CA1318087C - Simultaneously dyed and flame-retarded fabrics - Google Patents
Simultaneously dyed and flame-retarded fabricsInfo
- Publication number
- CA1318087C CA1318087C CA000567341A CA567341A CA1318087C CA 1318087 C CA1318087 C CA 1318087C CA 000567341 A CA000567341 A CA 000567341A CA 567341 A CA567341 A CA 567341A CA 1318087 C CA1318087 C CA 1318087C
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- Prior art keywords
- fabric
- dye
- cellulosic
- flame
- synthetic
- 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.)
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Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/82—Textiles which contain different kinds of fibres
- D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
- D06P3/8223—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl and ester groups
- D06P3/8238—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl and ester groups using different kinds of dye
- D06P3/8252—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl and ester groups using different kinds of dye using dispersed and reactive dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/667—Organo-phosphorus compounds
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Coloring (AREA)
Abstract
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.
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.
Description
~ 3 ~ 7 mis invention relates generally to dyeing and treating textile fabr~cs 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-(hydroxymetllyl) 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 b~lffer.
After the dye mix is padded and dried on the fabric, the treated fabric is heated to 204 to 218C to allow the disperse or polyester dyes to thermosol 131gO~7 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 103C, 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 un~ixed 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 ~ntiblaze l9T ~
(sometimes referred to herein for convenience as AB
l9T, 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 inventor~ 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 cost of an extra processing step and to produce a dyed fabric which has better properties.
~ r~ *,~
13~0~7 It is an object of the present invention to provide a process for simultaneously dyeing and imparting flame resistance to a synthetic/cellulose blend fabric.
It is a further object of the present invention to provide a process of dyeing a fabric.
It is a further ob;ect of the present invention to provide a novel dyebath.
Accordingly, in one of its aspects, the present invention provides a process for simultaneously dyeing and imparting flame resistance to a synthetic/cellulosic blend fabric containing at least 35% by weight of the synthetic component, comprising the steps of (1) applying a dyebath comprising 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; (2) drying and heating the fabric to allow the synthatic dye and 1ame retardant to thermosol into the synthetic fibers, then (3) treating the fabric to fix the dys onto the cellulosic fibers;
and finally (4) washing the fabric to remove any unfixed dye or components of the dyebath from the fabric. In a preferred embodiment, 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 wash and wear appearance performance, exeellent 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 are 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/cellulosie blends. The method is also useful for 100%
polyester, lO0~ eotton, 100~ nylon, and other cotton and polyester blends.
Aeeordingly, in another of its aspects, the present invention provides a proeess of dyeing a fabric comprising 65 to lO0~ cellulosie fibers to minimize shade change when applying a flame-retardant amount of tetrakis-(hydroxymethyl) phosphonium salt, eomprising the suecessive steps of (1) applying a dyebath eontaining a tinetorial amount of at least one dye for the eellulosie fibers and an amount of cyelie phosphonate ester sufficient to minimize dye migration, (2) drying t~e fabric to minimize migration; (3) treating the fabrie to fix the dye into the cellulosic fibers; (4) washing the fabric to remove any unfixed dye or components of tha dyebath from the fabric, and thereafter; (5) applying a flam~-retarding amount of a tetrakis-(hydroxymethyl) phosphonium salt.
l3.~a~7 - 4a -The process is also useful for minimiæing 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 thermoplas-tic fiber includes nylon or polyester. Cellulosic fibers include cotton, rayon, linen and blends thereof.
In yet another of its aspects, the present invention provides a dyebath comprising as its principal ingredients a tinctorial amount of at least one dye for the polyester ~ibres, a tinctorial amount of at least one dye for the cellulosic fibers, and a flame-retarding amount of a cyclic phosphonate ester n ame retardant.
In yet another of its aspects, the present invention provides a dyebath comprising as its principal ingredients a tinctorial amount of a vat dye, and up to about 100 grams/liter of a cyclic phosphonate ester flame retardant.
In finishing synthetic/cellulosic blends to impart flame resistance, the cellulosic and synthetic components should ideally be treated with specific chemicals to impart flame resistance to the 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 o ~ ~
salt, which is insolubilized with gaseou.s ammonia, or by using a THP/urea pad/dry/cure process, or both.
Cyclic phosphonates, as exemplified by Antiblaze l9T, are effective flame retardants for synthetic fibers. To maximize the favorable use o~
the cyclic phosphonate flame retardant and the dyelng operation, the synthetic fibers are treated Wit}l t}le 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 fabric~. Since the cyclic phosphonate 1ame 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 subseqllent 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 131~7 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 fo~lnd that a maximum dye yield is realiz'ed 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 ABlgT on tha 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 obs~rved 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 retardatlt treatment. Polyester contents in the 40 to 60%
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 1318~7 the nylon com~onent 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 processing9 e.g.~ 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 Cl~/urea-precondensate/ammonia). The PROBAN process, licensed by Albright & Wilson, is described in the following U.S.
patents: 4,078,101; 4,145,463; 4,311,85~; and 4,494,951, all to Alb~ight & Wilson, which disclose the THP salt/urea-precondensate process. See also U.S. 4,346,031 to Elgal et al. This process is considered e~ective and is widely promoted by at least two companies for impar~ng flame resistance to 100% cotton fab~ics; it is not promoted or adver~sgd for poIyester/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 ~abric to about 10 to 15 wt. of moistur~. The cotton fabric is then e~posed to gaseous ammonia. The precondensate is insolubilized by the ammonia. Fi~ation of ~e precondensate takes place mainlyinside of the cotton fiber, thus impar~ng durability to multiple - ~l 3 ~ 7 launderings.
The invention will now be illustrated with reference to the following examples in which all parts and percentages are by weight and temperatllres 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-ret~rdant 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 o~ the formulas:
~A) ~R'O~b 1- ~ R / 2 \ p ~
CH2 J c where a is O or l; 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 (Cl-C8), phenyl, halophenyl, hydroxyphenyl, tolyl, xylyl, benzyl, phenethyl, hydroxyethyl, phenoxyethyl, or dibromophenoxymethyl;
R2 is alkyl (Cl-C4); and R is lower alkyl (Cl-C4) or hydroxyalkyl (Cl-C4) or ~ O ~ _ R5 d20 9 ~3~8~7 where d is 0, 1 or 2; a is 1, 2 or 3; R2 i8 alkyl (Cl-C4); R is lower alkyl ~Cl-C4) or hydroxyalkyl (C1-C4); R :i 9 alkyl (C1-C4) phenyl, halopheny:L, hydroxyphenyl, hydroxyethyl, phenoxyethy:L, dibromophenoxyethyl, tolyl, xylyl, benzyl, or phenethyl; and R5 i8 monovalent alkyl (C1-C6), chlorophenyl, bromophenyl, dibromopheny]L, tribromophenyl, hydroxyphenyl, naphthyl, tolyl, xylyl, benzyl, or phenethyl; divalent allcylene (Cl-C6~, vinylene, o-phenylene, m-phenylene, p-phenylene, tetrachlorophenylene (o, m, or p), or tetrabromophenylene (o, m, or p); or trivalent phenyl.
The preferred compounds (see below3 are repre~ented by the formula:
O ' CH2CH3 0 ll I ,CH20 11 (C) (C~30)x~I-(OCH2r ~ CH20,~- PC~3)2 x in which X is 0 or 1, and u~ually a 50:50 mixture of the mono- and di-e~ters. The preparation of these cyclic phosphonate esters and their u8e as flame retardants are described in U.S. 3,789,091 and 3,849,368~
~ ntiblaze l9T, as described by the supplier Albrig~t & Wilson, Inc., of Richmond, Virginia, is a cyclic pho~phonate ester, available a~ an odorle~s vi5cou5 liquid (vi~c08ity 1 . 30 X 10 3 m2/s at 40C~ with a fla~hpoint of 171C (ASTM D-93).
~:nj ~ . .
lo 131~7 Tetrakin-(hydro~y~ethyl)phosphonium ~ulfate (TEPS~, also available from Albright ~ Wilson, Inc., under the name of Retardol S*and from American Cyanamid under the name Pyroset TK0, 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 T~PS, including tetrakis-~hydroxymethyl~phosphonium chloride (T~PC), available under the name of Retardol C*from Albright &
Wilson, and tetrakis-~hydroxymethyl)phosphonium oxalate, available a~ Pyroset TKS*from American Cyanamid Company.
T~PS when mixed with urea and heated strongly forms a relatively insoluble polymer, containing both phosphorus and nitrogen, inside the cotton fibers, and around bo~h the cotton and the nylon fibars.
Insolubillty of thi~ polymer i~ increased further by oxidizing the phosphoru~ with hydrogen peroxide.
-A S0/50 polye~ter/cotton 7 ounce 2xl twillfabric was simultaneously dyed and the polye~ter fibers flame retardant treated using a disperse/vat dye formulation containing a flAme retardant for the polyester fibers.
* trade-mark '~`~ !.
~3 1;~087 Dyestuffs in Pad sathConcentration (q/l) Polycron Dianix Blue FP (Disperse Blue 73) 18.2 Terasil Orange GFA~(Disperse Orange 44) 26.0 Foron Rubine S-2GFL~(Disperse Red 167-1) 6.0 Palanthrene Red LGG (Vat Red 32)3.0 Cibanone Olive SP~(Vat Blaclc 23) 44.0 Carvat Brown BRS~(Vat Brown 1)66.0 Chemicals in Pad Bath Antiblaze l9T 2S.0 8uffer N 1.5 Antimigrant B 20.0 The fabric was padded with the above pad bath solution, squeezed to reduce wet pick-up, slowly dried using infrared predryers, and then totally dried prior to the thermosol step with steam cans.
The treated fabric was heated to 216C 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/caustic sol~ltion 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 our wasl~oxes at 71C.
~ /Y~
131~87 A series of samples of 254 g/m2 65/35 polyester/cotton fabric was dyed by the method of Example 1, using varying concentrations of Antiblaze l9T 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 l9T. All of the dyebaths contained 2.0 g/l Buffer N. The dyes used in the bath were as follows:
Dyestuff oncentration (g/l~
Foron Navy ~lue S-2GRL 100 Pst.
(Dispers~ Blue 79) 24.00 Intrasil Orange YB~H'~50~ Liq. (Disperse Orange 29) 5.50 Foron Brilliant Yello~ S-7GL 50% Pst. 0.85 Palanthrene Navy Blue C~ll. 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 8, but no Antiblaze l9T. The remaining ive samples contained from 25 to 150 g/l of Antiblaze l9T. Color mea~urements made under CWF-10 Conditions (cool White Fluorescent illumination, 10 observer) are also presented in 13~0~7 Table I.
T~BLE I
Effect of Flame Re_ardant Concentration in Dy b__h_ n Color Yield Antimlgrant Antiblaze Strength * * *
B 19T ~ SSUM~ L C 11 g/lg~l Control20.0 0Standard I 0 25 6.~% strong-0.7a -1.180.41 Red 2 0 50 1.4~ strong-0.21 0.36~.32 R~d 3 0 75 2.4~ ueak0.23 1.54~.26 Red 4 ~ InD 1.8~ weak0.17 1.320.23 Red 0 150 l3.~ ~eak1.7J 1.66-~.19 Green Table I measures color yield by KSSUM values, KSSUM representing an integrated measure of color strength over a range of wavelengths. The values for ~ L measure lightness, a lower number indicating a darker shade or a higher yield. ~ C
is a measure of chroma, or brightness, and ~ H
is a measure of hue. The shifts of chroma and hue are relatively small, confirming that changes of KSSUM or ~ L can be taken at face value.
As shown by Table I, the use of 25 g/l Antiblaze l9T in the bath produced a significant increase in yield, compared with the control, since the KSSUM
value increased and ~ L decreased. The use of a very large cluantity of Antiblaze l9T in the dyebath 131~7 (150 g/l) produced the opposite effect, while the intermediate concentrations produced only small changes.
To assess the effect of AB19T on vat dye color yield, several pure vat dyes were applied to a 100%
cotton fabric. Subsequent inishing of these fabrics with THPS/urea demonstrated that shade change was better controlled with the ABl9 treatment than without. All fabrics were dyed in baths containing 30 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~% 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 l9T than for the corresponding controls.
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u ~ n ~ n C n '-131~0~7 EXAMoeLE 4 A 50/50 polyester/cotton 271 g/m2 2xl twill fabric was simultaneously dyecl and the polyester fibers flame retardant treatecl using a disperse/reactive dye formulat:ion containing a cyclic phosphonate flame retardant for the polyester fibers. The dye formulation was as follows:
DyestuffConcentration Lg~l~
Terasil Yellow E6GSLW
(Disperse Yellow 88) 8.0 Cibacron Yellow 6GP~
(Reactive Yellow 95)30.0 Au~iliaries Antiblaze l9T 25.0 Antimigrant B 20.0 Buffer N 1.5 The fabric was padded with the above solution to a 65% wpu, slowly dried with infrared predryers to minimize dye migration, totally dried on dry cans, and heated to a temperature of 216C for 60 seconds to allow the disperse dyes and Antibla~e l9T 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 dye tuff when passed through a 73-meter steamer. The excess dye was removed by passing the fabric through wash boxes at 82C. In subsec~uent operations, tetrakis-~hydroxymethyl) phosphonium salt~ were applied to 131~7 the substrate to provide an initial phosphorus content after oxidation of 3.0 -3.2%: The fabric was compressively shrunk by methods well astablished 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.
~31~7 TABLE I I I
.
~eJt D4#ucr~Ption Test Method Bottom W2iJ~ht Twlll Weight ~g/m ) ASrM D-3776 Z68 Tensile Strength Ikg) ASTM D-168Z 66.7 x 41.7 Tear Strength Ikg) ASTM D-1424 3.5 x 3.1 Shrlokage ~5 launderlngsl% AATCC 135,3,IIB 2.1 x 0.9 Seam Efficiency l%) FMT 5110 100 x 76 Random Tumblo Pilllng 160 min) ASTM D-3512 3.06 Flex Abrasion, cyclos 5500 x 4700 ~ash and Wear Appearance 3~60 Air Permeability (m /s-m ) 5450 0.107 Moisture Vapor rransport, gfm /24 hrs. 600 nointure Regain (%) 5.3 Re~istivlty 65~ Rll 1.0 x IO
40% 3.6 x l0 Colorfastness Launderlng IIA (3talningl AATCC 61-IIA 1120-F) 4.5 Crockiny - Dry AATCC-8 4 5 - Wet 4 0 Light AATCC 16A 4.0 Flame Resistance TestlDg FTM-191-5903*
Orig~nal - Char 12ngth Icm) IO.Z x 8.9 Afterflame ~sec) 0 x 0 Afterglow ~sec) ~ 0 x 0 50x - Char longth ~rml 10.4 x 9.7 Afterflamo ~QC) O X O
Afterglow ~a~c) 0 x 0 IOOx - Char length ~cm) 11.9 x 11.4 - 1 3 ~ 7 Afterflame ~aec) O x O
Afterglo~ ~aec) O x O
Melt/8urn Re~iatance NFPA-1971 Pase Shrinkage NFPA-1971 1.0 Llmiting Dxygen Index ~) ASTM D-2863 Unlaundered Z7.5 After 50 laund. Z7.2 after loo laund. Z7.3 *Theae re~ults aro typical of thoae achieved on production lot
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-(hydroxymetllyl) 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 b~lffer.
After the dye mix is padded and dried on the fabric, the treated fabric is heated to 204 to 218C to allow the disperse or polyester dyes to thermosol 131gO~7 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 103C, 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 un~ixed 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 ~ntiblaze l9T ~
(sometimes referred to herein for convenience as AB
l9T, 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 inventor~ 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 cost of an extra processing step and to produce a dyed fabric which has better properties.
~ r~ *,~
13~0~7 It is an object of the present invention to provide a process for simultaneously dyeing and imparting flame resistance to a synthetic/cellulose blend fabric.
It is a further object of the present invention to provide a process of dyeing a fabric.
It is a further ob;ect of the present invention to provide a novel dyebath.
Accordingly, in one of its aspects, the present invention provides a process for simultaneously dyeing and imparting flame resistance to a synthetic/cellulosic blend fabric containing at least 35% by weight of the synthetic component, comprising the steps of (1) applying a dyebath comprising 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; (2) drying and heating the fabric to allow the synthatic dye and 1ame retardant to thermosol into the synthetic fibers, then (3) treating the fabric to fix the dys onto the cellulosic fibers;
and finally (4) washing the fabric to remove any unfixed dye or components of the dyebath from the fabric. In a preferred embodiment, 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 wash and wear appearance performance, exeellent 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 are 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/cellulosie blends. The method is also useful for 100%
polyester, lO0~ eotton, 100~ nylon, and other cotton and polyester blends.
Aeeordingly, in another of its aspects, the present invention provides a proeess of dyeing a fabric comprising 65 to lO0~ cellulosie fibers to minimize shade change when applying a flame-retardant amount of tetrakis-(hydroxymethyl) phosphonium salt, eomprising the suecessive steps of (1) applying a dyebath eontaining a tinetorial amount of at least one dye for the eellulosie fibers and an amount of cyelie phosphonate ester sufficient to minimize dye migration, (2) drying t~e fabric to minimize migration; (3) treating the fabrie to fix the dye into the cellulosic fibers; (4) washing the fabric to remove any unfixed dye or components of tha dyebath from the fabric, and thereafter; (5) applying a flam~-retarding amount of a tetrakis-(hydroxymethyl) phosphonium salt.
l3.~a~7 - 4a -The process is also useful for minimiæing 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 thermoplas-tic fiber includes nylon or polyester. Cellulosic fibers include cotton, rayon, linen and blends thereof.
In yet another of its aspects, the present invention provides a dyebath comprising as its principal ingredients a tinctorial amount of at least one dye for the polyester ~ibres, a tinctorial amount of at least one dye for the cellulosic fibers, and a flame-retarding amount of a cyclic phosphonate ester n ame retardant.
In yet another of its aspects, the present invention provides a dyebath comprising as its principal ingredients a tinctorial amount of a vat dye, and up to about 100 grams/liter of a cyclic phosphonate ester flame retardant.
In finishing synthetic/cellulosic blends to impart flame resistance, the cellulosic and synthetic components should ideally be treated with specific chemicals to impart flame resistance to the 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 o ~ ~
salt, which is insolubilized with gaseou.s ammonia, or by using a THP/urea pad/dry/cure process, or both.
Cyclic phosphonates, as exemplified by Antiblaze l9T, are effective flame retardants for synthetic fibers. To maximize the favorable use o~
the cyclic phosphonate flame retardant and the dyelng operation, the synthetic fibers are treated Wit}l t}le 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 fabric~. Since the cyclic phosphonate 1ame 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 subseqllent 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 131~7 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 fo~lnd that a maximum dye yield is realiz'ed 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 ABlgT on tha 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 obs~rved 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 retardatlt treatment. Polyester contents in the 40 to 60%
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 1318~7 the nylon com~onent 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 processing9 e.g.~ 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 Cl~/urea-precondensate/ammonia). The PROBAN process, licensed by Albright & Wilson, is described in the following U.S.
patents: 4,078,101; 4,145,463; 4,311,85~; and 4,494,951, all to Alb~ight & Wilson, which disclose the THP salt/urea-precondensate process. See also U.S. 4,346,031 to Elgal et al. This process is considered e~ective and is widely promoted by at least two companies for impar~ng flame resistance to 100% cotton fab~ics; it is not promoted or adver~sgd for poIyester/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 ~abric to about 10 to 15 wt. of moistur~. The cotton fabric is then e~posed to gaseous ammonia. The precondensate is insolubilized by the ammonia. Fi~ation of ~e precondensate takes place mainlyinside of the cotton fiber, thus impar~ng durability to multiple - ~l 3 ~ 7 launderings.
The invention will now be illustrated with reference to the following examples in which all parts and percentages are by weight and temperatllres 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-ret~rdant 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 o~ the formulas:
~A) ~R'O~b 1- ~ R / 2 \ p ~
CH2 J c where a is O or l; 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 (Cl-C8), phenyl, halophenyl, hydroxyphenyl, tolyl, xylyl, benzyl, phenethyl, hydroxyethyl, phenoxyethyl, or dibromophenoxymethyl;
R2 is alkyl (Cl-C4); and R is lower alkyl (Cl-C4) or hydroxyalkyl (Cl-C4) or ~ O ~ _ R5 d20 9 ~3~8~7 where d is 0, 1 or 2; a is 1, 2 or 3; R2 i8 alkyl (Cl-C4); R is lower alkyl ~Cl-C4) or hydroxyalkyl (C1-C4); R :i 9 alkyl (C1-C4) phenyl, halopheny:L, hydroxyphenyl, hydroxyethyl, phenoxyethy:L, dibromophenoxyethyl, tolyl, xylyl, benzyl, or phenethyl; and R5 i8 monovalent alkyl (C1-C6), chlorophenyl, bromophenyl, dibromopheny]L, tribromophenyl, hydroxyphenyl, naphthyl, tolyl, xylyl, benzyl, or phenethyl; divalent allcylene (Cl-C6~, vinylene, o-phenylene, m-phenylene, p-phenylene, tetrachlorophenylene (o, m, or p), or tetrabromophenylene (o, m, or p); or trivalent phenyl.
The preferred compounds (see below3 are repre~ented by the formula:
O ' CH2CH3 0 ll I ,CH20 11 (C) (C~30)x~I-(OCH2r ~ CH20,~- PC~3)2 x in which X is 0 or 1, and u~ually a 50:50 mixture of the mono- and di-e~ters. The preparation of these cyclic phosphonate esters and their u8e as flame retardants are described in U.S. 3,789,091 and 3,849,368~
~ ntiblaze l9T, as described by the supplier Albrig~t & Wilson, Inc., of Richmond, Virginia, is a cyclic pho~phonate ester, available a~ an odorle~s vi5cou5 liquid (vi~c08ity 1 . 30 X 10 3 m2/s at 40C~ with a fla~hpoint of 171C (ASTM D-93).
~:nj ~ . .
lo 131~7 Tetrakin-(hydro~y~ethyl)phosphonium ~ulfate (TEPS~, also available from Albright ~ Wilson, Inc., under the name of Retardol S*and from American Cyanamid under the name Pyroset TK0, 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 T~PS, including tetrakis-~hydroxymethyl~phosphonium chloride (T~PC), available under the name of Retardol C*from Albright &
Wilson, and tetrakis-~hydroxymethyl)phosphonium oxalate, available a~ Pyroset TKS*from American Cyanamid Company.
T~PS when mixed with urea and heated strongly forms a relatively insoluble polymer, containing both phosphorus and nitrogen, inside the cotton fibers, and around bo~h the cotton and the nylon fibars.
Insolubillty of thi~ polymer i~ increased further by oxidizing the phosphoru~ with hydrogen peroxide.
-A S0/50 polye~ter/cotton 7 ounce 2xl twillfabric was simultaneously dyed and the polye~ter fibers flame retardant treated using a disperse/vat dye formulation containing a flAme retardant for the polyester fibers.
* trade-mark '~`~ !.
~3 1;~087 Dyestuffs in Pad sathConcentration (q/l) Polycron Dianix Blue FP (Disperse Blue 73) 18.2 Terasil Orange GFA~(Disperse Orange 44) 26.0 Foron Rubine S-2GFL~(Disperse Red 167-1) 6.0 Palanthrene Red LGG (Vat Red 32)3.0 Cibanone Olive SP~(Vat Blaclc 23) 44.0 Carvat Brown BRS~(Vat Brown 1)66.0 Chemicals in Pad Bath Antiblaze l9T 2S.0 8uffer N 1.5 Antimigrant B 20.0 The fabric was padded with the above pad bath solution, squeezed to reduce wet pick-up, slowly dried using infrared predryers, and then totally dried prior to the thermosol step with steam cans.
The treated fabric was heated to 216C 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/caustic sol~ltion 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 our wasl~oxes at 71C.
~ /Y~
131~87 A series of samples of 254 g/m2 65/35 polyester/cotton fabric was dyed by the method of Example 1, using varying concentrations of Antiblaze l9T 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 l9T. All of the dyebaths contained 2.0 g/l Buffer N. The dyes used in the bath were as follows:
Dyestuff oncentration (g/l~
Foron Navy ~lue S-2GRL 100 Pst.
(Dispers~ Blue 79) 24.00 Intrasil Orange YB~H'~50~ Liq. (Disperse Orange 29) 5.50 Foron Brilliant Yello~ S-7GL 50% Pst. 0.85 Palanthrene Navy Blue C~ll. 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 8, but no Antiblaze l9T. The remaining ive samples contained from 25 to 150 g/l of Antiblaze l9T. Color mea~urements made under CWF-10 Conditions (cool White Fluorescent illumination, 10 observer) are also presented in 13~0~7 Table I.
T~BLE I
Effect of Flame Re_ardant Concentration in Dy b__h_ n Color Yield Antimlgrant Antiblaze Strength * * *
B 19T ~ SSUM~ L C 11 g/lg~l Control20.0 0Standard I 0 25 6.~% strong-0.7a -1.180.41 Red 2 0 50 1.4~ strong-0.21 0.36~.32 R~d 3 0 75 2.4~ ueak0.23 1.54~.26 Red 4 ~ InD 1.8~ weak0.17 1.320.23 Red 0 150 l3.~ ~eak1.7J 1.66-~.19 Green Table I measures color yield by KSSUM values, KSSUM representing an integrated measure of color strength over a range of wavelengths. The values for ~ L measure lightness, a lower number indicating a darker shade or a higher yield. ~ C
is a measure of chroma, or brightness, and ~ H
is a measure of hue. The shifts of chroma and hue are relatively small, confirming that changes of KSSUM or ~ L can be taken at face value.
As shown by Table I, the use of 25 g/l Antiblaze l9T in the bath produced a significant increase in yield, compared with the control, since the KSSUM
value increased and ~ L decreased. The use of a very large cluantity of Antiblaze l9T in the dyebath 131~7 (150 g/l) produced the opposite effect, while the intermediate concentrations produced only small changes.
To assess the effect of AB19T on vat dye color yield, several pure vat dyes were applied to a 100%
cotton fabric. Subsequent inishing of these fabrics with THPS/urea demonstrated that shade change was better controlled with the ABl9 treatment than without. All fabrics were dyed in baths containing 30 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~% 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 l9T than for the corresponding controls.
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u ~ n ~ n C n '-131~0~7 EXAMoeLE 4 A 50/50 polyester/cotton 271 g/m2 2xl twill fabric was simultaneously dyecl and the polyester fibers flame retardant treatecl using a disperse/reactive dye formulat:ion containing a cyclic phosphonate flame retardant for the polyester fibers. The dye formulation was as follows:
DyestuffConcentration Lg~l~
Terasil Yellow E6GSLW
(Disperse Yellow 88) 8.0 Cibacron Yellow 6GP~
(Reactive Yellow 95)30.0 Au~iliaries Antiblaze l9T 25.0 Antimigrant B 20.0 Buffer N 1.5 The fabric was padded with the above solution to a 65% wpu, slowly dried with infrared predryers to minimize dye migration, totally dried on dry cans, and heated to a temperature of 216C for 60 seconds to allow the disperse dyes and Antibla~e l9T 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 dye tuff when passed through a 73-meter steamer. The excess dye was removed by passing the fabric through wash boxes at 82C. In subsec~uent operations, tetrakis-~hydroxymethyl) phosphonium salt~ were applied to 131~7 the substrate to provide an initial phosphorus content after oxidation of 3.0 -3.2%: The fabric was compressively shrunk by methods well astablished 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.
~31~7 TABLE I I I
.
~eJt D4#ucr~Ption Test Method Bottom W2iJ~ht Twlll Weight ~g/m ) ASrM D-3776 Z68 Tensile Strength Ikg) ASTM D-168Z 66.7 x 41.7 Tear Strength Ikg) ASTM D-1424 3.5 x 3.1 Shrlokage ~5 launderlngsl% AATCC 135,3,IIB 2.1 x 0.9 Seam Efficiency l%) FMT 5110 100 x 76 Random Tumblo Pilllng 160 min) ASTM D-3512 3.06 Flex Abrasion, cyclos 5500 x 4700 ~ash and Wear Appearance 3~60 Air Permeability (m /s-m ) 5450 0.107 Moisture Vapor rransport, gfm /24 hrs. 600 nointure Regain (%) 5.3 Re~istivlty 65~ Rll 1.0 x IO
40% 3.6 x l0 Colorfastness Launderlng IIA (3talningl AATCC 61-IIA 1120-F) 4.5 Crockiny - Dry AATCC-8 4 5 - Wet 4 0 Light AATCC 16A 4.0 Flame Resistance TestlDg FTM-191-5903*
Orig~nal - Char 12ngth Icm) IO.Z x 8.9 Afterflame ~sec) 0 x 0 Afterglow ~sec) ~ 0 x 0 50x - Char longth ~rml 10.4 x 9.7 Afterflamo ~QC) O X O
Afterglow ~a~c) 0 x 0 IOOx - Char length ~cm) 11.9 x 11.4 - 1 3 ~ 7 Afterflame ~aec) O x O
Afterglo~ ~aec) O x O
Melt/8urn Re~iatance NFPA-1971 Pase Shrinkage NFPA-1971 1.0 Llmiting Dxygen Index ~) ASTM D-2863 Unlaundered Z7.5 After 50 laund. Z7.2 after loo laund. Z7.3 *Theae re~ults aro typical of thoae achieved on production lot
Claims (22)
1. A process for simultaneously dyeing and imparting flame resistance to a synthetic/cellulosic blend fabric, containing at least 35% of the synthetic component, comprising the steps of:
(1) applying a dyebath comprising 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;
(2) drying the fabric and heating the fabric to allow the synthetic dye and flame retardant to thermosol into the synthetic fibers;
(3) treating the fabric to fix the dye on to the cellulosic fibers; and (4) washing the fabric to remove any unfixed dye or components of the dyebath from the fabric.
(1) applying a dyebath comprising 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;
(2) drying the fabric and heating the fabric to allow the synthetic dye and flame retardant to thermosol into the synthetic fibers;
(3) treating the fabric to fix the dye on to the cellulosic fibers; and (4) washing the fabric to remove any unfixed dye or components of the dyebath from the fabric.
2. The process of claim 1, further comprising the final step of 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°C to the fabric thus treated.
3. The process of claim 1 in which the cellulosic component of the blend is selected from the group comprising linen, rayon, cotton, and mixtures thereof.
4. The process of claim 3 in which the cellulosic component is cotton.
5. The process of claim 1 in which the blend comprises at least 50% polyester as the synthetic fiber.
6. The process of claim 1 in which the blend comprises from about 35% to about 65% by weight polyester as the synthetic fiber.
7. The process of claim 1 in which the cyclic phosphonate ester is represented by the formula:
in which x is 0 or 1.
in which x is 0 or 1.
8. The process of claim 7 in which from about 1% to about 25% w/v phosphonate ester is present in the dyebath.
9. The process of claim 1 in which the dyebath further comprises a wetting agent and an antimigrant.
10. 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.
11. The process of claim 2 in which said salt flame retardant is a prepolymer condensate of a tetrakis-(hydroxymethyl) phosphonium salt and urea which when exposed to ammonia forms an ammoniated prepolymer flame retardant network withinthe cellulosic fiber structure
12. The process of claim 2 in which said salt flame retardant is a tetrakis-(hydroxymethyl) phosphonium salt which when reacted with urea forms an insolublephosphorus-containing polymer in and on the cellulosic fibers.
13. The process of claim 2 in which said salt flame retardant 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) phosphnnium salt which when reacted with urea forms an insoluble phosphorus-containing polymer in and on the cellulosic fibers.
14. The process of claims 11, 12 or 13 in which the tetrakis-(hydroxymethyl) phosphonium salt is the chloride, sulfate, oxalate or phosphate salt.
15. A process of dying a fabric comprising 65 to 100% cellulosic fibers tominimize shade change when applying a flame-retarding amount of tetrakis-(hydroxymethyl) phosphonium salt, comprising the successive steps of:
(1) applying a dyebath containing a tinctorial amount of at least one dye force cellulosic fibers and an amount of cyclic phosphonate ester sufficient to minimize dye migration, (2) drying the fabric to minimize migration;
(3) treating the fabric to fix the dye into the cellulosic fibers;
(4) washing the fabric to remove any unfixed dye or components of the dyebath from the fabric and thereafter;
(5) applying a flame retarding amount of a tetralcis-(hydroxymethyl) phosphonium salt.
(1) applying a dyebath containing a tinctorial amount of at least one dye force cellulosic fibers and an amount of cyclic phosphonate ester sufficient to minimize dye migration, (2) drying the fabric to minimize migration;
(3) treating the fabric to fix the dye into the cellulosic fibers;
(4) washing the fabric to remove any unfixed dye or components of the dyebath from the fabric and thereafter;
(5) applying a flame retarding amount of a tetralcis-(hydroxymethyl) phosphonium salt.
16. The process of claim 15 in which the fabric contains up to 35 % of synthetic thermoplastic fibers blended with the cellulosic fibers.
17. The process of claim 16 in which the synthetic thermoplastic fibers are nylon or polyester.
18. The process of claim 15 in which the cyclic phosphonate ester is represented by the formula:
in which x is 0 or 1.
in which x is 0 or 1.
19. The process of claim 18 in which from about 1% to about 25% w/v of the cyclic phosphonate ester is present in the dyebath.
20. A flame resistant polyester/cotton fabric containing between 40% and 65 % of polyester, with Limiting Oxygen Index of at least 27 % after 50 launderings at 120°F.
21. A flame-resistant polyester/cotton fabric containing between 40% and 65% of polyester, with a Limiting Oxygen Index of at least 27% after 100 launderings at 120°F.
22. A flame-resistant polyester/cotton fabric containing between 40% and 65% of polyester, which when tested in accordance with FTM-191-5903 has 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°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US5293787A | 1987-05-22 | 1987-05-22 | |
| US052,937 | 1987-05-22 |
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| Publication Number | Publication Date |
|---|---|
| CA1318087C true CA1318087C (en) | 1993-05-25 |
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ID=21980879
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000567341A Expired - Fee Related CA1318087C (en) | 1987-05-22 | 1988-05-20 | Simultaneously dyed and flame-retarded fabrics |
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| Country | Link |
|---|---|
| EP (1) | EP0362271A1 (en) |
| JP (1) | JPH02504407A (en) |
| AU (1) | AU604922B2 (en) |
| BR (1) | BR8807557A (en) |
| CA (1) | CA1318087C (en) |
| FI (1) | FI895542A0 (en) |
| WO (1) | WO1988009411A1 (en) |
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| JPS63315680A (en) * | 1987-06-17 | 1988-12-23 | 日本サ−ファクタント工業株式会社 | Leveling agent for reactive dye and dyeing method |
| DE4007299A1 (en) * | 1990-03-08 | 1991-09-12 | Hoechst Ag | METHOD FOR THE ONE-BATH DYEING AND FLAME-RETARDANT FINISHING OF FLAT-SHAPED TEXTILE MATERIALS |
| AU655125B2 (en) * | 1992-10-23 | 1994-12-01 | Woollen Twine Products Pty Ltd | Woollen chord having removable colouring |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3849368A (en) * | 1971-11-15 | 1974-11-19 | Mobil Oil Corp | Fire retardant polymers containing thermally stable cyclic phosphonate esters |
| US3922406A (en) * | 1973-07-06 | 1975-11-25 | Ventron Corp | Rendering a cellulose-polyester fabric flame retardant |
| US3991019A (en) * | 1974-04-12 | 1976-11-09 | Stauffer Chemical Company | Process for forming a flame retardant article and article thereof |
| US4066812A (en) * | 1975-03-10 | 1978-01-03 | The William Carter Company | Fire retardant polyester textile materials and method of making same |
| DE2544550C3 (en) * | 1975-10-04 | 1979-05-17 | Bayer Ag, 5090 Leverkusen | Phosphonic acid esters and their use for flame retardant finishing |
| DE2933207A1 (en) * | 1978-10-10 | 1980-04-24 | Ciba Geigy Ag | Preventing dye migration in pad-dyed cellulose textiles - by using dye liquor contg. viscous carboxy-polymethylene polymer or ethylene!-maleic anhydride! copolymer thickener |
| US4748705A (en) * | 1986-06-05 | 1988-06-07 | Burlington Industries, Inc. | Flame resistant polyester/cotton fabric and process for its production |
| US4752300A (en) * | 1986-06-06 | 1988-06-21 | Burlington Industries, Inc. | Dyeing and fire retardant treatment for nomex |
| US4812144A (en) * | 1987-07-07 | 1989-03-14 | Burlington Industries, Inc. | Flame-resistant nylon/cotton fabric and process for production thereof |
-
1988
- 1988-05-19 BR BR888807557A patent/BR8807557A/en not_active Application Discontinuation
- 1988-05-19 JP JP50480488A patent/JPH02504407A/en active Pending
- 1988-05-19 WO PCT/US1988/001619 patent/WO1988009411A1/en not_active Application Discontinuation
- 1988-05-19 EP EP19880905106 patent/EP0362271A1/en not_active Ceased
- 1988-05-19 AU AU18093/88A patent/AU604922B2/en not_active Ceased
- 1988-05-20 CA CA000567341A patent/CA1318087C/en not_active Expired - Fee Related
-
1989
- 1989-11-21 FI FI895542A patent/FI895542A0/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02504407A (en) | 1990-12-13 |
| FI895542A0 (en) | 1989-11-21 |
| AU1809388A (en) | 1988-12-21 |
| BR8807557A (en) | 1990-04-17 |
| WO1988009411A1 (en) | 1988-12-01 |
| AU604922B2 (en) | 1991-01-03 |
| EP0362271A1 (en) | 1990-04-11 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |