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Publication numberUS3206328 A
Publication typeGrant
Publication dateSep 14, 1965
Filing dateMar 1, 1960
Priority dateMar 1, 1960
Publication numberUS 3206328 A, US 3206328A, US-A-3206328, US3206328 A, US3206328A
InventorsJohn T Shaw, Frank J Gross, William J Van Loo
Original AssigneeAmerican Cyanamid Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Process for imparting anti-static properties to hydrophobic textile materials and product thereof
US 3206328 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent PROCESS FOR IMPARTEWG ANTI-STATHC PROP- ERTEES T0 HYDROPHQBIC TEXTILE MATE- RIALS AND PRGDUCT THEREOF John T. Shaw, Middlesex, Frank J. Gross, New Brunswick, and William J. Van Loo, Middlesex, N1, assignors to American Cyanamid Company, New York, N .Y., a corporation of Maine No Drawing. Filed Mar. 1, 1960, Ser. No. 11,973

17 Claims. (CL 117-1383) This invention relates to novel products, processes for applying the same to modify formed substrates and to the durably modified substrates themselves.

More particularly, the present invention relates to novel compositions, processes for durably modifying textile materials and the so modified materials.

By modifying substrates and, in particular, textile materials as the term is employed herein, it is meant the impar'tation of a finish to said substrates Which may be characterized by a particular function. Thus, durable modification, as employed herein, is intended to include dyeing, the impartation of an anti-static finish, the impartat-ion of a durable fluorescent or brightening effect, the impartation of shrinkage resistance and animalization of cellulosic substrates and numerous other changes or modifications in suitable substrates.

The term substrate as that term is employed herein, is meant a base material which may either be a formed fabric and preferably, is or may be molded or extruded articles containing or made from hydrophobic synthetic resins. Preferably, the substrate or base is a formed textile material and may be knitted, woven, non-woven, felted, or otherwise formed.

By textile material as that term is employed herein, it is meant fibers, filaments, two, or fabrics which, as noted above, may be Woven, non-woven, knitted felted or otherwise formed, prepared from natural fibers of either vegetable or animal origin, synthetic fibers or combinations and mixtures of natural and synthetic fibers. Among the natural fibers contemplated are cotton, linen, hemp, ramie, jute and the like, and among the natural fibers of animal origin are Wool, vicuna and the like. Among the synthetic fibers are nylon, viscose rayon, cellulose acetate, polyester fibers and acrylic fibers. It will be noted that the present invention results in imparting durable anti-static properties to fabrics composed of synthetic hydrophobic fibers which are subject to the accumulation of static electricity. Such materials include nylon, the acrylic fibers, polyester fibers and the like. For many applications, the textile material is preferably cellulosic in origin or contains at least 50% of cellulose fiber, as for example cotton.

It is an object of the present invention to provide novel compositions of matter.

It is another object of the present invention to provide novel compositions of matter which, when applied to suitable substrates and, in particular, textile materials, produce a modification of the substrate.

It is a further object of the present invention to provide durably modified substrates and, in particular, durably modified substrates comprising textile materials.

It is a specific object of the present invention to provide novel anti-static compositions, processes for imparting anti-static properties to textile materials, and in particular synthetic hydrophobic textile materials, and to provide novel anti-static synthetic textile materials.

Still further objects of the present invention relate to novel compositions, methods of employing the same on suitable substrates and the substrates so finished, whereby improved durable dyeing, the impartatio-n of fluorescent brightening, the animalization of the fiber, the impartation of an anti-static finish, and numerous other modifications thereof may be readily and easily accomplished. Often more than one desirable modification is imparted to a substrate in a single finishing step.

These and other objects and advantages of the present invention will become more apparent from the detailed description set forth hereinbelow.

In accordance with the present invention, novel polymeric reaction products are prepared by reacting two diiferent compounds having the following general formulae:

where R and R are organic nuclei and X and X and Y and Y are functional elements which can react, the Xs and with the Ys. In general, the novel compounds or polymers are preferably formed in situ on the suitable substrate and particularly on textile material. This may be accomplished by way of illustration through the application of a polyfunctional textile agent, together with a second polyfunctional compound. The illustrative textile agent contains two or more groups which can react with two or more groups of the polyfunctional compound to form a polymer in the fibers and/ or on the fibers of the textile material.

The term textile agent, as it is employed herein, is principally a term of convenience in that many of the hereinafter illustrative X-RX polyfunctional compounds are dyes, brighteners, etc., which have known utility in the textile field.

In the general formulae above, R is an organic nucleus of a. homogeneous or heterogeneous organic chain or organic ring compound, as for example of a dye, molecule, anti-static agent, a water or grease repellent, an ultraviolet absorber, a softener, a fire retardant, a bactericide, a moth repellent, a brightener, or other suitable agent which may impart a desirable property to a substrate and in particular, to a textile fiber or fabric. R is the nucleus of a homogeneous or heterogeneous organic chain or organic ring compound.

X and X may be amino, hydroxy, mercapto, carboxy, carbamyl or sulfamyl, when Y and Y are epoxy-containing groups such as methylo1(CH OI-I) and in particular, methylol attached to carbon as tetrarnethylol acetone, vinyl (CH CH) or vinylidene (CH =C=). Additionally, X and X may be amino, hydroxy or mercapto when Y and Y are halogens, as in a dior tri-chlorotriazine,

a r N r r o1o JJR o1h\ o-o1 where R may be alkyl, aryl, alkaryl and aralkyl. Additionally, when X and X -are any of the substituents identified above, Y and Y may be isothiocyanato (MCS), isocyanato (NCO) or l-aziridinyl CH (I CH2 Additionally, YR --Y may be methylene-bis-acrylamide, (CH CHCONH) CH In accordance with the above illustrative examples of the functional groups for X and X and Y and Y it is preferable that these functional substituents on a given molecule are identical but this is not necessarily so. It

should further be noted that the various textile agents and second polyfunctional compound may be employed singly or in combination with one another.

The preferred polyfunctional textile agents (XRX are those having the following general formulae:

Where Z is a monovalent anion such as halide, and n is or 1, and

where in general Formulae 1 and 2 the values for X and X are as identified in the disclosure above.

It should be noted that in the general formulae above, substituents both reactive and non-reactive may be present in the molecule, providing there are still two reactive sites remaining in the molecule. For example, where there are two amino groups each may have one substituent, or only one NH group need be present considering each of the hydrogens being a reactive site.

The following compounds are illustrative of textile agents (XRX compounds) which may be employed in the present invention:

4,4'-diamino-2,2-stilbenedisulfonic acid 4,4-diaminodibenzyl-2,2'-disulfonic acid 4,4-diaminobiphenyl-2,2'-disulfonic acid 8-amino-1-naphthol-5 sulfonic acid Diaminopyridine Quaternized diaminopyridine l-alkyldiaminopyridinium salts Sulfonated phenylenediamines Trimellitic anhydride Dyes such as homofuchsine, Direct Yellow RFL Base,

para-fuchsine, and rosaniline 1,2-bis 4-aminophenyl) acetylene 4,4-diaminoazobenzene Bis(4-aminophenyl)sulfone 4,4'-diaminobenzophenone 4,4-diphenylamine 4,4'-diaminodiphenyl ether 4,4'-diaminodiphenyl sulfide Oxy-bis '(4-hydroxybenzene Thio-bis(4-hydr0xybenzene) 4,4-dihydroxybenzophenone 4,4-dihydroxystilbene 4,4-dihydroxybiphenyl 6-amino2-naphthol-4-sulfonic acid 1-amino2-naphthol-4-sulfonic acid 1,5-naphthalenediamine 5,6diaminonaphthalene-Z-sulfonic acid Z-methyl-1,3-naphthalenediol 2,7-naphthalenedithiol 1,3 naphthalenedisulfonamide The above illustrative compounds may be employed as textile agents to impart anti-static, water repelling, moth proofing, oil repelling, hand modifying, bactericidal and anti-felting properties, 'dyeability and improved dyeability, to textile substrates.

As illustrative of the polyfunctional compounds which may be employed to react with the textile agents, the polyglycidyl ethers of a polyhydric alcohol having an epoxy equivalency greater than 1 as for example, those described in United States Patents 2,730,427 and 2,752,269 are greatly preferred. These include specifically diglycidyl ether of ethylene glycol, digly-cidyl ether or propylene glycol, and the like. In addition to the polyglycidyl ethers, dibutyl carbonate, hexamethylene diisocyanate, triethylene melamine, divinyl sulfone, epichlor-ohydrin, 2,4-dichloros-triazine, 2,4,6-trichloro-s-triazine, 2,4-dichloro-6-methyl-s-triazine, 2,4-dichloro-6-butyl-s-triazine, 2,4-dichloro-6-phenyl-s-triazine, 2,4 dichloro o-benzyl-striazine, methylene-bishcrylamide, tetramethylol acetone and triphenyl cyanurate are illustrative compounds.

The textile agents and the polyfunctional organic compounds capable of reacting with each other to form the novel reaction products of this invention may be applied to suitable substrates and in particular, textile materials by conventional methods as for example by padding, dipping, spraying, immersion and the like. The two components, i.e., the textile agents as they are classified herein and the polyfunctional compounds, may be applied individually from separate baths or advantageously simultaneously from the same bath. Because of the wide variations in properties to be affected on textile materials according to this particular aspect of the present invention, the polyfunctional compounds may be applied in amounts varying over a comparatively wide range of from between .5% to about 25% based on the dry weight of the textile material. Where the finish is essentially an anti-static finish, the amount may vary from between .5% and 15% based on the dry weight of the fabric. Where the finish is essentially for purposes of optical brightening or dyeing, the polyfunctional compounds may be employed in amounts of from between .5% and 5% of the fabric. Shrinkage control usually requires between 2% and 20% and so on depending upon the particular finishes to be effected.

The textile agent and second polyfunctional compound may be employed in comparatively wide molecular ratio one to the other and still achieve very satisfactory results. Preferably they are employed in approximately equal molar quantities or with an excess of the second polyfunctional compound. As a general rule, they are employed in mole ratios of between about .01 mole to about 1 mole of the textile agent to about 1 mole of the second polyfunctional compound and preferably from between about .1 to about 1 mole of the former to 1 mole of the latter.

Normally the polymerization reaction between the two functional compounds is accelerated by the presence of alkaline material, and in general the modification of a substrate appears to be more durable when reaction is effected under alkaline conditions than when eifected on the acid side. Thus a suitable alkaline catalyst may be applied separately, with one of the components, or in combination with each of the components and simultaneously therewith as from a single bath. Such a catalyst may be an alkaline agent, such as alkali metal hydroxide used as sodium, potassium, lithium or ammonium hydroxide or the alkaline earth metal oxides and hydroxides; in addition, tertiary amines and triethyl amine, tributyl amine, dimethyl aniline and the like. In some instances, as when the reactants are definitely basic and a sufiicient alkaline medium is obtained, added catalyst is not required to effect polymerization. Preferably, polymerization is effected at a pH of between about 8 and about 13.

The polyfunctional compounds may be both water soluble and, as will be apparent, for many applications they are preferably so. However, as will be apparent from the examples below, solvent soluble polyfunctional compounds are fully contemplated as is the use of water soluble and solvent soluble compounds in a single application. Suitable'solvents will readily suggest themselves depending on the application to be effected. Thus, solvents such as benzene, xylene, carbon tetrachloride, acetone and the like may be employed.

The polymerization reaction, preferably carried out in situ on the substrate to be durably modified, is brought about by the application of heat to the treated fabric. The temperature required for the polymerization is usually from between about 125 F. and about 400 F. However, the time required to complete the polymerization varies inversely with the temperature used. That is, atthe lower curing temperature, the longer time is required and vice versa.

The finishes applied in accordance with the present invention to textile materials have improved durability to washing and particularly to washing under alkaline conditions.

The combination of 4,4-diamino-2,2'-stilbenedisulfonic acid and the diglycidyl ether of ethylene glycol imparts a particularly durable antistatic and optically brightened finish on nylon and other synthetic hydrophobic fibers.

In orderto illustrate the present invention more clearly, the following examples are given primarily by way of illustration. No specific details or enumerations contained therein should be construed as limitations on the present invention except insofar as they appear in the appended claims. All parts and percentages are by weight unless otherwise clearly designated.

EXAMPLE 1 Application of 4,4'-diamino-2,2-stilbenedisulfonic acid and diglycidyl ether of ethylene glycol on nylon as an antistatic Aqueous solutions were prepared containing 5% or 1 of the disodium salt of 4,4-diamino-2,2-stilbenedisulfonic acid and 10% of the diglycidyl ether of ethylene glycol, with and without the addition of 8% of zinc fluoborate on the weight of the diglycidyl ether solids.

Nylon talfeta was treated with the above solutions by padding, obtaining a 50% wet-pickup. After drying at 225 F. for 2 minutes, the fabrics were heated at 300 F. for 3 minutes. The treated fabrics contained the amounts of'4,4-diamino-2,2-stilbenedisulfonic acid shown in the Table I, and 5% of the diglycidyl ether of ethylene glycol on the weight of the fabric.

The treated fabrics were treated for their anti-static properties by the cigarette ash test, which may be described as follows: i

The treated fabric is exposed to an atmosphere of 40% relative humidity for four hours. Afterbeing stroked rapidly and heavily several times with a glass rod, the

fabric is held close to cigarette ashes. If the ashes do not jump and cling to the fabric, the fabric is considered to have good anti-static properties.

The washes applied to the fabrics were carried out at 160 F. using 0.1% of neutral soap and 0.1% of soda ash on the weight of the water used. The wash time was one hour. The results are shown in Table I,

A sample treated as in Experiment No. 5 (5% application) was still fluorescent under the ultra-violet lamp after 16 l-hour soap and soda Washes. I

Table I demonstrates that the use of an accelerator of the type normally employed with epoxy resins tends to adversely affect the durability of the finish in accordance with this invention. More importantly, Table I demonstrates that outstanding and durable anti-static properties may be imparted to nylon in accordance with the present invention.

EXAMPLE 2 Application of 4,4-didmin0-2,2'-slilbenedisulfonic acid and tetramethylol acetone on nylon as an anti-static A solution was prepared containing 10% of the disodium salt of 4,4'-cliamino-2,2'-stilbenedisulfonic acid and 10% of tetramethylol acetone.

Nylon taffeta was treated with the above solution by padding, obtaining a wet-pickup. After drying at 225 F. for 2 minutes, the fabric was heated at 300 F. for 3 minutes. The treated fabric contained 5% of each of the above agents on the weight of the fabric.

The test for anti-static properties and the Washes were carried out as in Example 1. The treated fabric showed good anti-static properties for 7 washes.

EXAMPLE 3 Application of 4,4'-diaminodibenzyl-2,2-disulfonic acid and the diglycidyl ether of ethylene glycol on synthetic fabrics as an anti-static Table II.

TABLE II Anti-static Experiment N0. Fabric 1 Durability N o. of Washes Nylon tafieta- 21 Nylon, spuni 15 Acrylic Fiber. 15 Acetate taffeta 4 EXAMPLE 4 Application of 4,4'-diominobip henyl -2,2' sulfonic acid and diglycidyl ether of ethylene glycol on nylon as an anti-static An aqueous solution was prepared containing 5% of TABLE I 4,4-diaminobiphenyl-2,2-disulfonic acid, 40% or sodium hydroxide on the weight of the biphenyldisulfonic acid, jPercent Anmtafic and 10% solids of diglycidyl ether of ethylene glycol Experiment N0. Stilbeue Zn (Bel Durability, (pH=-12.1).

Egg? Used Nq'oiwashes Nylon taffeta was treated with the above solution by 2.5 10 2.5 less than 10 Formula: HzN- om-onQ-am,

I a 510 o SOaNa SOsNa 1 Formula: HzN-(JH=CHNH2 3 Formula: HzN-NH2 I l SlOsNa H038 50311 S OsNa padding, obtaining a 50% wet-pickup. After drying at 225 F. for 2 minutes, the fabric was heated at 300 F. for 3 minutes. The treated fabric contained 2.5% of 4,4'-diaminobiphenyl-2,2-disulfonic acid and 5% of the diglycidyl ether of ethylene glycol. The tests for antistatic properties and the washes were carried out as described in Example 1.

The treated fabric showed good anti-static properties for 5 washes.

EXAMPLE 5 Application of 8-amin0-1-naphthol-5sulfonic acid and diglycidyl ether of ethylene glycol on nylon as an anti-static An aqueous solution was prepared containing 5% of S-amino-l-naphthol-S-sulfonic acid, 20% of sodium hydroxide on the weight of the naphtholsulfonic acid, and 10% of diglycidyl ether of ethylene glycol (pH:11.8).

Nylon taffeta was treated with the above solution by padding, obtaining a 50% wet-pickup. After drying at 225 F. for 2 minutes, the fabric was heated at 300 F. for 3 minutes. The treated fabric contained 2.5% of S-amino-l-naphthol-S-sulfonic acid and 5% of the diglycidyl ether of ethylene glycol.

The tests for anti-static properties and the washes were carried out as described in Example 1. The treated fabric showed good anti-static properties for 7 washes.

EXAMPLE 6 Application of trimellitic anhydride anddiglycidyl ether of ethylene glycol to nylon as an anti-static A solution in acetone was prepared containing 10% of trimellitic anhydride 5 and 10% of the diglycidyl ether of ethylene glycol.

Nylon taffeta was treated with the above solution by padding, obtaining a 50% wet-pickup. After drying at 225 F. for 2 minutes, the fabric was heated at 300 F. for 3 minutes. The treated fabric contained 5% of each of the above agents on the weight of the fabric.

The test for anti-static properties and the washes were carried out as in Example 1. The treated fabric showed good anti-static properties for 10 washes.

EXAMPLE 7 Application of disodiurn salt of 4,4-bis[2-amin0-4-(psulfoanilino)-s-triazin 6 ylamino]-stilbene-2,2-disulfonic acid and diglycidyl ether on nylon as an optical brightener A. 0.1% of 4,4-bis[2-amino-4-(p-sulfoanilino)-s-t1iazin-6-ylaminol]-stilbene-2,2'-disulfonic acid as the di sodium salt and 5% of diglycidyl ether on the Weight of the fabric were applied to nylon fabric from a single aqueous bath. The fabric was dried and cured for 3 minutes at 300 F.

Formula: liIzN (DH Formula: (|300 l coon B. 0.1% of the stilbenedisulfonic acid 6 on the weight of the fabric was applied to nylon fabric.

Both fabrics were inspected under an ultraviolet lamp for strength of fluorescence of the fabric. After the fabrics were washed at 140 F. with soap, they were inspected again for fluorescence under the ultraviolet lamp. The results are shown in Table III.

1 0none; 1slight; 2moderate; 3-high; 4very high.

EXAMPLE 8 Application of homofuchsine and diglycidyl ether of ethylene glycol 0n polyester fiber Aqueous solution A contained 0.5% of Cl. Basic Violet 14 (Cl. 42,510), i.e., homofuchsine, and 5% of diglycidyl ether of ethylene glycol.

Solution B contained 0.5% of (3.1. Basic Violet 14 alone.

Fabrics formed of polyester fibers were immersed in each of the above solutions at room temperature for three minutes. The excess solution was removed from each of the fabrics by squeezing to give a 70% wetpickup. After the fabrics were dried at 194 F. for 15 minutes, they were heated at 290 F. for three minutes.

After a IO-Ininute hand washing with neutral soap, the fabric treated with solution A contained notably more color than that treated with solution B.

EXAMPLE 9 Application of homofuchsine and diglycidyl ether on polyester fibers Aqueous solutions of Cl. Basic Violet 14 (0.1. 42,510), i.e., homofuchsine, and diglycidyl ether were prepared with the following compositions.

Fabrics formed of polyester fibers were immersed in solutions A and B at room temperature for three minutes. The excess solution in each fabric was removed by squeezing to give a wet-pickup.

The fabrics treated with solutions A and B were dried at (1) 194 F. for 4 minutes, or (2) 290 F. for 4 minutes. The fabrics were then hand washed for 10 min utes using neutral soap.

The fabrics treated with solution A were more strongly dyed with a violet color than those treated with solution B, and the difference was greater when the fabrics were dried at 290 F.

6 Formula:

\ SOaH i NHz 9 EXAMPLE 10 Improvement inwash fastness of basic dyes an acrylic fiber by pretreatment with 4,4-diamin-2,2-stilbenedisulfonic' acid and diglycidyl ether of ethylene glycol An aqueous solution containing of the disodium salt of 4,4'-diamino-2,2'-stilbenedisulfonic acid and 5% of diglycidyl ether of ethylene glycol was applied to a fabric of acrylic fiber by padding with a 65% wet-pickup. When the fabric had been dried at 110 F. for 15 minutes, it was dyed with 2% of Cl. Basic Green 5 (Cl. 52,020), Methylene Green B on the weight of the fabric. After rinsing in hot water, the fabric was washed using soap and soda ash. This fabric was much more strongly colored than a like piece of fabric of acrylic fiber which was dyed by the above procedure Without first receiving the. pretreatment.

While the present invention has been described primarily in connection with the use of two separate polyfunctional compounds capable of interacting to produce a durable textile modifying agent, it is contemplated that to some extent, similar-results may be achieved by the application of a single polyfunctional dye or textile treating agent which contains two or more groups which are capable of reacting With each other to form a polymer in or on the fibers of the substrate or the textile material. This concept is best illustrated by the general equation:

in which X, R and Y correspond to the groups identified supra for these designations.

In addition, while the description of the present invention herein has been limited to the use of a textile agent and second and different polyfunctional compound, other textile finishing materials, as for example, crease proofing resins, hand modifiers, textile softeners, wetting agents, lubricants and other textile finishing auxiliaries and agents may be employed, prior to, simultaneously with or after the procedures of this invention are employed. Thus, for example, finishes contemplated by the present invention may be applied simultaneously with or after preliminary treatment with, for example, resins employed to impart wrinkle resistance to the textile material. More specifically, a textile material may be finished with an aminoplast textile finishing resin, as for example, the formaldehyde condensates of urea, thiourea, ethylene urea, ethylene thiourea, 1,2 propylene urea, 1,3 propylene urea, guanamines, melamine, thiobisamides such as thiobispropionamide and the alkylated derivatives of these methylol compounds and then subsequently modified in accordance with the present invention.

We claim:

1. A process for reducing the tendency of an article containing hydrophobic synthetic resins to accumulate surface charges of static electricity which comprises applying thereto at least two polyfunctional compounds capable of reacting with each other, one of said polyfunctional compounds being a member of the group consisting of 4,4- diamino-2,2-stilbenedisulfonic acid, 4,4'-diaminodibenzyl- 2,2-disulfonic acid, 4,4-diaminobiphenyl-2,2'-disulfonic acid, S-amino-l-naphthol 5 sulfonic acid, 4,4-bis(2- amino-4-(p-sulfanilino)-s-triazin 6 ylamino) stilbene- 2,2-disulfonic acid and homofuchsine and the other of said polyfunctional compounds being a diglycidyl ether of a polyhydric alcohol having an epoxy equivalency greater than 1, and thereafter combining said compounds on the article by heating the article containing them at reaction temperatures.

1 Formula:

5/ (ill- N02 2. A process for reducing the tendency of an article containing hydrophobic synthetic resins to accumulate surface charges of static electricity which comprises applying thereto 4,4-diamino-2,2'-stilbenedisulfonic acid and a diglycidyl ether of a polyhydric alcohol having an epoxy equivalency greater than 1 and thereafter subjecting the so treated article to reaction temperatures.

3. A process for reducing the tendency of an article containing hydrophobic synthetic resins to accumulate surface charges of static electricity which comprises applying thereto 4,4'-diaminodibenzyl-2,2-disulfonic acid, and a diglycidyl ether of a polyhydric alcohol having an epoxy equivalency greater than 1 and thereafter subjecting the so treated article to reaction temperatures.

4. A process for reducing the tendency of an article containing hydrophobic synthetic resins to accumulate surface charges of static electricity which comprises applying thereto 4,4'-diaminobiphenyl-2,2-'disulfonic acid and a diglycidyl ether of a polyhydric alcohol having an epoxy equivalency greater than 1 and thereafter subjecting the so treated article to reaction temperatures.

5. A process for reducing the tendency of an article containing hydrophobic synthetic resins to accumulate surface charges of static electricity which comprises applying thereto 8-amino-l-naphthol-S-sulfonic acid and a diglycidyl ether of a polyhydric alcohol having an epoxy equivalency greater than 1 and thereafter subjecting the treated article to reaction temperatures.

6. A process for reducing the tendency of an article containing hydrophobic synthetic resins to accumulate surface charges of static electricity which comprises applying thereto 4,4'-diamino-2,2'-stilbenedisulfonic acid and the diglycidyl ether of ethylene glycol and thereafter subjecting the treated article to reaction temperatures.

7. A process for reducing the tendency of an article containing hydrophobic synthetic resins to accumulate surface charges of static electricity which comprises applying thereto 4,4'-diamino-2,2'-stilbenedisulfonic acid and the diglycidyl ether of ethylene glycol and thereafter subjecting the treated article to a temperature of from about F. to about 400 F.

8. A process for reducing the tendency of an article containing hydrophobic synthetic resins to accumulate surface charges of static electricity which comprises applying thereto 4,4-diam-ino 2,2. stil-benedisulfonic acid and diglycidyl ether and thereafter subjecting the treated article to reaction temperatures.

9. A process for treating textile material containing hydrophobic synthetic fibers, which textile material is subject to the accumulation of static electricity, which comprises applying thereto at least two polyfunctional compounds capable of reacting with each other, one of said polyfunctional compounds being a member of the group consist-ing of 4,4-diamino-2,-2'-stilbenedisulfonic acid, 4,4 diamino-dibenzyl 2,2 :di-sul-fonic acid, 4,4- diamino-biphenyl-Z,2'-disulfonic acid, S-amino-l-naphthol 5 sulfonic acid, 4,4-bis(2-amino-4-(p-sulfanilino)- s triaZin-6-ylamino)-stilbene-2,2 disulfonic acid and homofuchsine and the other of said polyfunctional compounds being a diglycidyl ether of a polyhydric alcohol having an epoxy equivalency greater than 1, and thereafter combining said compounds on the textile by heating the textile material containing them at reaction temperatures.

10. A process for reducing the tendency of nylon fabric to accumulate surface charges of static electricity and to optically brighten said fabric which comprises applying thereto 4,4'-diamino-2,2'-stilbenedisulfonic acid and the diglycidyl ether of ethylene glycol and thereafter subjecting the treated fabric to reaction temperatures.

11. Synthetic hydrophobic textile material having thereon in an amount sulficient to reduce the accumulation of surface charges of static electricity a polymeric reaction product of 4,4-diamino-2,2'-stilbenedisulfonic acid and a diglycidyl ether of a polyhydric alcohol having an epoxy equivalency greater than 1.

12. Synthetic hydrophobic textile material having thereon in an amount sufficient to reduce the accumulation of surface charges of static electricity a polymeric reaction product of 4,4-diaminodibenzyl-2, 2-disulfonic acid and a diglycidyl ether of a polyhydric alcohol having an epoxy equivalency greater than 1.

13. Synthetic hydrophobic textile material having thereon in an amount suflicient to reduce the accumulat-ion of surface charges of static electricity a polymeric reaction product of 4,4-diaminobiphenyl-2,2-disulfonic acid and a :diglycidyl ether of a polyhydric alcohol having an epoxy equivalency greater than 1.

14. Synthetic hydrophobic textile material having thereon in an amount suificient to reduce the accumula tion of surface charges of static electricity a polymeric reaction product of 8-amino-l-naphthol-S-sulfonic acid and a diglycidyl ether of a polyhydric alcohol having an epoxy equivalency greater than 1.

15. Synthetic hydrophobic textile material having thereon in an amount sufficient to reduce the accumulation of surface charges of static electricity a polymeric reaction product of 4,4-diamino-2,2-stilbenedisulfonic acid and the diglycidyl ether of ethylene glycol.

16. Synthetic hydrophoblic textile material having thereon in an amount sufficient to reduce the accumulation of surface charges of static electricity a polymeric reaction product of 4,4'-diamino-2,2-stilbenedisulfonic acid and diglycidyl ether.

17. Nylon material having thereon a polymeric reaction product of 4,4'-diamino-2,2-stilbenedisulfonic acid and the diglycidyl ether of ethylene glycol.

References Cited by the Examiner UNITED STATES PATENTS 2,506,486 5/50 Bender 260-47 2,730,427 1/56 Snen 117-139.5 X 2,752,269 6/56 Condo et a1. 117-139.4 2,839,431 6/58 Rimmer 117-139.5 2,846,397 8/58 Ackerman 117-33.5 X 2,885,388 5/59 Sallman et a1. 260-249.6 2,892,674 6/59 Sause et al. 117-144 X 2,903,381 9/59 Schroeder 117-161 2,933,473 4/60 Schmitz 260-97 2,980,676 4/61 Zuppinger et a1 260-249.6 3,018,287 1/62 Fleck et al. 117-33.5 3,026,216 3/62 Snookne 171-161 3,030,247 4/ 62 Schurb 260-47 3,046,075 7/62 Kantner et a1 8-17 3,066,005 11/ 62 Widemeyer et al. 8-1 X 3,073,662 1/63 Jaeger et a1. 8-116 X FOREIGN PATENTS 453,431 9/36 Great Britain.

WILLIAM D. MARTIN, Primary Examiner.

RICHARD D. NEVIUS, Examiner.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2506486 *Apr 21, 1948May 2, 1950Union Carbide & Carbon CorpThermosetting resin from a diphenol and a diglycidyl ether of a diphenol
US2730427 *Aug 13, 1952Jan 10, 1956American Cyanamid CoShrinkage control of cellulosic and wool textiles with diglycidyl ether compounds
US2752269 *Dec 1, 1951Jun 26, 1956Shell DevTreatment of textile materials
US2839431 *Aug 26, 1955Jun 17, 1958Du PontAntistatic agents for hydrophobic fiber
US2846397 *Oct 2, 1950Aug 5, 1958Ciba LtdWater-soluble salts of derivatives of 4:4'-diaminostilbene-2:2'-disulfonic acid for enhancing the brightness of organic fibrous material
US2885388 *Aug 21, 1953May 5, 1959Ciba LtdPolymerizable amide-like condensation products and process for their manufacture
US2892674 *May 21, 1956Jun 30, 1959Ici LtdTreatment of cellulosic materials
US2903381 *Sep 3, 1954Sep 8, 1959Shell DevTreatment of synthetic textiles with a polyepoxide having a plurality of 1,2 epoxy groups
US2933473 *Jul 9, 1956Apr 19, 1960Gen ElectricMercaptans as catalysts for polymerization of ethoxyline resins
US2980676 *Jul 15, 1958Apr 18, 1961Ciba LtdGlycidyl ethers of n-methylolamino-1:3:5-triazines
US3018287 *Nov 3, 1959Jan 23, 1962Fidelity Union Trust CompanyOptical brighteners for use with paper
US3026216 *Oct 5, 1959Mar 20, 1962Union Carbide CorpTreatment of textile fabrics with methylglycidyl ethers
US3030247 *Jul 28, 1955Apr 17, 1962Minnesota Mining & MfgStable heat-curing epoxy resin compositions
US3046075 *Nov 19, 1959Jul 24, 1962 Dyeing and finishing textile materials
US3066005 *Jan 21, 1959Nov 27, 1962Bayer AgProcess for the treatment of hydroxyl group-containing textile materials
US3073662 *Aug 25, 1958Jan 15, 1963 Process for the production of fast dye-
GB453431A * Title not available
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3337288 *Aug 20, 1963Aug 22, 1967Dainichiseika Color ChemReactive coloring matter, processes for producing the same and processes for coloring articles with the same
US3391019 *Feb 4, 1965Jul 2, 1968Ici LtdProcess for coating shaped hydrophobic polymeric materials with reaction product of halogenotriazine and polymer containing hydroxyl, amino or mercapto group
US3563375 *Jul 26, 1968Feb 16, 1971Auby Prod ChimMethod of selectively separating solid particles by electrostatic sorting in fluidized bed
US3705877 *Jun 8, 1970Dec 12, 1972Asahi Chemical IndAntistatic synthetic resin compositions containing trazine derivatives
US3743477 *Jun 24, 1968Jul 3, 1973Sandoz LtdProcess for reserving textiles of natural polyamide fibres and of synthetic fibres dyeable with acid dyes
US3852029 *Oct 20, 1971Dec 3, 1974Ciba Geigy AgStable concentrated solutions of direct dyes and process for their manufacture
US3952128 *Nov 4, 1974Apr 20, 1976Kao Soap Co., Ltd.Durable antistatic agent, hydrophobic fibers and fibrous structures having durable antistatic property and method of making same
US4418164 *Jul 19, 1982Nov 29, 1983E. I. Du Pont De Nemours And CompanyAramid fiber coated with polyfunctional aziridine
US5057371 *Jun 14, 1985Oct 15, 1991Minnesota Mining And Manufacturing CompanyAziridine-treated articles
Classifications
U.S. Classification442/115, 8/491, 428/394, 428/413, 427/393.1, 428/395, 442/130, 427/386, 260/DIG.200, 442/106
International ClassificationD06M13/192, D06M13/325, D06M13/358, D06M13/144, D06M13/11, D06M13/41, D06M13/127, C08G59/40, D06M13/335, D06P1/00
Cooperative ClassificationC08G59/40, D06M13/325, D06M13/144, D06P1/0056, D06M13/41, D06M13/11, D06M13/127, D06M13/335, D06P1/0064, Y10S260/20, D06M13/192, D06M13/358
European ClassificationD06P1/00N4, D06M13/358, D06M13/11, C08G59/40, D06P1/00N, D06M13/335, D06M13/41, D06M13/192, D06M13/127, D06M13/325, D06M13/144