , 313 313 293 293 Feed Time , ks 3.6 3.6 3.6 2.7 ' 2.7 Cook-Of f Time , ks 1.8 1.8 1.8 1.8 1.8 Cook-Of f Tei erature, *K 323 333 333 323 323 H# 4.68 x 10 5 2.61 x 10* 4.10 x 10* 1.01 x 10 5 4.4 x lθ Distribut ion Coeff icient (Mw Mn ) 3.4 8.1 4.6 8.1 3.2 % Below 20, 0U0 2.2 32.3 3.6 41.0 55.0 1 a nonionic surfactant manufactured and sold by Rohm and Haas 2 an anionic/nonionic surfactant manufactured and sold by Rohm and Haas 3, 4 an ethoxy lated alkyl phenol surfactant manufactured and sold by GAP 5 tert-butyl hydrαperoxide Ol o tn o tn TABLE I (Cont'd.) TABLE II Examples 1 to 7 Examples 8 to 10 Synthesis of Polyethylacrylate Homopolymers EXAMPLES 6 7 10 Monomer , pts Blend, Ethyl Acrylate 100 100 Ex. 2/Ex. 7 60/40 50/50 40/60 Su actant Facestock Vellum 80 Vellum 80 Vellum BO N-ili X-200 Coat Weight g/m 2 24 g. 24 g. 24 g. CO-436 Cθ-730 5.7 5.7 Quick Stick Buf er Recycled (Nl. ) 2 -θ3 .14 .14 Cardboard Good Good Good Initiator Poly- (MH 4 ) 2 S 2 0 8 .57 .57 i ethylene Good Good Good t-BHP .57 .57 0.500 kg ro AWC .29 .29 Shear, ks (NA) 0.1(C) (NA ) I Fe 3 +EDTA Trace Trace 90* Peel Chain Transfer (N/m) 208(P) 172(P) 156 ( P) n-DDM 5.00 10.00 Monomer Pre- POLYMERIZATION CONDITIONS Feed Emulsion Reactor Temperature, *K 328 328 Jacket Temperature, • _. 313 313 Feed Time, ks 3.6 3.6 Cook-Off Time, ks l.B 1.8 Cook-Off Temperature, *K 333 333 Mw 2.15 x 10* 1.78 X 10* MWD 2.3 2.3 % Below 20,000 28.0 21.0 Ol o ro Ol o Ol tn TABLE III EXAMPLE 11 12 13 14 15 16 Reactor Charge H 2 0 200 200 200 200 200 200 CO- 36 (60%) 1.0 1.0 1.0 1.0 1.0 1.0 Fe 3 +EDTA 0.1 0.1 0.1 0.1 0.1 0.1 Na 2 P 2 0 7 1.0 1.0 1.0 1.0 1.0 1.0 (NH 4 ) 2 C03 1.5 1.5 1.5 1.5 1.5 1.5 (NM 4 ) 2 S 2 θ8 4.0 4.0 4,0 ™ — - Pre-E ulsion H 2 0 300 300 300 300 300 300 CO-436 (60%) 20 20 20 20 20 20 TREM-L-40 (40%)7 10 10 10 10 10 10 Ethyl Acrylate 630 648 606 630 648 686 Acrylic Acid 70 52 14 70 52 14 Dodecyl Mercaptan 70 70 70 - - - I t-BHP 4.0 4.0 4.0 1.0 1.0 1.0 Accelerator H 2 0 100 100 100 100 100 100 AWC 2.0 2.0 2.0 2.0 2.0 2.0 Product Solids 8% 55 55.2 55.5 52.7 55.1 53.1 Viscosity, CPS 410 - - 1950 1000 2300 H 4.2 - - 5.0 5.1 6.3 Mw 1.0 x 10 1.1 x 104 1.3 x 10* 4.8 x 10* 5.7 x 10* 3.2 x 105 Disperslty Index 2.1 2.1 2.3 4.6 4.9 4.5 Wt. % Acrylic Acid 10 6 2 10 6 2 7 A sodium alkyl allyl sulfosuccinate manufactured and sold by Diamond Shamrock l ot o to K> ϋl Ol O Oi TABLE IV Exanples 17 to 42 EXAMPLE 17 18 19 20 21 22 23 24 % Acrylic Acid in High-Mol.-Wt. Polymer 10 10 * Acrylic Acid in I_σ_A-Mol.-Wt, Polymer 10 10 Wt. % of UftHfol.-Wt. Polymer in Blond 50 50 50 50 75 75 25 25 Crosslinking Agent* CX-100 (%) 0.4 0.4 0.4 0.4 0.B 0 0.8 U Flrvat Tack* 365.7(P) 77(P) 57β(P) 271(P) 443(P) 443(P) 462(P) 154(P> loop Tack (PE) 170(PS) 77(P) 230(PS) 160(PS) 250(PS) 420(PS) 100(PS) 150(PS) 1 _C-> 90* Peel (PE) 19Q(PS) 38(PS) 290(PS) 200(PS) 270(PS) 270(PS) 77(PS) 190(PS) 1 90* Peel (SS) 500(IPT) 120(PS) 410(PS) 230(PS) 420(SPS) 650(PS/P) 310(IPT) 460(IPT) Shear (0.5 kg) 78** 0.08(C) 0.75(C) 0.18(C) 1.98(C) 0.24(C) 245** 21.9(PP) 1/2" Mandrel (PE) <0,4 Pall 8.0 0.4 0.8-0.8 1.6-1.6 Pall <0.4 (12.7mm, 7 days) (11.2) 1.6-6.4 (11.2) Bleed Resistance Very Very Very at 6U » C (1 week) Good Poor Good Good Poor Good Good Good • Loop tack to glass **No slip TABLE IV (continued) Examples 17 to 42 EXAMPLE 25 26 27 28 29 30 31 32 % Acrylic Acid in High-Mol.-Wt. Polymer 10 10 % Acrylic Acid in Lα_c-Mol.-W . Polymer 10 10 Wt. % of Low-MoI.-Wt. Polymer in Ulend 75 75 50 50 50 75 25 75 Crosslinking Agent* CX-100 (%) 0.4 0.8 0 0.8 0 0.4 0.4 0.4 Flnat Tack* 270(P) 347(P) 193(P) 438(P) 158(P) 616(P) 443(P) 308(P) Loop Tack (PE) 230(PS) 150(P) 160(PS) 260(PS) 190(P) 270(PS) 38(PS) 190 (PS) 9ϋ β Peel (PE) 25D(PS) 120(P) 230(PS) 4ϋU(PS F) 220(S) 260{PS) 50-200*** ΙIO(PS) υi I 9ϋ # Peel (SS) 460(IPT> 390( IPD 58ϋ(IPT) 290(P) 2Θ0(PS) 620(IPT) 400(IPT) 230(PS) Shear (500 wk) 26.6(PS) 237** 1.98(C) l. 0.9(C) 240** 0.18(C) 1/2" Mandrel (PE) <0.4 Pall <0.4 8.0-9.6 8.0-9.6 0.4 6.4-1.6 Pall (12.7ntn, 7 days) (11.2) 8.0-3.2 9.6-9.6 4.8-4.8 (11.2) Bleed Resistance Very Very Very Very Very at 60"C (1 week) Good Good Good Good Good Good Good Poor •Loop tack to glass **No slip •••Slip stick /02014 -16- -ABUE TV (continued) Exaπ_μles 17 to 42 EXAMPLE 33 34 35 36 37 % Acrylic Acid in HighrMol.-Wt. Polyπer 10 10 % Acrylic Acid in Lαw→tol.- t. Polyπer Wt. % of I_ow-Mol.-«t. Polyser in Blend 25 5U 75 25 75 Crosslinking Agent* OC-lϋO (%) 0.4 0.4 0.4 0.4 0.4 Pinat Tack* 520(P) 347(P) 385(P) 115CP)*** 350(P) ocp Tack (PE) 100(PS) 160(K > ) 290{P) 40(1?_) 220(PS) 90* Peel (PE) 130(PS) 200(P) 250(PS) 35-12U*** 200(F/P) 90* Peel (SS) 39UCIPT) 540(IPT) 48ϋ(SPS) 380(IPT) 210{F/P) Shear (500/wk) 142** 30.9(PS/F) 1.16(C) 85** 0.2fe(C/ 16.9(P/F) ≠/l) 1/2" Mandrel (PE) Pail <0.4 0.8-0.8 Fail 1.6-3.2 (12.7_s_, 7 days) (11.2) 0.4-0.4 6.4-4.8 (11.2) Bleed Resistance Very Very at 60*C (1 week) Good Good Good Good Poor • Loop tack to glass **No slip • • •Slip stick TABLE IV (continued) Exa__ples 17 to 42 EXAMPLE 38 39 40 41 42 t Acrylic Acid in High-Mol.-Wt. Polymer 1 Acrylic Acid in Low-Hol.-+fc. Itolymer 10 10 Wt. % of Low→tol.-Wt. Polymer in Blend 25 50 50 50 50 Crosslinking Agent* CX-100 (%) 0.4 0.8 0 U.β 0 Pinat Tack* 17.5(P) 446(P) 269(P) 366(P) 192(P) Loop Tack (PE) 140(PS) 140(PS) 210(PS) 120(PS) 230(PS) 90 # Peel (PE) 120(P) 53-200*** 24ϋ(PS) 120(PS) 180(PS) 90* Peel (SS) 1 0(P) 46ϋ(IPT) 460{IPT) 330(F) 48ϋ(P) Shear (500wk) 2.73(C P) lb.9(P/C) 4.79(C) 7.5(PS) 4.74(C) 19.3(PS) 1/2" Mandrel (PE) 8.0-0.8 Fail 0.8-0.8 Pail 0.8-0.8 (12.Turn, 7 days) (11.2) (11.2) Bleed Resistance Very Very Very at 60 a C (1 week) Good Good Good Poor Good •Loop tack to glass • • No slip • **__lip stick Examples 11 to 42 While the results of Examples 1 to 10 establish the feasibility of the use of polyethyl acrylate homopolymers, in the formation of general-purpose pressure-sensitive adhesives from materials which would otherwise not have pressure-sensitiveadhesivecharacteristics, itwasdetermined touse a carboxylic acid as partofthe emulsionpolymerization system to form adhesives of varying properties, as a consequence of not only acid content but of the use of a crosslinking agent as well * The carboxylic acid employed was acrylic acid. In Table III, Examples 11 to 16 show, respectively, the conditions for the formation of high- and low-molecular-weight ethyl aer late/acrylic acid copolymers having 10 percent, 6 percent, and 2 percent by weight acrylic acid. Table IV, Examples 17 to 42, shows the adhesive properties of combinations of the polymers formed in Examples 11 to 16. In preparation of the polymers, 50 parts of the pre-emulsion was added to a reactor charge at 40'C and, while that temperature was maintained, the^ balance was added over 60 minutes. Heating continued for 30 minutes at 60'C. Five parts of the accelerator were added to the reactor charge and the balance to the pre- emulsion. Example 43 Anadhesiveformulation showinggoodalkali removability for use in recycle labeling of beverage containers was formulated from 25 parts by weight of a high-molecular- veight polymer containing about 96 percent by weight ethyl acrylate and 4 percent by weight acrylic acid and having a molecular-weight of about 400,000; and 75 percent by weight of a low-molecular-weight polymer containing 88 percent by weight ethyl acrylate and 12 percent by weight acrylic acid and having a molecular-weight of less tha about 12,000. A particular utility of the adhesive is t label recyclable beer kegs where the label is removed b caustic on recycle for refilling. Example 44 There was in the manner of the previous Example formed by emulsion polymerization high- and low-molecular weight polymers, each respectively containing 40 parts b weight styrene, 60 parts by weight 2-ethyl hexyl acrylate and 4 parts by weight acrylic acid. The high-molecular weight polymer had a weight-average molecular-weight (Mw) of 540,000 and a calculated entanglement molecular-weigh (Me) of 33,000 and was non-tacky. The low-molecular-weigh polymer had a weight-average molecular-weight (Mw) o 43,000 and a calculated entanglement molecular-weight o 33,000. Table V shows the properties of the low-molecular- weight polymer (LMP) and a mixture of oneparthigh-molecular- weight polymer per two parts low-molecular-weight polymer < MIX ) ' TABLE V Propertv LMP MIX Shear 25*C, min. 3 47 Loop Tack, N/m 275 10 Peel, N/m 538(c) 300(p) TheMIXprovided a low-tack, non-staining repositionable pressure-sensitive adhesive of improved cohesive strength.

Claims: l WHAT IS CLAIMED IS: 1. Apressure-sensitiveadhesivecompositioncomprising in combination, at least one high-molecular-weight polymer 5 having a molecular-weight greater than 10 times the entanglement molecular-weight of the polymer and at least one low molecular-weight polymer, the total low-molecular- weight polymer being present in an amount of from about 30 percent by weight to about 80 percent by weight based on I Q the total weight of said high-molecular-weight polymers and said low-molecular-weight polymers, said low-molecular- - weight polymer being formed at least in part of monomers identical to the monomers of said high-molecular-weight polymer, having a molecular-weight less than 2 times the 1 5 entanglement molecular-weight of the polymer, the monomeric content of said low-molecular-weight polymer differing by no more than about 30 percent by weight from the monomeric content of said high-molecular-weight polymer, said mixture of high- and low-molecular-weight polymers forming in o combination a pressure-sensitive adhesive having a glass- transition temperature at least 10"C below use temperature. 2. A pressure-sensitive adhesive composition as claimed in Claim 1 in which the low-molecular-weight = polymer differs from the high-molecular-weight monomer content by no more than 10 percent by weight. 3. A pressure-sensitive adhesive composition as claimed in Claim 1 in which the glass-transition temperature 0 of the combination of high- and low-molecular-weightpolymers is at least 20°C below the use temperature. 5 4. A pressure-sensitive-adhesive composition a claimed in Claim 1 in which the high- and the low-molecular weight polymers comprise a polymerized amount of an alky acrylate and styrene. 5. A pressure-sensitive-adhesive composition a claimed in Claim 4 in which the alkyl acrylate is selecte from the group consisting of 2-ethylhexyl acrylate, buty acrylate, isooctyl acrylate and mixtures thereof. 0 6. A pressure-sensitive-adhesive composition a claimed in Claim 1 in which the high- and low-molecular weight polymers comprise an interpolymerized amount of a unsaturated carboxylic acid. 5 7. A pressure-sensitive-adhesive composition as claimed in Claim 6 in which the carboxylic acid is acrylic acid or methacrylic acid. 0 8. A pressufe-sensitive-adhesive composition as claimed in Claim 5 in which the high- and low-molecular- weight polymers contain an interpolymerized amount of acrylic acid or methacrylic acid. _ 9. Apressure-sensitive adhesivecompositioncomprising in combination, at least one high-molecular-weight polymer having a molecular-weight greater than 10 times the entanglement molecular-weight of the high-molecular-weight polymer and at least one low molecular-weight polymer, the total low-molecular-weight polymer being present in an amount of from about 30 percent by weight to about 80 percent by weight based on the total weight of said high- molecular-weight polymers and said low-molecular-weight _ polymers, each of said high- and low-molecular-weight polymers being formed at least 20 percent by weight of monomers having a glass-transition temperature which if homopolymerized would be less than about 25*C, said low- 5 molecular-height polymer having a molecular-weight less than2timestheentanglementmolecular-weightofsuchpolymer, the comonomer contents of said high-molecular-weight polymer and the monomeric content of said low-molecular- weight polymer differing by no more than about 10 percent 1 0 by weight from the monomeric content of said high-molecular- weight polymer, said mixture of high- and low-molecular- weight polymers forming in combination a pressure-sensitive adhesive having a glass-transition temperature at least 30*C below use temperature. 15 10. A pressure-sensitive adhesive as claimed in Claim 9 in which at least about 50 percent by weight of the monomeric content of said high- and low-molecular- weight polymers is an alkyl acrylate. 20 11. A pressure-sensitive adhesive as claimed in Claim 10 in which at least about 60 percent by weight of the monomeric content of said high- and low-molecular- weight monomers is an alkyl acrylate. 5 12. A pressure-sensitive-adhesive composition as claimed in Claim 10 in which the alkyl acrylate is selected from the group consisting of 2-ethylhexyl acrylate, butyl acrylate, isooctyl acrylate and mixtures thereof. 0 13. A pressure-sensitive-adhesive composition as claimed in Claim 11 in which the alkyl acrylate is selected from the group consisting of 2-ethylhexyl acrylate, butyl acrylate, isooctyl acrylate and mixtures thereof. 5 14. A pressure-sensitive adhesive as claimed i Claim 9 in which the high- and low-molecular-weight polymer each include an interpolymerized amount of styrene. 15. A pressure-sensitive adhesive as claimed in Claim 10 in which the high- and low-molecular-weight polymers each include an interpolymerized amount of styrene. 16. A pressure-sensitive adhesive as claimed in Claim 12 in which the high- and low-molecular-weight polymers each include an interpolymerized amount of styrene. 17. A pressure-sensitive adhesive as claimed in Claim 13 in which the high- and low-molecular-weight polymers each include an interpolymerized amount of styrene. 18. A pressure-sensitive adhesive as claimed in Claim 10 in which the high- and low-molecular-weight polymers each contain an interpolymerized amount of an unsaturated carboxylic acid. 19. A pressure-sensitive adhesive as claimed in Claim 15 in which the high- and low-molecular-weight polymers each contain an interpolymerized amount of acrylic acid or methacrylic acid. 20. A pressure-sensitive adhesive as claimed in Claim 18 in which the high- and low-molecular-weight polymers each contain an interpolymerized amount of acrylic acid or methacrylic acid. 21. Apressure-sensitive-adhesivecompositioncomprising a high-molecular-weight polymer comprised of an interpoly¬ merized amount of 2-ethylhexyl acrylate and styrene, said high-molecular-weight polymer having a molecular-weight which is at least 10 times the entanglement molecular- weight, andalow-molecular-weightpolymerhavingamolecular- weight of less than 2 times the entanglement molecular- weight comprisedofaninterpolymerizedamountof2-ethylhexyl acrylate and styrene, and differing from the high- olecular- 0 weight polymer in monomer content by no more than about 10 percent by weight, said low-molecular-weight polymer being present in a concentration of from about 30 to about 80 percent by weight, based on the total weights of the high- molecular-weight polymer and the low-molecular-weight 5 polymer, andprovidingacompositionhavingaglass-transition temperature of at least about 20'C below use temperature. 22. A pressure-sensitive-adhesive composition as claimed in Claim 21 in which at least one of the high- o molecular-weight polymers and low-molecular-weight polymers contains an interpolymerized amount of an unsaturated carboxylic acid. 23. A pressure-sensitive adhesive as claimed in Claim 22 in which the carboxylic acid is acrylic acid. 24. A self-supporting film comprising in combination atleastonehigh-molecular-weightpolymerhavingamolecular- weight greater than 10 times the entanglement molecular- weight of the polymer and a plasticizing amount of at least one low molecular-weight polymer, said low-molecular- weight polymer being formed at least in part of monomers identical to the monomers of said high-molecular-weight polymer, having a molecular-weight less than 2 times th entanglement molecular-weight of the polymer, the monomeri content of said low-molecular-weight polymer differing b no more than about 30 percent by weight from the monomeri content of said high-molecular-weight polymer. 25. A self-supporting film as claimed in Claim 24 i which the low-molecular-weight polymer differs from th high-molecular-weight monomer content by no more than 1 0 percent by weight. 26. A self-supporting film as claimed in Claim 24 i which the low-molecular-weight polymer is present in concentration of from about 30 to about 80 percent b weight based on the weight of the high- and low-molecular weight polymers. 27. A self-supporting film as claimed in Claim 24 i which the high- and the low-molecular-weight polymer o comprise apolymerized amountofanalkyl acrylateand styrene. 28. A self-supporting film as claimed in Claim 27 i which the alkyl acrylate is selected fromthe group consisting of 2-ethylhexyl acrylate, butyl acrylate, isooctyl acrylate and mixtures thereof. 29. A self-supporting film as claimed in Claim 28 in which the high- and low-molecular-weight polymers comprise an interpolymerized amount of an unsaturated carboxylic acid.

Inventors: LIN KENNETH SHOU-CHEIN, LIN, KENNETH, SHOU-CHEIN
Applicants: AVERY INTERNATIONAL CORP, AVERY INTERNATIONAL CORPORATION
Application year: 1987
Main classification: C08L33
IPC codes: C08L33, C09J133