HUT57293A - Process for fabric treating - Google Patents

Description

The present invention relates to a method of treating tissues, in particular a method of treating fabrics with flame-retardant organic phosphorus properties.

Methods of treating cotton fabrics with flame retardant properties with tetrakis (hydroxymethyl) phosphonium compounds (hereinafter referred to as THP compounds) or urea-precondensed derivatives thereof are disclosed in U.S. Patent Nos. 2983623, 4068026, 4078101, 4145463 and 4494951. U.S. Patents. The treatment is carried out by impregnating the tissue with an aqueous solution of chemicals, then drying, treating the phosphorous compounds required for deposition of phosphorous on the tissue with ammonia, finally oxidizing and washing, so that the fabric retains its flame resistance after many uses during washing.

However, the efficiency of crosslinking used to promote the deposition of phosphorus in an insoluble form is not always ideal and some of the expensive phosphorus compounds used in the impregnation step are not crosslinked and are washed out and wasted during washing after crosslinking. The curing efficiency of cotton fabrics is higher than that of cotton / polyester fabrics, and more particularly than polyester / cotton fabrics, and in some cases these fabrics cannot be fired with THP compounds. In addition, despite the fact that many methods are suitable for providing the fabrics with adequate refractory properties, after crosslinking • ·

- The 3 properties obtained are greatly reduced after repeated washing.

We have developed a process that allows a greater amount of phosphorus to remain in the fabric after washing and to provide appropriate refractory properties to non-cellulosic fibers such as cotton and polyester blends.

Accordingly, the present invention relates to a process for treating refractory properties of organic fibrous materials containing reactive groups. According to the process, the material to be treated is first impregnated with a silicon compound (or precursor compound) containing at least two active hydrogen reactive groups followed by an aqueous solution of an organophosphorus compound, and the resulting twice impregnated material is dried and subjected to heat and / or ammonia treatment. undergo crosslinking.

The silicon compound is used in the first step to form the once impregnated material and the organic phosphorus compound in the second step to form the double impregnated material. The once impregnated material is generally maintained under conditions such that the silicon compound interacts with or reacts with the fabric prior to the second step.

The silicon compound (or its hydrolysis product) contains at least two groups which are capable of reacting or interacting with an active hydrogen-containing group, in particular a hydroxyl, amide or amine group (including ammonia). Preferably, the silicon compound is at least one of the following

the substituent group represented by R in the general formula described herein, which is capable of reacting alone or after hydrolysis with a hydroxyl group of an insoluble polymer, e.g. and at least one substituent represented by R 1 in the general formula described below, which is reacted or interacted with hydroxymethyl groups such as nitrogen, oxygen or hydroxymethyl groups primarily attached to phosphorus and / or ammonia or amide. able. The reaction or interaction conditions, which are usually carried out under heat and under acidic, neutral or alkaline conditions, are preferably adjusted so that when R (or a derivative thereof hydrolyzed) reacts or interacts, R ¹ does not react.

Preferably, the silicon compound is a compound of formula (R) _a SiR1 _b R2 _c wherein a and b are independently 0, 1, 2, 3 or 4;

c is 0, 1 or 2; and a + b + c is 4.

R and R ¹ are as defined above; And R ² is an inorganic organic group, that is, the first and the second, the first and the second. ......

- Step 5 under reaction conditions. Preferably a is 1, 2 or 3, particularly preferably 3, b is 3, 2 or 1, particularly preferably 1, and c is preferably 0. The substituent R may be hydrogen or halogen, for example chlorine or bromine, or hydroxy. or an ether, acetal, ketal or ester derivative thereof. Two R substituents may also form a divalent ether, acetal, ketal or ester group, or three R substituents may form a trivalent ether or ester group. Preferably R is a hydrolyzable group. Ester groups consisting of an alkoxide represented by R may be, alkoxy alkoxide, aryloxide or aralkoxy groups such as R ³ O group, wherein R ³ alkyl, such as 1-10 or 1-6 carbon atoms (e.g. methoxy, ethoxy or 2-ethylhexoxy); or an alkoxyalkoxylene group in which both the alkoxy group and the alkylene group contain from 1 to 8 carbon atoms (such as 2-butoxyethylene or 2-methoxyethylene). R ³ can also be an aryl group such as a C 6 -C 19 aromatic hydrocarbon group (such as phenyl, tolyl or xylyl); or an aralkyl group such as a C 7-20 aralkyl group such as benzyl or naphthylmethyl). The meaning of an ester group constituting the substituent R can be for example a carboxylate, for example a group R ³ COO wherein R ³ has the same meaning as defined above, especially acetoxy. Preferably R is hydroxy, more preferably alkoxy such as methoxy, ethoxy, propoxy, isobutoxy or butoxy.

Preferably, the silicon compound is a RÍSi (OR ³ ) 3 general.

- trialkoxysilane of formula 6. Thus, the R group generally allows the hydrolysis of the silane compound in the impregnating medium or prior to the reaction or interaction, for example, in the first step, to the hydroxysilane (or any cyclic product of silanol and any amino group R ¹ ). The hydrolysis. Hydroxysilane or its cyclic product or precursor may also be used. The impregnating medium is usually an aqueous solution, so that the silicon compound (in its original form or after hydrolysis) is generally soluble in water; the water solubility of the silicon compound is at least 10 g / l.

The R ¹ substituent may be an organic group, for example

An organic group having from 1 to 12 carbon atoms, such as from 1 to 6 carbon atoms, having at least one substituent or group containing at least one nitrogen, sulfur, oxygen or silicon atom, for example 1 to 4, in particular 2 to 4, atoms; containing a bonded active hydrogen atom, or an unsaturated substituent or group or a 3-membered ring group formed by a carbon and a carbon, sulfur or oxygen atom, which is an unsaturated group electrophilic and can be attacked by nucleophiles such as hydroxymethyl or ammonia. The substituent may also be a halide such as chloride or bromide. Preferably, the R ¹ group contains a basic group or a quaternary derivative, so that the silicon compound in the impregnating medium is preferably a zwitterion. Suitable substituents include, for example, -OH, Cl, -NH ₂ , -NH-, -SH, -Si-H, CH ₂ = CH-, CH ₂ = C (CH ₃ ) -, epoxy, -CN and = C = O. groups. The substituent R ¹ may be a -R ⁴ -X general • ·

wherein R ⁴ is an alkylene group such as a C 1-6 alkylene group such as methylene, ethylene,

1,3-propylene; or an arylene group such as a C 6 -C 13 arylene group such as ο-, m- and ρ-phenylene, tolylene or xylene; an aralkylene group such as a C 7-13 aralkylene group such as benzene. R ⁴ may also be cycloalkylene alkylene or cycloalkenylene alkylene, each of which has 6 to 10 carbon atoms, such as 2-cyclohexylethyl or 2- (cyclohexenyl) ethyl; or, for example, a C 5 -C 7 cycloalkylene group such as cyclohexylene. X is one of the foregoing substituents, preferably chloro, -amino, or cyano, or -NHR ⁵ , wherein R ⁵ is C 1-6 alkyl; an aromatic or aralkyl group such as a C 6 -C 18 aromatic or aralkyl group; or a group -R ⁴ NH 2 or -R ⁴ -NHR ⁵ ; an aminoalkylene group such as a C2-C10 aminoalkylene group such as 2-aminoethyl or 6-aminohexyl; or a benzylaminoalkylene group optionally substituted, for example, by a vinyl group, containing from 2 to 6 carbon atoms in the alkylene group, such as 2 - [(p-vinyl) benzyl] aminoethyl-; or -aminocarbonyl. Preferred silanes having amino fukciós group include those compounds in which X is an amino group or a -NHR ⁵ group; silane compounds having at least one amino group are preferred, in particular those having at least one amino group (NH ₂ ) in the molecule, or particularly preferred. ··· ··· * ····· ···· ····· · ···

They preferably contain one amino group and one or two imino groups (-NH-).

The olefinic unsaturated substituent or group may be, for example, an alkenyl or alkenylene group such as a C2-C8 alkenyl or alkylene group such as a vinyl or propenylene group or an alkenylene group substituted with an aryl group such as a C8-14 aryl group such as vinylphenyl. or a 2-phenyl or 2-phenylethenylene group, or a cycloalkenyl group, such as a C 5 -C 7 cycloalkenyl group such as cyclohexylene, may be R ¹ or X itself or be part of X; For example, when R ¹ is a group of formula R ⁴ X, such as a benzylamino group substituted with a vinyl group as described above or a 2,1-unsaturated carboxylic acid ester group such as attached to an alkylene group such as 1,3propylene. methacryloxy or acryloxy. The three-membered ring substituent may be cyclopropane, epoxide, episulfide and optionally substituted ethyleneimine. These groups may be R ¹ or part of X or X (such as R ^{4 in} X) wherein X and R ⁴ are as defined above; Accordingly, R ¹ may include three (glycidyl oxy) propyl or 2- (3,4-epoxycyclohexyl) ethyl. Preferably, however, the R ⁴ substituent contains only saturated carbon-carbon bonds.

Most preferred R ¹ substituents are 1,3-propylene derivatives substituted in the 3-position with X, where glycidyloxy may be substituted. -, methacryloxy, acryloxy, chloro, amine, cyano, ureido and 2- (aminoethyl) amino, especially when the 3 R substituent is three methoxy or ethoxy groups, corresponding to the formula R ¹ Si (OCH 3) 3 or R 1 -Si (OOC 2 H 5) 3. Accordingly, preferred silicon compounds are N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane. Vinyl trialkoxysilanes are also preferred.

The substituent R ² is an inorganic organic group, such as a C 1 -C 19 group having the same meaning as previously defined for R ³ , preferably a methyl group, and this group is non-reactive and does not hydrolyze.

The organic fibrous material is predominantly cellulosic or substantially cellulosic.

Preferred cellulose fibers are natural cotton, but can be ramitic, down, paper or carded or regenerated fibers (e.g. viscose or cuprammonium fibers) or partially etherified or esterified cellulose (e.g. cellulose acetate or propionate).

The material may be wholly cellulose fiber, such as 100% cotton, or it may contain cellulose and non-cellulosic organic fibers, or it may be wholly non-cellulosic organic fiber. Inorganic fibers such as glass fibers are generally not used.

The non-cellulosic fiber is preferably a polyester or polyamide fiber, but may also be acrylic fiber. The polyamide may be an aliphatic derivative, such as a polyamine (e.g., diamine), preferably · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

A copolymer of 10 alkylenediamine, such as C 4 -C 12 alkylenediamine, and a polycarboxylic acid, e.g., C 4 -C 14 dicarboxylic acid, such as an alkylene dicarboxylic acid (e.g. Nylon 66) or a polylactam (e.g. Nylon 6). The polyamide may also be an aromatic derivative such as aramides based on aromatic dicarboxylic acid and phenylene diamine. The acrylic type polymer may be a homopolymer of polyacrylonitrile or a copolymer of vinyl chloride, such as modacrylic fiber. The material may comprise at least 20% by weight of cellulosic fiber, up to 80% by weight, for example 10-80% by weight, preferably 25-80% by weight of a blendable fiber such as polyamide. Preferably, however, the material comprises cellulose fiber and polyester fiber. The material generally has a polyester fiber content of up to 80% by weight, for example up to 70% by weight, and a cellulosic fiber content of at least 20% by weight, for example at least 30% by weight; accordingly, the composition may comprise, for example, 1-80% by weight or 1-70% by weight, such as 15-70% by weight, preferably 22-38% by weight or 45-75% by weight of polyester fiber and 20-99% by weight or 30-99% by weight such as 30 to 85% by weight, preferably 62 to 78% or 25 to 55% by weight of cellulose fiber. The materials generally contain at least 45% by weight non-cellulosic fiber, such as polyester fiber, such as 45-100% by weight polyester, and preferred materials are 30-78% by weight cellulose fiber and 22-70% by weight polyester fiber or 30-62% cellulose fiber and 38 to 70% by weight of polyester fiber. The polyester is generally a condensation product consisting of units derived from an aliphatic alcohol such as dihydroxy alcohol, in particular ethylene glycol or butane nuts (or mixtures thereof), and an aromatic dicarboxylic acid such as terephthalic acid or other dicarboxylic acid such as isophthalic acid or sebacic acid.

If desired, the fibrous material may be a non-cellulosic material as described above containing groups capable of interacting with the silicon compound. Accordingly, the material may be a polyester wherein the silicon compound reacts with hydroxyl or ester groups; polyamide wherein the silicon compound reacts with an amide or an amine or carboxyl group; or polyacrylonitrile, wherein the silicon compound reacts with the nitrile group. The polyester used is a reaction product of a polyester as described above, and the polyamide is a reaction product of a polyamine such as a diamine such as a C4-12 diamine and a polycarboxylic acid such as a dicarboxylic acid such as a C4-14 dicarboxylic acid. The polyacrylonitrile may be a homopolymer or a copolymer of vinyl chloride, such as modacrylic fiber.

The fiber material may be yarn or nonwoven, but is preferably woven. Fiber blends, such as cellulose and other fiber blends, may be intimately blended or less blended, but common yarns of cellulose and other fibers, such as polyester fibers, such as cotton-polyester or polyester-cotton fibers, are preferred. including woven yarns in which a core of a single fiber, such as polyester, is covered with cotton fibers. The weft and weft yarns of the fabrics are preferably the same, but they can also be different, e.g.

12, for example, polyester cotton fiber. As used herein, the term " blend " also refers to a composite fiber, a composite / blend fiber, and a sheathed core fiber. Preferred material is a fabric having a weight of 0.05 to 1.0 kg per 1 m ² , such as 0.150 to 0.40 kg or 0.05 to 0.20 kg, such as polyester cotton shirt, sheets or curtain fabrics.

Prior to treatment with the silicon compound, the tissue is generally free of finishing agents or other finishing agents, such as plasticizers and resins, so any finishing agents that may be present on the fabric are generally removed, e.g., washed.

The silicon compound can be applied to the tissue in undiluted form, but is generally employed in an aqueous solution, e.g., an aqueous solution of 0.1 to 10% by weight, preferably 0.5 to 7% by weight, at pH 2-9. If desired, the solution may also contain a weak acid, such as acetic acid or phosphoric acid, to aid in the hydrolysis of the silicon compound. The weak acid is present in an amount of 0.1 to 1% by weight, and the pH of the solution is preferably 2 to 4. The amount of silicon compound used is 0.01 to 10% by weight, for example 0.1 to 5% by weight, preferably 0.5 to 4% by weight, based on the amount of untreated tissue. When impregnating the silicon compound into the tissue, the moisture uptake is generally 40 to 150% by weight. After treatment with the silicon compound, the tissue is optionally pre-dried (for example 0.1 to 5 minutes at 80-100 ° C) and then heat-treated at 90-150 ° C (e.g. 90-130 ° C). The duration of the heat treatment is 0.5 to 10 minutes, for example 1-5 minutes. It's impregnated

the tissue may be kept at room temperature for 10 to 60 hours, for example 10 to 30 hours, instead of heat treatment. If desired, impregnation with a silicon compound is a so-called impregnation. it can also be carried out by a minimum dosing process in which the moisture uptake of the tissue is, for example, 10 to 50% by weight. The tissue can then be dried or allowed to stand for, for example, 2 to 24 hours before the second step. Using a cationic or amphoteric blowing agent and a stabilizer, the so-called. we can also have a minimum clearance process. The silicon compound can be hydrolyzed to form the active compounds in aqueous solution or during drying or heat treatment to form a reactive silicon compound. It is believed that the silicon compound or reactive silicon compound reacts with the material, in particular the hydroxyl, amide or ester moiety therein, in this step of treatment or fixing. The reaction is carried out in particular through the reactive group R or its hydrolyzed derivative (e.g. hydroxy group) and as a result the resulting treated material contains an intact silicon-containing group, in particular R ¹ , as described above. The treated surface thus preferably dependent -SíRÍjjRZq groups, especially SiR ¹ groups, which are generally the cellulosic hydroxyl groups or hydroxyl groups are attached to the polyester chain terminators. Alternatively, active hydrogen groups of R ¹ may be reacted with the corresponding ester, amide or nitrile group of the polyester, polyamide or polyacrylonitrile. Unsaturated or 3-membered ring groups in R ^x may also be reacted with the fiber by addition of the hydroxyl or -NH groups of the fiber to the silicon compound.

In the second step of the process, the silicon-treated tissue material is treated with an organophosphorus compound.

Preferably, each of the hydroxyorgano groups in the tetra-hydroxy-organophosphonium compound is a C 1 -C 9 alpha-hydroxy-organo group, preferably a group of the formula H ⁰ C- (R ⁵ -R ⁶ ) wherein R ⁵ and R ⁶ are independently a hydrogen atom or a C 1-4 alkyl group such as methyl or ethyl. ^R5 is preferably hydrogen and R ⁶ is methyl or preferably hydrogen, such as tetrakis (hydroxymethyl) phosphonium (THP) compounds.

The general application of tetrakis (hydroxy-organo) -phosphonium compounds is described below, with reference to THP compounds, with appropriate molar ratios of other compounds instead of THP.

The material to be treated is treated with an impregnating solution which is an aqueous solution of a mixture of a THP salt and a nitrogen compound condensable therewith to form a water-soluble precondensate; or a solution of the precondensate of said salt and nitrogen compound; either a solution of a THP salt or a water-soluble self-condensate thereof, or a THP salt (at least partially neutralized) (e.g. THP hydroxide) in the presence or absence of a nitrogen compound. Alternatively, the impregnating solution may comprise the above precondensate and an additional nitrogen compound, such as urea, in the form of a solution having a molar ratio of total nitrogen compounds (free and bound) to THP (0.8-2): 1, e.g. 8 to 1.5): the first THE

the nitrogen compound preferably contains at least two, for example 2-4 -NH- groups, preferably two -NH- groups, more preferably two -NH2 groups. The nitrogen compound is generally bifunctional and may be an amine, but preferably an amide. A suitable nitrogen compound is biuret, guanidine, melamine, and methylolated melamine, but urea is particularly preferred for the purpose of the invention, in particular in the absence of melamine or methylolated melamine. The nitrogen compound is preferably urea in the form of a precondensate.

In a preferred embodiment of the invention, the solution comprises a precondensate of a THP salt, such as chloride or sulfate, and a nitrogen compound. The molar ratio of nitrogen compound to THP is (0.05-0.8): 1, such as (0.05-0.6): 1 or (0.22-0.8): 1, such as (0.25) -0.6): 1, especially (0.4-0.6): 1. The pH of the solution is 2-7.5, such as 4-6.5, e.g. 4-5. The ratio of total nitrogen atoms in the nitrogen compound or condensate to total phosphorus in the THP salt or condensate in the impregnating solution is generally 4: 1, for example (1-3): 1.

Concentration of the organic phosphorus compound in the aqueous solution

5-70% by weight, for example 5-35% by weight or 35-70% by weight (expressed as THP ⁺ ion), but preferably 20-35% by weight.

If desired, the solution may further comprise a wetting agent, such as a nonionic wetting agent, for example in an amount of from 0.05 to 0.5% by weight of the impregnating solution; a fabric softener such as polyethylene, preferably in an amount of 0.1 to 2% by weight; a salt of a strong acid and a weak base (such as ammonium or

16 alkaline earth metal chloride or nitrate or acid ammonium phosphate) in an amount of 0.1 to 5% by weight.

The organic phosphorus compound is impregnated so that the impregnated tissue contains up to 40% by weight of the organophosphorus compound, preferably 10-30% by weight, preferably 20-30% by weight, based on the original weight of the material, in THP ions. up. The impregnation may be carried out with a solution and the wet material, such as tissue, is generally squeezed so that it generally contains from 50 to 130% by weight, for example 60 to 100% by weight, of its original weight. Alternatively, the treatment may be carried out by a so-called minimum dosing process with a concentrated impregnating solution such as foam, in which case the moisture uptake is 10 to 50% by weight.

The organic phosphorus impregnated material is then dried to 0-20% by weight prior to ammonia crosslinking, e.g.

5 to 15% by weight, such as 10% by weight, prior to heat curing to a substantially anhydrous state. The% value is obtained from the weight gain of the impregnated fabric and the weight of the impregnating chemicals used. The drying can be carried out in a drying oven or on hot containers such as steam-heated containers at 80-120 ° C for 10 minutes to 1 minute. The dry material is then cured. The crosslinking is carried out with ammonia, usually ammonia gas. Ammonia diffuses through the material and / or enters the material through a perforated tube passing through the material. Equipment and methods for ammonia crosslinking are disclosed in U.S. Patent Nos. 4,145,463, 4,068,026, and 4,494,951, which are incorporated herein by reference.

The dried phosphorus impregnated with the organic phosphorus compound may also be cross-linked by heat treatment at a temperature of 100-200 ° C or 100-180 ° C, e.g. 5 minutes, for example 7-1 minutes. Cross-linking of materials containing at least a majority of cellulosic fibers, particularly 100% paut, at higher temperatures and for long periods of time should be avoided. It is possible to heat-cure the dried material, but the drying and heat-curing steps are preferably combined in a single step by heating the material under conditions suitable for heat-curing. If the heat-curing is followed by ammonia-curing, it is preferable to first allow the heat-cured fabric to regain its equilibrium moisture content prior to the ammonia treatment.

The increase in dry weight of the crosslinked fabric obtained in the THP impregnating and curing step is 10 to 50% by weight or 10 to 40% by weight, for example 10 to 30% by weight, such as 10 to 25% by weight or 15 to 30% by weight %, especially 20 to 30% by weight; Based on total organic phosphorus up to 16-36% by weight, for example 20-28% by weight.

Comparison of the process according to the invention with the conventional process carried out without a corresponding silicon treatment step shows that the process according to the invention. In the impregnation step, the initial uptake of the THP compound and the crosslinking efficiency may be higher and the loss of phosphorus compound during washing of the finished material may be reduced. Accordingly, with the same amount of all phosphorous compound applied to the material, the process according to the invention contains a greater amount of bound phosphorus and is more manageable than a crosslinked material which is initially treated without the use of a silicon compound. Therefore, the loss of phosphorus compound is reduced in the process of the invention. The improvement in flame-retardant properties, such as carbonization length, is clearly demonstrated by the fact that the fabric treated by the process of the present invention undergoes much more severe flammability tests than the untreated fabric.

The degree of crosslinking and the concentration of bound phosphorus resin of the finished product of the present invention allow the fabric to meet flame resistance standards such as BS6249 Part 1 (1984). B Index requirements that cured fabrics without initial silicon treatment do not meet. The strength of the finished product produced by the process of the invention is also less than that of fabrics produced without silicon treatment.

The following examples illustrate the process of the invention in more detail. All tissues in the examples were pretreated with a dressing removal procedure.

Example 1

(a) A polyester / cotton fabric, blended in a ratio of 67:33 by weight, of 0.246 kg / m 2 is impregnated with 2% (w / w) aqueous solution of 3- (2-aminoethyl) aminopropyltrimethoxysilane (Dow Corning Z6020). Excess liquid was removed from the material and dried at room temperature overnight to afford 1.6% silane treated tissue.

(b) The treated tissue is then impregnated with an aqueous solution of a 1: 2 molar ratio of condensate of cabamide and tetrakis (hydroxymethyl) phosphonium chloride, containing 25.2% by weight of dry solution (THP ⁺ ion). Excess fluid from the tissue is squeezed to obtain a moisture uptake tissue of up to about 50% by weight.

c) The resulting tissue was cured for 3 minutes at 150 ° C and kept in a controlled normal humidity room overnight to regain equilibrium moisture. The heat-cured fabric is cured with ammonia gas by passing through the apparatus described in U.S. Patent 4,145,463.

d) After the ammonia crosslinking, the tissue was washed with 10% w / w hydrogen peroxide solution, rinsed with water, washed with aqueous sodium carbonate solution, rinsed again and dried.

The phosphorus and nitrogen contents and the flame resistance of the final product thus obtained are determined. The assays are performed before and after washing 40 times at 93 ° C. Washing in mild water is a breeze.

- 20 according to DIN 53920, method 1. The measurement was performed according to BS 5438 (1989) 2A.

We have determined that the tested tissues meet the flame resistance requirements of the BS6249 B Index. The results of our analyzes are as follows:

Fabric P N [wt%] [wt%] finished product 2.39 2.19 After 40 washes 2.34 2.12

After 40 washes, the fabric still qualifies for flammability testing.

2-6. Examples

The procedure of Example 1 is repeated with 2 different fabrics and 3 different types of crosslinking as described in c) above.

Tissue A is 100% cotton with a weight of 0.240 kg / m ² , and fabric B is a 67:33 weight ratio polyester / cotton fabric as described in Example 1.

In each case, the tissues were impregnated and treated according to steps (a) and (b) of Example 1 above, and their moisture uptake in steps (b) and (4) to (6). in the Examples 74.1%, 74.7%, 53.7% and 61.9% respectively.

After step b), tissue A is c) cured so that

i) heat-curing at 150 ° C for 4 minutes; or ii) after drying at 100 ° C for 2 minutes, · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

Subjecting it to 21 ammonia crosslinking by passing the fabric through the chamber described in U.S. Patent 4,145,463; or iii) curing at 150 ° C for 4 minutes followed by ammonia curing through a chamber disclosed in U.S. Patent 4,145,463, followed by U.S. Pat.

In the case of fabric B, the crosslinking step c) following step b) is always carried out only by the crosslinking process i) or ii).

After the crosslinking steps i), ii) or iii), step d) is performed.

The finished tissues are subjected to flame resistance and analytical tests before and after washing 40 times at 93 ° C.

The results obtained on the test tissues produced by the process of the invention are as follows:

- 22 Finished goods

Example Curing agent process Fabric P [wt%] N [wt%] The length of the carbonization is, um Second heat (i) THE 1.99 1.54 96 Third heat (i) B 2.17 1.64 50 4. ammonia (ii) THE 3.00 3.07 74 5th ammonia (ii) B 2.12 2.09 60 6th heat and ammonia THE 2.82 2.84 78 crosslinking (Iii) After 40 washes analysis results the next ones: Example P N Γ massecr% 1 rtömecf% 1 Second 1.66 1.35 3. 1.55 1.17 4th 2.90 2.86 5th 2.19 2.12 6th 2.77 2.61

7th-9th Examples

Repeat steps 2-6. The same procedure as in Example 1 is followed by the same three types of crosslinking process but using a 67:33 weft polyester / cotton blend as the fabric to be treated. The weight of fabric per 1 m ² is 0.095 kg.

• ·

- 23 Analyze the phosphorus and nitrogen contents of the tissues so obtained, as well as A.-C. comparative samples which are similar but produced without silicone treatment. The analysis results are as follows:

Example Cross-linking P You would break% 1 N Dummy% 1 8th heat (i) 2.38 2.04 9th ammonia (ii) 2.23 2.45 10th heat and ammonia (iii) 2.53 2.47 THE. (I) 1.78 1.56 B (Ii) 1.96 2.18 C. (Iii) 2.00 2.11

10-13. Examples

The procedure of Example 1, except that the tissue to be treated is used as a well mixed cotton / polyester cloth 60/40 weight ratio, having a rain to 1 m ² weight of 0.268 kg, and the first treatment stage using four different concentrations of silane. Each of the tissues so treated meets the flame resistance requirements before and after washing. The results obtained are as follows:

• · • · • ·

- 24 Example Silane Finished Product After 40 Washes • H ra 'Φ Ό <D «Φ C Φ N W

N «t / 1 O X

• rH ra 'Φ T5 N φ to g Ü) to IS φ She C X Φ N cn

Γ ~ Ί o \ P

tendon CM She tendon tendon tendon CD tendon

She rh tendon STONE OJ co tn *> * » OJ CM CM OJ

STONE STONE OJ co tendon θ ' "you K. CM CM CM CM

d o o o ip in <w ö> Φ β: 0 P

o \ o

kill

Φ 6: O • P

co 00 CO co 00 She rh cn *. *> OJ CO CO co

'Cf θ ' σ> rh SHE σι · » * » *> OJ CO co CM

rH OJ d LO rH OJ d

H rH rH rH • «

Example 14

The procedure of Example 1 is repeated, except that the fabric to be treated is a 50:50, thoroughly blended polyester / cotton fabric having a mass of 0.095 kg / m and a 5% silane solution. The finished product thus obtained after 20 washes meets the flame resistance requirements. The analysis results obtained are as follows:

Finished product After 20 washes P [% by weight] 3.09 2.58 N [wt%] 2.82 2.23 carbonizing length [mm] 84 95

15th-17th Example

The procedure of Example 1 is repeated, but the following aqueous silane solutions are used in step a):

i) 2% by weight of 3-chloropropyltrimethoxysilane solution;

ii) 1% by weight solution of 3- [2- (p-vinylbenzyl) aminoethyl] aminopropyltrimethoxysilane iii), iv) 0.25% by weight and 2% by weight 3-glycidyloxy

propyl trimethoxy silane solution.

The silane solutions are trademarks of Dow Corning Z6076, Z6032, or Z6040.

Each finished product thus obtained meets the flame resistance requirements.

The carbonization length of the finished products shall be as follows:

ii) 74 mm; iii) 69 mm; iv) 65 mm.

Claims (15)

Claims A process for the formation of a flame-retardant property of organic fibers containing reactive groups, characterized in that: (a) first impregnating the material with a silicon compound or precursor having at least two active hydrogen-reactive groups and then impregnating with an aqueous solution of an organophosphorus compound; b) drying the material, then c)) crosslinking by heat at a temperature of at least 100 ° C and / or by treatment with ammonia. Process according to claim 1, characterized in that the organic fiber material is essentially cellulosic fiber, such as natural cotton, ramite, down, paperboard, viscose or cuproammonium fiber or cellulose acetate or propionate. 3. The process of claim 1 wherein the organic fiber material comprises cellulose and a non-cellulosic material such as polyester, polyamide or acrylic fiber. 4. A process according to claim 1 wherein the organic fiber is substantially non-cellulose fiber. 5. The method of any of claims wherein the silicone compound used is _(R) c SiR ^{1 2}} -1R compound, • · · 27 wherein (i) a and b are independently 0, 1, 2, 3 or 4; c is 0, 1 or 2; and a + b + c is 4; (ii) the substituent R or its hydrolysis product is capable of reacting or interacting with the hydroxyl or amide group of an insoluble polymer; (iii) the R ¹ substituent is capable of reacting or interacting with hydroxymethyl groups and / or ammonia or amide-NH 2 groups; and (iv) ^R2 represents an inert organic group; and the silicone compound of the above general formula is primarily a compound of the formula R ¹ Si (00113) 3 or R ² Si (OC ₂ H ₅ ) 3 in which R ¹ is 3-substituted 1,3-propylene wherein the substituents are glycidyloxy, methacryloxy, acryloxy, amino, cyano, ureido or 2- (aminoethyl) amino; a group or a chlorine atom; as such N- (2-aminoethyl) -3-aminopropyl trimethoxysilane; 3-aminopropyl-trimethoxysilane; or vinyl trialkoxysilane. 6. A process according to any one of claims 1 to 4, wherein the silicon compound is applied to the substance in the form of an aqueous solution at a concentration of 0.1 to 10% by weight, the aqueous solution preferably also comprising a weak acid such as acetic or phosphonic acid 0.1-1% by weight. 7. A method according to any one of claims 1 to 4, wherein: ♦ · · ♦ ♦ • • ♦ ♦ - 28, characterized in that the impregnation of step a) is carried out by treating the material with a solution containing the silicon compound or its precursor up to a moisture uptake of 40-150%, in particular when the impregnated material is subsequently treated with one or more of the following steps: i) drying at 80-100 ° C for 0.1-5 minutes, ii) heating at 90-150 ° C for 0.5-10 minutes, iii) keeping at room temperature for 10-60 minutes, especially if the impregnated material is to be dried. 8. A process according to any one of claims 1 to 3, wherein the impregnation step a) is carried out with a tetrakis (hydroxyorgano) phosphonium compound, preferably a compound in which the hydroxyorgano group is a C 1 -C 9 group, more preferably HO- A group of the general formula C (R ⁵ R ⁶ ) wherein R ¹ and R ^{2 are the} same or different and are hydrogen or C 1 -C 4 alkyl, such a compound being preferably tetrakis (hydroxymethyl) phosphonium compound (THP) or a water soluble condensate thereof or a water soluble condensation derivative thereof with an organic nitrogen compound such as urea, biuret, guanidine, melamine or methylolated melamine; or a mixture or a condensation or self-condensation derivative of one of the above organic nitrogen compounds with a phosphonium compound. 9. A process according to any one of claims 1 to 4, wherein the impregnation step a) is carried out with a solution containing a quantity of the organic nitrogen compound THP salt precondensate such that 4 · «· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · 29 (0.05: 1) - (0.8: 1), preferably (0.25: 1) - (0.6: 1), more preferably (0.4: 1) - (0.6: 1) 1) and the pH of the solution is 2-7.5 preferably 4-5; and the solution contains from 5% to 70% by weight of the organophosphorus compound, expressed as THP ⁺ , and the solution also contains one or more of the following: i) a wetting agent, in particular a nonionic wetting agent, preferably present in the impregnating solution in a concentration of 0.05 to 0.5% by weight; ii) a fabric softener, preferably in the impregnating solution In a concentration of 0.1 to 2% by weight; iii) a catalyst which is preferably present in a concentration of 0.1 to 5% by weight in the impregnating solution, preferably a strong acid and a weak base salt such as an ammonium salt or an alkaline earth metal chloride or nitrate or an acidic ammonium phosphate. 10. Process according to any one of claims 1 to 3, characterized in that during impregnation step a) the material is treated with the impregnating solution up to 40% by weight, preferably 20-30% by weight, of organic phosphorus, based on THP ⁺ ion and the original weight of material. with respect to. The method of claim 10, wherein the wet material is extruded to a moisture uptake of 50 to 130% by weight based on the original weight of the material. 12. A process according to any one of claims 1 to 3, characterized in that the treated material is treated with a concentrated impregnation solution by a minimum dosing process, preferably by foam application. 0 «» 0 0 · · · · ··· · ··· · · * * · · · · · U »» ·. ·· «0 * · * to obtain a moisture content of 10 to 50% based on the original weight of the material. 13. A process according to any one of claims 1 to 3, wherein the curing step c) is carried out in a chamber or oven at 100-180 ° C for a curing time of 10 to 0.5 minutes. 14. The process of claim 13, wherein the heat-curing is performed prior to ammonia-curing. 15. A process according to any one of claims 1 to 3, characterized in that the crosslinked material is subjected to at least one of the following treatments: i) subjecting the crosslinked resin in the treated material to a treatment for increasing insolubility; ii) oxidizing, iii) washing with aqueous base and water, and ii) oxidizing with excess oxidant at 0-40 ° C for 0.1-10 minutes; the oxidizing agent used is 0.5 to 15% by weight aqueous hydrogen peroxide solution or 1 to 10% by weight aqueous sodium perborate solution, or a gas containing molecular oxygen is passed or blown through the crosslinked material.