US3709658A - Method for decreasing the flammability of cellulosic fabrics - Google Patents

Method for decreasing the flammability of cellulosic fabrics Download PDF

Info

Publication number
US3709658A
US3709658A US3709658DA US3709658A US 3709658 A US3709658 A US 3709658A US 3709658D A US3709658D A US 3709658DA US 3709658 A US3709658 A US 3709658A
Authority
US
Grant status
Grant
Patent type
Prior art keywords
fabric
percent
fabrics
flammability
method
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
Inventor
W Walsh
H Rutherford
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NORTH CAROLINA (NORTH CAROLINA STATE UNIVERSITY), University of
Original Assignee
Research Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Grant date

Links

Images

Classifications

    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS, OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402Amides imides, sulfamic acids
    • D06M13/41Amides derived from unsaturated carboxylic acids, e.g. acrylamide
    • D06M13/412N-methylolacrylamides
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS, OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/288Phosphonic or phosphonous acids or derivatives thereof
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS, OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M14/00Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/18Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
    • D06M14/20Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of natural origin
    • D06M14/22Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of natural origin of vegetal origin, e.g. cellulose or derivatives thereof
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/18Grafting textile fibers

Abstract

Cellulosic fabrics are rendered less flammable by reaction of acrylamidomethyl cellulose with sodium hypophosphite in the presence of ionizing radiation and then with bromine.

Description

United States Patent 11 1 Walsh et al. a [451 Jan. 9, 1973 [54] METHOD FOR DECREASING THE [56] References Cited FLAMMABILITY OF CELLULOSIC UNITED STATES PATENTS FABRICS M 3,423,163 1 1969 t t l ..8 116.3 Inventors: William Kershlw Walsh; Henry 3,434,161 3/1969 I Ames Rutherford, both of Raleigh, 3,558,263 l/l97l Baitinger N.C. 3,300,273 l/l967 Kullman et a1. ..8/116.3 3,304,147 2/1967 Reinhardt et a1 ..8/116.3 Asslgnw Research Corponfiolh New York, 3,592,582 7/1971 Kullman et al. ..8/116.3 N.Y. 3,666,401 5/1972 Cahill et al. ..8/116.3 X

[22] Filed: NOV. 22, 1971 OTHER PUBLICATIONS PP N05 2011213 Walsh et al., Textile Research Journal, Vol. 35, pp.

52 us. Cl ..8/129, 8/116, 8/116 R, 'f' Emmi'fer-qemge Lesmes 8/1163, 8/120, 8/DlG. 18, 117/9331,

7 Attorney-Denms Clarke et a]. [51] Int. Cl ..D06m 13/40, @6111 15/36,

D06m 11/04 [57] ABSTRACT [58] Field of Senrch...8/l 16, 120, 116.3, 116 P, DIG. Cellulosic fabrics are rendered less flammable by reac- 18, 8/129 tion of acrylamidomethyl cellulose with sodium hypophosphite in the presence of ionizing radiation and then with bromine.

2 Claims, No Drawings METHOD FOR DECREASING THE FLAMMABILITY F CELLULOSIC FABRICS This invention relates to the modification of cotton or cellulosic textile fabrics. In one specific aspect, it relates to a method for decreasing the flammability of such fabrics and the modified fabrics thereby produced.

Cellulosic fabrics are widely used and the need for rendering such fabrics less flammable is very apparent. It is also known that the incorporation of phosphorous and/or halogen into fabrics decreases their flammability. However, prior art methods often result in other undesirable modifications of the fabric, such as making them stiff or harsh to the touch. We have discovered an improved approach to the incorporation of phosphorous and bromine into cellulosic fabrics wherein the soft hand of the fabric is not materially affected.

More specifically, the present invention is a method for decreasing the flammability of a cellulosic fabric which comprises reacting the fabric with an aqueous solution containing sodium hypophosphite in the presence of ionizing radiation and then with an aqueous solution containing bromine. The invention also contemplates the modified cellulosic fabric thereby produced.

In practicing the method of the present invention, the cellulosic fabric to be modified is treated with N- methylol acrylamide (NMA) in the presence of an acid catalyst according to the equation ll Cell-OH HOCHzNHC-CH=CH2 cellulose NMA ll Cell-OCHz--NHCCH=CH2 H2O acrylamidomethyl cellulose The procedure is described in more detail in US. Pat. No. 2,837,512 to Mantell.

The fabric reacted with NMA containing acrylamidomethyl cellulose is padded with an aqueous solution containing sodium hypophosphite at approximately neutral pH (hypophosphorous acid brought to pH 7 by addition of sodium hydroxide or like base) to pick up the desired amount of sodium hypophosphite, at least about percent by weight based on the dry fabric. Exposure of the padded fabric to ionizing radiation generates free radicals and causes the hypophosphite to react with and become affixed to the unsaturated portion of the acrylamidomethyl cellulose entity in the fabric. The most convenient source of ionizing radiation currently available is gamma radiation from radioactive isotopes of cobalt and from various uranium fission products. Irradiation is easily controlled and the extent of treatment will depend on the energy of the treating source. The amount of radiation employed should be sufficient to cause a major portion of the hypophosphite to become affixed to the fabric; excess radiation, which would tend to degrade the fabric, should be avoided. Satisfactory results are obtained using about 2 megarads of ionizing radiation generally at room temperature.

The resistance to burning of both cotton and rayon fabric were greatly improved by treatment with sodium hypophosphite. However, treatment with hypophosphite alone was not sufficient to completely inhibit combustion. It was found that reaction of residual double bonds in the phosphated acrylamidomethyl cellulose with bromine (aqueous bromine-bromide solution) made flame resistance virtually complete without adversely affecting the hand of the treated fabric. It was also found that the brominated fabrics had the added advantage of being somewhat anti-bacterial as determined by inhibition tests after incubation with nutrient media inoculated with staphylococcus. While this antibacterial effect diminished on repeated washing, it remained greater than that of untreated fabric.

Our invention is further described by means of the following illustrative examples:

1. Preparation of acrylamidomethyl cellulose Cotton fabric was padded with a solution containing 25 percent N-methylol acrylamide, 1 percent zinc nitrate, 1 percent hydroquinone and 0.1 percent surfactant to percent wet pickup, dried at 60 C., cured for 10 minutes at C. and then washed and dried. More conveniently, the fabric was padded with 25 percent NMA, 0.37 percent hydrochloric acid, and 0.1 percent surfactant, and then heated for 10 minutes at 70 C. without prior drying. The first method gave about a 12 percent increase in weight of cotton fabric and an 18 percent increase in weight of rayon treated. The second method gave about a 10 percent increase in weight for cotton and a 16 percent increase in weight for rayon.

2. Addition of sodium hypophosphite to acrylamidomethyl cellulose Acrylamidomethyl cellulose, cotton fabric with 11.1 percent weight gain from reaction with N-methylol acrylamide, was padded with an aqueous solution of sodium hypophosphite at pH 7. The padded fabric was dried, weighed, and irradiated with radioactive cobalt for 21 hours to a dose of 2.7 Mrads, washed and reweighed. The fabric containing 6.4 percent by weight of sodium hypophosphite after padding retained 5.1 percent of that salt after irradiation and washing.

Rayon fabric containing about 17 percent N- methylol acrylamide and cotton fabric containing 12% NMA were padded with 30 percent and 20 percent solutions of sodium hypophosphite, respectively. The padded fabrics were dried and irradiated 10 hours (1.3 Mrads), washed, dried and weighed. The rayon increased in weight by about 15 percent and the cotton by about 6 percent based on dry weight of material.

3. Addition of bromine to sodium hypophosphite containing acrylamidomethyl cellulose Cotton and rayon fabric treated according to the previous example were each immersed for 10 minutes in an aqueous solution containing 10 percent bromine and 15 percent potassium bromide. After rinsing and drying, additional weight gains of 3 percent and 7 percent for the rayon and cotton, respectively, were observed. The brominated fabrics had a soft hand.

When the brominated fabrics were subjected to the AATCC No. 344966 flammability test, the rayon showed zero afterflame and zero afterglow for both 12 and 2 second ignition times. The char lengths were 1.5

inches and less than 0.25 inches for the 12 second and 2 second ignition times, respectively. The cotton fabric, after twenty home launderings, had zero and 5 second afterflame times, zero afterglow, and 2.7 and 1.8 inch char lengths for the 12 second and 2 second ignition times. Untreated fabrics of the same type were virtually completely consumed in this test.

The process of the present invention is applicable to cellulose-containing fabrics generally. As used herein, the term fabrics" is meant to include textile fabrics of all kinds including woven and non-woven fabrics. The fabric may contain or be made from a natural cellulose material such as cotton or a regenerated cellulose material such as rayon.

Other variations in approach falling within the scope of the invention herein described will suggest themselves to those skilled in the art and our invention is as claimed.

We claim:

1. A method for decreasing the flammability of a cellulosic fabric which has been modified through reaction with an acidic solution of N-methylolacrylamide comprising reacting the fabric with an aqueous solution containing sodium hypophosphite in the presence of ionizing radiation and thereafter treating the fabric with an aqueous solution containing bromine.

2. A cellulosic fabric produced by the process of claim 1.

Claims (1)

  1. 2. A cellulosic fabric produced by the process of claim 1.
US3709658A 1971-11-22 1971-11-22 Method for decreasing the flammability of cellulosic fabrics Expired - Lifetime US3709658A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US20121371 true 1971-11-22 1971-11-22

Publications (1)

Publication Number Publication Date
US3709658A true US3709658A (en) 1973-01-09

Family

ID=22744936

Family Applications (1)

Application Number Title Priority Date Filing Date
US3709658A Expired - Lifetime US3709658A (en) 1971-11-22 1971-11-22 Method for decreasing the flammability of cellulosic fabrics

Country Status (1)

Country Link
US (1) US3709658A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4108748A (en) * 1975-03-28 1978-08-22 The United States Of America As Represented By The Secretary Of Agriculture Photofinishing of cotton textiles
WO2000022222A1 (en) * 1998-10-14 2000-04-20 Cotton Incorporated Methods for reducing the flammability of cellulosic substrates
WO2000029662A1 (en) * 1998-11-13 2000-05-25 Cotton Incorporated Methods for reducing the flammability of cellulosic substrates
US6491727B1 (en) 1999-06-09 2002-12-10 Cotton Incorporated Methods for reducing the flammability of cellulosic substrates

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3300273A (en) * 1963-06-24 1967-01-24 Russell M H Kullman Production of cellulosic materials with oxidizing power
US3304147A (en) * 1963-06-24 1967-02-14 Robert M Reinhardt Method of making cellulosic materials with oxidizing power
US3423163A (en) * 1966-07-19 1969-01-21 Du Pont Cellulosic textile fibers bearing grafted n-methylol amide
US3434161A (en) * 1965-10-05 1969-03-25 Research Corp Textile fabric treatment
US3558263A (en) * 1968-10-01 1971-01-26 American Cyanamid Co Potassium iodide cross-linking inhibitor for n-methylolacrylamide
US3592582A (en) * 1968-07-10 1971-07-13 Us Agriculture Process for production of cellulosic materials with increased oxidizing capacity
US3666401A (en) * 1970-12-11 1972-05-30 Atlantic Richfield Co Treatment of textiles to impart wrinkle-resistant and fire-resistant properties

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3300273A (en) * 1963-06-24 1967-01-24 Russell M H Kullman Production of cellulosic materials with oxidizing power
US3304147A (en) * 1963-06-24 1967-02-14 Robert M Reinhardt Method of making cellulosic materials with oxidizing power
US3434161A (en) * 1965-10-05 1969-03-25 Research Corp Textile fabric treatment
US3423163A (en) * 1966-07-19 1969-01-21 Du Pont Cellulosic textile fibers bearing grafted n-methylol amide
US3592582A (en) * 1968-07-10 1971-07-13 Us Agriculture Process for production of cellulosic materials with increased oxidizing capacity
US3558263A (en) * 1968-10-01 1971-01-26 American Cyanamid Co Potassium iodide cross-linking inhibitor for n-methylolacrylamide
US3666401A (en) * 1970-12-11 1972-05-30 Atlantic Richfield Co Treatment of textiles to impart wrinkle-resistant and fire-resistant properties

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Walsh et al., Textile Research Journal, Vol. 35, pp. 648 654 (1965). *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4108748A (en) * 1975-03-28 1978-08-22 The United States Of America As Represented By The Secretary Of Agriculture Photofinishing of cotton textiles
WO2000022222A1 (en) * 1998-10-14 2000-04-20 Cotton Incorporated Methods for reducing the flammability of cellulosic substrates
WO2000029662A1 (en) * 1998-11-13 2000-05-25 Cotton Incorporated Methods for reducing the flammability of cellulosic substrates
US6488718B1 (en) 1998-11-13 2002-12-03 Cotton Incorporated Methods for reducing the flammability of cellulosic substrates
US6491727B1 (en) 1999-06-09 2002-12-10 Cotton Incorporated Methods for reducing the flammability of cellulosic substrates

Similar Documents

Publication Publication Date Title
US3300336A (en) Metal containing compositions, processes and products
US5631072A (en) Method and means for increasing efficacy and wash durability of insecticide treated fabric
US3138802A (en) Process for imparting durable creases, wrinkle resistance and shape retention to cellulosic textile articles
US3841832A (en) Process for treating cellulosic material with formaldehyde in liquid phase and sulfur dioxide
US6309565B1 (en) Formaldehyde-free flame retardant treatment for cellulose-containing materials
US5458906A (en) Method of producing antibacterial fibers
US4472167A (en) Mild-cure formaldehyde-free durable-press finishing of cotton textiles with glyoxal and glycols
US5695528A (en) Treating agent for cellulosic textile material and process for treating cellulosic textile material
US5427844A (en) Articles of natural cellulose fibers with improved deodorant properties and process for producing same
US4443222A (en) Zinc pyrithione process to impart antimicrobial properties to textiles
US3617198A (en) Method of reducing the amount of free formaldehyde in sensitized fabric for postcure durable press processing
US4820307A (en) Catalysts and processes for formaldehyde-free durable press finishing of cotton textiles with polycarboxylic acids
US2615824A (en) Method and composition for imparting water resistance to textile material
US4975209A (en) Catalysts and processes for formaldehyde-free durable press finishing of cotton textiles with polycarboxylic acids
US3620826A (en) Process for improving soiling characteristics of hydrophobic textile material
US4936865A (en) Catalysts and processes for formaldehyde-free durable press finishing of cotton textiles with polycarboxylic acids
US4072784A (en) Fixation of multivalent metal salts of carboxyl-containing vinyl monomers on fibrous substrates
US2983623A (en) Flame proofing agents derived from methylol phosphorus polymers
US3819518A (en) Scorch-resistant water-soluble flame-retardants for cellulose
US2999056A (en) Irradiation bonding of acidic compounds to shaped polymeric structures
US3666400A (en) Sizing of yarns and fibers with combinations of polymers and crosslinking agents
US3607356A (en) Imparting flame resistance to fibrous textiles from an alkaline medium
US3395970A (en) Method of carbonizing polyacrylonitrile impregnated cellulose, cyanoethylated cellulose and acrylonitrile graft copolymerized cellulose textiles
Walsh et al. Delayed Cure With Ionizing Radiation1
US2653140A (en) Textile finishing compositions

Legal Events

Date Code Title Description
AS Assignment

Owner name: RESEARCH CORPORATION TECHNOLOGIES, INC., 6840 EAST

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:RESEARCH CORPORATION, A NOT-FOR-PROFIT CORP. OF NY.;REEL/FRAME:005437/0829

Effective date: 19891221

Owner name: UNIVERSITY OF NORTH CAROLINA, THE, (NORTH CAROLINA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:RESEARCH CORPORATION TECHNOLOGIES, INC., A NON-PROFIT CORP. OF DE.;REEL/FRAME:005437/0839

Effective date: 19891221