Cyanoacrylate Adhesive Composition Having Sustained Toughness

United States Patent [19] Millet et al. [54] CYANOACRYLATE ADHESIVE COMPOSITION HAVING SUSTAINED TOUGHNESS [75] Inventors: George H. Millet, Oakdale; Edward R. Harrell; Charles D. Wright, both of White Bear Lake, all of Minn. Minnesota Mining and Manufacturing Company, St. Paul, Minn. [21] Appl. No.: 551,571 [22] Filed: NOV. 14, 1983 [51] Int. Cl.4 ........................ .. C08K 5/01; C08K 5/02; CO8K 5/03 [52] U.S. Cl. .................................. .. 524/486; 524/470; 524/375; 524/369; 524/259; 524/81 [58] Field of Search ............. .. 524/469, 486, 504, 521, 524/81, 259, 369, 464, 470; 525/80, 244, 302; 526/298, 299 [73] Assignee: [56] References Cited U.S. PATENT DOCUMENTS 3,134,747 5/1984 Amos et al. ....................... .. 524/469 3,427,274 2/1969 Cornell ........ .. 524/153 3,433,661 3/1969 Maggart et al. .. 524/486 3,496,250 2/1970 Czerwinski . . . . . . . . . . .. 525/65 3,655,825 4/1972 Souder et al. . . 3,668,274 6/1972 Owens et al. 3,699,127 10/1972 O’Su1livan et al. ............... .. 524/755 4,560,723 Dec. 24, 1985 [11] Patent Number: [45] Date of Patent: 3,864,426 4/1975 Salensky ............................. .. 525/65 4,038,345 7/1977 O'Sullivan et al. ............... .. 525/284 4,102,945 7/1978 Gleave . . . . . . . . . . . . . . . . . . . .. 525/293 4,105,715 8/1978 Gleave .... .. 525/276 4,425,471 1/1984 Millet ....... .. 526/75 4,440,910 4/1984 O’Connor ......................... .. 524/850 FOREIGN PATENT DOCUMENTS 0087304 8/1983 European Pat. Off. . 47-51807 12/1972 Japan . W083/02450 7/1983 PCT Int‘l Appl. . Primary Examiner—John Kight Assistant Examiner—Kriellion Morgan Attorney, Agent, or Firm——Dona1d M. Sell; James A. Smith; David R. Cleveland [57] ABSTRACT Cyanoacrylate adhesive compositions containing (a) a toughener (e.g., a core-shell copolymer such as an MBS, ABS, or MABS copolymer), the toughener op- tionally being treated to remove impurities which cause premature polymerization of cyanoacrylates, and (b) cyanoacrylate-compatible, touglhener-compatible sus- tainer (e.g., an organic compound containing one or more unsubstituted or substituted aryl groups, such as diphenylmethane or dichlorobenzene). The inclusion of sustainer provides improved retention of toughness after heat aging of cured bonds of the adhesive. 5 Claims, No Drawings 4,560,723 1 CYANOACRYLATE ADHESIVE COMPOSITION HAVING SUSTAINED TOUGHNESS TECHNICAL FIELD This invention relates to cyanoacrylate adhesive compositions having improved toughness. BACKGROUND ART Cyanoacrylate adhesive compositions typically are regarded as having insufficient impact resistance and toughness, a shortcoming which is manifested by low peel strength. Various measures have been proposed to increase the peel strength of cyanoacrylate adhesives. Among such measures are the inclusion of an additive in such adhesives. One proposed additive is prepared by grafting styrene on a rubbery copolymer backbone (e.g., polybutadiene or a styrene-butadiene copolymer), shown in Japanese Published Patent No. 47-51807. An- other proposed additive is selected from acrylonitrile- butadiene-styrene (“ABS”) terpolymers, methacrylate- butadiene-styrene (“MBS”) terpolymers, and vinyli- dene chloride-acrylonitrile (“VAC”) copolymers, shown in U.S. Pat. No. 4,102,945. These latter additives are part of a class of materials which frequently are referred to as “core-shell” or “core-sheath” copoly- mers, and their chief use is not as an additive for cyano- acrylates, but rather as impact modifiers for polyvinyl chloride resins. DISCLOSURE OF INVENTION Although the additives described in the aforemen- tioned references may provide an improvement in cya- noacrylate adhesive peel strength, that improvement rapidly disappears if cured bonds of the resulting adhe- sive are aged for extended periods of time (e.g., by accelerated aging at temperatures of 70° C. or more for periods of time of one week or more). A further disad- vantage of the additives described in the aforemen- tioned U.S. Pat. No. 4,102,945 is that the shelf-life im- .provement said to be obtained through the use of such additives is not always realized in actual practice. For example, Example No. 17 of U.S. Pat. No. 4,102,945 describes a mixture containing 100 parts of methyl cya- noacrylate and 20 parts of an MBS terpolymer sold by Rohm & Haas under the trademark “Paraloid KM 611”. The inclusion of such MBS terpolymer is said to in- crease the shelf-life of the uncured adhesive at 55° C. from 31 days (methyl cyanoacrylate alone) to 54 days (methyl cyanoacrylate plus MBS). When this example was repeated using commercially available “Acryloid KM 611” (formerly sold as “Paraloid KM 611”), the mixture of methyl cyanoacrylate and MBS terpolymer solidified within 15 minutes at room temperature. Simi- lar results were obtained when several other commer- cially available copolymers (e.g., “Blendex BTA III F” MBS terpolymer, “Blendex 436” MABS copolymer, and “Acryloid KM 330” acrylic copolymer) were com- bined with methyl or ethyl cyanoacrylate using the method described in U.S. Pat. No. 4,102,945. Of the copolymers which we have examined, only “B1endex 10l” ABS terpolymer does not cause rapid gelation of methyl or ethyl cyanoacrylate (although cure speed does decrease after aging). The present invention provides, in one aspect, a cya- noacrylate adhesive composition comprising (a) cyano- acrylate monomer, (b) cyanoacrylate-compatible co- polymer which comprises a thermoplastic polymer l0 15 20 25 30 35 40 45 50 55 60 65 2 formed onto a rubber polymer (said cyanoacrylate- compatible copolymer is hereafter sometimes referred to as a “toughener”), said toughener optionally being treated to remove impurities which cause premature polymerization of cyanoacrylates, and (c) cyanoacry- late-compatible, toughener-compatible sustainer which provides improved retention of peel strength (e.g., T- peel strength) after heat aging of a cured bond of said adhesive composition. In addition, the present invention provides a method for making adhesive bonds, and bonded articles made thereby. DETAILED DESCRIPTION In the practice of the present invention, the cyanoac- rylate monomer typically is an ester of 2-cyanoacrylic acid, and a liquid at room temperature and atmospheric pressure. Preferred cyanoacrylate monomers have the formula CN I CH2=CCOOR wherein R is a C146 alkyl, cycloalkyl, alkenyl, cy- cloalkenyl, or aryl radical. R can be unsubstituted or can be substituted with groups which do not adversely affect the adhesive utility of the cyanoacrylate mono- mer, and can contain hetero atoms (e.g., oxygen) which likewise do not adversely affect such utility. R can be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, octyl, ethyllnexyl, dodecyl, ethox~ yethyl, benzyl or chloroethyl. Preferably R is cyclo- hexyl, alkoxyalkyl or a C1.(, alkyl or alkenyl radical. Most preferably, R is methyl, ethyl, n-butyl, or allyl. The cyanoacrylate monomer can be used singly or in admixture. Methods for preparing the cyanoacrylate monomer are well known to those skilled in the art, and cyanoacrylate monomers suitable for use in this inven- tion are commercially available from a variety of sources. The amount of cyanoacrylate monomer can be varied to suit particular applications. In general, the amount of cyanoacrylate monomer (and. the corresponding amounts of toughener and sustainer) should be adjusted to provide the desired degree of bonding and handling performance therewith (e.g., to provide a flowable liq- uid having a T-peel strength of 3.6 or more kg/cm of width on 0.45 mm thick C1018 cold rolled steel after heat aging of a cured bond thereof for 14 days at 71° C.). A preferred amount of cyanoacrylate monomer is about 50 to 91 percent by weight, more preferably 60 to 80 percent by weight, based on the total weight of cyano- acrylate monomer, toughener, and sustainer. The toughener (the second ingredient) improves the crack propagation characteristics of compositions of the invention. Suitable tougheners preferably are finely divided, room temperature solid copolymers which have been formed in stages to provide particles with a rubbery (e.g., elastomeric) polymer (e.g., copolymer) core which is wholly or partially surrounded by a shell of thermoplastic polymer (e.g., copolymer) which is harder than the core. The toughener is “cyanoacrylate- compatible”, that is, it is soluble or swellable in the cyanoacrylate monomer but does not by itself initiate polymerization of the cyanoacrylate monomer. The toughener optionally is treated to remove cyanoacry- late polymerization-causing impurities, a procedure 4,560,723 3 outlined in more detail below. Suitable tougheners can be selected by treating to remove any such impurities, mixing the treated toughener with the cyanoacrylate monomer, and observing the behavior of the resulting liquid mixture. For suitable tougheners, the toughener- cyanoacrylate monomer mixture will form a stable or apparently stable dispersion which typically has a milky-white appearance. Suitable tougheners, when combined with cyanoacrylate monomer but not com- bined with sustainer, will also provide cured bonds having initial peel strength higher than that obtained through the use of cyanoacrylate monomer alone, and when further combined with sustainer will provide cured bonds having long-term peel strength. For a non- suitable toughener, the toughener-cyanoacrylate mono- mer mixture typically will form a high-viscosity clear or opalescent mixture, or will fail to form a dispersion or mixture. An unsuitable toughener, when combined with cyanoacrylate monomer but not combined with sus- tainer, will not provide cured bonds with improved initial peel strength. Preferred tougheners are formed by polymerizing (e.g., grafting) acrylonitrile, methyl methacrylate, sty- rene or mixtures thereof onto a rubbery core formed by polymerizing mixtures of butadiene, butadiene and sty- rene, or butadiene and acrylonitrile. Tougheners made from monomer mixtures containing or including acrylo- nitrile, butadiene, and styrene will be referred to herein a as “ABS” tougheners. Tougheners formed from mono- mer mixtures containing or including methyl methacry- late, butadiene, and styrene will be referred to herein as “MBS” tougheners. Tougheners formed from monomer mixtures containing or including methyl methacrylate, acrylonitrile, butadiene, and styrene will be referred to herein as “MABS” tougheners. If desired, other mono- mers can be combined with those listed above or used in “ ~- place thereof, e.g., ethylenically unsaturated monomers such as butyl acrylate, hexyl acrylate, ethylhexyl acry- L » late, isooctyl acrylate, isoprene, or known crosslinking agents such as divinyl benzene, diacrylates, or dimetha- ' ' crylates. The toughener should be free of cyanoacrylate polymerization-causing impurities. Without intending to be bound by theory, such impurities are believed to be salts (e.g., sodium chloride), soaps, or other nucleo- philic species which typically are used in the manufac- ture of the toughener or present in the monomer mix- ture from which the toughener is made. Commercially available copolymers (e.g., core-shell copolymers) typi- cally contain sufficiently high levels of such polymeri- zation-causing impurities to render such copolymers undesirable for use in the present invention. However, through the treatment procedure described below, commercially available copolymers can be rendered sufficiently free of polymerization-causing impurities so that such treated copolymers can be used as tougheners in the present invention. Except for the treatment pro- cedure, the means for preparing the toughener is well known in the art. References describing copolymers which are suitable for use as tougheners include U.S. Pat. Nos. 3,496,250, 3,655,825, 3,668,274 and 3,864,426. Preferred commercially available copolymers which can be used as is or treated as described below include “Blendex BTA III F”, “Acryloid KM 680”, “Acryloid KM 653”, “Acryloid KM 611”, and “Acryloid KM 330” copolymers, all of which are commercially avail- able from Rohm and Haas Company, “Blendex 101” copolymer, commercially available from Borg-Warner l0 15 20 25 30 35 40 45 50 55 60 65 4 Corp., “Metablen C 223” copolymer, commercially available from M & T Chemicals, Inc., and “Kane Ace- B” copolymer, commercially available from Kaneka America Corp. “Blendex 436" copolymer, formerly commercially available from Borg-Warner Corp., can also be treated to provide a suitable toughener. If cyanoacrylate polymerization-causing impurities are present in the copolymer, the copolymer should be treated to remove them. A preferred treatment proce- dure employs extraction and an acidic wash, and can be carried out as follows. All washes are performed at 60° C. A 300 gram portion of solid, granulated copolymer is washed and filtered five times using 3.5 liter portions of deionized water. The filtercake is washed and filtered once using a solution of two milliliters of 28% hydro- chloric acid in 3.5 liters of methanol, followed by wash- ing and filtering four times with 3.5 liter portions of methanol. The filtercake is next washed once with water (this water wash step was not performed for all the examples shown below, but has been found to be useful in order to prevent caking and lump formation), filtered, and dried for 16 hours at 49° C. and about 60 millimeters Hg. Use of fewer than three water or metha- nol wash steps, or use of water wash alone, may fail to provide a sufficient degree of treatment. The suitability of the treatment procedure chosen can be evaluated by combining cyanoacrylate monomer with about ten weight percent of the treated toughener, and observing whether or not the resulting mixture is shelf stable. If, owing to polymerization of the cyanoac- rylate monomer, the viscosity of the mixture increases either rapidly or within an inconveniently short time, then further treatment of the toughener is required. Preferably, the viscosity of the mixture does not exceed about 30,000 cps when stored for three days at 71° C. Many commercially available copolymers contain chlo- ride ion and basic groups, and the thoroughness of the toughener treatment can be further evaluated by moni- toring the level of chloride ion (in ppm) and the basicity (in milliequivalents of KOH per gram) of the treated toughener. For example, commercially available sam- ples of “Blendex BTA III F” terpolymer contain about 100 ppm by weight chloride ion, and have a basicity of about 10-3 milliequivalents of KOH per gram. A level of treatment sufficient to reduce the chloride ion con- centration of “Blendex BTA III F” terpolymer to less than about 10 ppm and the basicity to less than about 10-4 milliequivalents of KOH per gram appears to be sufficient to provide the desired degree of shelf stability when the thus-treated toughener is combined with cya- noacrylate monomer. The amount of toughener can be varied to suit partic- ular applications. High level of toughener increase the viscosity of the resulting adhesive. A preferred amount of toughener is about 7 to 25 percent by weight, more preferably 15 to 25 percent by weight, based on the total weight of cyanoacrylate monomer, toughener and sus- tainer. Mixtures of tougheners can be used if desired. The sustainer (the third ingredient) preserves and in some cases enhances the toughness of compositions containing cyanoacrylate monomer and toughener, especially after cured bonds made with such composi- tions are aged above room temperature. A suitable sus- tainer will enable compositions of the present invention to exhibit a high aged toughness (e.g., T-peel strength after aging of a cured bond for 14 days at 71° C.) and a “smooth peel” (progressive) failure mode, while a com- position containing only cyanoacrylate monomer and 4,560,723 5 toughener will have a lower aged toughness and a “zip” (catastrophic) or “zip-stick" (alternate catastrophic- smooth peel) failure mode. The manner in which the sustainer functions is not understood. Based on the work carried out to date, no fully satisfactory structural definition has been found for the sustainer. In general, the sustainer is an organic substance which is a liquid or solid at room temperature and atmospheric pressure. The sustainer is "cyanoacrylate-compatible”, that is, it is soluble or miscible in the cyanoacrylate monomer and does not by itself initiate polymerization of the cyanoac- rylate monomer. The sustainer also is “toughener-com- patible”, that is, it will swell or partially dissolve the toughener core. The following tests have been found to be helpful for selecting toughener-compatible sustain- ers, although it should be noted that some sustainers which do not appear to be toughener-compatible in the tests nonetheless function adequately in the present invention. The tests are useful in indicating which sus- tainers are likely to be toughener-compatible. The first test is useful for selecting potential sustainers which are liquids at room temperature, and is carried out as follows. A one gram solid slab of test rubber whose structure corresponds (either exactly or approxi- mately) to the structure of the toughener core is com- bined with twenty-five ml of potential sustainer. The extent to which the test rubber dissolves or swells in the potential sustainer is measured after three days at room temperature. The test rubber may wholly dissolve, in which case no solid test rubber will remain. The test rubber may partially dissolve (in which case the test- rubber will decrease in weight) and in such case swirl- ing the mixture of test rubber and potential sustainer may reveal schlieren patterns. If the test rubber is not partially or wholly dissolved, it is removed from the potential sustainer, dipped in acetone, briefly dried, and weighed. For a toughener-compatible sustainer, the test rubber should dissolve or partially dissolve in the poten- tial sustainer, or be swollen by about 50 weight percent or more. For an unsuitable potential sustainer, the test rubber typically will not dissolve or partially dissolve, and will swell by less than about 50 weight percent. Some unsuitable potential sustainers may appear to be toughener-compatible (and vice-versa) in this test, but based on the work carried out to date it appears to be a generally reliable predictor of toughener-compatibility. The second test is carried out as follows. For a liquid potential sustainer, two grams of toughener granules (e.g., Blendex “BTA III F” terpolymer) are combined with ten milliliters of potential sustainer in a mixing vessel at room temperature and mixed with a spatula until a smooth mixture is obtained. For a solidpotential sustainer, the potential sustainer is first melted, then 10 milliliters of molten sustainer are combined with tough- ener granules as described above. A toughener-compat- ible sustainer should swell or partially dissolve the toughener granules, yielding a high-viscosity (e.g., about 5,000 cps or more), opalescent mixture. An un- suitable potential sustainer typically will provide a low- viscosity, milky dispersion or a low-viscosity, visually clear mixture, or will fail to dissolve an appreciable portion of the toughener granules. Some sustainers (e.g., diethyl adipate) may appear to be unsuitable when evaluated using this test, but nonetheless function ade- quately in the invention. However, no sustainers have yet been found which appear to be toughener-compati- ble in this test and do not function adequately in the present invention. 10 15 20 25 30 35 40 .45 50 55 60 65 6 A third test, modified for use in this invention and described below in Example 3, is a double-torsional fracture energy test. In such test (based on the work carried out to date), a test specimen containing a tough- ener-compatible sustainer will exhibit a fracture energy of 5>48 hours 3 +250 ppm NaCl 24" C. 4 hours 4 +50 ppm NaCl 24“ C. 4 hours 5 +30 ppm NaCl 24° C. < 16 hours 6 +20 ppm NaCl 24" C. < 106 U This Example and Comparative Example illustrate the use of a variety of sustainers in the present inven- tion. In general, toughener-compatible sustainers pro- vided a controlled crack propagation, with fracture energies of about 5 X 105 ergs/cm: or more. Some runs 55 (Comparative Example 3) or butyl benzyl phthalate exhibited fracture energies of 107 ergs/cm or more, a 60 (Comparative Example 4) were substituted for the di- 1O3-fold improvement over the results obtained with the use of_cyanoacrylate alone, cyanoacrylate plus tough- ener alone, or cyanoacrylate plus diphenyl ether alone. EXAMPLE 4 AND COMPARISON EXAMPLES 2-4 The composition of Example 3, run 11, modified by the addition of 0.1 parts by weight gallic acid adhesion 65 phenyl ether used in Example 4. The resulting Compar- ative Example compositions were tested as described above. Set out below in Table V are the Example number or the Comparative Example number, identity of the sus- tainer or comparison material, and the T-peel strength and failure mode measured initially and after one day or seven days aging at 71° C. 4,560,723 13 TABLE v 14 'l'~l’cel strength kg/cm width (failure mode) Ex. No. or Sustainer or Aged 1 day Aged 7 days Comp. Ex. No. comparison material lnitial at 71" C. at 71" C. Ex. 4 diphenyl ether 5.4(Sl‘) 7.2(Sl’) 6.6(Sl’) Comp. Ex. 2 —- 6.3(Sl’) 0.9—4.5(ZS) 0.4—4.3(ZS) Comp. Ex. 3 n-oetyl cyanoacetate 6.3(S1’) 0.5—4.8(ZS) 0—0.5(Z) Comp. Ex. 4 butyl benzyl (0.5—7(ZS) 1.3-5.4(ZS) 0.5—5.5(ZS) phthalate ' TABLE VI-continued Percent weight gain 15 Run Sustainer or Test rubber Test rubber N0. comparison material A”) B0) 26 2-phenoxyethanol 4.3 4.3 This example shows that diphenyl ether as used in Example 4 provided sustained high peel strength and controlled fracture behavior, advantages not offered by the compositions of Comparative Examples 2 through 4. EXAMPLE 5 Sustainer Swell Testing Approximate 25 ml samples of several liquid sustain- ers and comparison materials were combined with ap- proximate 1.5 gram, generally cubic slabs of two solid test rubbers. The resulting combinations were allowed to stand for three days at room temperature. In some instances the test rubber completely or partially dis- solved. In the remaining instances, the test rubber swelled, and the extent of swelling was measured by rinsing the swollen test rubber, in acetone, allowing the acetone to drain from the swollen rubber, and weighing to determine the amount of weight gain. Set out below in Table VI are the run no., identity of the sustainer or comparison material, and the effect of the sustainer upon the test rubbers. TABLE VI Percent weight gain Run Sustainer or Test rubber Test rubber No. comparison material A“) Bill 1 cumene D“) d“) 2 partially hydrogenated 52.3 83.3 polyphenyl(5) 3 diphenylmethane D d 4 1,1-bis(3,4-dimethylphenyl)ethane 125 122 5 1-methylnaphthalene d d 6 bromobenzene D D 7 chlorobenzene D D 8 1,2-dichlorobenzene D D 9 1,2,4-trichlorobenzene D d 10 1,3-dimethoxybenzene 128 148 11 diphenyl ether d 128 12 4-bromophenyl phenyl ether 114 197 13 Mixture of phenyl ether and 112 101 biphenylyl phenyl ethers“’) 14 nitrobenzene D 1 1 1 15 benzonitrile d 118 16 acetophenone D 105 17 tricresyl phosphate 8.0 10.0 18 4-ybutylphenyl diphenyl 11.7 7.] phosphate 19 butyl benzyl phthalate 10.7 10.9 20 r_i-butyl cyanoacetate 2.4 4.1 21 dioctyl phthalate 36.8 37.2 22 diethyl succinate 34.7 26.2 23 diethyl adipate 64.7 47.9 24 dimethyl sebacate 69.1 46.0 25 dibenzyl sebacate 25.5 15.6 20 25 30 35 40 (”"l’liol‘lcx 1502". styrene-bmadiene rubber (23.5 wt. % bound styrene), commer- cially available from Goodyear Tire and Rubber Co. m“lntene 50", polybutadicne rubber. commercially available from International Synthetic Rubber Co. ‘DD = Completely dissolved the test rubber. mm] = Partially dissolved the lest rubber. ‘5l“XA-202()“. “’l“Dowthcrm G“. Test rubber A is believed to approximate the struc- ture of the core of the MBS terpolymer “Blendex BTA III Test rubber B is believed to approximate the structure of the core of the ABS terpolymer “Blendex 101”. In general, those runs in Table VI in which the percent weight gain of Test rubber A is more than 50 weight percent (or a “D” or “d” value) are indicative of toughener—compatibility if the tested sustainer is com- bined with “Blendex BTA III F” terpolymer. Similarly, those runs in Table VI in which the percent weight gain of Test rubber B is more than 50 weight percent (or a “D" or “d" value) are indicative of toughener-compati- bility if the tested sustainer is combined with “Blendex 101” copolymer, with Run nos. 4 and 5 being exceptions to the latter general rule. EXAMPLE 6 Using the method of Example 1, several treated tougheners and sustainers were combined with cyano- acrylate monomer (“CA-3” adhesive, modified by the 5 inclusion of 0.1 weight percent tannic acid as adhesion 50 55 60 65 promoter), and the resulting composition then evalu- ated for T-peel strength when applied to 25.4 mm by 203 mm by 1.02 mm 3003-0 aluminum alloy strips. Prior to bonding, each strip was cleaned using an “FPL Etch” procedure carried out as follows. Each strip was immersed for ten minutes in a 71 ° C. solution of “Oakite No. 164” aluminum cleaner, rinsed in tap water for one minute, immersed for ten minutes in a 71° C. chromic- sulfuric acid bath (prepared from 30 parts water, 10 parts concentrated H2SO4, and 1 part sodium dichro- mate), rinsed for two minutes in tap water, air dried for ten minutes, and dried in a forced air oven for ten min- utes at 71° C. Control compositions were prepared without sustainer. Bond thickness was regulated at about 0.04 mm by including 0.04 mm glass beads in the bondline. Set out below in Table VII are the run number, type and amount (in weight percent) of toughener, type and amount (in weight percent) of sustainer, and the T-peel strength for the resulting compositions measured ini- tially (after a two day cure at room temperature) and after aging for two days or five days at 93° C. or for fourteen days at 71° C. 4,560,723 15 1 16 TABLE V11 T0ug11cncr Suslz1i11ur T—1’cc1 slrcnhlh. kg/cm widlh R1111 Amount. Amount. Aged 2 days Aged 5 days Aged 14 days No Type wt. '74: Type wt. % lnitiul :11 93" C. at 93° C. at 71° C. 1 MBS-1“) 15 -— — (1.7 3.9 3.7 4.2 2 MBS-2(3) 15 — — 4.7 2.9 2.7 2.1 3 A125”) 15 — — 6.4 4.1 3.11 3.9 4 MABSW 12 — — 5.4 4.0 4.4 4.6 5 MBS-1 15 cumcnc 12.5 5.9 5.0 4.6 4.9 6 MBS-1 15 biphcnyl 12.5 8.6 7.4 7.0 7.3 7 MBS-2 15 biphenyl 12.5 4.9 — 4.8 4.2 4.7 8 ABS 15 biphenyl 12.5 5.5 5.1 5.1 5.2 9 MABS 12 hiphenyl 10 6.4 6.3 5.3 5.9 10 MBS-1 15 4—bromnbipheny1 12.5 7.0 6.9 6.7 6.3 11 MBS-1 15 ' terphenyl 12.5 5.2 5.2 5.3 5.0 12 MBS-1 15 partially hydro- 12.5 6.3 ' 5.1 5.5 5.4 genated poly- - pheny1(5) 13 MBS-1 15 diphenylmethane 12.5 7.1 6.3 6.5 6.4 14 MBS-2 15 diphenylmethane 12.5 5.0 4.7 4.5 4.6 15 ABS 15 diphenylmethane 12.5 5.7 5.4 5.2 5.6 16 MABS 12 diphenylmethane 10 6.1 5.2 5.1 5.4 17 MBS-1 15 1.1-bis(3,4-dimethy1- 12.5 6.8 5.4 5.6 5.5 pheny1)ethane 18 MBS-1 15 1-methylnuphthalenc 12.5 7.6 6.4 6.8 6.4 19 MBS-2 15 1-methylnuphthalene 12.5 5.0 4.2 3.9 3.9 20 MABS 12 1-methylnaphthalene 10 5.7 5.4 5.1 4.9 21 MBS-1 15 bromobenzene 12.5 8.4 6.9 7.4 7.5 22 MBS-1 15 ch1or0benzene 12.5 8.0 6.9 7.3 6.4 23 MBS-2 15 chlorobenzene 12.5 5.2 4.8 4.5 4.8 24 ABS 15 chlorobenzene 12.5 5.9 5.7 5.5 5.6 25 MABS 12 chlorobenzene 10 6.4 6.5 6.1 6.3 26 MBS-1 15 4-bromochlorobenzene 12.5 7.6 6.3 6.3 6.4 27 MBSv2 15 4-bromochlorobenzene 12.5 5.8 4.7 4.8 4.8 28 ABS 15 4-bromochlorobenzene 12.5 6.1 5.7 5.4 5.6 29 MABS 12 4-bromochlorobenzene 10 6.6 6.3 5.4 5.2 30 MBS-1 15 1,2-dichlorobenzene 12.5 8.0 7.4 7.4 7.2 31 MBS-2 15 1.2-dichlorobenzene 12.5 5.8 5.5 5.3 5.3 32 ABS 15 1,2-dichlorobenzene 12.5 5.8 5.7 5.7 5.5 33 MABS 12 1,2—dich1orohenzene 10 5.4 5.4 5.3 4.3 34 MBS~2 15 1,Z.4—trich1orobenzene 12.5 5.3 4.3 4.5 4.9 35 ABS 15 1.2,4-trichlorobenzene 12.5 5.8 5.4 5.0 5.0 36 MABS 12 1,2,4-trichlorobenzene 10 5.5 5.1 5.7 5.4 37 MBS-2 15 1,3-dimethnxybenzene 12.5 5.6 5.7 5.3 4.7 38 ABS 15 1,3-dimethoxybenzene 12.5 5.0 6.2 5.5 5.5 39 MABS 12 1,3-dimethoxybenzene l() 5.8 5.8 5.4 5.4 40 MBS-1 15 diphenyl ether , 12.5 7.5 6.7 6.9 6.3 41 MBS-2 15 diphenyl ether 12.5 5.4 5.0 4.6 4.9 42 ABS 15 diphenyl ether 12.5 5.9 5.8 ‘ 5.4 5.4 43 MABS 12 diphenyl ether 10 5.4 5.4 5.1 4.6 44 MBS-1 15 4-bromophenyl 12.5 7.7 6.9 6.5 6.3 phenyl ether 45 MBS-1 15 mixture of phenyl ether 12.5 5.4 5.0 5.4 5.4 I and biphenylyl phenyl ethersm 46 MBS-1 15 nitrobenzene 12.5 8.1 7.3 6.9 7.9 47 MBS-2 15 nitrobenzene 12.5 5.1 5.4 5.4 5.3 48 ABS 15 nitrobenzene 12.5 6.0 6.3 5.6 5.7 49 MABS 12 nitrobenzene 10 6.7 7.0 6.6 5.4 50 MBS-1 15 benzonitrile 12.5 7.9 5.9 5.7 8.4 51 MBS-1 15 acetophenone 12.5 7.5 6.3 4.2 7.5 52 MBS-2 15 acetophenone 12.5 5.1 4.5 4.5 5.1 53 ABS 15 acetophenone‘ 12.5 5.5 5.4 5.0 5.9 54 MABS 12 acetophenone 10 6.9 5.9 5.0 6.3 55 MBS-1 15 benzophenone 12.5 7.9 7.7 7.7 8.5 56 MBS-2 15 benzophenone 12.5 4.9 5.4 5.2 4.4 57 ABS 15 benzophenone 12.5 5.3 6.5 5.3 4.6 58 MBS-1 15 tricresyl phosphate 12.5 3.8 6.1 6.3 5.0 59 MABS 12 tricresyl phosphate 10 6.7 6.0 6.3 5.6 60 MBS-1 15 4-t-butylphenyl 12.5 5.9 7.4 7.7 5.5 diphenyl phosphate I 61 MBS-2 15 4-t_-butylphenyl 12.5 4.4 4.3 4.3 3.2 diphenyl phosphate 62 MABS 12 4-t-butylphenyl 10 7.4 6.9 6.8 6.5 diphenyl phosphate 63 MBS-1 15 diphenylmethane 6.25 6.6 6.1 6.6 6.3 1,2-dichlorobenzene 6.25 64 MBS-1 15 4-bromochlorobenzene 6.25 6.6 6.6 7.1 6.7 benzophenone _ 6.25 65 MBS-1 15 acetophenone 6.25 7.9 7.5 7.5 6.8 4-t_—buty1pheny1 4,560,723 17 18 TABLE VII-continued Toughcner Sustaincr '1‘-Peel strength. kg/cm width Run Amount. Amount, Aged 2 days Aged 5 days Aged 14 days No. Type wt. % Type wl. % Initial at 93° C. at 93" C. at 71"‘ C. diphenyl phosphate 6.25 :.j.;i ”"‘ll1cmlcx IITA III F" MHS lcrpulymer, coninicreiully uvzniluhlc from Rohm and Hans 0).. treated using the mclhod