United States Patent (19) (11) 4,210,567 Kösters 45 Jul. 1, 1980 54 PLASTISOL OF AN ACRYLATE POLYMER 3,405,087 10/1968 Fryd ..... 260/33.6 AND A PLASTICIZER 3,415,288 12/1968 Marshak ............................... 138/141 3,634,299 1/1972 Shim et al. .......................... 260/31.8 (75 Inventor: Bernhard Kösters, Heidelberg, Fed. 3,666,710 5/1972 Makhlouf et al. ... 260/33.6 UA Rep. of Germany 3,686,111 8/1972 Makhlouf et al................... 260/31.2 3,699,067 10/1972 Stockman ........ ... 260/29.1 SB 73) Assignee: Teroson G.m.b.H., Heidelberg, Fed. 3,701,747 10/1972 Osmond....... ... 260/33.6 Rep. of Germany 3,701,747 10/1972 Osmond et al. ..................... 260/33.6 3,705,122 12/1972 Gwinner....... 260/2.3 X A (21) Appl. No.: 881,745 3,784,501 - 1/1974 Pettit ................................... 260/31.6 22 Filed: Feb. 27, 1978 3,790,523 2/1974 Orvis ........ ... 260/30.6 3,829,397 8/1974 Sheppard ..... 260/31.8 M Related U.S. Application Data 4,071,653 1/1978 Boessler et al. ...................... 428/332 63 Continuation of Ser. No. 630,271, Nov. 10, 1975, aban FOREIGN PATENT DOCUMENTS doned. 118967 2/1946 Australia . 287850 1/1965 Australia . (30) Foreign Application Priority Data 4988 11/1967 Australia . Jul. 3, 1975 (DE Fed. Rep. of Germany ....... 25297.32 846793 1/1977 Belgium . Nov. 15, 1974 (DE) Fed. Rep. of Germany ....... 2454235 362023 11/1936 Canada . 444273 9/1947 Canada . 51 Int. C.? ...................... C08L 33/08; CO8L 33/10; 615435 2/1961 Canada . C08L 33/12 934498 9/1955 Fed. Rep. of Germany . 52 U.S. Cl. ............................... 260/31.8 R; 215/233; 1808653. 10/1973 Fed. Rep. of Germany . 260/29.1 R; 260/30.6 R; 260/31.2 R; 260/31.4 2327958 1/1975 Fed. Rep. of Germany . 2454235 12/1976 Fed. Rep. of Germany . R; 260/31.8 B; 260/31.8 M; 260/33.2 R; 2543542 4/1977 Fed. Rep. of Germany . 260/33.6 UA; 428/344; 521/73; 521/182 1250419 12/1960 France. 58) Field of Search ..................... 260/29.1 R, 31.8 R, 846.197 9/1958 United Kingdom . 260/31.8B, 31.8 M, 30.6R, 31.2R, 31.4R, 33.2 101.2003 12/1965 United Kingdom . R, 33.6 UA; 428/344; 215/233 1114142 5/1968 United Kingdom . (56) References Cited 1206407 9/1970 United Kingdom . U.S. PATENT DOCUMENTS OTHER PUBLICATIONS 2,413,259 12/1946 Soday ..................................... 260/36 Acrylic Granules, I. C.I.. Technical Data Sheet, AGTD 2,558,396 6/1951 Thomas..... ... 260/29.6 101, 4th Ed. 2,600,122 6/1952 Meyer et al... ... 260/34.2 FEnt Sik Lopedia Polimerov,” Moscow, "Sovetskaya 2,773,046 12/1956 Dunn et al. ... ... 260/30.6 entsiklopedia,” (1974) vol. 2, pp. 540-541. 2,860,110 1 1/1958 Godshalk ............................... 260/17 2,867,667 1/1959 Dermer et al. ... ... 260/615 “Ullmans Enzyklopodie Der Technischen Chemie', 2,872,429 2/1959 Schwartz et al. ... 260/30.6 (1960), Band 11, Seite 14. 2,898,318 8/1959 Coffey et al. ... ... 260/31.6 Chemisches Zentrol Blatt, Nos. 20432, 54.633. 2,934,509 4/1961 Crissey et al. ... 260/30.6 Plasticizer Technology, vol. 1, pp. 228-242. 2,989,492 6/1961 Sanderson .............................. 260/17 Encycl. of Pol. Sci. and Tech., (1966), vol. 4, pp. 3,010,930 1 1/1961 Schroeder. ... 260/31.6 730-735. 3,050,412 8/1962 Coe........................................ 117/75 Acrylharze, Rohm and Haas, Lackrohistoffe, p. 14. 3,218,287 11/1965 Schmidle et al. ... 260/33.6 3,232,903 2/1966 Schmidle et al. ... 260/33.6 Plastisole und Organosole, Deutsche Farbenzeitschrift, 3,261,788 7/1966 Carter et al. ............................. 260/4 (1965), p. 93. 3,365,414 1/1968 Fisk et al. ........................... 260/33.4 Primary Examiner-Stanford M. Levin 4,210,567 Page 2 Attorney, Agent, or Firm-Lowell H. McCarter; C. to C10 alcohols, acrylates of aliphatic C1 to C10 alcohols, Edward Parker styrene and alpha-methyl styrene. The glass transition (57) ABSTRACT temperature of the polymer is above 35 C., its average degree of polymerization more than 400 and its average Subject of this invention are plastisols based on selected plasticizers and on polymers of certain acrylic or meth particle size in the plastisol is 0.1 to 500 microns. acrylic monomers, viz. mainly (i) t-butyl acrylate, a C1-4 alkyl, especially methyl, acrylate or cyclohexyl methacrylate, and optionally also (ii) one or more co monomers selected from methacrylates of aliphatic C2 18 Claims, 1 Drawing Figure U.S. Patent Jul. 1, 1980 4,210,567 01 009 000! 4,210,567 1. 2 polymer has a glass transition temperature of above 35 PLASTSOL OF AN ACRYLATE POLYMER AND A C. and an average degree of polymerization of more PLASTICZER than 400, and in that the particle size of the polymer in the plastisol is from 0.1 to 500 microns. This is a continuation, of application Ser. No. 630,271 5 It is disclosed in "Plasticiser Technology', edited by filed Nov. 10, 1975, now abandoned. Paul E. Bruins, Reinhold Publishing Corporation, New The invention relates to novel plastisols based on York, Volume 1 pages 228-241, that various conven acrylate polymers and organic plasticizers. tional organic plasticizers can be used with acrylic poly Plastisols are generally understood to mean disper mers so long as the proportion of plasticizer is small, sions of organic plastics in plasticizers, which are gelled 10 on heating to an elevated temperature. The presently about 10%. However, the present invention relates conventional plastisols generally comprise pulverulent exclusively to plastisols, which is a special form of dis polyvinyl-chloride dispersed in a compatible liquid plas persion of polymer in the plasticizer, not mentioned in ticizer which forms a paste. Polyvinyl-chloride plasti the above reference. In a plastisol the proportion of sols are used for numerous different purposes, particu 15 plasticizer is inevitably more than 10% and the polymer larly as sealing compounds, as anti-corrosive coatings has to be very finely divided. The plastisol is a viscous for metals, for impregnating and coating textile sub liquid or paste at room temperature, and has the prop strates, as cable insulations, etc. erty of gelling on heating, so that upon cooling a hard However, several serious problems occur in the pro ened, homogeneous, elastic solid is obtained. duction and use of PVC-plastisols. In fact, the produc 20 U.S. Pat. No. 2,413,259 describes the use of certain tion of PVC itself represents a problem because persons high-boiling oily liquids as plasticizers for acrylic and working in the production area may be exposed to a methacrylic resins. The mixtures there described are (1) health risk by the vinyl chloride. Of late this has led to hot-melt mixtures, (2) solutions of the plasticizer and the closing of a large number of PVC factories. Resid resin in a third substance as solvent and (3) masticated ual monomer in the PVC could also endanger people 25 blends prepared on a two-roll mill or Banbury mill (in during processing, and possibly even the final consumer the manner of compounding rubber). This patent also if the plastigel comes into contact with foodstuffs. does not disclose plastisols. The average particle size of When using PVC-plastisols, it is disadvantageous that the polymer used is preferably increased proportionally PVC is both sensitive to light and heat and tends to split with the decrease of its glass transition temperature T. off hydrogen chloride. The splitting off of hydrogen 30 The glass transition temperature is preferably above 60' chloride represents a particularly serious problem be C. cause during use the plastisol must be heated to an ele To obtain usable results, the degree of polymerization vated temperature, and any hydrogen chloride liberated of the polymer used must be at least about 400. Advan under these conditions has a corrosive effect and, for tageously the degree of polymerization is between 400 example, corrodes metal substrates. Attempts have been 35 and 20,000, corresponding to an average molecular made to counteract thermal decomposition by adding weight of about 40,000 to 2,000,000. heat stabilizers, but these compounds are frequently The preferred polymer component consists substan toxic so that they cannot be used where the plastisol tially wholly of one kind of units derived from t-butyl comes into contact with foodstuffs. The above acrylate, methyl, ethyl, n-propyl, isopropyl, n-butyl, indicated problems are further exacerbated in that in sec-butyl or t-butyl methacrylate or cyclohexyl methac certain special cases PVC-plastisols require relatively rylate, i.e. is essentially a homopolymer. Methyl meth high baking temperatures in order to obtain very short acrylate is preferred. The alcohol acrylate or methacry gelling times so that the danger of PVC-decomposition late comonomers preferably have an alkanol alcohol is further increased. component, i.e. are unsubstituted and saturated, and the It is the object of the invention to develop novel 45 plastisols which also have the excellent processing and type (i) monomers, i.e. those listed above, will generally product characteristics of PVC-plastisols but which gel predominate over those of type (ii). The preferred co at lower temperatures and are also chlorine-free so that polymers are those in which one of the monomers is there can be no splitting off of chlorine or hydrogen methyl methacrylate and constitutes at least 40%, pref chloride. It has surprisingly been found that this prob 50 erably at least 50%, by weight of the total monomer lem can be solved in that for the production of the units, and the other component is a C2-4 alkyl methacry plastisols particular acrylic polymers are used and pro late, especially n-butyl methacrylate, or a C1-4 alkyl cessed with plasticizers.