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Publication numberUSRE28533 E
Publication typeGrant
Publication dateAug 26, 1975
Filing dateOct 29, 1973
Priority dateOct 15, 1964
Publication numberUS RE28533 E, US RE28533E, US-E-RE28533, USRE28533 E, USRE28533E
InventorsManfred Drawert
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Synthetic polyamides of a dimeric fatty acid, a lower aliphatic carboxylic acid, ethylene diamine, and a co-diamine
US RE28533 E
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent Drawert et a1.

Related US. Patent Documents Reissue of:

1641 Patent No.: 3,622,604

issued: Nov. 23, 1971 Appl. No.: 815,279 Filed: Apr. 9, 1969 US. Applications:

[63] C mtinuatlon-inpart of Ser. No. 527.107, Feb. 14, 1966, abandoned, which is a continuation-in-part of Ser, No. 495,319, Oct, 12. 1965, abandoned.

[30] Foreign Application Priority Data Oct. 15, 1964 Germany Sch 35965 Feb. 19, 1965 Germany Sch 36567 Mar. 26. 1965 Germany Sch 36782 U.S. Cl. 260/4045; 260/18 N; 106/20; 106/27; 106/243 [51 Int. Cl. C09f 7/00 [58] Field of Search .1 260/4045 [56] References Cited UNITED STATES PATENTS 2.379.413 7/1945 Bradley 260/4045 2,886,543 5/1959 Peerman et a1 .1 260/4045 3,037,871 6/1962 Floyd et a1 t 260/4045 3,224,893 12/1965 Floyd et a1 260/4045 3,253,940 5/1966 Floyd et a1 260/4045 3,256,304 6/1966 Fischer et a1. 260/4045 3,268,461 14/1966 Jacobson .t 260/4045 1297,7311 1/1967 Fischer et al7 260/4045 3,408,317 10/1968 Vertnik 260/4045 3,412,115 11/1968 Floyd et a1 260/4045 3,420,789 1/1969 Wilson 260/4045 3,483,237 12/1969 Peerman et a1." 260/4045 3,499,853 3/1970 Griebsh e1 L11, 260/4045 Primary liruminerGlennon H. Hollrah Attorney, Agent, or FirmCurtis, Morris & Stafford [57] ABSTRACT Synthetic polyamides, useful as hinders in the formulation of priming inks, formed between a dimeric fatty acid, an unsubstituted lower aliphatic monocarboxylic acid, ethylene diaminc, and certain aromatic, cyeloaliphatic, and other aliphatic diamines. including aliphatic ether diamines; methods for preparing such poly-amides.

H Claims, No Drawings 1 SYNTHETIC POLYAMIDES ()F A DIMERIC FATTY ACID, A LOWER ALlPl-lATlC CARBOXYLIC ACID, ETHYLENE DlAMlNE. AND A CO-DIAMINE Matter enclosed in heavy brackets appears in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.

This application is a continuation-in-part of applica tion Ser. No. 527,107, filed Feb. 14, 1966 (now abandoned and of application Ser. No. 495 ,319. filed Oct. 12, 1965 (now abandoned).

This invention relates to synthetic polyamides comprising dimeric fatty acids and to methods for making the same. In particular, this invention relates to synthetic polyamides notable either for their good solubility in alcohols. particularly in ethanol, or for good solubility in solvent mixtures coupled with a high-softening point, and to methods of making such polyamides.

The polyamides of the invention are used to advantage as printing ink binders.

Polyamides comprising polymerized unsaturated fatty acids and ethylene diamine. and having a molecular weight range of from 3,000 to 5,000, are known in the art. However, only butanolic solutions of such products are stable at room temperature.

It has also been proposed in the prior art to increase the solubility of polyamides by the incorporation therein of branch-chain alkylol amines or branched dicarboxylic acids, or of branch-chain diamines having an amino group on a tertiary carbon atom.

Although certain progress has been made in the prior art toward increasing the solubility of polyamides, the disadvantages of prior art polyamides include a strong tendency toward blocking in sheets printed with inks comprising the polyamides as binders, an insufficient resistance of solutions of the polyamides to gelation, and a lack or low degree of reversibility of gel formation in such solutions. A further disadvantage in those prior art polyamides having improved solubility is that their softening point is too low to permit them to be used as printing ink binders.

U.S. Pat. No. 3,253.94!) granted May 31. I966 teaches high-melting point alt'ohol-solable polycarbonamide compositions comprising. the condensation product of (A) polyalkylenc polyamines of the general structure H N(R'NH),,H where R is an alkylene radical havingfrom 2 to 3 carbon atoms and n is an integerfrom I to 4, with at least one-half of the mixture of said polyalkylene polyamines being those in which n= 1, l B J low aliphatic monocarboxylic acids of the general structure RC OOH where R is selected from the group consisting of hydrocarbon and saturated aliphatic hydrocarbon radicals of from one to four carbon atoms, and (C) polymeric hydrocarbon fat acids; the equivalents ofamine groups employed being substantially equivalent to the equivalents of carboxylic groups employed, where at least 90 equivalent percent of the carboxylic acid groups employed are derived from the polymeric fat acids and the low aliphatic monocarboxylic acids, with the equivalent ratio of polymeric fat acids to low aliphatic monocarhoxylic acids being in the range of90:l0 to 65:35.

The present invention concerns new polyamides and their preparation by the thermal polycondensation of monocarboxylic acid. diamine. and dimerized fatty acid which may optionally contain smaller quantities of trirneric fatty acid and monomeric fatty acid. The monocarboxylic. acid is a straight-chain unsubstituted (i.e. hydrocarbon) aliphatic carboxylic acid having [one] two to five carbon atoms. suitably a lower alkanoic monoacid such as acetic acid. As the diamine are used mixtures of ethylene diamine with either (1) [a branched trimethyl-heramethylene diamine or a straight-chain unsubstituted (i.e., hydrocarbon) aliphatic codiamine having six to twelve carbon atoms, particularly a C C alkylene diamine; or-(Z) certain aromatic and cycloaliphatic codiamines or (3) certain ether codiamines.

In particular. aromatic amines of the formulas R1 R 111 01 a-l unt-" H1.

II It. i i. it 3 R. R1 R1 H K I NH: R4 a Re R: RI

and

H|N(Hlll IJI I and cycloaliphatic diamines of the formula can be employed wherein x is zero or a small integer and wherein il -R are hydrogen or lower alkyl. Those cyclic amines in which at most two of the substituents R,Ri; are lower alkyl are of particular interest because of their current commercial availability.

As ether codiamines, materials having the formula can be used, wherein n is an integer from 3 to 5 inclusive, x is an integer from O to 3 inclusive, and R is an alkylene radical having from one to 12 carbon atoms. which radical may optionally have one or two alkyl substituents having from I to 4 carbon atoms thereon.

According tothe invention. suitable aromatic and cycloaliphatic codiamincs include p-phenylene diamine, m-toluylene diamine; 4,4" -diamino diphenylmethane; 3,3"-dimethyl-4,4'-diamino diphenylmethane; 4,4- diamino diphenylpropane; 4,4'diamino dicyclohexylmethane; 3,3'-dimethyl-4.4diamino dicyclohexyl- 3 methane; xylylene diamine; bis-(,B-aminoethyl) benzene; bis-( B-aminoethyl l-dimethylbenzcne; bis- (aminomethyl)-cyclohexanc; 3-aminomethyl-3,5,5- trimethyl-cyclohexylamine; lmcthyl-4( 1 -amino- 1 methylethyl)-cyclohexylamine; and 9,9-bis-(3- aminopropyl )-fluorene.

Suitable ether codiamines include L7-diamino-4- oxa-heptane; l-diamino-6-oxa-undecanc; l,7-diarnino-3,S-dioxaheptane; 1,10-diamino -4,7- dioxa-decane; l,l-diamino-4,7-dioxa- S-methyldecane; 1,1 l-diamino-4,8-dioxa-undecane; 1,1 ldiamino- 4,8-dioxa--methyl-undecane; 1,]2-diamino- 4,9-dioxa-dodecane; l 3-diamino-4, l O-dioxatridecane; l,l4-diamino-4,l l-dioxa-tetradecane; 1,11- diamino-4,8-dioxa-5,6-dimethyl-7-propionylundecane; l,l4-diamino-4,7,lO-trioxa-tetradecane; l ,13- diamino- 4,7,lO-trioxa-S,S-dimethyl-tridccanc; l,l6- diamino-4,7,l0,l3-tetra-oxa hexadecane; 1,1 ldiamino-4,8-dioxa-6 6-dimethyl-undecane; and 1,20- diamino-4,17-dioxa-eicosane.

Preferred embodiments of the invention include those in which the equivalence ratio between ethylene diamine and the codiamine is between 0.8:0.2 and (:0.5. especially at 0.7:0.3, and in which the equivalence ratio between the dimeric fatty acid and the monocarboxylic acid lies between 0.8102 and 0.7:O.3, particularly at 0.752025. When rrimethyllmrume!hy- Iem' tli'uminc is employed as the rv-diumine, i! is used with vllzylem' diumim' a! an equivalence ratio of 0.8:.2.

In the process of the invention. the greater the proportion of the aromatic. cycloaliphatic, long chain, or ether codiamine present, the better are the solubility properties of the resultant polyamide. The greater the proportion of ethylene diamine present, the higher is the softening point of the resultant polyamide.

The polyamides of the present invention do not have the disadvantages earlier described for known polyamides. They are soluble. even at room temperature. up to 60 percent in lower alcohols. particularly ethanol. The solutions are resistant to gclation, and any gelation occurring at low temperatures is reversible at room temperature. Sheets printed with compositions comprising the polyamides of the invention show little tendency to block, in contrast with those printed with known ethanol-soluble printing ink resins. Also, ink resins according to the invention show outstanding adherence and good shine on conventional carriers. especially on pretreated polyethylene. The scratch resistance of printed sheets is excellent. particularly for those polyamides comprising an ether codiamine. Resistance to cracking and scaling is also at high levels. The mechanical properties of the resin films, such as hardness and elasticity, as well as the properties desirable in the coating arts. all meet the demands imposed on them.

Production of the polyamidc resins of the invention involves reaction of the diamines, dimeric fatty acid, and monocarboxylic acid at condensation temperatures between about 180C and about 250C, especially at about 230C Any remaining water of condensation is conveniently removed by applying a vacuum for l to 2 hours. In place of the free dimeric fatty acids, their amide-forming derivatives can also be used, such as their esters, in particular those which easily undergo aminolysis, such as the methyl and ethyl esters.

For preparation of the polyamides of the invention, those dimeric fatty acids are used which can be obtained by the free radical. ionic, or thermal polymerization of fatty acids. The fatty acid can be saturated or a monoor poly-cthylenically or acetylcnically unsaturated natural or synthetic aliphatic monobasic acid, suitably having eight to 24 carbon atoms. These fatty acids can be polymerized by different means, but all give functionally similar products which can generally be characterized as polymeric fatty acids. The polymer products usually contain a predominant amount of dimeric fatty acids, and smaller amounts of trimeric or higher polymeric, as well as monomeric, fatty acids. The term dimeric fatty acid" as used in the specification and claims is to be understood to refer also to such mixtures containing small quantities of non-dimeric materials.

Polymerization of saturated fatty acids can be carried out at elevated temperatures with peroxide catalysts such as di-t-butyl-peroxide, for example. The straight chain and branch-chain acids such as caprylic, pelargonic, capric, lauric, myristic, palmitic, isopalmitic, stearic, arachidic, behinic, and lignoceric acids are suitable saturated fatty acids. However, this process is of little interest because of the small yield.

The polymerization of ethylenically unsaturated fatty acids is much more common. This can be done with or without catalysts, but uncatalyzed polymerization requires higher temperatures. Suitable catalysts are acid or alkaline clays, di-t-butyLperoxide, boron trifluoride and other Lewis acids, anthroquinone, sulfur trioxide, and the like. The monomeric fatty acids commonly p0- lymerized include the branched-chain and straightchain, polyand/or mono-ethylenically unsaturated acids such as 3-octene acid, I l-dodecene acid, linderic acid, lauroleic, oleic, elaidic, vaccenic, gadoleic, cetoleic, erucic, linoleic, linolenic, elaostearic, arachidic, clupanodonic, nisinic, and chaulmoogra oil acid.

The acetylenically unsaturated fatty acids, which can be polymerized in the absence of catalysts because of their higher reactivity, seldom occur in nature and are expensive to synthesize. For this reason they are economically less interesting. A number of acetylenically unsaturated fatty acids, either straight chain or branch chain, mono-unsaturated or polyunsaturated, can be used for the preparation of polymeric fatty acids. For example, 6-octadecyn, 9-octadecyn, l3-dokosyn. and l7-0ctadecen-9,l l-diyn acids can be mentioned.

Because of their low cost and relatively easy polymerizability, oleic acid and linoleic acid are preferred as starting materials for the preparation of polymeric fatty acids.

The usual approximate composition of the commercial dimeric fatty acid product prepared from an unsaturated C,,,--fatty acid is: 5-15 percent by weight of C,,,monocarboxylic acid. 60-80 percent by weight of C -,,,dicarboxylic acid, and 10-35 P y Weight of C -,,tricarboxylic acid and higher carboxylic acid products.

The mixture obtained by polymerization can be fractionated by the usual distillation or solvent extraction methods. They can he hydrogenated before or after distillation in order to decrease the degree of unsaturation using high pressure hydrogen in the presence of a hydrogenation catalyst.

The preferred content of dimeric fatty acids in the fatty acid used in the present invention is between and I00 percent by weight. The content of mixtures of monomeric. dimerie. and trimerie fatty acids can be determined either by gas chromotography or according to the microdistillation method of Paschke. J. Am. Oil Chem. Soc. XXX]. No. 1, 5 (1954).

A better understanding of the present invention and of its many advantages will be had by referring to the following specific examples, given by way of illustration.

EXAMPLE 1 400 grams of a commercially available dimerized fatty acid (0.75 equivalent) prepared from an unsaturated C,,,fatty acid and having a content of about 75 percent dimeric fatty acid. 15 percent trimeric fatty acid. and percent monomeric fatty acid, 28.] grams of glacial acetic acid (0.25 equivalent). 39.45 grams Of ethylene diamine (0.70 equivalent), and 32,7 grams of hexamethylene diamine (0.3 equivalent) were mixed together and heated to 125C. over a period of about minutes under a nitrogen atmosphere with stirring. This temperature was maintained for half an hour, then the mixture was raised to 225 C. over a period of 2 hours and held at this temperature for 3 additional hours. Finally, a vacuum of 15 mm. Hg. was applied for l more hour at a temperature of 225 C.

The resulting product had an amine number of 2.64, an acid number of 2.02, and a ring-and-ball softening point of 113C.

The polyamide obtained was soluble in ethanol throughout the entire concentration range up to 60 percent.

Examples 2-10 tabulated in tables 1 and 11 below were prepared in analogous fashion using other monocarboxylic acids and aliphatic codiamines. The polyamide products are all soluble in ethanol. and their alcoholic solutions can be prepared either cold or at the boiling point.

TABLE 11 Upper limit of solubility Amine Aid Softening in ethanol, Ex. No. No. No. point (C) percent 2 2.61 2.20 119 (it) 3 l .80 1 .71 l 24 4 2.05 1.37 112.5 00 5 2.22 2. l 3 126 6 1.59 1.58 l 15 50 7 1.53 2.84 l 16 50 B 2.91 1.23 12] 45 9 2. 10 2.24 1 19 45 10 2.87 2.41 121 10 'Disqilved in 24 hrs. in cold solvent. Dissolved in hr. in werm solvent.

Example 1 l 200 grams of dimeric fatty acid (0.75 equivalent), 14.05 grams of acetic acid (0.25 equivalent), 19.7 grams of ethylene diamine (0.7 equivalent), and 17.15 grams of m-toluylene diamine (0.3 equivalent) were mixed and heated to C. over a period of 15 minutes. This temperature was maintained for 30 minutes.

Thereafter, the temperature was raised over a period of 2 hours to 225 C. and held at this temperature for a further 3 hours. Finally, a vacuum of about 15 mm. Hg. was applied for a further hour.

The polymer product had an amine number of 2,23, an acid number of 3.69. and a softening point (ring and ball) of 1 12C.

Additional polyamides were prepared according to the invention in an analogous fashion. Tables 111 and 1V summarize the results of further Examples 12-24.

TABLE 1 Purity Monoear' Dimeric (dimer 11))11'. Ethylene Equivalence fatty acid content acid Equivalence Lliamine (o-diumine ratio of Example No lgm in percent) (gm. ratio of acids tgm.) (gm) diamines 2 200 Ca. 75 14.05 Ac 075L025 1 1.72 22.78 NDA 07:03 3 200 Ca. 75 14.05 Ac 0.75:0.25 22.55 15.18 NDA 08:02 4 200 (:i. 75 14.05 Ae 0.75:0.25 16.90 30.38 NDA 01110.4 5 200 ('a. 75 20.3 Ac 0.80:0.20 25.03 16.87 NDA 0.8102 6 200 Ca. )9 14.05 Ac 0.75:0.25 19.72 22.711 NDA 0.7103 7 400 (11. 75 21.05 Ac (1.801020 42.24 27.75 TMD 0.14102 200 Cu. 75 17.52 Pr 0.751025 19.72 22.78 NDA 07:11.3 1 400 (a 75 41.25 Pr 0751025 33.89 43.55 HDA 0610.4 10 200 (a 75 20.51 lr 0.701050 21.17 30.08 DDA 0.71113 Nolv Ac acetic .leul lr pro itnnt and NBA lfl-tlimninu nmnme 1M1) trnnethxl he\nmetlt \1enc tliumine HDA- hU\ilrl\L1h10060131111100. DDA 1.12'1lt-lfl1111ll(1lItle'L-IIH.

TABLE 111 liquh- 1L|U1\- 1w Dimerie Mtmu alenee Ethylene alenee ample fall earboydie ratio of diamine ratio of No acid lgm 1 acid igm. acids 1pm.) ('wdiarninelgin.) diamines 12 200 14.05 Ac ..I1 25 10. 1S.l7|)-|1hk11 \1Cl1C tlinmine 0 710.3 13 200 1-1 05 Ae .1125 1) 7 27 R 4:1"(1111111111U Lli \he|i \1meth;|ne 0 711.3 14 200 1-1 05 Ac 0 25 10.7 31 7 .1." '-dnnuth 1 -1.-1'- liamino diphenylmethame 0.7.0 .1 1 200 14.05 Ac :025 19.7 20.8 4.4 (115111111111-t11CC1U1'lU\}1011;111:1116 0,7 0.1 1! 200 1-105 Ac .025 1*).7 33.45 3.5 tlimeth l4.-J-tlian1ino L11L \L'1U1IU.\ \1101;111:010 0.7.0 3 17 200 14.05 Ae 11.25 16.8 31.0 1.J-hisJaminoethyl -hen/ene 1|(i;0.-1 1H :00 i At- 0 25 22.5 170.5 1 -1'1 1\-(l|n11l1ULIKh}112.S-(11111Ulh"Will/C110 .2 1') 400 1-1 05 At 0 750.25 ,1) -15 47.75 huninometh 1-3.5.5'trimeth lqcloheolnmine ll) 40!) 7.7 P 0 75:11.2 5) 45 do 3 21 400 2 llu 0.710 1 -12 25 51.30 R-nminometh 1-3.5.5-trimetli I cyclohmylamine 3 21 200 I0 05 Au 0x02 1850 11 (\0 1-meth \1 -l( 1 i1l11i110-l-lllclhfl-clhyll eyclohuylamine 23 200 l-& 05 Au 0 75.0 Z5 19 7 22,18 l-meth \l-4( l-amino-I-mcthyl-ethfl) eycloheolamine 3 24 200 14 05 Ac 0 7510.25 10 7 40.2 LU-11151aimlfloprupxl )t1uorene 3 Not. At- .ittllt .ltul lr ump-mt .md 1111 hntyru .uenl

TABLE IV with stiiri in an inert gas atmosphere. l'he tempera ture was held at l25 C. for one-half hour. then raised Summing to 225 C. o ver a period of 2 hours. and left at the latter Ewmnlv Amins' Avid W ((7) temperature for 5 hours. During the last 2 hours, a vac- !2 1 58 1% H5 5 uum of about l5-2U mnt/Hg. was applied.

The resulting polyamide resin had an amine number (5 1H6 135 I13 5 of 2.59. an acid number of 2.64, and a ring and ball :1 softening point of l2(l.5 C. The product could easily l 2 I2 m be dissolved in ethanol by shaking. either at room temu 2 so 2.51 I I7 perature or at the boiling point. in 2.41 3 (is I21: 3i 3 i Additional polyamides were prepared according to i 410 5.5.1 14 the invention in an analogous fashion. Tables V and VI 34 summarize the results of further Examples 26-35.

TABLE V Dimcric Monocar- Equivalence lath lcnc Equivalence lfvample fat!) boxylic ratio ol diamme ratio of No. acid lgnrl acid ignrl acids (grit! (foaliammc {gm I diamincs 2h IUU l4.(l5 Ac 0.75: i970 H14 1.] l-diannno-fwmaundccane 0.71)} 27 400 28.10 Ac 0.751),. 3) 44 4&4 l.l()-diamino-4.7-dioxa-decane (1.71),? IR Zlltl i8 b5 Ac (J 70.0 3(l Z l l 3 28.71 1. llHIiamin04 7dioxa 5-meth l-dccanc 0.71).? 1*) -l(l(l 18 l(! Ac (3.750 '5 39.44 53 (v5 l l l'diamino4,l'Ldioxa-undecane 0.7.0.? .11) IUU l4 (J5 Ac (1 75.0 5 lUT/(J 28.60 l.l laliamino kfi flmethyLumieeane ().7:(J "l 31 It"! 10.51 Ac (LHIHLZH l 7(1 Z2 l. l Z-diamino-4.9dioxa'dodecanc r .13 21M: 14.05 Ac H 0.35 22.50 2(I.h(l l, I .ldiamino-4.lll dioxmtridecanc (18:01 33 Ztltl l-l U5 Ac I) 7'51) 25 21.50 30.6 1 l3 ll1lI'l\ll1U--l 7 lU-UlUGlH'ILlCCLlflC (1.8.1) 34 1H0 FY35 Pr ((325 19.71 24.72 1. ll)Llll1flllfl0-4JillUXiFdCCflnC (I 7:(J.3 35 ion Ion Bu (1.751(i 25 10.70 do 07:03

Nole Ac let-tic acid \H lut ric acid PF'proplnnlt and TABLE VI What I claim:

35 [1. A synthetic polyamide prepared by cocondens- Summing ing. at a temperature between about C. and about m 250 C, substantially equivalent amounts of an acid Fumlilc Am'm' (of l component consisting essentially of (l a dimeric fatty out 12 acid prepared by polymerizing a monobasic acid of an l aliphatic hydrocarbon having eight to 24 carbon atoms H3 5 and (2) a monobasic straight chain alkanoic acid hav- 1 l l ing one to five carbon atoms. and of an amine compo- :62 nent consisting essentially of ethylene diamine and a m4 I) cwdiaminc selected from the group consisting of( 1 an 3 45 alkylene diamine having six to 12 carbon atoms; (2) an m m aromatic diamine having one of the following formulas:

Solutions of the polyamides according to the invention can be prepared in concentrations of at least 3U W percent either at boiling temperatures or at room tem- HIN"lclH") (CIH'IlNHI peraturc.

For purposes of comparison, Examples 1 to 20 of R R US. Pat. No. 2.450.940 were repeated. The product R H k prepared according to Example I of the patent is insol- R, uble in ethanol. A 30 percent solution in isopropanol E gels at room temperature. A 30 percent solution buta H I nol showed a strong increase in viscosity after several a a R weeks standing. The polyamide prepared according to 8nd Example ll) of the patent also did not given stable 3U 6 percent solutions in the alcohols mentioned.

EXAMPLE ZS Four-hundred grams of dimeriaed l'atty acid (().75 a (QHmNIh equivalent) 28.1 g. of acetic acid {U25 equivalent). m

45.08 g. of ethylene diamine (0.8 equivalent). and 25.12 g. of l.7-diamino-4-oxaheptane (0.2 cquivt'ilent: ere mixed with one another and heated to I25" C.

(3| a cycloaliphatic diaminc having one of the follow ing formulas:

(CI-LLNH wherein .r in said formulas is zero or a small whole number from 1 to 3 inclusive, and wherein R,R, are hydrogen and up to two of said radicals R, R.; may be lower alkyl; and (4) an ether diamine of the formula wherein n is an integer from 3 to 5 inclusive, is zero or an integer from to 3 inclusive, and R is an unsubsituted alkylene radical having one to l2 carbon atoms or such a raical having one or two alkyl substituents thereon. said substituents having one to four carbon atoms. the equivalence ratio between said Climerie fatty acid and said monobasic acid being between 0.8:U.2 and (J.7:0.3. and the equivalence ratio between said ethylene diamine and said codiamine being between (18:02 and ().5:().5.]

2. A polyamide as in claim 1 wherein said monocarboxylic acid is acetic acid.

3. A polyamide as in claim 1 wherein a mixture of ethylene diamine and an alkylene diamine having six to l2 carbon atoms is employed.

4. A polyamide as in claim 3 wherein said alkylene diaminc is 1.6-diaminohexane. l.9-diaminononane, or 1.1 Z-diaminododecane or trimethyl-hexamethylene diamine] S. A polyamide as in claim I wherein a mixture of ethylene diamine and an aromatic diamine is employed.

6. A polyamide as in claim 5 wherein said aromatic diamine is l,4-bis(aminoethyl)-benzene or 9,9-bis- (aminopropyl J-fluorene.

7. A polyamide as in claim I wherein a mixture of ethylene diamine and a cycloaliphatic diamine are employed.

8. A poly-amide as in claim 7 wherein said cycloaliphatic diamine is 3-aminomethyl-3 5.5-trimethyleyclohcxylaminc.

9. A polyamidc as in claim 1 wherein a mixture of ethylene diamine and an ether diamine is employed.

[0. A polyamide as in claim 9 wherein said ether diamine is l.lU-diamino-4.7-dioxa-decane. LII)- diamino-4 7- diota-5-methyl-deeane. l.l3-diamino- 4.7.lO-tri0xa-decane. and ],12-diamino-4.9-dioxadodecane.

ll. l .vvnt/u'tit Ul \tlHil(l( prcparctl cocomlcnsing. at a temperature bctwccn about 1801'. and about 250% .\Itl7.\!rlllll(lll L(/lll\((l('tll amountw ol an acitl com poncnt conxixting mscntiull) o/u tlimcricjitltv acid ])l'(- pared by polymerizing u monobasic acid ofctn aliphatic hydrocarbon having eight to 24 carbon atomsand (2) acetic acid. and of an amine component consisting essentially of ethylene diamine and trinzcth 'lhcxamethylct1c diamine. the equivalence ratio between .raid tlimcricjattv ucitl and .ruitl acetic acid being 0.80:0.20, and the equivalence ratio between said ethylene tliaminc and said trime- Hui/IRWINlLIllV/CIIK tliamine being 0.8.0.2.

l2. A .rvnthctic polvamide prepared by coconclcttying.

[Oat a temperature between about 180C. anzl about (2) a monobasic straight chain alkanoic acid having two to five carbon atoms, and of an amine component consisting csxrentially of ethylene diamine and a co-diaminc selected from the group consisting of l a straight chain alkylcnc tliaminc having six to 12 carbon atoms; (2) an aromatic dirt/nine having one of thefollowing formulas:

l 2 E X QX CXHQX Q is H2N 1 2 6 R3 R R R and H N(CH (CH NH (3) a cycloaliphatic zliaminc having one of thcfolltm'int formulas:

a aii a i REEL;

a ut

wherein x in .midjinmulax ix zero or a .s'nmll whole number from I to 13 inclusive, and wherein R R are hydrogen and up to two of said radicals R, R may be methyl; and (4) an ether diamine oftheformula H N( CH R()) (H ),,NH

wherein n is an integerfrom 3 I05 inclusive, x is zero or an integer from I to 5 inelaxive, and R is an unsubstituted alkylene razlieal having I to 1.? earbon atoms or .s'm'h a radieal having a methyl .vubxriment thereon, the equivalence ratio between mid dimeriefiitty aeld and said monobaxie and being between 0.8.0.2 and (1.7.03, and the equivalence ratio between said ethylene diamine and A'uid ('odiamine being between 0.8.0.2 and (Li-(L5.

P041150 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTIDN Patent Re. 28553 Dated August 26, 1975 Inventor(s) Manfred Drawert 6t 8.]...

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby ccrrected as shown below:

In Claim 12, column 11, line 20, replace the formula by I C I 2 e -I 1- In Claim 12, column 12, line 11, replace 2" by 2 In Claims 2, 5, 5, 7, and 9, line 1 of each, replace "1" Signed and Scaled this I sixth D y of January 1976 SEAL A rtesr:

RUTH C. MASON C. MARSHALL DANN 8 ffi (mnmissimwr njParems and Trademarks

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2379413 *Jun 28, 1940Jul 3, 1945American Cyanamid CoAmides of high molecular weight carboxylic acids
US2886543 *Aug 17, 1954May 12, 1959Gen Mills IncPolyamide resin
US3037871 *Jan 13, 1959Jun 5, 1962Gen Mills IncPolyamide resin binder for printing inks
US3224893 *Sep 10, 1962Dec 21, 1965Gen Mills IncPolyamides of improved solubility from polyalkylene polyamines, hydroxy monocarboxylic acid, and hydrocarbon polymeric fat acids
US3253940 *Sep 10, 1962May 31, 1966Gen Mills IncPolyamides of improved melting point and increased solubility for ink binders
US3256304 *Mar 1, 1962Jun 14, 1966Gen Mills IncPolymeric fat acids and process for making them
US3268461 *Mar 12, 1962Aug 23, 1966Johnson & Son Inc S CPrinting ink vehicles
US3297730 *Nov 17, 1965Jan 10, 1967Gen Mills IncPolyamides of polymeric fat acids
US3408317 *Oct 19, 1964Oct 29, 1968Gen Mills IncLow melting polyamide resin of fractionated polymeric fat acids and a mixture of ethylene diamine and diaminopropane
US3412115 *Nov 2, 1964Nov 19, 1968Gen Mills IncPolyamide resin
US3420789 *Feb 11, 1963Jan 7, 1969Coates Brothers & CoPolyamide resins having solubility and resistance to gelling in alcohol solutions
US3483237 *Nov 1, 1965Dec 9, 1969Gen Mills IncPolyamide compositions of a polymeric fat acid and a mixture of diamines
US3499853 *Mar 22, 1968Mar 10, 1970Schering AgPolyamides
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US5162490 *Jun 1, 1990Nov 10, 1992Schering AgPolyamide resins based on dimerized fatty acids, process for producing them, and process for manufacturing printing inks by the use of said polyamide resins
US5714526 *Dec 13, 1995Feb 3, 1998Henkel CorporationMethod of preparing resin/pigment compositions for printing inks
US5882388 *Oct 16, 1996Mar 16, 1999Brady Usa, Inc.Water resistant ink jet recording media topcoats
US6406775Jul 12, 1999Jun 18, 2002Brady Worldwide, Inc.Modifiers for outdoor durable ink jet media
US6437037Sep 14, 2000Aug 20, 2002Westvaco CorporationRosin-fatty acid vinylic polyamide polymer supported latices
US6734280Dec 11, 2001May 11, 2004Meadwestvaco CorporationRosin-fatty acid vinylic polyamide polymer resins
US8133556Aug 12, 2009Mar 13, 2012Brady Worldwide, Inc.Durable multilayer inkjet recording media topcoat
WO2011019609A1Aug 6, 2010Feb 17, 2011Brady Worldwide, Inc.Durable multilayer inkjet recording media topcoat
WO2011137056A1Apr 25, 2011Nov 3, 2011Brady Worldwide, Inc.Full color, inkjet-printable, self-laminating lablel
Classifications
U.S. Classification564/152, 524/599, 106/31.35, 106/243, 528/295.3, 106/31.67
International ClassificationC09D11/10, C08G69/34
Cooperative ClassificationC09D11/102, C08G69/34
European ClassificationC09D11/102, C08G69/34