AU604922B2 - Simultaneously dyed and flame retarded fabrics - Google Patents

Description

C~ "Y AU-AI-18093/88 4 T WORLD INTELLEALPER OR ZA INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (51) International Patent Classification 4 D06P 3/82, 3/60, 1/667 D06M 13/26 (11) International Publication Number: WO 88/ 09411 Al P r (43) International Publication Date: 1 December 1988 (01.12.88) (21) International Application Number: PCT/US88/01619 (22) International Filing Date: (31) Priority Application Number: (32) Priority Date: (33) Priority Country: 19 May 1988 (19.05.88) 052,937 22 May 1987 (22.05.87) (71) Applicant: BURLINGTON INDUSTRIES, INC. [US/ US]; 3330 West Friendly Avenue, Greensboro, NC 27420 (US).

(72)Inventors: JOHNSON, James, R. 1315 Easthurst Road, McLeansville, NC 27301 FINLEY, Randolph, L. 605 McQueen Street, Florence, SC 29501

(US).

(74) Agents: CRAWFORD, Arthur, R. et al.; Nixon Vanderhey, 2000 North 15th Street, Suite 409, Arlington, VA 22201 (US).

(81) Designated States: AT (European patent), AU, BE (European patent), BR, CH (European patent), DE (European patent), DK, Fl FR (European patent), GB (European patent), IT (European patent), JP, KR, LU (European patent), NL (European pat-nt), NO, SE (European patent).

Published With international search report.

Before the expiration of the time limit for amending the claims and to be republished in the event of the receipt of amendments.

A.D.J.P. 23 FEB 1989

AUSTRALIAN

2 1 DEC 1988 PATENT OFFICE T h i s document contains the (54) Title: SIMULTANEOUSLY DYED AND FLAME-RETARDED FABRICS F Section 49 and is correct for printing.

(57) Abstract Synthetic/cellulosic blend textile fabrics are simultaneously dyed and the synthetic component simultaneously treated to impart flame resistance in a single step with good color yield. Additional fabric finishing may be used to impart flame resistance to the cellulosic component of the fabric.

,.J

1- -7 I I I I SO 88/09411 PCT/US88/01619 SIMULTANEOUSLY DYED AND fEL'ME-RETARDED FABRICS CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of earlier application Serial No. 052,937 filed May 22, 1987 which, in turn, is a continuation-in-part of Serial No. 870,892 filed June 5, 1986, now U.S.

TECHNICAL FIELD OF ThE INVENTION This invention relates generally to dyeing and treating textile fabrics to impart flame resistance.

Synthetic/cellulosic blend textile fabrics are simultaneously dyed and the synthetic component flame retardant treated in a single step. Additional fabric finishing may be used to treat the cellulosic component of the fabric to impart flame resistance.

In addition, fabrics composed entirely or predominantly of cellulosic fibers are treated to minimize shade change when flame-retardant treating with tetrakis-(hydroxymethyl) phosphonium salts.

Polyester/cellulosic blends are continuously dyed on a commercial scale according to conventional procedures with mixtures of disperse and vat dyes.

The dyes are typically mixed with an antimigrating agent, a surfactant, a defoamer and a buffer.

After the dye mix is padded and dried on the fabric, the treated fabric is heated to 2040 'to 218 0 C to allow the disperse or polyester dyes to thermosol I nar i WO 88/09411 PCT/US88/,01619 2 into the polyester fibers. The fabric is then cooled on cans and padded with a reducing bath containing sodium hydrosulfite and caustic, then steamed at slightly above atmospheric pressure at about 103°C, rinsed, and oxidized with hydrogen peroxide or sodium bromate to fix the vat dyes onto the cotton fibers.

The dyed substrate is then scoured in hot water to remove any unfixed dyestuffs and auxiliary materials and finally dried, usually over several steam cans.

It is often desirable to impart flame resistance to fabrics, particularly synthetic/cellulosic blended fabrics, notably polyester/cotton and nylon/cotton blended fabrics. There are several flame retardants that can be thermosoled into dyed and undyed synthetic fibers. Cyclic phosphonate flame retardants, as exemplified by Antiblaze 19T (sometimes referred to herein for convenience as AB 19T, explained and identified in more detail below), appear to be among the most effective systems available commercially as flame retardant finishes for the synthetic components of such blends, the finish being applied by a pad/dry/thermosol process.

The present inventors have recognized the possibility of incorporating not only the cyclic phosphonate flame retardant but also a suitable dye or mixture of dyes into the synthetic component of the blend to give the substrate some flame resistance, save the Scost of an extra processing step and to produce a dyed fabric which has better.properties.

It is an object of this invention to apply a flame retardant chemical for the synthetic fibers to a synthetic/cellulosic blend fabric during a continuous dyeing process in order to impart a

U

wo.188/09411B PCT/US88/01619 3 significant level of flame resistance to the synthetic fiber of the blend, and thereby to produce a synthetic/cellulosic fabric with superior flame resistance. Another object of this invention is to provide a dyeing and flame retardant treating process in which the color yield is not significantly reduced by subsequent finishing operations, especially for fabrics predominantly of cellulosic or of all cellulosic fibers.

DETAILED DESCRIPTION OF THE INVENTION This invention includes a process for simultaneously dyeing and imparting flame resistance to a synthetic/cellulosic blend fabric containing at least 35% by weight synthetic, by applying a dyebath containing a tinctorial amount of at least one dye for the synthetic fibers, a tinctorial amount of at least one dye for the cellulosic fibers, and a flame retarding amount of a cyclic phosphonate ester flame retardant to the synthetic/cellulosic blend fabric; drying and heating the fabric to allow the synthetic dye and flame retardant to thermosol into the synthetic fibers, then (3) treating the fabric to fix the dye onto the cellulosic fibers; and finally washing the fabric to remove any unfixed dye or components of the dyebath from the fabric. A final finishing step of applying a flame retardant finish to the cellulosic fibers has been shown to produce a flame resistant fabric with a Limiting Oxygen Index (LOI) of at least 27% after 50 and 100 home launderings, a soft handle suitable for use in apparel end uses, good U" j WO 88/09411 PCT/US88/P1619 4 wash and wear appearance performance, excellent strength and comfort characteristics, and good colorfastness performance.

This invention provides a process for dyeing synthetic/cotton fabrics and at the same time improving the flame resistance of the synthetic fiber. The flame retardant used is not limited to the cyclic phosphonates, which aie presently preferred; other water-soluble high-boiling systems are expected to be suited to the process. Also, stable emulsions of water-insoluble systems should work if the total system is compatible with the dyestuffs and dyeing conditions.

The use of this method is not limited to synthetic/cellulosic blends. The method is also useful for 100% polyester, 100% cotton, 100% nylon, and other cotton and polyester blends. .The process is also useful for minimizing shade change of all cellulosic (usually 100%) fabrics when THP salts are applied to them. As used in this specification and in the appended claims, the term synthetic thermoplastic fiber includes nylon or polyester.

Cellulosic fibers include cotton, rayon, linen and blends thereof.

In finishing synt-'etic/cellulosic blends to impart flame resistance, the cellulosic and synthetic components should ideally be treated with specific chemicals to impart flame resistance to the I individual fibers. Tetrakis-.(hydroxymethyl) phosphonium salts (henceforth designated THP salts), such as THPS, are very effective for imparting flame resistance to cellulosic materials. This can be accomplished by using either a THP/urea precondensate WO 88/09411 PCT/US88/01619 salt, which is insolubilized with gaseous ammonia, or by using a THP/urea pad/dry/cure process, or both.

Cyclic phosphonates, as exemplified by Antiblaze 19T, are effective flame retardants for synthetic fibers. To maximize the favorable use of the cyclic phosphonate flame retardant and the dyeing operation, the synthetic fibers are treated with the flame retardant first; the cellulosic fibers are flame retardant treated during subsequent processing.

The cyclic phosphonate flame retardants are compatible with the dyebath and processing conditions conventionally used in the dyeing (only) of synthetic/cellulosic blends. Simultaneous application saves two complete processing steps in the production of flame resistant fabrics. Since the cyclic phosphonate flame retardants are high-boiling solvent-type materials and the normal dyestuffs are somewhat soluble in them, there is a minimum of migration of the dyestuff during the drying step.

Depending upon the solubility of the dyestuff system being applied, the antimigrant chemicals can be eliminated from the formulation.

Demonstrated advantages of the invention include: improved dye yield of cotton vat dyes; treatment of the synthetic contributing to the overall flame resistance of the substrate; minimization of adverse shade change with subsequent cellulosic flame retardant chemical application; imparting a smoother appearance after dyeing to the fabric, particularly polyester/cotton fabric; improved shade control; and reduced washdown after multiple home launderings.

A wide range of vat dyes have been evaluated for 1: i I I If lli l WO 88/09411 PCT/US88/91619 6 use in the process of this invention and, as expected, it has been found that certain optimum dyes clearly perform better than others. Polyester dyes (generally disperse dyes) have also been evaluated on 65/35 polyester/cotton blends, and it has been found that a maximum dye yield is realized around 2% AB19T level in the bath. At a 5% level, the disperse dye yield is equal to that obtained when 3% alginate antimigrant is used. It has been found that as the concentration of the AB19T is increased to 15%, the dye yield is decreased; however, more phosphorus or AB19T is fixed in the polyester fiber as the concentration of the flame retardant is increased, as would be expected. This decrease in dye yield may be due to the presence of' excess AB19T on the surface, causing the dyes to establish an equilibrium between the "excess" AB19T and the polyester fiber. This phenomenon is related to the distribution coefficient of the dyes between the AB19T phase and polyester. The amount of flame retardant applied to the fabric is based upon the amount of phosphorus to be retained in the fibers balanced against the dye yield desired. Similar results are observed with nylon/cotton blends.

Polyester/cellulosic blend fabrics containing at least 35% by weight polyester, balance cellulosic fibers (usually cotton), are a preferred class of fabrics for simultaneously dyeing and flame retardant treatment. Polyester contents in the 40 to weight range are most effectively treated. Other fibers forming the balance of the blend may include linen, rayon or, preferably, cotton. Another class of blended fabrics are nylon/cellulosic blends with 1 i IlrC WO 88/09411 PCT/US88/01619 7 the nylon component representing 40%, often about half, of the blend, balance cellulosic fibers, again usually cotton.

The fabrics dyed and flame-retardant finished according to the invention can be in any desired stage of processing, they can be treated as woven or knit fabrics. One flame retardant process suitable only for cotton fibers which provides satisfactory and durable flame resistance, known as the PROBAN process, consists of treating the cotton fabric with a prepolymer of tetrakis-(hydroxymethyl) phosphonium salt and urea, followed by ammoniation (THP/urea-precondensate/ammonia). The PROBAN process, licensed by Albright Wilson, is described in the following U.S. patents: 4,078,101; 4,145,463; 4,311,855; and 4,494,951, all to Albright Wilson, the disclosures of which are hereby incorporated by reference to the extent necessary to explain the THP salt/urea-precondensate process. See also U.S. 4,346,031 to Elgal et al.

This'process is considered effective and is widely promoted by at least two companies for imparting flame resistance to 100% cotton fabrics; it is not promoted or advertised for polyester/cotton blends or nylon/cotton blends.

The THP/urea-precondensate/ammonia process consists of applying a THP/urea-precondensate to cotton fabric and drying the fabric to about 10 to wt.% of moisture. The cotton fabric is then exposed to gaseous ammonia. The precondensate is insolubilized by the ammonia. Fixation of the precondensate takes place mainly inside of the cotton fiber, thus imparting durability to multiple -1 L '1 WO 88/09411 PCT/US88/01619 8 launderings.

The invention will now be illustrated with reference to the following examples in which all parts and percentages are by weight and temperatures reported in degrees Celsius. Some formulations are expressed on a weight per volume basis with g/l indicating grams per liter. The materials used are more fully described as follows: Among the flame-retardant materials used in accordance with the present invention are thermally stable cyclic phosphonate esters prepared by reacting alkyl-halogen-free esters with a bicyclic phosphite. As a class, these cyclic phosphonate esters are represented by one of the formulas: 1

SR

2

CH

0 3 (R'O)b p OCH 2 C I CHO c a where a is 0 or 1; b is 0, 1 or 2, c is 1, 2 or 3 and a+b+c is 3; R and R' are the same or different and are alkyl (C 1

-C

8 phenyl, halophenyl, hydroxyphenyl, tolyl, xylyl, benzyl, phenethyl, hydroxyethyl, phenoxyethyl, or dibromophenoxymethyl; R is alkyl (C 1

-C

4 and R 3 is lower alkyl

(C

1

-C

4 or hydroxyalkyl

(C

1

-C

4 or 0 1 N CIZ 3 0 -R 5 COcH 2 CN /Pi 4 0 ICulo e -I rC WO 88/09411 1 WO 8809411PCT/US88/01619 9 where d is 0, 1 or 2; e is 1, 2 or 3; R2is alkyl (C 1 -C 4 R 3 is lower alkyl (C 1 -C 4 or hydoxalyl C-C 4

R

4 is alkyl

(C

1 -C 4 phenyl, halophenyl, hydroxyphenyl, hydroxyethyl, phenoxyethyl, dibromnophenoxyethyl, tolyl, xylyl, benzyl, or phenethyl; and R monovalent alkyl (C 1 -C 6 chiorophenyl, bromophenyl, dibromophonyl, tribromophenyl, hydroxyphenyl, naphthyl, tolyl, xylyl, benzyl, or phenethyl; divalent alkylene (C 1 -C 6 vinylene, o-phenylene, m-phenylene, p-phenylene, tetrachiorophenylene m, or p), or tetrabromophenylene m, or or trivalent phenenyl.

The preferred compounds (see below) are represented by the formula: 0 CH 2 CH 3 0 11 1 CH 2 O 1 3 )XP-OH2 H PCH 3 2

X

CR3 in which X is 0 or 1, and usually a 50:50 mixture of the mono- and di-esters. The preparation of these cyclic phosphonate esters and their use as flame retardants are described in U.S. 3,789,091 and 3,849,368, the disclosures of which are hereby incorporated by reference.

Aniiblaze 19T, as described by the supplier Albright Wilson, Inc., of Richmond, Virginia, is a cyclic phosphonate ester, availabl~e as an odorless viscous liquid '(viscosity 1.30 x 10-3 m 2 /Is at 0 C) with a flashpoint of 171 0 C (ASTN D-93).

I

WO 88/09411 PCT/US88/01619 Tetrakis-(hydroxymethyl)phospsphonium sulfate (THPS), also available from Albright Wilson, Inc., under the name of Retardol S and from American Cyanamid under the name Pyroset TKO, is a pale, straw-colored liquid that is miscible with water and has a pungent odor. Several related compounds can be used in place of THPS, including tetrakis- (hydroxymethyl)phosphonium chloride (THPC), available under the name of Retardol C from Albright Wilson, and tetrakis-(hydroxymethyl)phosphonium oxalate, available as Pyroset TKS from American Cyanamid Company.

THPS when mixed with urea and heated strongly forms a relatively insoluble polymer, containing both phosphorus and nitrogen, inside the cotton fibers, and around both the cotton and the nylon fibers.

Insolubility of this polymer is increased further by oxidizing the phosphorus with hydrogen peroxide.

EXAMPLE 1 A 50/50 polyester/cotton 7 ounce 2x1 twill fabric was simultaneously dyed and the polyester fibers flame retardant treated using a disperse/vat dye formulation containing a flame retardant for the polyester fibers.

il ~~lii iii I~ILl^_i WO 88/09411 PCT/US88/01619 Dvestuffs in Pad Bath Concentration (g!L Polycron Dianix Blue FP (Disperse Blue 73) Terasil Orange GFA (Disperse Orange 44) Foron Rubine S-2GFL (Disperse Red 167:1) Palanthrene Red LGG (Vat Red 32) Cibanone OliVe SP (Vat Black 23) Carvat Brown BRS (Vat Brown 1) 18.2 26.0 44.0 Chemicals in Pad Bath Antiblaze 19T Buffer N Antimigrant B 25.0 20.0 The fabric was padded with the above pad bath solution, squeezed to reduce wet pick-up, sli.ly dried using infrared predryers, and then totally dried prior to the thermosol step with steam cans.

The treated-fabric was heated to 216 0 C in a gas oven for 60 seconds (1.37 m/s) to diffuse the color into the polyester fibers with dry heat (thermosoling).

The vat dye was reduced by application of a sodium hydrosulfite/caust.c solution after which the fabric passed through a 73-meter steamer. The excess dye was removed in two open wash boxes and the remaining vat dyes were fixed by oxidation using sodium bromate. The final shade was developed by soaping through four washboxes at 71 0

C.

9 t for the polyester fibers, a tinctorial amount of at least one dye for the cellulosic fibers, and a flame-retarding amount of a cyclic phosphonate ester flame retardant.

/3 WO 88/09411 PCT/US88/01619 12 EXAMPLE 2 A series of samples of 254 g/m 2 65/35 polyester/cotton fabric was dyed by the method of Example 1, using varying concentrations of Antiblaze 19T to examine the effect on the dye yield. For purposes of comparison, a control fabric was dyed in a bath containing 20 g/l (grams/liter) of Antimigrant B, an alginate antimigrant, but no Antiblaze 19T. All of the dyebaths contained g/l Buffer N. The dyes used in the bath were as follows: Dyestuff Concentration (q/1_ Foron Navy Blue S-2GRL 100 Pst.

(Disperse Blue 79) 24.00 Intrasil Orange YBLH 50% Liq. (Disperse Orange 29) 5.50 Foron Brilliant Yellow S-7GL 50% Pst. 0.85 Palanthrene Navy Blue Coll. Liq. (Vat Blue 16) 18.21 Cibanone Yellow 2GNP (Vat Yellow 33) 0.31 Patcovat Black SNAP (Vat Black 16) 35.02 Table I shows the results of color measurements made on a series of six samples. The first fabric, the control, was dyed in a bath containing 20 g/l of Antimigrant B, but no Antiblaze 19T. The remaining five samples contained from 25 to 150 g/1 of Antiblaze 19T. Color measurements made under 0 Conditions (cool White Fluorescent illumination, 100 observer) are also presented in i WO 88/941 PCTUS8/06 WO 88/09411 PCT/US88/01619 Table I.

TABLE I Effect of Flame Retardant Concentration in Dyebath on Color Yield Antimigrant

B

1 0 0 g/l Control 20.0 Antiblaze Strength 19T (KSSUM) Standard aL 4C AH 1 2 3 4 6.8% strong 1.4% strong 2.4% weak 1.8% weak 13.9% weak -0.78 -0.21 0.23 0.17 1.77 -1.18 0.36 0.41 Red 0.32 Red 1.54 0.26 Red 1.32 0.23 Red 1.66 -0.19 Green Table I measures color yield by KSSUM values, KSSLM representing an integrated measure of color strength over a range of wavelengths. The values for AL measure lightness, a lower number indicating a darker shade or a higher yield. A C is a measure of chroma, or brightness, and AH* is a measure of hue. The shifts of chroma and hue are relatively small, confirming that changes of KSSUM or can be taken at face value.

As shown by Table I, the use of 25 g/l Antiblaze 19T in the bath produced a significant increase in yield, compared with the control, since the KSSUM value increased and AL decreased. The use of a very large quantity of Antiblaze 19T in the dyebath SUBSTITUTE SHEET SUBSTITUTE

SHEET

Aj *d '11 ^*a WO 88/09411 PCT/!US88/01619 14 (150 g/1) produced the opposite effect, while the intermediate concentrations produced only small changes.

EXAMPLE 3 To assess the effect of AB19T oii vat dye color yield, several pure vat dyes were applied to a 100% cotton fabric. Subsequent finishing of these fabrics with THPS/urea demonstrated that shade change was better controlled with the AB19 treatment than without. All fabrics were dyed in baths containing g/l of dye and 50 g/l of AB19T. The wet pickup was 65%. Fabrics were also dyed with 30 g/l of an alginate antimigrant to act as a control fabric.

Each of'these fabrics was finished with an 1.8% owf add-on of a tetrakis-(hydroxymethyl) phosphonium sulfate/urea system and the impact on shade change was assessed. The results are presented in Table II.

In some instances, the nature of the THPS/urea and/or AB19T chemistry does not provide a compatible environment for the vat dye, resulting in possible destruction of the chromophore. Those examples are not cited. Color yield even with the THPS finish is maintained in some instances and not significantly reduced, at least to an unacceptable level, in other instances. As can be seen from Table II, the strength of dyeing as indicated by the strength values is significantly greater for those samples dyed in the presence of Antiblaze 19T than for the corresponding controls.

1 0/91 PCTS88/.161 TABLE II 1 -0 (Con't 00 '00 g/l Alginate TIIPS Finished Dyestuff Strength A L LC* 16If il

A

Liq. (Vat Red 32) ?atcovat Olive AR Dbl. Pst.

?3lanthrene Blue CLF Coll.

fVat Blue 66) Cibanone Yellow 2GNI 81 Pst.

(Vat Yellow 33) Palanthrene Brill. Green FF13 (Vat Green 1) Cibanone Black~ SIIA Dbl. Pst.

(Vat Black 16) Sandothrerne Grey HJB Pst.

Cibanone Olive S Pst.

(Vat Black 25) 1.93% -15.61 2.71 0.39 1.84 Or -9.29% 1.27 -2.16 -0.48 Or 10.9% -1.15 1.00 -0.11 Red -12.01 1.62 -0.39 1.49 BI -0.19 0.30 1.50 Red 0.72 0-.42 -0.25 Red 0.14 0.69 '-1.07 Red -19.0% 3.27 0.56 -0.04 Carvat Brown BSQ Pst.

(Vat Brown 1) 1.34 -0.42 0.85 Yel

U

E; R1,515,110Z I I W i m i TABLE II Effect of Antiblaze 19? on Color Yield of Wit-Dyed Cotton q/1 Antlblaze 19T

C

-1 fit Dyestuff Palanthrene Brill. Red LGG Coll.

Liq. (Vat Red 32) ?a tcovat Olive AR DbI Pst.

*?alanthrene Blue CIA' Coll.

(Vat Blue 66) Cibanone Yellow 2GII 81 Pst.

(Vat Yellow 33) Palanthrene Brill. Green FFB (Vat Green 1) Cibanone Black SlIA Dbl. Pst.

(Vat Black 16) Sandothrene Grey IIB Pst, Cibanone Olive S Pst.

(Vat Black 25) Carvat Brown BSQ Pst.

(Vat Brown 1) Strength 6L* LbC 39.9% -3.24 -3,48 A H11 -1.07 Red 10.0% -1.34' 0.45 -0.11 Red 16.7% -1.98 2.35 0.36 Red 31.5% -0.92 4.67 0.01 20.8% -1.86 2.44 -0.17 Yel 37.3% -4.09 -1.20 0.58 Red 64.4% -7.40 0.45 -0.09 2.7% -0.17 1.07 -0.11 49.0% -5.31 2.49 0.24 00) 00 Ch 0 Go

C

'.0 Table II (Con' L) Dyestuff Palanthrene Brill. Red LGG Coil.

Liq. (Vat Red 32) ?atcovat Oliva AR Dbl. Pst.

Palanthrene Blue CLF Coll.

(Vat Blue 66) Cibanone Yellow 2GH 8% Pst.

(Vat Yellow 33) PaI-threne Brill. Green FF13 (Vat Green 1) Cibanone Black SNA Dbl. Pst.

(Vat Black 16) Sandothrene Grey NJB Pst.

Cibanone Olive S Pst..

(Vat Black 25) Carvat Brown BSQ Pst.

(Vat Brown 1) g/l Antiblaze 19T TOIPS Finished Strength b L16 AC, A1 39.31 -3.19 4.65. -1.01 Red 1.6% 0.46 0.69 1.96 Gr 6.28% -0.81 0.42 -0.01 16.9% 0.34 -3.32 -0.28 21.16% -1.65 3.05 '0.97 18.6% -2.46 0.06 1.83 47.6% -5.75 0,86 -0.18 0.69 1.50 0.15 31.0% -3.40 2.09 1.25 Yel

F

V

U

,.1 WVO 88/09411 PCT/US88/01619 16 EXAMPLE 4 2 A 50/50 polyester/cotton 271 g/m 2 2x twill fabric was simultaneously dyed and the polyester fibers flame retardant treated using a disperse/reactive dye formulation containing a cyclic phosphonate flame retardant for the polyester fibers. The dye formulation was as follows: Dyestuff Concentration (g/1J Terasil Yellow E6GSLW (Disperse Yellow 88) Cibacron Yellow 6GP (Reactive Yellow 95) 30.0 Auxiliaries Antiblaze 19T 25.0 Antimigrant B 20.0 Buffer N The fabric was padded with the above solution to a wpu, slowly dried with infrared predryers to minimize dye migration, totally dried on dry cans, and heated to a temperature of 216 0 C for 60 seconds to allow the disperse dyes and Antiblaze 19T to diffuse into the polyester fibers. The reactive dye was fixed to the cotton by applying a soda ash/salt brine to activate the reactive dyestuff when passed through a 73-meter steamer. The excess dye was removed by passing the fabric through wash boxes at 82°C. In subsequent operations, tetrakis- (hydroxymethyl) phosphonium salts were applied to i i j WO 88/09411 PCT/US88/01619 the substrate to provide an initial phosphorus content after oxidation of 3.0 The fabric was compressively shrunk by methods well established in the trade to soften the handle.

The fabric was tested in accordance with NFPA 1975 Recommendations and the results reported in the following Table. Fabric produced by this method has excellent colorfastness, strength, wash and wear, and handle characteristics suitable for apparel use in the uniform market.

A

1 i 'i1 WO 88/09411 PCT/US88/01619 TABLE III Test Method Test Description 2 eight (g/m ASTH Tensile Strength (kg) ASTM Tear Strength (kg) ASTM Shrinkage (5 launderings) AATCC Seam Efficiency FMT I Random Tumble Pilling (60 min) ASTH Flex Abrasion, cycles Wash and Hear Appearance 3 2 Air Permeability (m /s*m 5450 2 Moisture Vapor Transport, g/m /24 hrs.

Moisture Regain Resistivity

RH

Colorfastness Laundering IIA (staining) AATC Crocking Dry AATC( et D-3776 D-1682 D-1424 S135,3,IIB 5110 D-3512 Bottom eight Twill 268 66.7 x 41.7 3.5 x 3.1 2.1 x 0.9 100 x 76 3.06 5500 x 4700 3.60 0.107 680 5.3 1.0 x 3.6 x 12 10 13 10 C 61-IIA (120-F) C-8 Light Flame Resistance Testing Original Char length (cm) Afterflame (sec) Afterglow (sec) Char length (cm) Afterflame (sec) Afterglow (sec) lOOx Char length (cm) AATCC 16A FTH-191-5903* 10.2 x 8.9 Ox 0 Ox 0 10.4 x 9.7 Ox 0 0x 0 11.9 x 11.4 SUBSTITUTE SHEET

<I

WO 88/09411 PCT/US88/01619 Afterf lame (sec) Afterglow (sec) Melt/Burn Resistance Shrinkage Limiting Oxygjen Index (Z) Unlaundered After 50 laund.

after 100 laund.

IIFPA-1 971 RFPA-1971 ASTH D-2863 0Ox 0 O x 0 Pass 1 .OZ 27.5 27.2 27.3 *These results are typical of those achieved on production lot SUBSTITUTE

SHEET

I

Claims (35)

1. A process for simultaneously dyeing and imparting flame resistance to a polyester/cellulosic blend fabric, containing at least 35% by weight polyester, comprising the successive steps of: applying a dyebath containing a tinctorial amount of at least one dye for the polyester fibers, a tinctorial amount of at least one dye for the cellulosic fibers, and a flame retarding amount of a cyclic phosphonate ester flame retardant to the polyester/cellulosic blend fabric; drying the fabric and heating the fabric to allow the polyester dye and flame retardant to thermosol into the polyester fibers; treating the fabric to fix the dye on -to the cellulosic fibers; and washing the fabric to remove any unfixed dye or components of the dyebath from the fabric.

2. The process of claim 1 in which the cellulosic component of the blend is linen, rayon, cotton, or mixtures thereof.

3. The process of claim 2 in which the cellulosic component is cotton. .i WQ 88/09411 PCT/US88/01619 t 21

4. The process of claim 1 in which the blend contains at least 50% polyester. The process of claim 1 in which the blend contains from about 35% to about 65% by weight polyester.

6. The process of claim 1 in which the cyclic phosphonate ester is represented by the formula: 0 CH2CH 3 0 II 2 (CH 3 0) (OCHCH2 PCH3 SCH 2 O PCH3)2-x CH3 in which x is 0 or 1. The process of claim 6 in which from about 1% to about 25% w/v phosphonate ester is present in the dyebath.

8. The process of claim 1 in which the dyebath also contains a wetting agent and an antimigrant.

9. The process of claim 1 in which a disperse dye is present for the polyester component and a vat dye is present for the cellulosic component. A process for simultaneously dyeing and imparting flame resistance to a polyester/cellulosic i I WO 88/09411 PCT/US88/0.1619 22 blend fabric, containing at least 35% by weight polyester, comprising the successive steps of: applying a dyebath containing a tinctorial amount of at least one dye for the polyester fibers and a tinctorial amount of at least one dye for the cellulosic fibers, and a flame retardina amount of a cyclic phosphonate ester flame retardant to the polyester/cellulosic blend fabric; drying the fabric anc heating the fabric to allow the polyester dye and flame retardant to thermosol into the polyester fibers; treating the fabric to fix the dye onto the cellulosic fibers; washing the fabric to remove any unfixed dye or components of the dyebath from the fabric; and thereafter applying a flame retarding amount of a tetrakis-(hydroxymethyl) phosphonium salt flame -retardant to the fabric to provide an LOI value of at least 27.0% after 50 launderings at 49 0 C to the fabric thus treated.

11. The process of claim 10 in which the flame retardant of step is a prepolymer condensate of a tetrakis-(hydroxymethyl) phosphonium salt and urea which when exposed to ammonia forms an ammoniated 1 5 prepolymer flame retardant network within the cellulosic fiber structure.

12. The process of claim 10 in which the flame retardant of step is a tetrakis-(hydroxymethyl) A 0 illumination, 100 observer) are also presented in i WO 88/09411 PCT/US88/01619 I 23 phosphonium salt which when reacted with urea forms an insoluble phosphorus-containing polymer in and on the cellulosic fibers.

13. The process of claim 10 in which the flame retardant of step is a tetrakis-(hydroxymethyl) phosphonium salt and urea which when exposed to ammonia forms an ammoniated prepolymer flame retardant network within the cellulosic fiber structure in combination with a tetrakis- (hydroxymethyl) phosphonium salt which when reacted with urea forms an insoluble phosphorus-containing polymer in and on the cellulosic fibers.

14. The process of claim 11, 12 or 13 in which the tetrakis-(hydroxymethyl) phosphonium salt is the chloride, sulfate, oxalate or phosphate.salt. The process of claim 10 in which the cellulosic component of the blend is linen, rayon, cotton or mixtures thereof.

16. The process of claim 15 in which the cellulosic component is cotton.

17. The process of claim 10 in which the blend contains at least 50% polyester. 18 The process of claim 10 in which the blend contains from about 35% to about 65% by weight polyester. SUBSTITUTE SHEET I i r; i WO 88/09411 PCT/US88/01619

19. The process of claim 10 in which the cyclic phosphonate ester is represented by the formula: O CH 2 CH 3 O 1 CH20 (CH 3 0) (OCH 2 C< CH 2 0 >PCH 2-x CH 2 O >PC 3 2 CH3 in which x is 0 or 1. The process of claim 19 in which from about 1% to about 25% w/v of the cyclic phosphonate ester is present in the dyebath.

21. The process of claim 10 in which the dyebath also contains a wetting agent and an antimigrant.

22. The process of claim 10 in which a disperse dye is present for the polyester component and a vat dye is present for the cellulosic component.

23. A dyebath containing as its principal ingredients a tinctorial amount of at least one dye for the polyester fibers, a tinctorial amount of at least one dye for the cellulosic fibers, and a flame-retarding amount of a cyclic phosphonate ester flame retardant. i r

24. A dyebath containing as its principal ZL~i 1 WO :88/09411 PCT/US88/01619 ingredients a tinctorial amount of a disperse dye, a tinctorial amount of a vat dye, and up to about 100 grams/liter of a cyclic phosphonate ester flame retardant. A dyebath as in claim 24, containing as its principal ingredients a tinctorial amount of a disperse dye, a tinctorial amount of a vat dye, and up to about 50 gram/liter of a cyclic phosphonate ester flame retardant.

26. A process .of dyeing a fabric comprising to 100% cellulosic fibers to minimize shade change when applying a flame-retarding amount of tetrakis-(hydroxymethyl) phosphonium salt, comprising the successive steps of: applying a dyebath containinga tinctorial amount of at least one dye for the cellulosic fibers and an amount of cyclic phosphonate ester sufficient to minimize dye .migration, drying the fabric to minimize.migration; treating the fabric to fix the dye into the cellulosic fibers; washing the fabric to remove any unfixed dye or components of the dyebath from the fabric, and thereafter; applying a flame retarding amount of a tetrakis-(hydroxymethyl) phosphonium salt.

27. The process of claim 26, in which the flame retardant of step is a prepolymner condensate of a tetrakis-(hydroxymethyl) phosphonium salt and urea A r II si- i-1 WO 88/09411 PCT/US88/01619 26 which when exposed to ammonia forms an ammoniated prepolymer flame retardant network within the cellulosic fiber structure.

28. The process of claim 26, in which the flame retardant of step is a tetrakis-(hydroxy- methyl) phosphonium salt which when reacted with urea forms an insoluble phosphorus-containing polymer in and on the cellulosic fibers.

29. The process of claim 26 in which the flame retardant of step is a tetrakis-(hydroxymethyl) phosphonium salt and urea which when exposed to ammonia forms an ammoniated prepolymer flame retardant network within the cellulosic fiber structure in combination with a tetrakis- (hydroxymethyl) phosphonium salt which when reacted with urea forms an insoluble phosphorus-containing polymer in and on the cellulosic fibers. The process of claim 27, 28 or 29 in which the tetrakis-(hydroxymethyl) phosphonium salt is the chloride, sulfate, oxalate, or phosphate salt.

31. The process of claim 26 in which the cellulosic component of the blend is linen, rayon, cotton or mixtures thereof. 32: The process of claim 26 in which the fabric consists entirely of cellulosic fibers.

33. The process of claim 26 in which the fabric contains up to 35% of synthetic thermoplastic fibers L! r- WO 88/09411 PCT/US88/01619 blended with the cellulosic fibers.

34. The process of claim 33 in which the synthetic thermoplastic fibers are nylon or polyester. The process of claim 26 in which the cyclic phosphonate ester is represented by the formula: O H CHH 3 O CH3 in which x is 0 or 1. -36. The process of claim 35 in which from about 1% to about 25% w/v of the cyclic phosphonate ester is present in the dyebath.

37. The process of claim 26 in which the dyebath also contains a wetting agent and an antimigrant. 38: A process for simultaneously dyeing and imparting flame resistance to a nylon/cellulosic blend fabric, containing at least 40% by weight cellulosic fiber, balance nylon, comprising the successive steps of: i,,;9 SAI SUBSTITUT SHEET WO88/09411 PCT/US88/01619 28 applying a dyebath containing a tinctorial amount of at least one dye for the cellulosic fibers and a flame retarding amount of a cyclic phosphonate ester flame retardant to the nylon/cellulosic blend; drying the fabric and heating when necessary to allow the cyclic phosphonate ester flame retardant to.diffuse into nylon; treating the fabric to fix the dye into the cellulosic fibers; washing the fabric to remove any unfixed dye or components of the dyebath from the fabric, and thereafter; applying a flame retarding amount of a tetrakis-(hydroxymethyl) phosphonium salt to the substrate in sufficient quantities to provide an LOI value of at least 27.0% to the fabric thus treated.

39. The process of claim 38 in which the flame retardant of step is a prepolymer condensate of a tetrakis-(hydroxymethyl) phosphonium salt and urea ihich when exposed to ammonia forms an ammoniated prepolymer flame retardant network within the cellulosic fiber structure. The process of claim 38 in which the flame retardant of step is tetrakis-(hydroxymethyl) phosphoiium salt which when reacted with urea forms an insoluble phosphorus-containing polymer in and on the cellulosic fibers.

41. The proc of -lai-- 2 i wih th f 1 i 'I 29 41. The process of claim 39 or 40 in which the tetrakis-(hydroxymethyi) phosphonium salt is the chloride, sulfate, oxalate or phosphate salt.

42. The process of claim 38 in which the cellulosic component of the blend is linen, rayon, cotton, or mixtures thereof.

43. The process of claim 39 in which the cyclic phosphonate ester is represented by the formula: S 0 CH 2 CH 0 2 3 I -CH. 2 o II S PCHCH 3 x CH3 in which x is 0 or 1.

44. The process of claim 3 in which from about 1% to about 25% w/v of the cyclic phosphonate ester is present S in the dyebath.

45. The process of claim 38 in which the dyebath also contains a wetting agent and an antimigrant.

46. A flame resistant polyester/cotton fabric containing between 40% and 65% of polyester when made by a process as claimed in any one of claims 1-22 or 26-46, said fabric having a Limiting Oxygen Index of at least 27% after launderings at 120 0 F.

47. A flame-resistant polyester/cotton fabric containing between 40% and 65% of polyester when made by a process as claimed in any one of claims 1-22 or 26-46, said fabric having a Limiting Oxygen Index of at least 27% after 100 launderings at 120 0 F. 30

48. A flame-resistant polyester/cotton fabric containing between 40% and 65% of polyester when made by a process as claimed in any one of claims 1-22 or 26-46, said fabric having, when tested in accordance with FTM-191-5903, a char length of less than 15.2 cm and afterglow and afterburn values of less than 1 second after 100 home launderings at 49 0 C. DATED this 20 day of September 1990 BURLINGTON INDUSTRIES INC Patent Attorneys for the Applicant: F.B. RICE CO. S* **o o0 %1L 1.~ INTERNATIONAL SEARCH REPORT International Application No -1 PCT/US 88/01619 I. CLASSIFICATION OF SUBJECT MATTER (It several classificatidn symbols apply, Indicate all) According to International Patent Classification (IPC) or to both National Classfication and IPC IPC 4 D 06 P 3/82; D 06 P 3/60; D 06 P 1/667; D 06 M 13/26 II. FIELDS SEARCHED Minimum Documentation Searched I Classification System IClassification Symbols IPC 4 D 06 P; D 06 M Documentation Searched other than Minimum Documentation to the Extent that such Documents are Included In the Fields Searched III. DOCUIMENTS CONSIDERED TO iE RELEVANT' Category Citation of Document, with indication, where appropriate, of the relevant passages I Relevant to Claim No. I Y US, A, 4066812 (WILLIAM B. KAUPIN) 1-4 3 January 1978 see claims 1,6; column 3, line 57 column 4, line 17; column 5, lines 39-47 A 6 Y American Dyestuff Reporter, voltime 57, 1-4 no. 10, 6 May 1968, (New York, US), "A study of fire retardancy of polyester/cotton sheeting", pages 40-44 see page 43, column 1, "Effect on dyestuffs" and columns 2 and 3, "Conclusions" A 9,10,15- 17,.22,26, 31,32,47- 49 P,A EP, A, 0248553 (BURLINGTON INDUSTRIES, 1,26-31, INC.) 9 December 1987 33,34,41, see claims 1-10 47-49 SSpecial categories of cited documents: Io later document published after the international filing date document definng the general state of the art which is not or priorit at and not n con with te aplicion but cited to understand the principle or theory underlying the considered to bo of perticular relevance invention E earlier document but published on or after the International document of particular relevance: the claimed Inventlin filing date cannot be considered novel or cannot be considered to document which may throw doubts on priority claim(a) or Involve an inventive sate which is cited to establish the publication date of another document of particular relevance;' the clalmed Invention citation or other speclal reason (as specified) cannot be considered to involve an Inventive step when the document referring to an oral disclosure, use, exhibition or document is combined with one or more other such docu- other means ments, such combination being obvious to a person skilled document publlehed prior to the International filing date but in the art later than the priority date claimed document member of the same patent family IV. CERTIFICATION 4 Date of the Actual Completion of the International Search 2nd September 1988 Internatlonal Searching Authority EUROPEAN PATENT OFFICE Form PCT/ISA/210 (second sheet) (January I)19 DIat of Mailing of this Internatlonal Search Report international Application No. PCT/ Us 88 /01619 Ill. DOCUMENTS CONSIDERED TO Of RELEVANT (CONTINUED FROM THE SECOND SHEET) category Citation of Documenft, with indication, winare appropriate, of the ro*evaflt passages Reeant to Claim No P,A EP, A, 0249375 (BURLINGTON INDUSTRIES, 1 INC.) 16 December 1987 see claims 1-11 A US, A, 3922406 (JAY C. CHAPIN) 1,47-49 November 1975 see claim 1; column 1, line 1 column 2, line 29 A I Chemical Abstracts, volume 83, no. 24, 1 December 1975, (Columbus, Ohio, US), J.D. Timpa e.t al.: "Dyes as they taffect the burning characteristics of flame-retardant textiles", see pages 92-93, abstract 194949y, U. Agric. Res. Serv., South. Reg., (Rep.) 1975, ARS-S-60, 169-72 A DE, A, 2933207 (CILIA-GEIGY) 24 April 1980 1-5,9,10,1 see examples 8-14 15-18,22, 23 A Chemical Abstracts, volume 98, no. 26, 1,6 June 1983, (Columbus, Ohio, US), see page 81, abstract 217132c, JP, A, 57199869 (iTEIJIN LTD) 7 December 1982 A US, A, 3991019 SHIM) 9 November 1976* 1,26,38 see claims 8,13; column 3, line~s 8-28 A US, A, 3849368 (JAMES J. ANDERSON et al.) 1,6,26, 19 November 1974 35,38 see claims 1-7; column 20, lines 1-1 cited in the application A GB, A, 1531830 (BAYER) 8 November 1978 38 see page 5, lines 11-13; page I example 12 Form PCT ISA1210 (eatra iiheat) (Januar'y 193) International Application No. PcT/US 88 016 19 FURTHER INFORMATION CONTINUED FROM THE SECOND SHEET V.0D OBSERVATIONS WHERE CERTAIN CLAIMS WERE FOUND UNSEARCHABLE'1 This International search report has not been established In respect of certain claims under Article 17(2) for thoi following reasons: I.]Claim numbers because thoy relate to subject matter not required to be searched by this Authority, namely: claim numbers........because they relatc to parts of the International application that do not comply with the prescribed require- menits to such an extent that no meaningful International search can be carried om, spekfcaily: C~alm nmbeors.......because V"y NO dependen claims and are not drafted Ini accordance w4Ut te second! and third sentences of PCT Rule 0.4(s). VLC2 OSuRVATONBS WHERE UNITY OP INVENTION 12 LACKING I This International Searching Authority found multiple Inventions In this International application as follows: See Form PCT/ISA/206 sent to you on August 17th, 1988. 1.MAs all required additional search fees were timely paid by the applicant, this International search report covers all searchable claims of the International application. As only some of the required additional search fees weon timely paid by the applicant, this international s"arch report covers only those claims of the International application fotr which fees were paid, specdifcally claims., No required additional search feet were timely paid by the applicant. Consequently, this International esrmch report is restricted to the Invention first mentioned In the claims; I s covered by claim numbers:I 4.7As all searchablecilms could be searched without effort lustifying an additional fee, the International Searching Authority did not Invite payment of any additional lee. Remadit on Protest SThe additional aoaicih fees were accompanied by applicants protest. No protest accompanied the payment of additional search fees. Farm PCTIISAII (supplemental sheet (January 1045) ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. US 8801619 SA 22615 This annex lists the patent family members relating to the patent documents cited in the above-mentioned international search report. The members are as contained in the European Patent Office EDP file on 07/11/88 The European Patent Office is in no way liable for these particulars which are merely given for the purpose of information. Patent document Publication Patent family Publication cited in search report date member(s) date US-A- 4066812 03-01-78 None EP-A- 0248553 09-12-87 JP-A- 62299574 26-12-87 AU-A- 7246587 10-12-87 US-A- 4748705 07-06-88 EP-A- 0249375 16-12-87 JP-A- 63028985 06-02-88 US-A- 4752300 21-06-88 US-A- 3922406 25-11-75 None DE-A- 2933207 24-04-80 None US-A- 3991019 09-11-76 US-A- 3887656 03-06-75 US-A- B557856 10-02-76 US-A- 3849368 19-11-74 NL-A- 7215415 17-05-73 FR-A,B 2164579 03-08-73 DE-A,C 2255971 24-05-73 US-A- 3789091 29-01-74 GB-A- 1418497 24-12-75 CA-A- 1008870 19-04-77 JP-A- 48057988 14-08-73 JP-A- 56084750 10-07-81 JP-A- 60099167 03-06-85 GB-A- 1531830 08-11-78 DE-A,B,C 2544550 14-04-77 FR-A,B 2326536 29-04-77 JP-A- 52046197 12-04-77 0 SFor more details about this annex: see Oflicial Journal of the European Patent Office, No. 12/82