US3279882A

US3279882A - Process of stabilizing proteinaceous materials through treatment with a polyethyleneimine and a polyaziridine

Info

Publication number: US3279882A
Application number: US380909A
Authority: US
Inventors: Giuliana C Tesoro
Original assignee: JP Stevens and Co Inc
Current assignee: JP Stevens and Co Inc
Priority date: 1964-07-07
Filing date: 1964-07-07
Publication date: 1966-10-18
Anticipated expiration: 1983-10-18
Also published as: CH460696A; GB1078747A; DE1469483A1; CH950465A4

Description

United States Patent 3,279,882 PROCESS OF STABILIZING PROTEINACEOUS MA- TERIALS THROUGH TREATMENT WITH A PGLYETHYLENEIMINE AND A POLYAZIRIDINE Giuliana C. Tesoro, Dobbs Ferry, N.Y., assignor to J. P. Stevens & Co., Inc., New York, N.Y., a corporation of Delaware No Drawing. Filed July 7, 1964, Ser. No. 380,909 15 Claims. (Cl. 8127.6)

The present application is a continuation-in-part of applicants copending application Serial No. 105,285, filed April 25, 1961, now US. Patent No. 3,165,375, the entire disclosure of which is relied on and incorporated herein by reference.

The present invention relates to a method for treating proteinaceous materials in order to improve the physico-chemical properties thereof and more particularly, the present invention relates to a method for improving the dimensional stability and shrink resistance of textile materials containing wool, which employs a group of polyfunctional compounds. The present invention also pertains to products obtained by the aforesaid method.

In the above identified application there is disclosed a method for shrink-proofing textile materials containing wool by treating them with certain polyaziridinyl compounds. Polyaziridinyl compounds in which the nitrogen atom of the aziridine rings is an amino nitrogen, i.e., attached, to a substituted or unsubstituted hydrocarbon residue, are aminoaziridine compounds and are shown to be vastly superior for the purpose of improving the physicochemical properties of woolen textiles to those aziridinyl compounds in which the nitrogen atom of the aziridinyl groups is an amido nitrogen. However, because the amidoaziridine compounds are generally more economical and easier to prepare than are the aminoaziridine compounds, the amidoaziridine compounds are important for large scale, commercial operations in the shrink proofing of wool. It is therefore extremely desirable to improve the effectiveness of amidoaziridine compounds for shrink proofing of textile materials.

Accordingly, it is the object of the present invention to provide a method for treating proteinaceous materials, particularly textile materials containing wool, with amidoaziridine compounds to improve and enhance the physicochemical properties of the treated material which improves the eflectiveness of the amidoaziridine compounds and overcomes the disadvantages and drawbacks of other methods and compositions.

It is a further object of the present invention to provide a method for improving the effectiveness of amidoaziridine compounds for the treatment of textile materials containing wool in order to obtain a dimensionally stable textile product.

It is a further object of the present invention to provide a method for the shrink-proofing of woolen textile materials with amidoaziridine compounds that is unexpectedly superior to prior methods employing amidoaziridine compounds.

It is a further object of the present invention to pro vide dimensionally stable textile materials containing wool which have been treated according to the foregoing methods.

In attaining the above objects, one feature of the present invention resides in treating the proteinaceous materials with an aziridine compound and a particular polyamine compound, to be described hereinafter, whereby the dimensional properties of the treated material are greatly improved.

Another feature of the present invention resides in applying to the textile materials containing wool, a com- 3,279,882 Patented Oct. 18, 1966 position containing an amidoaziridine compound and an acyclic polyamine whereby an unexpected improvement in the dimensional properties of the treated textile are obtained.

Another feature of the present invention resides in treating textile material containing wool with a composition containing an amidoaziridine compound, an acyclic polyamine and certain other compounds which impart desirable functional properties such as water and/or oil repellency.

Other objects, features and advantages of the present invention will become apparent from the following detailed description hereof.

According to the present invention, the physico-chemical properties of proteinaceous materials such as textile materials containing wool can be vastly improved by applying thereto certain amidoaziridine compounds and certain acyclic polyamines as will be described hereinafter.

The effectiveness of polyaziridine compounds in which the nitrogen atom of the aziridine ring is an amide nitrogen for the dimensional stabilization of wool can be greatly increased by employing the amidoaziridine compounds in admixture with certain acyclic polyamines. The results obtained according to the present invention are comparable to the excellent results obtained by using the arninoaziridine compounds described in applicants copending application Serial No. 105,285. Moreover, since the polyaziridines of the amide type are generally more economical and easier to prepare than the polyaziridines of the amine type, the increased effectiveness of compounds of the amidoaziridinyl type when employed in combination with the economic acyclic polyamines is a very desirable and useful result representing a considerable advantage and improvement in the art of textile treatment.

The aziridine compounds which are employed for purposes of the present invention as Will be described in detail can be represented by the formula:

wherein R R and R have the meaning given above and X is selected from the group consisting of oxygen and sulfur.

Further polyaziridines of the amide type suitable for purposes of the present invention are the carboxamides which are represented by the structural formula:

(III) R1 R1 NC O R-C ON H Rg-C C-R; H H

wherein R R and R have the meaning given above and R represents a divalent organic group such as alkylene containing from 2 to carbon atoms, hydroxy-substituted alkylene, and the like.

Included among the amidopolyaziridines are the carbamates which are represented by the structural formula:

wherein R, R R and R have the meaning given above.

Additional polyaziridine compounds of the amide type include substituted ureas represented by the structural formula:

wherein R, R R and R have the meaning given above.

Still further examples of polyaziridine compounds included among the amide type are the sulfonamides represented by the structural formula:

Representative compounds included within Formulae 11 through V-I described above are listed. below.

The polyamines that can be employed in practising the methods of the present invention generally contain at least five amino groups per molecule and include polyalkylene polyamines containing the repeating unit represented by the structural formula:

(v11 FlTT-CmHml wherein R; is selected from the group consisting of hydrogen and alkyl and m has a value of 2 to 6.

Additional polyamines are the polyaminopolyalkylene 7 5 oxides containing the repeating unit represented by the structural formula:

(VIII) [-tf-(o H onomm LE4 J in which R and m have the same meaning as given above and b is an integer with a value of 1 to 20.

According to the method of the present invention the textile material which may be in the form of fibers, threads, yarns or fabrics is contacted with a solution containing the polyaziridine of the amide type together with a polyamine. Water is the preferred solvent vehicle although any inert organic solvent can also be employed providing it does not interfere with the reaction or does not deleteriously afiect the final product. In practice, the reactants can be employed in varying amount ranging, for example, from 10 parts polyaziridine and parts polyamine to 90 parts polyaziridine and 10 parts polyamine. The optimum ratio of reactants for a specific mixture can be suitably varied so as to produce the most desirable product.

In general, the pH of the treating solution can, if desired, be adujsted to about '6 to 7 with acid in order to avoid possible damage to the woolen fabric or fiber which may result at elevated temperature from the alkalinity of the solution.

The total concentration of the reagent including polyaz-iridine plus polyamine that is employed for the treatment of the woolen textile can be varied over a considerable range, however, concentrations of 1% to about 10% based on the weight of the textile material treated are generally preferred.

Many methods for applying the reagent solution to the textile material can be utilized for the purposes of the present invention including spraying, dipping, padding and the like. Excess solution is squeezed out, for example, by passing the fabric through pad rolls or by centrifuging.

After impregnation, the textile is dried and then heated for a brief period of time to complete the reaction of polyaziridine and polyamine with each other and with the wool. Heating for about 1 to 10 min. at a temperature varying from 250 F. to 350 F. is generally sufficient. It is understood, of course, that both the duration and the temperature at which the heating is carried out can be varied from the stated figures. Generally, the textile material is washed to remove the unreacted materials which then completes the process.

It has been observed that Woolen textile materials treated according to the methods of the present invention exhibit a shrinkage which is reduced from an excessive value of as much as 50% after 5 launderings for some woolen fabrics to less than about 5% area shrinkage under optimum conditions of treatment. Moreover, other properties of wool, such as the color, and, appearance and strength are not significantly altered. The shrink-proofing treatment of the present invention is extremely flexible in that it may be applied before or after dyeing with equally good results. The fabrics treated according to the new process are capable of undergoing other treatments, particularly chemical treatments such as creasing, reducing treatments and the like.

As explained above, one feature of the present invention resides in the treatment of textiles containing woal with a treating bath which, in addition to the polyaziridine and polyarnine, also contains multi-functional finishes employing various finishing agents to impart certain specific properties. For example, fluoro-chemicals, such as fluoro-organic compounds, can be added to improve stain repellency and water repellency. Surprisingly, it has been found that the durability to laundering and dry cleaning of fluoro-chemical finishes applied in conjunction with the new shrink-proofing process is greatly improved when compared to the durability of the fluorochemical finishes applied alone. Thus, the present invention permits one to obtain a highly desirable combination of properties including, for example, shrink resistance, water repellency and stain repellency, in a single finishing step.

Although reference is made herein to woolen textile materials, it will be understood that it is intended to include fabrics and similar textile materials such as yarns containing 100% wool as well as mixtures of wool fibers with various other materials such as regenerated cellulose, cellulose, linen, polyester fibers and the like. In textile materials wherein blends of wool are used with natural or synthetic fibers, the wool generally comprises at least about 10% by weight.

The following examples are considered as illustrative of the method of the present invention and are not considered limiting thereof in any way. Test methods employed to obtain the results set forth in the examples are as follows.

Stifiness: ASTM Dl388-55T Cantilever Method Flex abrasion: ASTM D1175-61T /2 1b. head, 2 lbs.

toggle Reflectance: Photovolt 610, Search Unit 6104, Green Filter Colorfastness:

To washAATCC 61-1962, Test 1A, 105 F.

To light-AATCC 16A-1963, 20 fadeometer hours. To crockingAATCC 8-1961.

To perspiration-AATCC 15-1962.

Shrinkage: Measurement after laundering according to the following washing procedure-18 x 18" specimens with 10" x 10" markings. Washed in automatic agitator home-type washing machine at 105 F. with 5 lb. load using detergent (Fab or Tide) and a running suds for 15 minutes. Washed specimens were rinsed and extracted in the washer for the full cycle and dried flat-bed pressed for 5 seconds at 275 F.- 300 F. and conditioned for a minimum of 12 hours at 65% R.H. and 70 F. on a flat horizontal surface. Specimens measured for shrinkage in warp and filling directions. The above washing procedure was repeated as many times as required.

Oil repellency: Test Method Minnesota Mining and Manufacturing Co. Appendix A, pages 1-2. Measured after laundering (same washing procedure as for shrinkage), and after dry cleaning (Minnesota Mining and Manufacturing Co. Test method, Laboratory Dry Cleaning Procedure, Appendix A, page 4, Technical Bulletin).

Example 1 Percent Shrinkage Percent Percent Weight Flex Stiffness Reagent Gain 1L 5L Abrasion Warp OWF (W. G.) Warp W F W F 7.3 5 9 3. 9 4. 7 9. 4 l0. 1 195 108 4.7 4 3 3.9 5.8 9.4 11.7 352 196 Untrl. Cn 5. 9. 5 15.0 15. 0 1, 100 110 tro The test results obtained and tabulated above demonstrate that the polyaziridinyl compounds of the amide type when used alone are relatively ineffective and result in a small reduction in shrinkage when compared to an untreated control sample of fabric.

Example II The exact procedure was employed in this example as employed in Example I with the exception that bis(1,2- propylene) adipamide (BPA, product of Interchemical Corp.) was used in place of the APO of Example I. The fabrics were treated in exactly the same methods and tested under the same conditions. The results are shown in the table below:

Percent Shrinkage Percent Percent Flex Stiifness Reagent W. G. 1L 5L Abrasion Warp OWF Warp W F W F The above table shows that the adipamide compound which is a polyaziridinyl compound of the amide type was not particularly effective in substantially reducing the are-a shrinkage when compared with the untreated control. At best, the improvement in shrink-proofing as compared to an untreated control was about 5%.

Example III Samples of plain weave woolen flannel identical to that employed in Example I were impregnated with aqueous solutions containing tris-aziridinyl phosphineoxide (APO) and tetraethylene-pentamine (TEPA), using a laboratory padder. Before application to the fabric the reagent solution was neutralized with acetic acid to a pH of 7 and 0.2% Triton X-100 non-ionic surface active agent was added to the pad solution. The padded samples were then framed and dried at 150 F. then cured at 300 F. for 5 minutes in a forced air draft oven. The fabric samples were thoroughly rinsed in lukewarm water, then framed and dried.

Percent Percent Shrinkage Stilt- APO-TEPA Regent Percent After 5L ness Reflec- Weight Ratio OWF W. G. Warp tanee 2:1 12. 7 10. 5 4. 0 4. 5 246 62 1:2 10.7 5. l 4. 5 4. 5 247 55 TEPA alone 10.8 15.0 15. 0 62 APO alone 9. 2 6. 9 9.6 11.5 196 Example IV Samples of plain weave woolen flannel identical to that employed in Example III were treated following the exact same procedure as described in Example III with the exception that the polyamine contained the repeating unit:

Lt... l

which was used in admixture with the tris-aziridinyl phosphine oxide (APO). The results are tabulated below:

The results shown in the table above further clearly show the unexpected improvement in percentage area shrinkage obtained when using a mixture of the polyamine with an amide type polyaziridine compound.

Example V Samples of plain weave woolen flannel identical to that employed in Example III were treated with a mixture of tris-aziridinyl phosphine oxide and a polyethyleneimine with an average molecular weight of 30,000 to 40,000 (PEI) following the exact same procedure as employed in Example III. The padded samples were framed and dried at 150 F. then cured at 250 F. for 5 minutes in a forced draft oven. The fabric samples were thoroughly rinsed in Warm Water then framed and dried and tested according to the prescnbed methods above. The results of the tests are shown in the table below.

Percent Percent Shrinkage Flex Stiff- APO-PEI Re- Percent After 5L Abraness Reflec- Weight Ratio agent W.G. sion Warp tance OWF Warp It is apparent that treatment with polyethyleneimine alone was not satisfactory for reducing the shrinkage to an acceptable level. Furthermore, the sample treated with PEI alone was badly discolored while the other samples exhibited no discoloration.

Example Vl Example V was repeated using an APO-PEI mixture in 2:1 Weight ratio, and varying the reagent concentration. The padded samples, after drying at 150 F., were cured at 250 F. for 5 minutes in a forced draft oven. The cured fabric samples were thoroughly rinsed in warm water, :thenframed and dried. The'test results are reported below:

Percent Percent Shrinkage Flex Reagent Percent After 5L Abrasion Stiffness Reflec- OWF W. G. Warp Warp tance Similar results were obtained when the tris-aziridinyl phosp'hineoxide APO) in the mixture was replaced by each of the following:

(a) OKs-Cs CHCH3 NCO(OH2)4CON I CH OH:

(0) CH1 CH2 NCONH(OH2)GNHC ON\ C 3 CH2 (6) CH3CE CH-CH2 NC 0 O CH2CHzOCHzCH OC ON LE2 Hz In each case, the mixture of polyaziridine with PEI was vastly more effective than the :polyaziridine alone or the PEI alone.

Example VII Example V was repeated, employing APO-PEI in 2:1 weight ratio in combination with a polyfiuoroalkyl acrylate emulsion marketed under the trade name of Scotchgard FC-208 by the Minnesota Mining and Manufacturing Co., for the treatment. After drying at 150 F., the padded samples were cured at 250 and 300 F. for 5 minutes in a forced draft oven. The samples were thoroughly rinsed in warm water, then framed and dried and tested according to the procedure described above. The following table reports the results thereof:

Percent Percent Percent Curing Sample APO PEI Seotch- Percent Temp.

OWF OWF gard W.G F. OWF

Percent Shrink- Oil Repellency Oil Repelleney After age After 5L Dry Cleaning Sample W F Dry 1L 5L 1 Cycle Cycles Cycles Example VIII The following example illustrates the results obtained when fabric treated according to the new process is dyed after the shrink-proofing treatment.

Example V was repeated, but an APO-PEI mixture in 2:1 weight ratio was used for the treatment. The amount of reagent applied was 5.7% on weight of fabric OWF). The padded samples were framed and dried at 150 F., then cured at 250 F. for 5 minutes in forced air draft oven. The fabric samples were thoroughly rinsed in warm water, then framed, dried and relaxed.

The samples so treated were dyed with 1% Capracyl Red B (Col. Ind. No. Acid Red 178) pre-met-allized dye and also with 1% Alizarine Direct Blue A (Col. Ind. No. Acid Blue 25) acid dye, according to standard wool dyeing procedure.

The dyeings resulted in an excellent uniform shade.

Example IX A mixture of 4% APO2% PEI was applied for the treatment of plain weave woolen flannel samples previously dyed with 1% Capracyl Red B (Col. Ind. No. Acid Red 178) pre-metallized dye and also with 1% Alizarine Direct Blue A (Col. Ind. No. Acid Blue 5) dye. The samples padded with the APO-PEI mixture were framed and dried at 150 F., then cured at 250 F. for 5 minutes. The fabric samples were thoroughly rinsed in warm water, then framed, dried and relaxed. The applicatlon resulted in a 5.5% weight galn.

Percent Shrinkage After 5L Flex Stiffness Sample Count Abrasion Warp Warp W F RA 1. 1. 0 37 x 36 375 135 BA 2. 3. 5 36 x 37 550 123 R 8. 5 5. 5 37 x 37 375 65 B 13.0 12.0 38 x 38 925 90 RA: Dyed red, then shrink-proofed. BA: Dyed blue, then shrink-proofed. R: Dyed red, not shrink-proofed.

l3: Dyed blue, not shrink-prool'ed.

It is understood that various other modifications will he apparent to and can readily be made by those skilled in the art without departing from the scope and spirit of this invention. Accordingly, it is not intended that the scope of the claims appended hereto be limited to the description set forth herein but rather that the claims be construed as encompassing all the features of patentable novelty which reside in the present invention including all features which would be treated as equivalents thereof by those skilled in the art to which the invention pertains.

What is claimed is:

1. A method for improving the physico-chemical properties of proteinaceous materials comprising treating said materials with polyfunctional amidoaziridine compounds and a polyethyleneimine containing at least 5 amino nitrogens per molecule, wherein the proportions of polyaziridine to polyimine range from 10:90 to :10 in parts by weight.

2. A method for improving the dimensional properties of textile materials containing wool which comprises applying to the textile material a polyfunctional amidoaziridine compound corresponding to the structure:

R1 X 01R: L N

wherein R R and R are selected from the group consisting of hydrogen and lower alkyl, and X is a member selected from the group consisting of I oxygen and sulfur, and

a polyethyleneimine containing at least 5 amino nitrogens per molecule, wherein the proportions of polyaziridine to polyimine range from 10:90 to 90:10 in part by weight. 3. A method of improving the dimensional properties of textile materials containing wool which comprises applying to the textile material a polyfunctional aziridine compound corresponding to the structure:

R1 R1 RzC G Rz N-o 0 R-O o N l Re -O R;

wherein R R and R are selected from the group consisting of hydrogen and lower alkyl and R represents a divalent aliphatic organic group, and

a polyethyleneimine containing at least 5 amino nitrogens per molecule, wherein the proportions of polyaziridine to polyimine range from 10:90 to 90:10 in parts by weight.

5. A method for improving the dimensional properties of textile materials containing wool which comprises applying to the textile material a polyfunctional aziridine compound corresponding to the structure:

wherein R R and R are selected from the group consisting of hydrogen and lower alkyl and R represents a divalent aliphatic organic group, and a polyethyleneimine containing at least 5 amino nitrogens per molecule, wherein the'proportions of poly- 'aziridine to polyimine range from 10:90 to 90:10 in parts by weight.

6. A method for improving the dimensional properties of textile materials containing Wool which comprises applying to the textile material a polyfunctional aziridine compound corresponding to the structure:

CH3 CH2 compound is:

10. The method of claim 1 wherein the aziridine OH: on,

11. The method of claim 1 wherein the aziridine compound is:

CHg-OH l/NCOOCHICHflOCHECHzO ON CH3 12. The method as defined in claim 7 wherein the textile material is heated from about 250 F. to about 350 F. in order to cure the reaction and is thereafter washed to remove unreacted materials.

13. A textile material containing wool treated according to the method as described in claim 1.

14. A woolen fabric treated according to the method as described in claim 7.

15. In a method for imparting desirable dimensional properties to a textile material containing wool wherein previous methods employing amidoaziridine compounds have not produced satisfactory reduction in shrinkage, the improvement whereby an increased effectiveness in shrinkproofing is obtained resulting in a satisfactory textile material and which improvement comprises applying to the textile material a mixture of an amidoaziridine compound and a polyethyleneimiue containing at least five nit-rogens per molecule, wherein the proportions of polyaziridine to polyimine range from 10:90 to 10 in parts by weight, and thereafter heating to cure the reaction and washing to remove unreacted materials.

References Cited by the Examiner UNITED STATES PATENTS 2,677,681 5/ 1954 Gill 8-l28 2,730,427 1/1956 Suen 8128 2,817,602 12/1957 Pardo 117141 2,859,134 11/1958 Reeves 8l27.6 2,889,289 6/1959 Reeves 8l27.6 2,891,877 6/1959 Chance 8127.6 2,925,317 2/1960 Moore 8127.6 2,950,197 8/1960 Allen 96-111 2,964,404 12/ 1960 Burness 96-85 3,080,259 3/1963 La Fleur 1l7-141 OTHER REFERENCES Alexander et aL: Biochem. Journal, vol. 52, pp. 177- 184 (1952).

NORMAN G. TORCHIN, Primary Examiner.

J. CANNON, Assistant Examiner.

Claims

1. A METHOD FOR IMPROVING THE PHYSICO-CHEMICAL PROPERTIES OF PROTEINACEPOUS MATERIALS COMPRISING TREATING SAID MATERIALS WITH POLYFUNCTIONAL AMIDOAZIRIDINE COMPOUNDS AND A POLETHYLENEIMINE CONTAINING AT LEAST 5 MINO NITROGENS PER MOLECULE, WHEREIN THE PROPORTIONS OF POLYAZIRIDINE TO POLYIMINE RANGE FROM 10:90 TO 90:10 IN PARTS BY WEIGHT.