DE1419599A1 - Process for the production of flame-proof textiles - Google Patents

Description

. concerning
Terfaires for the production of flame retardant textiles «"

The invention relates to a method to produce textile thread, - fibers, yarns, webs and fabrics flameproof, i.e. to make non-flammable *:. . -.--. =.

It is known to introduce certain flame-retardant substances into cellulose acetates in order to make the fabrics, threads, yarns and fibers both flame-proof and non-afterglowing. Various chlorinated substances are known for this introduction .i ^nd -i ^e spinning mass for threads, fibers and yarns. In the older patent application H 20 031, a method for making textile fabrics, fibers, yarns and spun fabrics flame-resistant is based

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Calluloseacetet described, whereby the Flammsiqherheit ο. by introducing a trisCPolybromo-aliphatic. ■ ·. or -aromatischem) phosphate having a bromine content of at least 5-0 wt -.% in an amount of 2,5 to 10 parts by τέ, based on .Gelloseacetat, is achieved in the Gelluloseacetat-spinning solution. This ensures high security was lambing against Del and .Nachglimmen he can see. ■ -. ■.,

JiIs was found:; that - if.flameproof textile fabrics., prepared as described above, subjected to a treatment by applying a finishing preparation - although the finish preparation itself * "is flame-resistant, a number of cases have become known are where finished flame retardant fabrics burned freely when a flame reached them.

It is not easy to understand why this is done can. It appears that such finishes, upon thermal decomposition, leave hard, carbon-containing layers on the fibers form. Bine such layer acts as a wick for that molten fiber which forms underneath; The glow such a wick increases the temperature of the melted one Substance to one in which it decomposes with a flare.

It has been found that webs, fibers, yarns are threads

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and tissue * based on cellulose acetate with the above bromophosphate ester can be finished - without the flame resistance to impair that already existed by applying a layer of a finishing (dressing) preparation that contains a non-sticky, fum-forming, contains synthetic, organic, polymeric material on the surface, provided that

a) the preparation is not easily flammable,

b) the temperature of the thermal decomposition of this polymer Material is not significantly above that of the "flame-proof" cellulose acetate and

c) the decomposition products at the decomposition temperature are soft and can be sticky.

The decomposition temperature of the flame-resistant CaI-lulose acetate and the sizing formulation can be determined by taking 0.05 to 0.1 g of the fabric or the Solids from the preparation in an open test tube (76 mm long, 9 »5 mm wide) with an increase in temperature by 5 ° / min. heated and write down the temperature at which the sample becomes noticeably charred, this temperature is called the decomposition temperature.

The nature of the decomposition products of the finish formulation can be determined by taking a sample of the film-forming Solids of the finish preparation in one

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open test tube (76 mm long, 9 »5 mm wide) by immersion of the test tube for 15 minutes in an oil bath, which is kept at the decomposition temperature. Then take the test tube out of the oil bath and check the decomposition residue with a wire. Are the decomposition products Soft or soft and sticky in the heat of this test, it could be found that the apron preparation has satisfactory properties for use as a non-flammable coating for having flame-resistant cellulose acetate fabric. As a precaution to avoid the possibility that any were unexpected chemical intermediate reactions take place between the cellulose acetate and the finish coating, sure to take place can be a mixture of equal parts by weight of flame-resistant cellulose acetate and solid body of the finish preparation be subjected to the above investigation at the decomposition temperature, the decomposition products such as are desired soft or soft and sticky.

The experiments to determine the decomposition temperature and the type of decomposition are carried out without excluding air from carried out on the material to be examined.

If the decomposition products are not soft or soft and sticky, they form a hard black one, for example PiIm in the test tube or a hard sintered mass,

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the application of this finishing preparation to the flame-resistant cellulose acetate fabric would make it flame-resistant Severely endanger properties.

It is believed that the burning of such finished. Fabric relies on the fact that the hard decomposition products from the finish coat that form when it decomposes only undergoes further decomposition at one. temperature, which is noticeably higher than that Decomposition temperature of the flame-resistant fabric, see above that eventually a breakdown of the finish coat takes place on the fiber, the temperature of which is higher than the decomposition temperature, as described, increases, with this decomposition becoming flammable products that then burn themselves.

The nature of the problem to be solved becomes clearer if one imagines that a "flame-resistant" cellulose acetate fabric produced as described above, coated with chlorinated rubber, which is itself non-flammable, results in such a finished fabric which is easily combustible. If 25% by weight of tris (dibrom.- _: j) ropyl) phosphate is added to the chlorinated rubber - the latter is also an agent for making it flame resistant - the fabric treated in this way still burns freely when it is hit by a flame. However, if the set j

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in tris ~ (dibromopropyl) phosphate increased to 75%, see above ^; gives' the AppreturzulDereitung with chlorinated rubber, "if a seven flaminbeständiges Gelluloseacetatgewebe" Open - '■' - "is --gebracht, an apertured tissue sufficient ■" -Flammbeständigkeit. It appears that the intrusion ^; Tris (dibromopropyl) phosphate in sufficiently large quantities changes the nature of the decomposition products of the chlorinated rubber to such an extent that they become soft, often soft and sticky, at the decomposition temperature

After the process according to the invention, a finished, flame-resistant textile fabric is produced, '^; which consists in the fact that a fabric made from fiber material based on cellulose acetate with flame-retardant agents uniformly dispersed therein or from such fibers, yarns or threads is covered with a coating of a non-sticky, film-forming, synthetic, organic polymer or polymer-containing preparation tongue temperature are soft and can be sticky . "Cellulose acetate" means primary gelatin

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loose acetate, which in a mixture (90-10 parts by weight) is easily soluble in methylene chloride and alcohol, and secondary cellulose acetate, which is found in both acetone and is also easily soluble in a mixture of methylene chloride / alcohol (90:10 parts by weight).

It is known that the flammability of organic polymeric substances varies widely from highly flammable substances such as nitrocellulose, which already burns with explosive violence, over flammable substances such as cotton and regenerated cellulose which burn freely to substances that are not easily flammable, such as cellulose acetate (in photography known as the basic material of the "security film"), Ethyl cellulose and a copolymer of vinyl acetate with vinyl caproate or with vinyl chloride.

The measure according to the invention consists in that on the cellulose acetate fabric produced from yarns, threads or fibers - wherein the .Cellulose acetate spinning mass is a tris (iolybromo-aliphatic or aromatic) phosphate with a bromine content of at least 50 wt .-% in one Amount of 2.5-10% by weight, preferably 5-7%? based on cellulose acetate contains - a film-forming, organic polymer or polymer-containing preparation »preferably

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in the form of a solution, emulsion or dispersion applied wherein the pesticide of the preparation is dissolved or suspended in a volatile liquid carrier.

According to the "process according to the invention for the finishing of cellulose acetate, film-forming, Non-sticky, synthetic, organic polymer comprises synthetic substances of at least four different ones Groups. .

The first group includes organic derivatives of cellulose which, however, do not form at room temperature are sticky, e.g. non-sticky, film-forming cellulose ethers such as ethyl cellulose.

The second group comprises polymers of vinyl and vinylidene monomers which form long carbon chains, with at least some of the carbon atoms attached to aeyloxy groups, carboxylic acids or their anhydride, carboxyamide, N-substituted carboxyamide, carbalkoxy and carbalkoxyalkyl groups groups of different character, but do not affect the above groups may be present, such as aromatic and haloaromatic groups _o Examples of such substances are non-tacky, film-forming polymers and MischpoljTnere of vinyl acetate and

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Methyl methacrylate, copolymers of partially alkylated esters of maleic acid with viriylidehmonocyclic aromatic Hydrocarbons such as 'styrene, copolymers' from Acrylic acid with methacrylic acid, polymers of 'alkyl oxyalkyl methacrylates and copolymers of alkylated N-methylqlacrylamide with vinylidene-monoOyclisehen 'aromatic hydrocarbons are oJff en.

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The third group includes alkylated aminoplast-forming condensation products such as those of alkylated dimethylolurea and alkylated methylolurea-melamine mixed condensate products. '

The fourth group comprises halogenated polymeric hydrocarbons such as chlorinated synthetic rubbers.

The flammability of the above synthetic polymers is in no case greater than that of the cellulose acetates and in the pail, where the decomposition temperature of the polymer and / or the nature of the decomposition products is such that it does not comply with the requirements specified above,

the decomposition temperature can be reduced and the decomposition products by introducing tria- (polybromoaliphatic- or «Aromatic) phosphate - as mentioned above in connection with the cellulose acetate spinning pulp -

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soft, generally soft and sticky in the finish preparation. It is assumed that the soft products formed during the decomposition of cellulose acetate and those formed during the decomposition of the finish melt together flameproof machendem means the required for those ensuring the desired th llammfest properties minimum over * - 'increases, it is sufficient that glatnmfestigkeit by a small proportion of an additive ^mitschmilzt: to erho ^' hen ■ ■ - ■ '. ■■■ "- ■ . ■. ^■: - .: ^....::. -. ■. ■ - ■ · .. ■■: .- ■:

As an example of a finishing material - which at Heating does not melt easily, but -if tris (dibromopropyl) phosphate or tricresyl phosphate in increasing amounts is admixed - becomes more and more meltable and in as the above is mixed in, less flammable is ethyl cellulose. Thus ethyl cellulose can the Basis for a satisfactory finish preparation form, from which an over-train can be formed, which meets the requirements of the invention. One also receives similarly a satisfactory finish formulation with a butyl ether of a methylolurea by adding tris (dibromopropyl) phosphate. In each ' Case must be the Sμbstanz-, which to the actual coating- compound of the finishing preparation is added with

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this be compatible.

Me sizing preparation can be used on the cellulose acetate in any conventional form, for example as an aqueous solution, as an aqueous solution of an ammonia or volatile. Amine salt, if a polymer with free carboxyl groups or a carboxylic acid anhydride group is used as Solution in an organic solvent in which the cellulose acetate used is practically insoluble, or applied as an aqueous emulsion or suspension <> The trisCPolybromoaliphatic and aromatic) phosphates are in certain organic solvents, such as toluene and xylene, in which the cellulose acetates are essentially are insoluble, easily soluble.

The uptake of the finish preparation by the cellulose acetate only needs to be done in very small amounts by weight, based on fibers, threads, yarns and fabrics of the desired feel, appearance and use, for example 0.1 to 5 $, preferably 0.5 to 3 # »where 1 to 2 wt .- ^ of which is often an appropriate amount is. The flame resistance of the flame-retardant cellulose acetate is sufficient to prevent any tendency to ignite due to the presence of a very thin surface coating of to prevent this finishing preparation.

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The. Finishing preparations can be applied to the? .., Applied we re fibers "■ ... threads, yarns, and fabrics made of cellulose acetate, - by.-The lake in Bad _r through we 1 ches e = ine solution, suspension, or emulsion of the Appreturzubereitung in the mold contains · How they "apply to the material to be treated ". should be applied. Removal of the compartment from the bath, which is generally kept at about room temperature, is: The impregnated material is fed between rollers in order to remove any excess of preparation ^: and to ensure uniform impregnation. The concentration of the bath used should be coordinated with the pressure that is applied with the rollers during passage in order to ensure the desired absorption of film-forming substances. Then the material is dried .. - ■ ".- ■ - - ^: " ■ -

The invention also includes flaiam-resistant fibers. Threads, yarns and fabrics made from cellulose acetate, which is used in is evenly distributed 'a flame-proofing agent contains and produced by spinning cellulose acetate -

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represents, for example up to 10% by weight, preferably 5 to 7% of a trisCPolybromaliphatic or aromatic) Phosphate, based on cellulose acetate, contains; wotei these fibers, threads, yarns and fabrics make a coating a film-forming, synthetic, organic polymer or polymer-containing preparation and the

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flammability of the polymer is not noticeably greater than that of the cellulose acetate, while the decomposition temperature the polymer or polymer-containing preparation is not significantly higher than that of the flame-retardant cellulose acetate and the decomposition products of the polymer or polymer-containing preparation are at the decomposition temperature are soft and possibly sticky. Other flame retardant substances that can be used are tris (chloroethyl ) phosphate, aluminum pyrophosphate and substances, which are known under the trade name "PHOSCAED" by which the ^ complex organic, halogen-containing polyphosphonate esters with at least some bromine and at least 50 wt% total chlorine are preferred.

While it is often appropriate to consider the final treatment a fabric made of one or more flameproof cells To make loose acetates, it may be useful to use a film-forming synthetic organic polymer The preparation containing it is easy to apply to the flame-retardant yarns as a size before weaving. Such Yarns can be colored. The fabric is then not desized after weaving. Examples of such substances are bridal satin (bridal satin), taffeta (poult taffeta), which no further finishing agent is applied after weaving require 'not stained and' by water Dry cleaning doesn't get groovy. .

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Such sizes can be applied in the known sizing or slashing machines. The amount of solids absorbed by the yarns is generally higher than that for conventional finishing preparations and is 2.5 to 6%, preferably 3 to 4% by weight. -% based on yarn. The sizing preparation can be more concentrated than the finishing preparation, for example 5 to 7% in order to allow greater absorption from the sizing bath, and the bath itself can be heated above room temperature, for example to 40 to 50 C. In Such a sizing bath can contain further additives to change the handle of the fabric.The handle of a flame-resistant cellulose acetate fabric can be improved by adding up to 25 % urea, calculated on the weight of a polymeric ester such as vinyl acetate-carboxylic acid copolymer .

With regard to the amount of synthetic polymers or a preparation containing such substances, which are on the surface of the fibers, threads, yarns and tissue is located, it is evident that this depends on the stage in which it is applied and depends on the intended use of the material. 0.1 to 10 wt .- # based on the material to be treated can be applied. In cases where higher amounts of finish are required

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#erdeny used, it is desirable that the finish or-sizing a £ lamb-proofing agent containing -.-

.If the treatment under discussion is the application of the final finish, it is appropriate to carry out all over- _; Any pretreatments that may be applied, ... such as desizing and degreasing, must first be carried out in the usual way.

, · "..! The following examples illustrate the invention.,

. ■ For application to a yarn or fabric of a secondary cellulose acetate ', · were dispersed in the uniformly 7% .trisr · · .- (dibromopropyl) phosphate and; which had a Zei-reduction temperature between 180 and 220 ⁰ C, A finishing formulation with polyvinyl acetate: was used. This preparation contained 2 parts by weight of polyvinyl acetate, 1 part of tkris (dibromopropyl phosphate and 1 part of zinc resinate. A 5% solution of the finish preparation was made in toluene. The oellulose acetate material was pulled through this and then passed between rollers so that one uptake of 60 wt .-% based on cellulose acetate er.reiohteo The material treated in this way was then dried.,;.

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Example 2

It would be a flame retardant fabric made from primary cellulose acetate used, in the yarn 5 wt .-% tris (dibromopropyl) phosphate were uniformly dispersed. It had a decomposition temperature of 240 C. The finish preparation contained 2 parts by weight of polyvinyl acetate, 1 part by weight of tris (dibromopropyl) phosphate and. 1 part by weight of zinc resinate. It was applied in the form of a 3% solution in toluene, by pulling through the fabric made of primary cellulose acetate and then using rollers to make a recording of 60% based on the dry weight of the fabric. The material so treated was then dried.

Example 3

The measures of Examples 1 and 2 were repeated, the finish formulation contained 3 parts of ethyl cellulose and 1 part of tris (dibromopropyl) phosphate.

Example 4-

A coating preparation was produced from 10 parts by weight of a butylated urea-formaldehyde condensation product in the form of a viscous solution with 66 % total solids content, 10 parts of zinc resinate and 1.75 parts of tris (dibromopropyl) phosphate. It became a 3% solution

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prepared in toluene and according to Example 1 on Flame-resistant cellulose acetate applied. The other Treatment was carried out according to this example.

Example '5 ' ■ -.,.-.-.

The steps of Example 4- were repeated using a coating preparation composed of 1 part by weight of chlorinated Rubber and 3 parts tris (dibromopropyl) phosphate. According to the above example, a 2% solution of the preparation was prepared and used.

Example 6

9 parts by weight of a textile finish emulsion, which is said to be a copolymer of a butylated methacrylamide according to the French patent. / Contained and 1,162,967 Example XV had a solids content of 33%, was tris (dibromopropyl ^ phosphate to 1 part - dispersed in water - admixed It was further water was added until the solids content is reduced to 3%, after which a flame-retardant cellulose acetate accordingly. Example 1 was drawn through this bath.

Example 7

The measures of Example 6 were repeated below

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Use of 4 parts by weight of .ein'emulsion of .ein Vinyl acetate-vinyl chloride ^ copolymers with 55% solids content and 1 part tris (DilDrompropyl) phosphate, dispersed in water, in the form of a 3-strength dispersion.

Example 8

The following emulsions were used in succession:

a) Emulsion of a copolymer of vinyl acetate and 2-ethylhexyl acrylate with a solids content of 56%, diluted with 18 parts by weight of water.

b) Emulsion of a copolymer of vinyl acetate and Vinyl caproate with 56% solids content, diluted with 18 Qew. Parts of water. "'"' '"'"

c) Emulsion of a copolymer of vinyl acetate with an unsaturated acid, as is available under the trade name "Vinamul 6000", with a solid content of 56%, diluted with 27 parts by weight of water «

d) Emulsion of a poly-2-ethoxyethyl methacrylate with 33% solids content, diluted with 16 parts by weight Water.

e) Emulsion of a polymethyl methacrylate with 33 % solids content, diluted with 10 parts by weight of water.

These emulsions were made with a correspondingly large amount of water diluted to make a finishing preparation with a solid

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to obtain content of 3 wt .-%. Through these baths were Primary and secondary flame retardant yarns and fabrics Cellulose acetates are drawn and then drawn between rolls to an intake of 60% on dry weight basis of the fabric, squeezed off and then dried.

When applied, emulsions a, b and β essentially had a solids content of 3 % and c and d of 2%.

Example 9

2 parts of a solid polymer of styrene and maleic anhydride and / or a partially alkylated ester of maleic acid, as available under the trade name "Stymer IiB ¹ ", were dissolved in water with 0.24 parts of ammonia solution (density 0.88) while warming. The whole was made up to 100 parts with water.

This solution was applied to a fabric made of primary cellulose acetate by pulling it through the bath whereupon the absorption amount of 60%, based on the dry weight of the fabric, by squeezing between rollers was set »Then the material thus treated was dried. When heating and drying ammonia escaped and the polymer became insoluble in water.

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Example 10

3 parts of an alkali-soluble copolymer of vinyl acetate, such as under the trade name "Bevaloid 170" available, were dissolved with heating in water with 0.12 parts of ammonia solution (density 0.88). Then became with. Water made up to 100 parts and the procedure of Example 9 continued. When heating and drying ammonia developed and the polymer became insoluble in water.

The decomposition temperatures of on the cellulose acetate, after drying, remaining polymerizate or polymer-containing compositions all of the above examples were between 180 and 22O ⁰ G all. Decomposition products were soft at the decomposition temperature and in most cases sticky films cast therefrom were either non-flammable or had a low level of flammability, not significantly above that of the cellulose acetate used.

Yarns and fabrics that the various treatments were subjected to the above examples, have sufficient flame resistance. You direct the flame do not continue if they are in contact with a flame coming from outside and do not glow afterwards if they are tested according to the British Standard Method No. 2963/1958.

809809/0979 '- ■ Claims

Claims (3)

1A-22 781 1418599 claims .. *. - - 1. Process,.-Zur- production of a finished, ^ - ■ ·· - flame-resistant textile fabric, thereby g ^:: e. ke η ^: η -. '· ζ eich η et: that one is on a fabric made of · Fase: i? material in the form of, cellulose acetate, which is uniformly dispersed: contains a flame retardant, ^r or on ■ fibers, threads or Yarns for the listening position - such fabric applies a coating of a non-sticky, film-free preparation containing synthetic organic polymers and uses such a preparation whose flammability is not significantly greater than that of the cellulose acetate itself, - 'whose temperature is not significantly higher than that of the cellulose acetate and whose decomposition products are soft and possibly sticky at the decomposition temperature. " 2 «,. A method according to claim 1, characterized in that one ^{uses such a 7} geluloseaeetat ■ which is a trisCPolybromaliphatic or aromatic ^ phosphate with a bromine content of at least 50% by weight in an amount of 2, 5 to 10% by weight, based on cellulose acetate. · · '^ -. ".: 809809/0979 1A-22 781 - 22- 1A1S599 3. Procedure according to. Claim 1 or 2, characterized in that the coating is used as a finish preparation brings up. Φ. Process according to Claim 3, characterized in that an uptake of 0.1 to 5 % By weight, based on cellulose acetate, of finish preparation adheres to. 812144 ORIGfNAL INSPECTED 80 980 9/097 9