US3080208A

US3080208A - Treatment of wool and related materials

Info

Publication number: US3080208A
Application number: US46883A
Authority: US
Inventors: Iachan Abrahao
Original assignee: Individual
Current assignee: Individual
Priority date: 1960-07-25
Filing date: 1960-08-02
Publication date: 1963-03-05
Anticipated expiration: 1980-03-05
Also published as: GB938759A

Description

This invention deals with or relates to a process for improving protein fibers, especially of wool, in order to obtain new products having greater chemical reactivity and related better qualities. This improvement of said fibers, as Well as of textile goods made therefrom is brought about by chemically modifying the exposed, outer surface of said fibers.

Prior art processes for treating wool, hair and related nitrogen containing fibers, such as mass made nitrogenous fibers, e.g. those precipitated from protein containing solutions, the protein being derived e.g. from milk casein, or from peanuts and others, are well known. Said processes are primarily concerned with the improvement of the textile properties of the fibers, such as resilience, dyeability, smoothness, break resistence, fiexural strength and the like.

According to the invention, the improvement of protein-fibers is effected by forming new reactive sites in the proper protein molecule.

Through a number of tests the inventor has discovered that by treating protein containing fibers, especially Wool, with materials having two or more reactive groups in the molecule, at least one of which is a imino or amino group, and simultaneously reacting the thus treated fibers with a reactive aldehyde, especially with formaldehyde, the fiber protein molecule acquires new reactive sites, which in turn are capable of further reaction with other substances.

Such property of the treated fibers of further reacting with other substances is especially valuable as the fibers will enable the bonding of chemical residues or radicals of dyes, of finishing materials, of moth-proofing agents and other substances which may be employed for the aftertreating of fibers and textile materials.

These and other advantages are secured by treating the fibers with a solution or a dispersion of a reactive amino or imino compound, including amino-acids, amino-phenols, amino-arylene-sulfonic acids, the corresponding imino compounds as well as reaction mixtures containing aminoacids along with other non deleterious materials, such as protein hydrolyzates, in the presence of a reactive aldehyde such as formaldehyde.

In short the invention consists in impregnating e.g.

by soaking the fibers either in a loose condition or in felted or interwoven state, or as a textile good, such as non-finished fabric, in the selected reaction medium, or both, containing a controlled amount of the reactive amino or imino-compound, and containing also a corresponding amount of formaldehyde, at a temperature up to 100 C., at atmospheric pressure.

The fibrous material will absorb a substantial amount of the reactive aminoor imino-compound, up to 70- States atent O 100% of the contents thereof in the treating bath. The

thus absorbed amino or imino compound can be chemically bonded to the fibrous material by reacting same in situ, that is, in the same bath, with formaldehyde. This chemical bonding of the reactant to the fibers may be noticed by the increase in weight, of the fiber, which may amount to 645% related to the weight of the fibers, measured at a given degree of dryness, or with the same amount of moisture in the fibrous material at the start.

By such a chemical treatment following advantages are secured:

(l) The treated wool and like materials exhibit a betfor bonding or fixing of dyes, the thus obtained dyeings "ice are Wash proof and will resist better to the effects of light, having also a warmer feel.

(2) The treatment in question reduces the shrinking of wool to 30-40% of that of the non-treated wool.

(3) The stretch-resistance of wool is increased of from 15 to 20% by this treatment.

(4) Through a proper selection of the reactants there will be formed further reactive groups on the protein nucleus, especially on the aromatic nucleus thereof, thus allowing further reactions of the treated wool so as to combine same with other reactants in condensation reactions.

The treatment according to this invention permits such further condensation reactions comprising:

(a) Reaction of the modified wool protein molecule with reactive substituted aromatic compounds, such as anthranylic acid derivatives, imparting thereto fluorescent or optical bleaching properties, by combining the optically active grouping with the reactive wool protein molecule.

(b) Reaction of the thus modified wool protein molecule with reactive compound selected from the quaternary ammonium, .sulfonium and phosphonium compounds, such as dichlor benzyltriphenyl phosphonium chloride or 2,2- dioxy 3,5,3',5'-tetrachloro-tri-phenyl-methane-Z"-sulfonic acid or a salt thereof, or 3,4-dichlor benzene-l-N-methylsulfonarnide. By such treatment the wool becomes mothproof.

Other compounds showing a related reactivity are other halogen-triphenyl methane derivatives, substituted arylsulfonamides, amino-halogen phosphonium compounds and reactive substituted urea and thiourea compounds.

By a proper selection of such reactants the wool or any other related material becomes antimetabolite, according to the definition of R. I. Pence; Pence, R. 1., Soap & Chemical Specialties, August 1959, i.e., the wool treated according to this invention becomes miticide and larvicide upon condensation reaction e.-g. with a substituted sulfonamide compound or the like.

(0) Due to the formation of new reactive sites in the protein molecule, the fibers treated in accordance with this invention show also greater reactivity toward a crosslinking with synthetic resins, respectively with the corresponding resin-forming materials or a pie-condensate thereof. Of course thus treated fibers will thereafter be subjected to a further treatment in order to complete the setting reaction in situ, which is not intended to be within the scope of this invention.

(d) The wool or like protein-fibers treated according to this invention are also likely to combine actually with basic dyes, the resulting dyeings showing deeper shades and greater brilliancy.

(5) By further reacting the new acid groups introduced in the protein molecule, according to this invention, with salt-forming reagents further effects can be secured, such as water repellency or water-proofing, fire or flame-proofing, antistatic effects on the treated wool or like materials, according to the character of the metal or other salt forming group attached to the carboxyl group or groups,

formed by the process of this invention on the protein molecule, thus providing the modified woolen material which is within the scope of this invention.

In order to better understand the present invention and to illustrate the Way of effecting same, following examples are given.

Example 1.100 g. of wool (fibers or yarn) are treated with 1000 ml. of a solution comprising 2% by weight of glycine in 3% acetic acid aqueous solution together with 300 ml. of formaldehyde commercial solution. The reaction is allowed to take place by heating to about C. for 60 minutes. After completion of the reaction the wool is removed from the treating bath, squeezed or centrifuged in order to remove the excess of bath liquor and rinsed. After drying in contact with air, to the same degree of moisture as before the treatment, the wool weighs 113.0 g., thus showing an increase of 13% by weight.

Example 2.Treating wool (yarn or fabric) as described in Example 1, but replacing the glycine reactant by 1000 ml. of a 1% solution of amino-undecanoic acid in a 3% acetic acid aqueous solution and adding thereto 300 ml. of a commerical formaldehyde solution, the resulting wool shows an increase in Weight of 11%.

Example 3.-Using the treating solution as in Example 1, viz 1000 ml. of the glycine-acetic acid solution, plus 300 or 330 ml. of formalin, the treatment may also be efiected at room temperature. Time required to obtain a comparable effect (as in Example 1),-72 hours. Weight increase of the treated wool-8.4%

Example 4.In this example, the wool (in the form of a strand of yarn or astrip of knitted fabric) is treated in a bath containing a 3% acetic acid aqueous solution, (1000 ml.) and in which is dissolved also 1% of sulfonilamide, plus 330 ml. of formalin, for 60 minutes on a water-bath, at 90l0 C. Weight increase of the treated wool8.8%.

Example 5.This example illustrates the use of an acetic acid aqueous solution (3% of acetic acid) containing also 2%, by weight, of a commercial casein hydrolyzate, obtained by the usual acid hydrolysis of milk casein and 300 ml. of formalin. Operating otherwise as outlined in Example 1, the weight increase of the treated wool is 8%.

Example 6.-Using a hydrolyzate of comminuted horn in lieu of the casein hydrolyzate as in the preceding example, the wool shows a weight increase of 8.2%.

Example 7.Replacing the casein hydrolyzate of Example by a hydrolyzate of Wool refuse or scrap and operating as described above, the treated wool shows an increase of weight amounting to 8.5%.

Example 8.Also a technical grade gelatin hydrolyzate may be employed in the treating bath, as explained in Example 5. In this case, the weight increase of the treated wool amounted to 8.8%.

Example 9.An especially effective reactant is sulfanilic acid employed at a relative amount of 1% by weight in solution in the 3% acetic acid solution, con taining also 300 ml. of formalin per liter of said acetic acid solution as in Example 1 or 5 and effecting the treatment at a temperature in the range of 90-100 C. The thustreated wool shows a. weight increase of 11.6%.

Example 10.In place of sulfanilic acid there is used a 1% anthranilic acid treating bath, containing the other ingredients as specified in Example 1 or Example 5, cmploying the procedure outlined in Example 1. When using a 1% solution of anthranilic acid in the acetic-acid solution a Weight increase of about 7% is obtained.

The thus treated wool exhibits. an optical bleaching effect which adds to the luster and brightness of the wool.

Example 11.-As an example of the use of an aminophenol, one may employ a 1% solution of ortho-aminophenol in the treating bath, comprising acetic acid and formaldehyde as stated in Example 1, but without'glycine and subjecting the wool to the treatment therein explained. In this case the Weight increase is 6.5%.

Example 12.Operating with a treating bath as in Example 3, but replacing the 2% glycine by a 1% amino undecanoic acid solution and extending the period of treatment to 120 hours, the increase of weight amounts to 11.2%. Comparable results are obtained by effecting the treatment at 37 C., for 72 hours, viz a weight increase of 10.7%.

Although the above examples show the process of the. invention as applied solely to Wool it is understood that same. can also be applied to textile goods consisting of two or-more fibrous components, one of which is wood or a wool-like material, such as precipitated or regenerated protein fiber.

In this way it is possible to obtain special effects on ablendedmaterial, consisting eg of wool and a cellulosic fibrous material.

Further, the action of the treating bath may be accompanied by that of a physical agent, e.g. by applying to the yarn of fabric, being treated a mild stretching, e.g. in the range of from 10 to 50% based on the original length of the material. This stretching may be effected either during the bath-treatment, or when the treated wool is being dried. Also a steaming treatment may be combined with the process of this invention.

According to this invention, thev treatment of the Woolen material is effected in a single operation, i.e. the material is soaked in the acetic acid solution of the reactive aminoor imino-compounds, in the presence of the formaldehyde compound, preferably with heating at a temperature in the range of l00 C.

It is indeed surprising that the formaldehyde will react to bind the aminoor imino-compound chemically to the fibrous material. As already explained above the treat ment according to the invention may be followed by further treating the wool or like material with moth-proofing, flame-proofing, water-proofing or other finishing treatment with greatly enhanced effects over those obtained by prior art processes.

I claim:

1. In a process for chemically modifying wool and fibrous materials precipitated from protein-containing solutions, said fibrous materials being in the form of loose fibers, yarns and fabrics made therefrom, prior to the finishing thereof, the improvement comprising treating said fibrous materials, with an aqueous acidic solution of an organic nitrogen-containing compound having a nitrogen-containing reactive group and at least one additional reactive group, said solution containing formaldehyde, until the said material shows a weight increase of at least 6% as compared with the starting ma terial at the same degree of moisture, said nitrogen-containing compound being a compound selected from the group consisting of an aliphatic amino acid, an aliphatic imino acid, a mixture of aliphatic amino acids, a mixture of aliphatic imino acids, a mixture of at least an aliphatic amino acid and an aliphatic imino acid, an amino aryl sulfonic acid, an aryl amino acid, an aryl imino acid, an aryl amino phenol, and an aryl imino phenol, thereby chemically modifying the outer surface of said material to contain a reactive group.

2. In a process for chemically modifying wool and fibrous materials precipitated from protein-containing solutions, said fibrous materials being in the form of loose fibers, yarns and fabrics made therefrom, prior to the finishing thereof, the improvement comprising treating said fibrous materials with an aqueous acidic solution of amino-undecanoic acid, said solution containing formaldehyde, until the said material shows a weight increase of at least 6% as compared with the starting material at the same degree of moisture.

3. In a process for chemically modifying wool and fibrous materials precipitated from protein-containing solutions, said fibrous materials being in the form of loose fibers, yarns and fabrics made therefrom prior to the finishing thereof, the improvement comprising treating said fibrous materials with an aqueous acidic solution of anthranilic acid, said solution containing formaldehyde, until the said material shows a weight increase of at least 6% as compared with the starting material at the same degree of moisture.

4. In a process for chemically modifying wool and fibrous materials precipitated from protein-containing solutions, said fibrous, materials being in the form of loose fibers, yarns and fabrics made therefrom, prior to the finishing thereof, the improvement comprising treating said fibrous materials with an aqueous acidic solution of sulfanilamide, said solution containing formaldehyde, until the said material shows. a weight increase of at least 6% as compared with the starting material at the same degree of moisture.

5. In a process for chemically modifying wool and fibrous materials precipitated from protein-containing solutions, said fibrous materials 'being in the form of loose fibers, yarns and fabrics made therefrom, prior to the finishing thereof, the improvement comprising treating said fibrous materials with an aqueous solution containing 3% of acetic acid, from about 1% to about 3% of an organic nitrogen-containing compound having a nitrogen-containing reactive group and at least one addi tional reactive group and from about 20% to 35% of a commercial formaldehyde solution until the said material shows a weight increase of at least 6% as compared with the starting material at the same degree of moisture, said nitrogen-containing compound being a compound selected from the group consisting of an aliphatic amino acid, an aliphatic imino acid, a mixture of aliphatic amino acids, a mixture of aliphatic imino acids, a mixture of at least an aliphatic amine acid and an aliphatic imino acid, an amino aryl sulfonic acid, an aryl amino acid, an aryl imino acid, an aryl amino phenol, and an aryl imino phenol, thereby chemically modifying the outer surface of said material to contain a reactive group.

6. In a process for chemically modifying wool and fibrous materials precipitated from protein-containing solutions, said fibrous materials being in the form of loose fibers, yarns and fabrics made therefrom, prior to the finishing thereof, the improvement comprising treating said fibrous materials with an aqueous solution containing 3% of acetic acid, from about 1% to about 3% of amini-undecanoic acid, and from about 20% to 35% of a commercial formaldehyde solution until the said material shows a weight increase of at least 6% as 6 compared with the starting material at the same degree of moisture.

7. In a process for chemically modifying wool and fibrous materials precipitated from protein-containing solutions, said fibrous materials being in the form of loose fibers, yarns and fabrics made therefrom, prior to the finishing thereof, the improvement comprising treating said fibrous materials with an aqueous solution containing 3% of acetic acid, from about 1% to about 3% of anthranilic acid, and from about 20% to of a commercial formaldehyde solution until the said material shows a weight increase of at least 6% as compared With the starting material at the same degree of moisture.

8. In a process for chemically modifying wool and fibrous materials precipitated from protein-containing solutions, said fibrous materials :being in the form of loose fibers, yarns and fabrics made therefrom, prior to the finishing thereof, the improvement comprising treating said fibrous materials with an aqueous solution containing 3% of acetic acid, about 1% of sulfanilamide, and about 33% of a commercial formaldehyde solution until the said material shows a slight increase of at least 6% as compared with the starting material at the same degree of moisture.

References Cited in the tile of this patent UNITED STATES PATENTS 2,428,603 Alwood Oct. 7, 1947 2,485,250 Alexander et a1 Oct. 18, 1949 2,508,713 Harris et a1 May 23, 1950 2,763,649 Albrecht et al Sept. 18, 1956 2,890,097 Coe June 9, 1959

Claims

1. IN A PROCESS FOR CHEMICALLY MODIFYING WOOL AND FIBROUS MATERIALS PRECIPITATED FROM PROTEIN-CONTAINING SOLUTIONS, SAID FIBROUS MATERIALS BEING IN THE FORM OF LOOSE FIBERS, YARNS AND FABRICS MADE THEREFROM, PRIOR TO THE FINISHING THEREOF, THE IMPROVEMENT COMPRISING TREATING SAID FIBROUS MATERIALS, WITH AN AQUEOUS ACIDIC SOLUTION OF AN ORGANIC NITROGEN-CONTAINING COMPOUND HAVING A NITROGEN-CONTAINING REACTIVE GROUP AND AT LEAST ONE ADDITIONAL REACTIVE GROUP, SAID SOLUTION CONTAINING FORMALDEHYDE, UNTIL THE SAID MATERIAL SHOWS A WEIGHT INCREASE OF AT LEAST 6% AS COMPARED WITH THE STARTING MATERIAL AT THE SAME DEGREE OF MOISTURE, SAID NITROGEN-CONTAINING COMPOUND BEING A COMPOUND SELECTED FROM THE GROUP CONSISTING OF AN ALIPHATIC AMINO ACID, AN ALIPHATIC IMINO ACID, A MIXTURE OF ALIPHATIC AMINO ACIDS, A MIXTURE OF ALIPHATIC IMINO ACIDS, A MIXTURE OF AT LEAST AN ALIPHATIC AMINO ACID AND AN ALIPHATIC IMINO ACID, AN AMINO ARYL SULFONIC ACID, AN ARYL AMINO ACID, AN ARYL IMINO ACID, AN ARYL AMINO PHENOL, AND AN ARYL IMINO PHENOL, THEREBY CHEMICALLY MODIFYING THE OUTER SURFACE OF SAID MATERIAL TO CONTAIN A REACTIVE GROUP.