US3681060A - Preparation of flame-retardant fabrics - Google Patents

Preparation of flame-retardant fabrics Download PDF

Info

Publication number
US3681060A
US3681060A US61490A US3681060DA US3681060A US 3681060 A US3681060 A US 3681060A US 61490 A US61490 A US 61490A US 3681060D A US3681060D A US 3681060DA US 3681060 A US3681060 A US 3681060A
Authority
US
United States
Prior art keywords
fabric
weight
catalyst
melamine
phosphoric amide
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
US61490A
Other languages
English (en)
Inventor
Stephen B Sello
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.)
JP Stevens and Co Inc
Original Assignee
JP Stevens and Co Inc
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
Application filed by JP Stevens and Co Inc filed Critical JP Stevens and Co Inc
Application granted granted Critical
Publication of US3681060A publication Critical patent/US3681060A/en
Anticipated expiration legal-status Critical
Assigned to BANKERS TRUST COMPANY, A NY BANKING CORP. reassignment BANKERS TRUST COMPANY, A NY BANKING CORP. SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: J.P. STEVENS & CO.
Assigned to J.P. STEVENS & CO., INC. reassignment J.P. STEVENS & CO., INC. RELEASE SECURITY INTEREST & ASSIGNMENT. Assignors: BANKERS TRUST COMPANY
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/423—Amino-aldehyde resins
    • D06M15/43—Amino-aldehyde resins modified by phosphorus compounds
    • D06M15/433—Amino-aldehyde resins modified by phosphorus compounds by phosphoric acids
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/92—Fire or heat protection feature
    • Y10S428/921—Fire or flameproofing

Definitions

  • the fabric is then heated to cause said melamine derivative and said phosphoric amide to coreact and form an insoluble product on the fabric. It is essential that more than 1.0 mole of melamine derivative be used for each mole of phosphoric amide, that the amount of insoluble reaction product formed on the fabric be such that the weight gain is at least 14% after removal of any soluble product by a hot process wash (e.g. 15 minutes at 90 C.) and that the nitrogen to phosphorus weight ratio of the insoluble product be at least 5.0 to l.
  • This invention relates to a process for rendering cellulose-containing fabrics flame retardant by forming on said fabrics an insoluble product containing nitrogen and phosphorus.
  • British Pat. 790,663 discloses flame proofing cellulosic fabrics by treating them with an aqueous solution containing a derivative of phosphoric acid such as N,N,N" trirnethylphosphoric triamide and a rnethylolmelamine as a fixing agent and heating the treated fabric. No catalyst is employed and we have found that when using such a procedure the amount of flame-proofing agent fixed on the fabric is insufiicient to impart satisfactory flame retardance.
  • a derivative of phosphoric acid such as N,N,N" trirnethylphosphoric triamide and a rnethylolmelamine
  • durable flame retardancy is imparted to fabrics without unduly damaging or stiifening the fabric by applying to the fabric a melamine derivative prepared by reacting melamine with either formaldehyde or formaldehyde and an alkanol, a phosphoric amide of the formula where R is alkyl of 1 to 4 carbon atoms and a catalyst which is an acid, an acid forming salt, an oxidizing agent or a neutral salt.
  • the fabric is then heated to cause said melamine derivative and said phosphoric amide to coreact and form an insoluble product.
  • the insoluble reaction product have a nitrogen to phosphorus weight ratio of at least 5.0 to l, and that the amount of insoluble reaction product formed on the fabric be such that the weight gain is at least 14% after removal of any soluble chemi cals by a hot process wash.
  • the amount applied to the fabric should not be greater than about 1.5% by weight based on the weight of the fabric and when a neutral salt is used, the amount applied to the fabric should not be greater than 6% by weight based on the weight of the fabric.
  • the present invention provides a method of rendering cellulose-containing fabric durably flame retardant by forming on said fabric insoluble reaction products containing phosphorus and nitrogen employing certain reactants in critical ratios and amounts and certain catalysts in specific amounts.
  • the fabric is impregnated with an aqueous solution containing a melamine derivative, a phosphoric amide and catalyst, and then an insoluble product is formed by heating.
  • the insoluble reaction product formed must have a nitrogen to phosphorus weight ratio at least 5.0 to 1 and the weight gain cannot beless than 14% after the removal of the soluble products from the fabric by a severe hot process wash (e.g., C. for 15 minutes in an aqueous bath containing 0.1% by weight Na CO and 0.1% by weight of nonionic detergent).
  • the fabric 3 must have a phosphorus content equal to at least 0.6% by weight of the finished fabric, i.e., total Weight of fabric plus flame-retardant finish.
  • the melamine derivative is an N-methylol derivative of melamine having from 2 to 6 methylol groups or a lower alkyl ether derived from such an N-methylol compound wherein the sum of CH OH groups and CH OX groups is from 2 to 6 with X being a lower alkyl group of 1 to 4 carbon atoms and preferably being methyl.
  • the melamine derivative is thus defined by the formula where R at each occurrence is independently hydrogen or CH OZ with Z being hydrogen or alkyl of 1 to 4 carbon atoms and with at least two of said R groups being CH OZ.
  • the N-methylol compounds (wherein Z is always hydrogen) can be prepared by reacting melamine with 2 or more moles of formaldehyde according to known procedures.
  • the lower alkyl ethers can be prepared by known procedures such as by reacting the N-methylol compounds with an alkanol or coreacting melamine, formaldehyde and alkanol, said alkanol containing l to 4 carbon atoms and preferably being methanol. If desired, mixtures of the above-described melamine derivatives can be used.
  • the phosphoric amide is a compound of the formula where R is an alkyl group of 1 to 4 carbon atoms.
  • R is an alkyl group of 1 to 4 carbon atoms.
  • suitable phosphoric amides are N,N',N"-trimethylphosphoric triamide and N,N',N"-triethylphosphoric triamide.
  • the mole ratio of melamine derivative to phosphoric amide greatly affects the stiffness of the treated fabric when sufiicient amounts of these reactants are used to give durable flame retardancy and curing is effected by dry heating.
  • the stiffness of the treated fabric drops sharply when the mole ratio approaches 1 to 1.
  • the fabric is made excessively stiff when less than one mole of melamine derivative is employed per mole of phosphoric amide while at a mole ratio of 1:1 results are marginal with acceptable stiffness being obtained only some of the time.
  • more than 1 mole preferably at least 1.07 moles of melamine derivative should be employed per mole of phosphoric amide. Particularly outstanding results are obtained when from 1.75 to 5.0 moles of melamine derivative are used per mole of phosphoric amide. This preferred range gives a very high yield of insoluble reaction product and excellent durability.
  • the insoluble reaction product be present in an amount equal to at least 14% by weight based on the weight of the fabric after washing the treated fabric for 15 minutes at 90 C. in an aqueous solution containing 0.1% of sodium carbonate and 0.1% of nonionic detergent (Triton X-lOO, a mixture of closely related compounds having the formula where x has an average value of about
  • Triton X-lOO a mixture of closely related compounds having the formula where x has an average value of about
  • the catalyst used can be an acid, an acid forming salt, an oxidizing agent or a neutral salt which is alkali metal chloride, bromide, iodide or nitrate.
  • catalytic compounds are: hydrochloric acid; zinc nitrate; zinc chloride; magnesium chloride; magnesium nitrate; amine hydrochlorides, including alkylamine hydrochlorides where the alkyl group is preferably 1 to 8 carbon atoms such as methylamine hydrochloride, and alkanolamine hydrochlorides, preferably of 1 to 8 carbon atoms such as 2-amino-2-methyl-1-propanol hydrochloride and N,N',N"-nitrilotriethanol hydrochloride: ammonium salts such as ammonium tartrate, citrate, oxalate, formate, nitrate, or ammonium dihydrogen phosphate; peroxy compounds such as hydrogen peroxide, peroxymonosulfates of alkali metals or
  • the stiffness of the flame retardant fabric increases as the concentration of catalyst increases.
  • concentration of catalyst on the fabric during the coreaction of melamine derivatives and phosphoric amide should not be greater than about 1.5% by weight of the weight of the fabric when an acid, acid forming salt or oxidizing agent is used as the catalyst and 6% by weight when a neutral salt is used as catalyst.
  • the minimum amount of catalyst used should be about 0.05% by weight based on the weight of the fabric for acids, acid yielding salts and oxidizing agents and about 1.0% for neutral salts.
  • the phosphoric amide, melamine derivative and catalyst are applied from an aqueous solution by padding, brushing, spraying or other impregnation technique.
  • the critical concentration of reactants and catalyst and the required add-on of reaction product are obtained by controlling the concentrations of compounds in the aqueous solutions and the wet pick-up of solution of the fabric.
  • the phosphoric amide and melamine derivatives are coreacted by heating at a temperature of about to 210 C.
  • this coreaction can be effected by dry heating, such as in an oven, without either unduly deteriorating the physical strength of the fabric or giving an excessively stiff product.
  • dry heat can be used is very advantageous, since many plants where fabrics are finished do not have wet fixation (e.g., steaming) equipment.
  • the coreaction can be effected by Wet fixation, i.e., heating the fabric while maintaining the moisture content at a level of at least 10% based on the weight of the fabric.
  • aqueous dispersion containing the coreactants and catalyst also may contain additives for other purposes, such as wetting agents. For instance, it is on occasion advisable to add a wetting agent if it is necessary to improve penetration and evenness.
  • the fabric is preferably washed to rinse out any soluble chemicals, such as catalyst, and unreacted starting material, and then dried, as on a tenter frame or in a forced-draft oven. (The washing step may be carried out in boiling water, if desired.)
  • the flame-retardant finish which results is durable through repeated cycles of laundering and drying.
  • the present invention can be used with cellulose-containing fabrics which are knitted, woven or non-woven.
  • the cellulose can be from any source, including such natural sources as seed fibers such as cotton, bast fibers such as flax (linen), ramie, jute, and hemp, as well as regenerated cellulose such as rayon, where wood may serve as the source of cellulose.
  • seed fibers such as cotton
  • bast fibers such as flax (linen), ramie, jute, and hemp
  • regenerated cellulose such as rayon, where wood may serve as the source of cellulose.
  • 'Ihe benefits obtainable through this invention are most noticeable with fabrics whose fibers are wholly cellulosic, but blended fabrics such as cotton-polyester blends can be used wherein up to about 50% or more of the fibers are non-cellulosic.
  • Flame Retardancy (Limiting Oxygen Index), the minimum value of the volume fraction (expressed in decimal form) of oxygen in a metered oxygen-nitrogen mixture, using a flammability index tester (Type FL-lol, General Electric 00.): C. P. Fenimore and F. J. Martin, Combustion and Flame, vol. 10, No. 2, 135 (June 1966), and Modern Plastics, vol. 43, No. 11, 141 (November 1966).
  • a limiting oxygen index of about 0.260 or greater is passable.
  • EXAMPLE 1' A series of aqueous baths were prepared containing 0.5% by weight of methyl amine hydrochloride and varying relative amounts of N,N',N"-trimethylphosphoric triamide and trimethylolmelamine. The baths were adjusted to pH 7 with HCl.
  • TPA N,N'N"-trimethylphosphoric triamide.
  • Example 6 The general procedure of Example 1 was repeated using aqueous pad baths containing 9.5% by weight iN, N', N"- trimethylphosphoric triamide and 19.0% by weight trimethylolmelamine.
  • the catalyst and catalyst concentrations of each bath, along with the results obtained, are specified in Table 6.
  • EXAMPLE 4 EXAMPLE 7 The procedure of Example 2 was repeated, but the 30 chemicals were used in such a concentration as to get about 16% weight gain.
  • Example 1 The general procedure of Example 1 was repeated using an aqueous pad bath containing 9.2% by weight of N,N', N"-triethylphosphoric triamide, i.e., (C H NH) P--O, 14% by weight of trimethylolmelamine and 10% by weight of Z-amino-Z-methyl-l-propanol hydrochloride.
  • EXAMPLE 5 The general procedure of Example 1 was repeated using aqueous pad baths containing 9.5% by weight of N,N',N"- trimethylphosphoric triamide and 19.0% by weight trimethylolmelamine. The catalyst and catalyst concentration of each bath, along with the results obtained are given in Table 5..
  • An aqueous bath was prepared containing 20% by Weight of trimethylolmelamine, 10% by weight of N, N,N"-trimethylphosphoric triamide and 1.5% by weight of NaCl.
  • the pH of the bath was adjusted to pH 7 with HCl and then lightweight rayon fabric was padded therein. The Wet pick-up was 119%.
  • the padded sample was dried at 66 C. and then dry cured at 182 C. for 5 minutes. The sample washed, neutralized, rinsed and dried as described in Example 1. A weight gain of 26.5% was obtained. Flame retardance is given in Table 8.
  • Two aqueous pad baths were prepared, one containing N,N',N"-tris(hydroxymethyl) N,N',N"-trimethylphosphoric triamide and the other containing N,N',N- trimethylphosphoric triamide and trimethylolmelamine.
  • the catalyst in both baths was the hydrochloride of 2- amino-Z-methyl-I-propanol (1.1% on the weight of the bath).
  • Example 2 Samples of the same fabrics as used in Example 1 were padded in the aqueous baths so as to give a wet pick-up of about 80%. The padded samples were dried for 1% minutes in a forced draft oven at approximately 82 C. and then dry-cured for 5 minutes at 163 C. The padded samples were then washed, neutralized, rinsed and dried as in Example 1 and evaluated. Results are shown in Table 9, with the amounts of reactants given in terms of compound on the fabric after padding, i.e., OWB times percent weight pick-up or OWF. The results show that the losses in flex abrasion resistance and tear strength are much greater with N,N,N"-tris (hydroxymethyl)-N,N',N-trimethylphosphoric triamide.
  • an oxidizing agent or a neutral salt of an alkali metal and an anion selected from the group consisting of chloride, bromide, iodide and nitrate, and heating said impregnated fabric to a temperature of about 60 to- 210 C.
  • a process as claimed in claim 1 wherein said catalyst is an alkylamine hydrochloride or an alkanolamine hydrochloride.
  • a process for treating cellulose-containing fabric to render said fabric flame retardant comprising applying to said fabric an aqueous solution of (a) a melamine derivative of the formula where R at each occurrence is independently selected from the group consisting of hydrogen and -CH OZ with Z being hydrogen or alkyl of 1 to 4 carbon atoms, provided that at least two of said R groups are --CH OZ,
  • a process for treating cellulose-containing fabric to render said fabric flame retardant comprising applying to said fabric an aqueous solution of (a) a melamine derivative of the formula where R at each occurrence is independently selected from the group consisting of hydrogen and -CH OZ with Z being hydrogen or alkyl of 1 to 4 carbon atoms, provided that at least two of said R groups are CH OZ,
  • a catalyst which is an acid, an acid forming salt, an oxidizing agent, or a neutral salt of an alkali metal and an anion selected from the group consisting of chloride, bromide, iodide and nitrate,
  • a process as claimed in claim 8 wherein said phosphoric amide is N,N',N"-trimethylphosphoric triamide.
  • a process as claimed in claim 8 wherein said melamine derivative is trimethylolrnelamine.
  • a process as claimed in claim 8 wherein the amount of the insoluble product formed on said fabric is equal to at least 14% by weight of the weight of the fabric as measured after the treated fabric has been subjected to a hot process wash to remove any soluble chemicals.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
US61490A 1970-08-05 1970-08-05 Preparation of flame-retardant fabrics Expired - Lifetime US3681060A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US6149070A 1970-08-05 1970-08-05

Publications (1)

Publication Number Publication Date
US3681060A true US3681060A (en) 1972-08-01

Family

ID=22036120

Family Applications (1)

Application Number Title Priority Date Filing Date
US61490A Expired - Lifetime US3681060A (en) 1970-08-05 1970-08-05 Preparation of flame-retardant fabrics

Country Status (4)

Country Link
US (1) US3681060A (enrdf_load_stackoverflow)
JP (1) JPS5529196B1 (enrdf_load_stackoverflow)
DE (1) DE2137356A1 (enrdf_load_stackoverflow)
GB (1) GB1359886A (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3969291A (en) * 1974-03-06 1976-07-13 Sumitomo Chemical Company, Limited Intumescent fire-retardant coating compositions containing amide-polyphosphates
US4136037A (en) * 1975-12-22 1979-01-23 Leblanc Destin A Phosphoramide-hydroxymethyl phosphine condensation products for textile fire retardation

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1114105A (en) * 1978-09-05 1981-12-15 Ray E. Smith Intumescent composition

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1006386B (de) * 1954-11-05 1957-04-18 J R Geigy A G , Basel (Schweiz) Verfahren zur Herabsetzung der Entflammbarkeit von cellulosehaltigem Material

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3969291A (en) * 1974-03-06 1976-07-13 Sumitomo Chemical Company, Limited Intumescent fire-retardant coating compositions containing amide-polyphosphates
US4136037A (en) * 1975-12-22 1979-01-23 Leblanc Destin A Phosphoramide-hydroxymethyl phosphine condensation products for textile fire retardation
US4148602A (en) * 1975-12-22 1979-04-10 Leblanc Research Corporation Phosphoramide-hydroxymethyl phosphine condensation products for textile fire retardation

Also Published As

Publication number Publication date
GB1359886A (en) 1974-07-17
DE2137356A1 (de) 1972-02-10
JPS5529196B1 (enrdf_load_stackoverflow) 1980-08-01

Similar Documents

Publication Publication Date Title
US3897584A (en) Rendering fibrous material flame retardant with cyan amide/halomethyl phosphonic acid systems
US4090844A (en) Process of producing high performance durable-press cotton
US2482755A (en) Flameproofing of fibrous material
JPH08209534A (ja) 織物材料に難燃性および柔軟性を与えるための組成物
US3310419A (en) Process for treating cellulosic material with flameproofing composition
US2828228A (en) Textile fire retardant treatment
US3619113A (en) Flame-retardant finish for cellulosic textile materials
US4154890A (en) Process for imparting flame retardant property to cellulosic containing materials
US3681124A (en) Process for preparing durable flame-retardant synthetic-cellulosic fabric blends
US3079279A (en) Blends of imidazolidinones and aminoplasts and method for finishing cellulose containing textile material
US3681060A (en) Preparation of flame-retardant fabrics
US4066391A (en) Flame retardant finish for textiles
US4095945A (en) Process for treating textile articles
US3428480A (en) Flame-retardant cellulosic material,composition and method for making same
US3310420A (en) Process for flameproofing cellulosic textile material
US3632297A (en) Process for rendering cellulose-containing fabrics durably flame-retardant by wet-curing a melamine resin and a phosphoric acid amide on the fabric
US3644083A (en) Durable flame retardant finish for cellulosic textile materials
US3933426A (en) Process for making textiles containing cellulose crease-resistant
US3656885A (en) High strength wrinkle resistant cotton fabrics produced by a process involving both monosubstitution and crosslinking of the cotton
US3888779A (en) Flame retardant composition containing tetrakis (hydroxymethyl) phosphonium oxalate
US3919439A (en) Method of application of THPOH-NH{HD 3 {B fire retardant finish to textiles
US3168415A (en) Textile finishing composition, application process, and resulting product
US3825630A (en) Phosphonate carbamates
US3556840A (en) Method for improving the flame retardant properties of a cellulosic material
US4196260A (en) Process for flameproofing cellulosic fibrous material

Legal Events

Date Code Title Description
AS Assignment

Owner name: BANKERS TRUST COMPANY, A NY BANKING CORP., NEW YO

Free format text: SECURITY INTEREST;ASSIGNOR:J.P. STEVENS & CO.;REEL/FRAME:005271/0777

Effective date: 19891020

AS Assignment

Owner name: J.P. STEVENS & CO., INC., GEORGIA

Free format text: RELEASE SECURITY INTEREST & ASSIGNMENT.;ASSIGNOR:BANKERS TRUST COMPANY;REEL/FRAME:007074/0390

Effective date: 19931210