US3104443A

US3104443A - Method and composition for fulling fabrics

Info

Publication number: US3104443A
Application number: US700543A
Authority: US
Inventors: Frederick T Lense
Original assignee: Monsanto Chemicals Ltd
Current assignee: Monsanto Chemicals Ltd; Monsanto Chemical Co
Priority date: 1957-12-04
Filing date: 1957-12-04
Publication date: 1963-09-24
Anticipated expiration: 1980-09-24

Description

United States. Patent M 3,104,443 METHOD AND COMPGSITEON FQR FULLENG FABRIQS Frederick T. Lense, Birmingham, Ala, assiguor to Monsanto Chemical Company, St. Louis, Me, a corporation of Delaware N0 Drawing. Filed Dec. 4, 1957, filer. No. 700,543 Claims. (QB. 26-49) This invention relates to fulling and/or felting of fabrics containing W001 and other animal fibers such as carnels hair, rabbit hair, etc. One particularly preferred embodiment of this invention relates to methods and compositions for fulling and/ or felting wool fabrics, and especially for fulling and/or felting such fabrics in the presence of an acid bath.

In the past, the foregoing treatments of animal fiber fabrics (-i.e., fabrics made up either completely or only partly of such animal fibers) have been largely carried out in aqueous solutions containing soaps. These soaps served several purposes, among which were lubrication and cleansing of the fabric. Since soaps are completely ineffective in acid media and relatively ineffective in neutral media, it has been necessary to maintain the solutions containing such soaps in an alkaline pH rangein spite of the fact that alkaline solutions tend to attack and degrade wool.

With the relatively recent advent and commercial availability of non-ionic surface-active agents (which retain their surface activity even in acidic solutions), therehas been a tendency for fabric processers to change their processing operations from alkaline fulling and/or felting to acidic fulling and/or felting with non-ionic surface-active agents. This has been effected by using common acids such as sulphuric acid, acetic acid, orthophosphoric acid, etc. to acidify the aqueous solutions of nonionic surface-active agents.

It has now been found that unexpectedly outstanding beneficial results are obtained by utilizing a fulling and/or felting solution containing (in addition to a non-ionic surface-active agent) an alkylarenesulfonic acid. More particularly it has been found that a combination of certain alkylarenesulfonic acids and non-ionic surface-active agents will give synergistic results in acid fulling and/or felting of wool fabrics-particularly with respect to removal of dirt and oil from the fabric.

The particular alkyl'arenesulfonic acids which must be utilized in the present invention are those containing an aromatic nucleus, at least one sulfonic acid group (-SO H), and at least one long-chain alkyl group (e.g., an alkyl group containing between about 6 to about 25 carbon atoms, and preferably between about 9 and about carbon atoms). The preferred aromatic nucleus is a benzene ring, but naphthalene, biphenyl, indole, or higher aromatic carbocyclic ring systems, or other cyclic compounds containing an aromatic type resonance (e.g., heterocyclic compounds such as pyridine, quinoline, thiophene, and the like) can also be utilized.

The alkylarenesulfonic acids can contain more than one of the long-chain ialkyl groups, and can also contain (in addition to the one or more long-chain alkyl groups) one or more shorter alkyl groups such as methyl, ethyl, propyl, etc. radicals. In general, particularly from the point of view of simplicity, availability, and water BJMAQ Patented Sept. 24, 1963 solubility, the monoalkyl substituted sulfonic acids (or at least the sulfonic acids containing only one of the longchain alkyl groups) are preferred over the more highly substituted sulfonic acids. Likewise, the present sulfonic acids can contain more than one sulfonic acid group (e.g., as in diand trisulfonic acids), but in general the monosulfonic acids are preferred. From the foregoing it will be apparent that a particularly preferred embodiment of this invention involves the use of monoalkylbenzenesulfonic acids in the acid fulling and/or felting of woolen and other animal fiber fabrics.

Typical examples of the above-discussed alkylarenesulfonic acids are: n-hexylbenzenesulfonic acid; Z-ethylhexylbenzenesulfonic acid; nonyltoluenesulfonic acids (especially those in which the nonyl group is derived from a propylene trimer); n-decylxylenesulfonic acid; n-decylnaphthalenedisulfonic acid; 3-n-dodecyl-5-ethylbenzenesulfonic acid; dodecyl and tridecylbenzenesulfonic acids (wherein the dodecyland tridecylbenzenes are obtained by alkylation of benzene with propylene tetra mer or butylene trimer); n-tetradecyltoluenedisulionic acid; n-hexadecylbenzenesulfonic acid; octadecylbenzenedisulfonic acid; and the like. Although the foregoing compounds have been referred to as specific materials, it will be readily appreciated that they will generally occur and be used as the isomeric mixtures which normally result from alkylation of the particular aromatic nucleus in question and subsequent sulfonation of the alkylated aromatic compound.

The other essential component of the aqueous acidic baths of the present invention is a non-ionic surface-active agent-numerous examples of which are well known and commercially available. Particularly preferred categories of such non-ionic synthetic surface-active agents are (1) condensation products of ialkylphenols and ethylene oxide, (2) condensation products of aliphatic alcohols and ethylene oxide, (3) condensationproducts of aliphatic mercaptans and ethylene oxide, and (4) condensation products containing both ethylene oxide and propylene oxide. Further elaboration with respect to these preferred categories is set forth below:

(1) CONDENSATION PRODUCTS OF ALKYL- PHENOLS AND ETHYLENE OXIDE The alkyl groups on the alkylphenols should generally contain between about 6 and about 20 carbon atoms, and preferably between about 8 and about 15 carbon atoms. While :alkylphenols containing more than one alkyl group per phenol nucleus can be utilized, it is generally preferred to use monoalkylphenols. The amount of ethylene oxide to be condensed with the alkylphenols depend to some extent upon the size and number of said alkyl groups. In general, between about 4 and about '15 mols, and preferably between about 6 and about 12 mols, ofethylene oxide will be condensed with each mol of alkylpheno-lthe higher proportions of ethylene oxide being utilized with the phenols containing the larger number of carbon atoms in the alkyl groups. Typical examples of the foregoing category of alkylphenol/ ethylene oxide nonionic synthetic detergents are condensation products of 1 mol of n-hexylphenol and 5 mols of ethylene oxide; 1 mol of Z-ethylhexylphenol and 6 rno-ls of ethylene oxide; 1 mol of n-octylphenol and '6 mols of ethylene oxide; 1 mol of nonylphenol (obtained by alkylation of phenol with a trimer of propylene) and 10 mols of ethylene oxide; 1 mol of n-decylphenol and 8 mols of ethylene oxide; 1 mol of n-dodecylphenol and 14 mols of ethylene oxide; 1 mol of dodecylphenol (from alkylation of a phenol with propylene tetrarner or butylene trimer) and 12 mols of ethylene oxide; 1 mol of n-octadecylphenol and 15 rnols of ethylene oxide.

(2) CONDENSATION PRODUCTS OF ALIPHATIC ALCOHOLS AND ETHYLENE OXiDE The aliphatic alcohols utilized in these condensates are long-chained alkyl alcohols containing between about 10 and about 20 carbon atoms, and preferably between about 12 and about 16 carbon atoms. As in the case of the alkylphenol condensation products, the amount of ethylene oxide to be condensed with such alcohols will depend to some extent upon the number of carbon atoms in the alcohol. In general, between about 4 and about 15 mols of ethylene oxide, and preferably between about 5 and about 12 mols of ethylene oxide will be condensed with each mol of alcohol. Typical condensates of this category are as follows: 1 mol of decyl alcohol and 4 mols of ethylene oxide; 1 mol of n-dodecyl alcohol and 5 mols of ethylene oxide; 1 mol of tridecyl alcohol (e.g., the oxo alcohol prepared from propylene stetramer or butylene trimer) and 5 mols of ethylene oxide; 1 mol of oxo-tridecyl alcohol and 9 mols of ethylene oxide; 1 mol of 0x0- tridecyl alcohol and 15 mols of ethylene oxide; 1 mol of n-tetradecyl alcohol and 8 mols of ethylene oxide; 1 mol of n-hexadecyl alcohol and 12 mols of ethylene oxide; 1 mol of n-octadecyl alcohol and mols of ethylene oxide; 1 mol of eicosyl alcohol and 14 mols of ethylene oxide.

(3) CONDENSATION PRODUCTS OF ALIPHATIC MERCAPTANS AND ETHYLENE OXIDE The aliphatic mercaptans utilized in these condensates are long-chain alkyl mercaptans containing between about 8 and about 20 carbon atoms, and pereferably between about 9 and about carbon atoms. As in the abovediscussed categories, the amount of ethylene oxide to be condensed with such mercaptans Will depend upon the chain length of the alkyl portion of the mercaptan, but will generally range from about 4 to about 15 mols, and preferably from about 7 to about 12 mols of ethylene oxide per mol of mercaptan. Typical examples of such condensation products are as follows: 1 mol of 2-ethylhexyl mercaptan and 4 mols of ethylene oxide; 1 mol of n-octyl mercaptan and 6 mols of ethylene oxide; 1 mol of n-decyl mercaptan and 7.5 mols of ethylene oxide; 1 mol of nonyl mercaptan (e.g., from propylene trimer) and 8 mols of ethylene oxide; 1 mol of branched-chain dodecyl mercaptan (e.g., from propylene tetramer or butylene trimer) and 10 mols of ethylene oxide; 1 mol of n-tetradecyl mercaptan and 11 mols of ethylene oxide; 1 mol of n-octadecyl mercaptan and 10 mols of ethylene oxide; 1 mol of eicosyl mercaptan and 14 mols of ethylene oxide.

(4) CONDENSATION PRODUCTS OF BOTH ETHYLENE OXIDE AND HIGHER ALKYLENE OXIDES These products are of the type often referred to as block polymers of ethylene oxide and higher alkylene oxides, of which condensation products of ethylene oxide and propylene oxide (with or without fatty acids, alcohols, mercaptans, alkylphenols, etc.) are preferred materials. Typical examples of these latter categories are those described in U.S. 2,674,619 and US. 2,677,700, the disclosures of which are incorporated herein by reference.

It should be understood that the categories of non-ionic synthetic surface-active agents discussed .above are merely preferred categories, and that the present invention is not limited to the use of only those non-ionic surface-active agents. For example, the well known class of non-ionic surface-active agents made up of condensation products aroaaas of long-chain aliphatic acids and ethylene oxide can also be utilized, as well as many others with which those skilled in the art will be familiar.

The foregoing sulfonic acids and non-ionic surfaceactive agents are formulated and used in amounts to give a weight ratio of sulfonic acid to non-ionic surface-active agents between about 1:5 and about 5:1, and preferably between about 1:3 and about 1:1. For convenience in handling and shipping, the combination of sulfonic acid and ncnionic surfacecctive agents 'will often be formulated in concentrated form, said concentrates to be solved and diluted with considerable proportion of water for utilization in treating fabrics according to the present invention. in actual use, between about 0.2 and about 20 ounces, preferably between about 2 and about 5 ounces, of the mixture of sulfonic acid and non-ionic surface-active agents will be dissolved in each gallon of water utilized in the aqueous treating solution.

In preparing concentrates of the sulfonic acids and nonionic surface-active agents it will generally be desirable to incorporate between about 5 and about 20% by weight (based upon the total concentrate) of water in order to reduce the viscosity of the concentrate and make it easier to handle and dilute for ultimate use.

The solutions utilizing the combination of materials described herein must be maintained in .an acidic pH range (i.e., pH less than 7). They are preferably maintained at a pH between about 2 and about 5. If necessary or desirable, other acids (such as sulfuric acid, acetic acid, phosphoric acid, etc.) may be used (in addition to the aforedescribed ingredients) in order to maintain the pH in the desired range. These other acids can also be used to produce the compositions of the present invention from mixtures of a non-ionic surface-active agent and an alkylarenesulfonate salt. Thus, for example, a mixture of sodium dodecylbenzene sulfonate and a non-ionic surface-active agent can be acidified with sulfuric acid to produce a mixture of the sulfonic acid, the non-ionic agent and sodium sulfate. When used as described herein (particularly in solutions having pH less than about 5) the sodium sulfate will merely behave as an inert diluent not having any particular effect upon the utility of the essential components, i.e., the sulfonic acid and the non-ionic surface-active agent.

The operations using the ingredients described in this invention can be carried out in the same manner as any of the prior art fulling and/or felting operations-particularly acid fulling and/or felting operations. Since such operations and practices are well known to those skilled in the textile art, the details thereof will not be repeated here.

The following example will serve to illustrate the outstanding and beneficial results obtained when using solutions formulated according to the present invention:

Example Loomstate wool fiber fabrics were processed in a laboratory fulling mill in the presence of solutions containing the various ingredients indicated in the following table. The fabric was fulled for 15 minutes, rinsed with water, and then analyzed with respect to (1) the amount of oil remaining in the fabric and (2) the effectiveness with which dirt had been removed from the fabric. The results are set forth in the accompanying table. From the table it is apparent that the combination of sulfonic acids and non-ionic detergents of this invention are much more effective than either of the components taken aloneeven when the individual component alone is used at a concentration as great as that of the combination. The results also demonstrate that the elfect of the sulfonic acid is not merely one of acidifying the solution, since acidification with the more common acids (e.g., sulfuric acid) does not produce a comparable result. It was also noted that the acid solutions of the present invention were particularly 5 outstanding with respect to the ease with which .they are rinsed from the processed fabric with only a water rinse.

thereof and (b) between 0.2 and 5 parts by weight of a condensation product of an alkylphenol containing from TABLE Additives Oil Content After Test Dirt Fulling N on-Ionic Surface-Active Removal and Alkylarenesulfonie Acid Agent (Condensation Rinsing, Products) Percent A Water Only Very Poor.-. 3. 91 B. Dodecylbenzenesulfonic Poor- 2.91

Acid (3 oz./gal. H20). tert.-Do(lecylmercaptan+ Good 2. 37

7.8 E.O (3oz./gal.H2O). D tert.-D0clecylmercaptau+ do 1. 28

7.8 12.0 (3 ozJgal. H2O, plus H1504 to bring pH of bath to 3.0). E Dodecylbenzenesulfonic tert.-Dodecyhnercaptau+ Excellent. 0. 41

Acid (1 oz./gal. H10). 7.8 E.(). (2oz./gal. H20). F Dodecylbenzenesultonic Oxo-tridecyl alcohol+9 do 0. 13

Acid (1.5 oz./gal. E.O. (1.5 0z./gal. H 0). 20).

I claim: about 8 to about 15 carbon atoms 1n the alkyl group 1. A composition of matter comprising (a) one part by weight of an alkylbenzenesulfonic acid containing from about 6 to about 25 carbon atoms in the alkyl group thereof and (b between about 0.2 and about parts by weight, for each part by weight of said acid, of a nonionic synthetic surface-active agent selected from the group consisting of (1) a condensation product of an alkylphenol containing from about 6 to about 20 carbon atoms in the alkyl group thereof with between about 4 and about 15 molar proportions of ethylene oxide, (2) a condensation product of an aliphatic alcohol containing from about to about 20 carbon atoms therein with between about 4 and about molar proportions of ethylene oxide and (3) a condensation product of an aliphatic mercaptan containing from about 8 to about carbon atoms therein with between about 5 and about 15 molar proportions of ethylene oxide.

2. A composition of matter comprising (a) 1 part by weight of an alkylbenzenesulfonic acid containing from about 6 to about carbon atoms in the alkyl group thereof and (b) between about 3 and about 1 part by weight of a non-ionic synthetic surface-active agent selected from the group consisting of (1) a condensation product of an alkylphenol containing from about 6 to about 20 carbon atoms in the alkyl group thereof with between about 4 and about 15 molar proportions of ethylene oxide, (2) a condensation product of an aliphatic alcohol containing from about 10 to about 20 carbon atoms therein with between about 4 and about 15 molar proportions of ethylene oxide and (3) a condensation product ofan aliphatic mercaptan containing from about 8 to about 20 carbon atoms therein with between about 5 and about 15 molar proportions of ethylene oxide.

3. A composition of matter comprising (a) one part by weight of an alkylbenzenesulfonic acid containing from about 9 to about 15 carbon atoms in the alkyl group thereof and (b) between about 0.2 and about 5' parts by weight of a condensation product of an aliphatic mercaptan containing from about 9' to about 15 carbon atoms therein with between about 7 and about 12 molar proportions of ethylene oxide.

4. A composition of matter comprising (a) one part by weight of an alkylbenzenesulfonic acid containing from about 9 to about 15 carbon atoms in the alkyl group thereof and (b) between about 0.2 and about 5 parts by weight of a condensation product of an aliphatic alcohol containing from about 12 to about 16 carbon atoms therein with between about 5 and about 12 molar proportions of ethylene oxide.

5. A composition of matter comprising (a) one part by weight of an alkylbenzenesulfonic acid containing from about 9 to about 15 carbon atoms in the alkyl group thereof with between about 6 and about 12 molar proportions of ethylene oxide.

6. A composition of matter comprising (a) one part by weight of an alkylbenzenesulfonic acid containing from about 6 to about 25 carbon atoms in the alkyl group thereof; (b) between about 0.2 and about 5 parts by weight of a non-ionic synthetic detergent selected from the group consisting of (1) a condensation product of an alkylphenol containing from about 6 to about 20 carbon atoms in the alkylgroup thereof with between about 4 and about 15 molar proportions of ethylene oxide, (2) a condensation product of an aliphatic alcohol containing from about 10 to about 20 carbon atoms therein with between about 4 and about 15 molar proportions of ethylene oxide and (3) a condensation product of an aliphatic mercaptan containing from about 8 to about 20 carbon atoms therein with between 5 and about 15 molar proportions of ethylene oxide; and (c) between about 5% and about 20% by weight of water (based upon the total weight of the mixture).

7. A composition of matter comprising (a) about 30% by weight of dodecylbenzenesulfonic acid; (b) about 60% by weight of the condensation product of tertiary dodecylmercaptan with about 8 molar proportions of ethylene oxide; and (0) about 10% by weight of water.

8. In a process of fulling fabrics, the improvement which comprises performing the said fulling with said fabrics being wetted with an aqueous solution of a mixture of (a) an alkylbenzenesulfonic acid containing from about 6 to about 25 carbon atoms in the alkyl group thereof and (b) a non-ionic synthetic surface-active agent; said fulling bath being maintained at a pH between about 2 and about 7, and the weight ratio of said alkylbenzenesulfonic acid to said non-ionic surface active agent in said aqueous solution being between about 1:5 and about 5:1.

9. In a process of fulling wool fabrics, the improvement which comprises performing the said fulling with said wool fabrics being wetted with an aqueous solution containing between about 2 and about 5 ounces (per gallon of water) a mixture of (a) about one part by weight of dodecylbenzenesulfonic acid and (b) about two parts by weight of a condensation product of tertiary dodecyl mercaptan with about 8 molar proportions of ethylene oxide; said solution being maintained at a pH between about 2 and about 5.

10. A process for the fulling of woolen fabric which comprises applying to said fabric an aqueous solution having a pH between about 2 and about 7 and containing between about 2 and about 5 ounces (per gallon of said aqueous solution) of a mixture of an alkylbenzenesulfonic acid and a non-ionic synthetic surface active agent, and subjecting said fabric containing said aqueous solution to mechanical working in a fulling machine, the Weight ratio of said alkylbenzenesulfonic acid to said non-ionic surface active agent in said mixture being between about 1:5 and about 5:1.

References Cited in the file of this patent UNITED STATES PATENTS Daimler et a1 June 4, 1929 Schoeller et a1 Aug. 21, 1934 OTHER REFERENCES Textile World, August 1932, p. 80 (256).

Claims

8. IN A PROCESS OF FULLING FABRICS, THE IMPROVEMENT WHICH COMPRISES PERFORMING THE SAID FULLING WITH SAID FABRICS BEING WETTED WITH AN AQUEOUS SOLUTION OF A MIXTURE OF (A) AN ALKYLBENZENESULFONIC ACID CONTAINING FROM ABOUT 6 TO ABOUT 25 CARBON ATOMS IN THE ALKYL GROUP THEREOF AND (B) A NON-IONIC SYNTHETIC SURFACE-ACTIVE AGENT; SAID FULLING BATH BEING MAINTAINED AT A PH BETWEEN ABOUT 2 AND ABOUT 7, AND THE WEIGHT RATIO OF SAID ALKYBENZENESULFONIC ACID, TO SAID NON-IONIC SURFACE ACTIVE AGENT IN SAID AQUEOUS SOLUTION BEING BETWEEN ABOUT 1:5 AND ABOUT 5:1.