DK142793B - Method and composition for flame retardant keratin- and / or cellulose-fiber-containing textile materials and concentrate for the preparation of the composition. - Google Patents

Description

(11) PUBLICATION MANUAL 1 ^ 4-27 9 3 DENMARK is') in,. ci.a o 06 h ii / ot '(21) Application No 4917/75 (22) Filed on 31 · Okfc. 1975 (24) Race 31 · Oct. 1975 (44) The application presented and - _ the writ of publication published on 2ο »JSI1 · 1 9o1

DIRECTORATE OF ^. u _ J

PATENT AND TRADE MARKET (30) Pnontet requested from it

Nov 1 1974, 47456/74, GB

Sep 11 1975 # 37493/75 # GB

(71) I.W.S. NOMINEE COMPANY LIMITED, Wool House, Carlton Gardens, London S.W.1, GB.

(72) Inventor: Ladislav Benisek, 35 West View Avenue, Burley-in-Wharfedale, Ilkley, Yorkshire, UB: Gerald Keith Edmondson, 40 Willow Crescent, Brad = ford BD2 1LR, GB.

(74) Plenipotentiary in the proceedings:

Office of Industrial Energetic v. Svend Schønning .__ (54) Process and preparation for flame retardation of keratin and / or cell = Lulose fiber-containing textile materials and concentrate for the preparation of the preparation.

The present invention relates to a method and composition for flame retardant keratin and / or cellulose fibrous textile materials by means of an emulsion containing a flame retardant. In this specification, when referring to keratin-containing or cellulosic materials or fibers, these terms also include, where the context permits, mixtures containing other materials or fibers, if they are simply not present in sufficient quantities to destroy the flame retardant effect on the mix as a whole.

2 142793

For the use of keratin-containing materials, a number of successful aqueous flame retardants based on anionic complexes of titanium, zircon and tungsten are known and are disclosed in British Patent Nos. 774,257 and 780,810 and in Danish Patent Application No. 2595/74. These methods are particularly successful for flame retardant treatment of fully woolen fabrics and some woolly blends. More specifically, the latter relates to flame resistance treatment of polyamide textiles by treatment with an anionic complex of tungsten under acidic conditions, in which an anionic complex of titanium or zircon may also be present, e.g.

In all the aforementioned writings, the complexes of pure aqueous preparations are mentioned.

Danish Patent Application No. 4978/71 discloses a method for improving the flame resistance properties of polyamide-containing textile materials by treatment with a complex titanium compound formed with an organic chelating agent or fluoride ions. An aqueous treatment solution set forth in said application Example 20 contains sodium fluoroborate, titanium tetrachloride and hydrochloric acid. Again, these are only water-based treatments. Swedish Patent No. 395019 relates to a method for improving the fire resistance properties of natural or synthetic polyamide fibers by means of an anionic complex of zirconium with an organic chelate-forming agent or fluoride ions, for example potassium fluoro zirconate.

Again, application of the flame retardant from aqueous solution is indicated.

However, there are certain highly sensitive textile fabric designs that are affected by relaxation and / or felt shrinkage during low temperature aqueous flame retardant treatments or even by cold batch fouling followed by rinsing and drying. In addition, various treatments of keratin fibers with solutions based on non-aqueous or organic solvents are already used. For example, there are after-treatments where the "wet" processes are based solely on solvent treatments. In addition, in some cases, wool fabrics must be process washed with solvents prior to a flame resistance treatment based on an aqueous solution to avoid the adverse effect of spinning and weaving lubricants on the flame resistance of the wool.

The existing use of organic solvents in the treatment of wool creates a need for solvent-based flame retardant treatments for wool and wool-rich blends. Certain solvent-based flame-resistance treatments are already available, such as tris (dibromopropyl) phosphate treatment and other inorganic or organic phosphates, but these treatments are not solid for washing or for chemical purification.

In the case of cellulosic materials, there is also a need for a flame retardant based on organic solvents, especially one suitable for use with upholstery fabrics and other upholstery fabrics and usable fabrics in situ, ie. when placed on upholstered objects, furniture or the like.

It is therefore the object of the invention to provide a method of flame retardant treatment of keratin fiber-containing and / or cellulose-fiber-containing textile materials, wherein the flame retardant can be applied from a liquid composition to a large extent based on one or more organic solvents, so that effective and washable and clean-resistant flame resistance to fine or shrink-sensitive fabrics without damaging them, or so that the treatment mixture can be applied to upholstered furniture without the danger of damage to the upholstery or the furniture itself. It has been found that a complex compound chemically closely related to the aforementioned metal fluoroborates, namely zinc fluoroborate, is particularly well suited for application from a predominantly organic solvent-based liquid composition, without necessarily providing better flame resistance than known treatment agents applied from pure aqueous solutions.

Accordingly, the process of the invention is characterized in that zinc fluoroborate is applied to a textile material from a composition wherein the zinc fluoroborate is at least partially present in the aqueous phase of an emulsion water and one or more organic solvents.

The invention also relates, as mentioned, to a composition for carrying out the method described. It is peculiar in that it contains 0.1-20 wt.% Zinc fluoroborate, 0.1-20 wt.% Water, emulsifier, any additives and, for the residue, one or more organic solvents.

Examples of additives which may be included in the composition include pH-regulating additives.

Emulsifiers used in compositions of the invention are preferably nonionic. Anionic emulsifiers can be used with satisfactory results, but they are less preferred.

The invention further relates to a concentrate which, by dilution with water and one or more organic solvents, forms said composition. According to the invention, this concentrate consists of zinc fluoroborate and an emulsifier and optionally additives. Optionally, a concentrate may also be prepared containing the amount of water needed in the final composition to be added to the material to be treated and any additives desired.

When preparations containing simple metal compounds are fed to keratin-containing or cellulosic materials, these treatments will not produce an effect that is resistant to washing, although in many cases the effect will be fixed to chemical purification unless a "charged" system is used. , ie a system containing water.

Examples of keratin-containing fabrics which can be treated in accordance with the invention include fabrics of mohair, alpaca, vicuna, llama, cashmere and especially wool.

The treated materials can be in the form of loose raw material, yarns, yarns or textile fabrics which may be woven, woven or knitted. The invention is particularly directed to the treatment of fine textile fabrics which could be detrimental to a complete treatment based on water.

The composition and method of the invention can be applied to all cellulosic fabrics, e.g., of rayon fibers, but are of particular interest in cotton fabrics. It can also be applied to mixtures of keratin-containing and cellulosic fibers.

It is increasingly common for carpets, curtains and upholstery or upholstery fabrics to be cleaned in situ by a spraying or vacuum application technique. The process of the present invention can advantageously be combined with such cleaning operations.

Preferably, as mentioned, the aqueous phase comprises only a minor portion of the emulsion, typically 1 to 20% by weight of the fibers, and 1 to 10% in the case of wool fibers treated at below pH 3, the remainder being one or more organic solvents; the emulsion will generally be of the water-in-solvent type.

The amount of zinc fluoroborate to be applied to the material is generally greater in the case of cellulosic material than keratin-containing material, but is largely in line with other flame retardant treatments. Thus, according to the invention, 1-6% of zinc fluoroborate, based on the fiber weight, can be applied to a material containing keratin fibers; and, according to the invention, up to 25% on the weight of the fiber, on a material containing cellulosic fibers.

The solvent-based emulsion can be prepared by i) dissolving zinc fluoroborate in water and emulsifying this solution into the solvent, ii) dissolving a zinc salt or other zinc compound in the solvent, dissolving fluoroboric acid in water and emulsifying the aqueous phase into the solvent; a zinc salt or other zinc compound in a co-solvent which is miscible with a main solvent, mixes the co-solvent with the main solvent, dissolves fluoroboric acid in water and emulsifies the aqueous phase into the combined solvent phase.

As an organic solvent, according to the invention, halogenated hydrocarbons may be used particularly or wholly or partially. Examples of suitable solvents are mineral turpentine, perchlorethylene, trichlorethylene, chloroform, tetrachloromethane and various aromatic solvents.

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For emulsifying the aqueous phase into the solvent phase, any suitable commercially available emulsifier may be used. Examples include "Entol Supreme", "Softkleen", "Milling Aid KFS" and "Solugan LE" (trademarks not registered in Denmark). Those mentioned are non-ionic; Anionic emulsifiers may be used, but are generally preferred to a lesser extent.

No advantage is obtained on cellulosic materials when using the zinc fluoroborate under acidic conditions, it is preferable in cellulosic fibers to avoid the use of acidic conditions so as to avoid the risk of degradation of the fibers. Zinc fluoroborate can be used in preparations with the normal pH value of zinc fluoroborate solutions which are about pH 6-7.

The emulsion may be applied in any convenient manner, for example, by fouling, dipping or spraying; the latter method is preferred for treating fabrics in the home, for example by applying on upholstery or upholstery in situ. The emulsions may also be applied in dry-cleaning apparatus or where the fabric is suitable for use in conventional textile finishing apparatus.

The process of the invention will be explained in greater detail hereinafter by some embodiments describing the preparation of typical compositions of the invention and their use. The treated wool fabrics were tested for flammability according to F.A.R. 25,853, the results being presented with the following abbreviations: B.T. - burning time (sec); C. L. - charcoal length (cm); F. L. - full length; D.C. - purification (chemical purification).

The percentages given in the examples are all weight percent unless otherwise expressly stated in the text.

Example 1

An emulsion of 50% aqueous solution of zinc fluoroborate was prepared in a mixture of 75% trichloroethane and 25% (S) high boiling mineral turpentine "Crispin" according to the following recipe: 142793 7 50 g of "Crispin" ("Entol Supreme") 30 g Zn (BF4) 2 (50%)

This preparation was readily prepared by simply stirring the components in a beaker. A fully welded tie 2 feed (weight 186 g / m) was then sprayed evenly with the emulsion for ep uptake of 30%. This sample of the wool fabric was dried in air and the ignition properties tested in accordance with F.A.R. 25,853. The results are shown in the table below: B.T. C L.

Treated with 10% Zn (BF4) 2 (50%) <1 8.75

Untreated 25 F.L.

Example 2

An emulsion was prepared according to the following recipe: (§) 70 g of "Crispin" (S) 1 g of emulsifier ("Avivan" WA) 30 g of Zn (BF 4) 2 (50%)

A woolen textile fabric as in Example 1 was treated with this preparation in the same manner as described in Example 1. The textile fabric was then tested in accordance with F.A.R. 25,853, and the results are shown in the table below:

Initially After 5 chemical cleanses, B.T. C. L. B.T. C. L.

Treated with 9%

Zn (BF4) 2 (50%) 0.0 5.75 0.0 2.1

Untreated 30 Fb. 30 F.L.

U2793 8

The textile fabrics used in the following examples generally have a lower weight than the majority of upholstery fabrics and upholstery fabrics, and to the extent that they are lighter, they are more difficult to fire proof. It will therefore be understood that the invention is not limited to the treatment of upholstery fabrics and upholstery fabrics, but can be applied to any cellulosic fabric or woolen fabric.

Example 3

A zinc fluoroborate emulsion is prepared as in the example

ISLAND

1. A cotton yarn fabric weighing 249 g / m was sprayed with the composition to provide doses of 11% and 2.5%, respectively, of the zinc fluoborate (50%) relative to the weight of the fabric. The textile was then treated as in Example 1 and the results were as shown in the following table: B.T. C. L.

Treated with 11%

Zn (BF4) 2 (50%) 30 P.L.

Treated with 35%

Zn (BF 4) 2 (50%) 0. 8.13

Untreated 10 F.L.

Example 4 n

Cotton fabrics (249 g / m) in the form of 20 g large samples were treated in 500 ml large conical flasks to liquid 1:10 with a preparation containing perchlorethylene as an organic solvent and with sufficient 50% zinc fluoroborate. producing samples of 25, 30 and 35% Zn (BF4) 2 (50%), respectively, based on the weight of the textile fabric, using 3 g / l of Entol Supreme as water-in-oil emulsifier.

The flasks were shaken for 30 min. after which time the fog due to the emulsion had disappeared, showing that the zinc fluoroborate had been extracted and transferred onto the cotton.

The flame test results are shown in the table below: 142793 9 B.T. C. L.

Zn (BF 2) 2 (50%) 25% of the weight 25 F.L.

Zn (BF 2> 2 (50%) 30% by weight 9.3 11.25)

Zn (BF 2) 2 (50%) 35% of the weight <0.5 2.75

Untreated 12 F.L.

Example 5 2

A 55/45 wool / cotton blend having a weight of 137 g / m was sprayed with an emulsion of aqueous zihfluoroborate as described in Example 1 to apply 7.4 and 28%, respectively, based on the weight of the textile fabric. aqueous zinc complex. The treated drug samples were tested as described above, the results are shown in the following table: B.T. C. L.

Treated with Zn (BF 2) 2 (50%), 28% of the body weight / 2 10.63

Treated with Zn (BF ^) 2 (50%), 7.4% of the substance weight 30 F.L.

Untreated 12 F.L.

Example 6

The 55/45 wool / cotton blend used in Example 5 was treated as described in Example 4. 30% zihkfluoroborate was extracted and transferred to the fibers of the preparation for 30 minutes. shaking. The test results were as follows: B.T. C. L.

Zn (BF 4) 2 (50%) 30% of substance weight 0 11.25

Untreated 12 F.L.