FI94154B - Method for treating fabric - Google Patents

Abstract

Flame retardant cellulosic fabrics having reduced shrinkage are obtained by treatment of fabric with a tetrakis hydroxymethyl phosphonium compound or condensate and then curing with ammonia, followed by treatment involving reaction of the fabric with a non self-condensing methylolamide under aqueous acid conditions. The order of treatment can also be reversed.

Description

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Method for treating fabric

The invention relates to a method of treating a cellulosic fabric to make it non-flammable and non-wrinkle.

The burning of cotton fabrics has been slowed by impregnation with tetrakis (hydroxymethyl) phosphonium compounds (THPs) or their precondensates, followed by curing with heat or ammonia-10a. The flame retardant properties of these fabrics are washable. However, their other physical properties, especially non-wrinkle and shrinkage, are often weaker, which limits their use as easy-care fabrics for clothing, for example.

15 In an effort to overcome these limitations on

The treatment of cured THP fabric with resin followed by thermosetting was studied at the Southern Regional Research Center [Rowland and Mason, Textile Research Journal (1977) 365-71 and 721-8].

The present invention provides a flame retardant treated fabric which also has an improved combination of strength and ease of care properties.

The invention relates to a process for treating a cellulosic fabric to make it spontaneously flammable and non-wrinkle by impregnation under known conditions with a tetrakis (hydroxymethyl) phosphonium compound and non-condensable methylolamide. The process is characterized in that the impregnation is carried out in two steps in an arbitrary order, in which step: 1 is impregnated with a solution of a phosphonium compound or its condensate, followed by curing to a polymer, and in step 2 is impregnated with at least two methylol group-containing methylolamides or methylol urea. a solution of its O-alkylated derivative, in particular 1,3-N, N-dimethylol-4,5-dihydroxyethylene urea, followed by treatment of the fabric under aqueous acidic conditions at a pH of less than 3, preferably less than 1, to react methylolamide with the fabric.

The process is preferably carried out by impregnating a fabric containing a cured polymer derived from a tetrakis (hydroxymethyl) phosphonium compound or a condensate thereof with a non-self-condensing methylamide having at least 2 methylol groups (which may optionally be alkylated) and reacting the methylolamide with the fabric under aqueous hap-10 conditions at a pH below 3.

In this preferred method, the fabric initially contains a cured THP polymer. The fabric may be impregnated with an aqueous solution of a THP salt mixed with a nitrogen compound condensable with THP, such as melamine, methylated melamine or urea, or with a precondensate solution of said salt and nitrogen compound or a THP salt or at least partially neutralized THP salt, e.g. hydroxide, with or without a nitrogen compound solution, after which the impregnated fabric may be dried and cured by heat and / or ammonia. The fabric is preferably impregnated with a solution of a THP salt, e.g. chloride or sulphate, and a urea precondensate, the molar ratio of urea to THP being 0.05-0.8: 1, e.g. 0.05-0.6: 1, e.g. US as described in U.S. Patent No. 2,983,623 or 4,078,101, and cured with ammonia, for example, as described in U.S. Patent No. 2,983,623, 4,068,026 or 4,494,951. After curing, the fabric is usually post-treated by oxidation with hydrogen peroxide, rinsing, neutralization and rinsing. The fabric is then dried. The cured fabric usually contains 8-25, for example 8-20 or 14-20% cured THP polymer (based on the weight of the untreated fabric); light fabrics have a higher THP content than 35 heavier fabrics.

The fabric containing cured THP is impregnated with it-. an uncondensed methylolamide having at least two methylol groups or, optionally, an aqueous solution of its alkyl ether. These methylolamides, also called "reagent resins", do not substantially self-condense under the conditions under which they are reacted, i. cured with fabric cellulose. These compounds generally do not contain N-H groups, except for a small number of such groups which may be present in the degradation products in equilibrium with said compounds. These methylolamides are preferably methylolated cyclic ureas or their O-alkylated derivatives. Such compounds of formula 10a may have the formula Z - N (R *) - CO - N (R2) -Z, wherein each group Z is a group CH2OH or CH2OR, wherein R is an alkyl group, for example an alkyl group having 1 to 6 carbon atoms , such as a methyl group, R 'and R together form a divalent aliphatic group which, together with 2 nitrogen atoms and a carbonyl group, forms a 5-, 6- or 7-atom ring. The divalent aliphatic group may have the formula -CR 2 R 4 - (Y) n ~ CR 2 R 2 -, wherein each of R 1, R 2, R 1 * and R 2, which may be the same or different, is a hydrogen atom, a hydroxyl group or an alkoxyl group, for example an alkoxyl group having 1 to 6 carbon atoms, such as a methoxyl group, n is 0, 1 or 2, preferably 0 or 1, and Y is an oxygen atom 4 or a group NR, wherein R is an alkyl group, for example an alkyl group having 1 to 6 carbon atoms, such as a methyl group, 8 9 8 9 25 or a group CR R, wherein each of R and R, which may be the same or different, is a hydrogen atom or an alkyl group, for example an alkyl group having 1 to 6 carbon atoms, such as a methyl group, or a hydroxyl group or an alkoxyl group, for example 1- An alkoxyl group having 6 carbon atoms, such as a methoxyl group, provided that two or more hydroxyl or alkoxyl groups, 3 6 8 9 which are R, R, R or R, must be attached to different carbon atoms, a that when n is 2 at least one 8 9 the group Y is a group CR R.

Thus, a divalent aliphatic group in which the free valences are two atoms apart may be a group having 2 to 6 carbon atoms, for example, a 1,2-ethylene group or a 1,2-dihydroxyethylene group / -CH (OH) -CH ( OH) -7 · A divalent aliphatic group in which the free valences are three atoms apart from each other may be a group having 3 to 10 carbon atoms, for example a 1,3-propylene group optionally having at least one hydroxysyl, alkyl (e.g. methyl) -) or a methoxyl substituent, for example on a carbon atom 2 8 9 6 8 or 3, such as in the groups -CHO-CR R -CHR-, in which R is hydrogen or a methyl group, R is hydrogen or a hydroxyl or methyl group and R is hydrogen or a methyl or methoxyl group. A divalent aliphatic group in which the free valences are three atoms apart may also be a group having 2 to 6 3 carbon atoms of the formula -CHR -O-CHR -3 7 5 3 5 15 or -CHR -NR -CHR-, wherein R and R are as defined above, but preferably hydrogen atoms. The divalent aliphatic group in which the free valences are four atoms apart may be a group having 4 to 10 carbon atoms, for example a 1,4-butylene group optionally having at least one hydroxyl, alkyl (for example methyl) or methoxyl substituent.

In another type of methylolated cyclic urea, the groups R and R shown above together form a tetravalent aliphatic group so that together with the nitrogen atoms and carbonyl groups of the two groups ZN-CO-NZ form two fused 5-, 6- or 7-membered groups. -atomic ring. Such tetravalent 3 5 3 5 groups generally have the formula -CR- (YJ ^ -CR, wherein R, R, Y and n are as defined above. Preferably n is 0, and the group is an acetylenyl group of the formula -CH- CH.

Examples of methylolated cyclic ureas are dimethylolethylene urea and in particular 1,3-N, N-dimethylol-4,5-dihydroxyethylene urea, but also dimethylolpropylene urea and analogs 4-methoxy, 5.5-35 dimethyl and 5- hydroxy compounds and 5-oxa and 5-alkylimino analogs of dimethylolpropylene urea and tetramethylolacetylene diurea.

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The fabric containing the cured THP polymer is impregnated with an aqueous solution of methylolamide containing, for example, 40-250, such as 80-180, especially 110-180 g / l methylolamide, and having a pH in the acidic range, usually less than 3, e.g. 1-2 or especially less than 1. The pH of the methylolamide solution is usually adjusted with an acid, in particular for curing at low temperatures, for example below 50 ° C; mineral acids such as hydrochloric acid and especially sulfuric acid are preferred. The higher the amount of acid added, the higher the cure rate or degree of cure; the impregnation solution is usually 0.1 to 10, for example 0.5 to 10, preferably 1 to 6, such as 1 to 4 or 4 to 6 M, relative to the acid. The solution may contain added soluble salts, for example salts of mono-, di- or trivalent metals and anions from strong acids, such as chlorides, nitrates and sulphates 2-200, for example 2-50 or 10-200, for example 10-70, such as about 50 g / l; examples of the salts include ammonia salts, for example ammonium chloride, and salts of alkali-20 metals, alkaline earth metals such as magnesium, and zinc and aluminum, and these salts can increase the cure rate. The amount of zinc salts, for example zinc quinitrate, may be 2 to 20 g / l, and the amount of magnesium salts, for example magnesium chloride, may be 10 to 50 g / l.

. The solution may contain a wetting agent such as a nonionic and / or anionic wetting agent, for example 0.1-5 g / l, as well as an optical brightener which is stable under acidic conditions, for example 10-30 g / l.

Particularly in the case of curing at high temperatures, for example at temperatures above 50 ° C, the soluble salts described above which lead to acidic aqueous solutions can be used in the aqueous solution of methylolamide, in particular when the pH of the impregnation solution is to be adjusted to 2-6, for example 3- 6.

35 The above may be used in such treatments. along with or instead of a soluble salt, a water-soluble carboxylic acid having, for example, 2 to 6 carbon atoms and usually 1 to 3 hydroxyl groups, such as glycolic, citric, malic, lactic, tartaric and mandelic acid , for example 3-100, such as 10-70 g / l.

5 The fabric is impregnated with a solution and the wet fabric is usually compressed so that the wet impregnation is 50-120%, for example 60-90% (based on the dry weight of the fabric containing cured THP). Alternatively, the solution can be applied by the method of the smallest possible addition, with a wet acceptance of only 10-50%. The dry mass yield of methylolamide is usually 3-20, for example 6-20, such as 7-15% (calculated on the same basis). The fabric can then be cured at a moisture content of 6-90%, such as 30-90%, for example after the above compression, or at a moisture content of 6-30%, for example after the smallest possible addition as such or after drying or after partial drying of the compressed fabric.

20 The moisture content of the fabric at the beginning of curing can be calculated from the current mass of the impregnated fabric, the initial mass of the fabric and its moisture content (obtained from loss of mass on drying), the solids and water content of the impregnation solution and the wet reception.

The presence of an aqueous solution in the fabric swells this, and in curing the fabric reacts with methylolamide to obtain a cured fabric in which the methylolamide is cured to the fabric, e.g., bound to a cellulose, e.g., a cellulose crosslinker and / or cured to a cured THP polymer. An aqueous medium is present on the fabric throughout the curing, so that at the end of the curing, the cured fabric is impregnated with the aqueous medium and therefore still in an expanded state. Such curing can be called wet or wet curing as opposed to dry curing, where wet impregnation

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The fabric is dried to remove moisture and thereby form a collapsed impregnated dry fabric, and then the dry fabric is cured.

If the moisture content of the fabric at the beginning of curing is 6-30%, the pH of the aqueous solution of methylolamide impregnated into the fabric is usually 1-2, preferably 1-2. The fabric is usually allowed to stand at a temperature below 50 ° C, for example 10-40 ° C and preferably at ambient temperature, such as 15-40 ° C for 5-50, for example 10-30 and especially 10-30 hours, while being taken care of. , the moisture content of the fabric does not fall outside the above-mentioned range of 6-90%, preferably 6-30%, for example by wrapping the fabric in a plastic film. If desired, the fabric can be cured at a temperature of 50-180 ° C for 1 min to 6 hours, for example at a temperature of 90-140 ° C for 2-20 min, although temperatures of 140-180 ° C can also be used; in all cases, again, great care is taken to keep the moisture content in a given range throughout the curing, for example by curing in a steam chamber, if necessary at elevated pressure, and preferably with saturated steam. Under these high temperature conditions, the pH of the solution in the fabric may be 2-6, preferably 3-5 when the fabrics are to be heated to, for example, above 90 ° C, and 2-3 when the fabrics are heated to 50-90 ° C. The curing time, pH and heat-25 state are usually chosen so that the curing rate is as high as possible but the possible deterioration of the fabric is kept to a minimum.

If the moisture content of the fabric is 30-90%, for example 30-60% or 40-75%, such as 45-65%, at the beginning of curing, the pH of the aqueous impregnation solution in the fabric is usually less than 1, and the fabric curing time, temperature and other conditions are otherwise in the same area as in the curing of the drier fabric. The moisture content is maintained in the range of 6-90%, for example 30-90%, during curing. If a large amount of acid has been added to the impregnation solution, for example so much that the bath is 3-10, such as 3-6 N with respect to acid 8 941 54, the curing time can be reduced to 1 minute to 5 hours, such as 0.5 to 4 hours, when curing at ambient temperature, such as 15-40 ° C.

The fabric can be cured without external tension 5 or compression. The impregnated fabric is preferably cured under tension in at least one of the warp or weft directions, for example under external forces and / or under internal stresses. Thus, in a continuous process in which the impregnated fabric is passed from impregnation baths, preferably through press rolls, and then to the take-up rollers for curing, the fabric can be wound on the take-up rollers under at least such tension as to prevent the fabric from hanging, and it is preferable to maintain during; the tension may even increase during curing. The fabric can also be taken to the receiving rolls under high tension, which tension is kept at least unchanged during curing, but it is preferred that the tension of the fabric be the lowest anti-hanging tension. If the impregnated fabric is not dried, it is preferable during curing to prevent liquid from flowing through the roll, for example by rotating the roll slowly, whereby the loss of moisture is not significant; if desired, the fabric can be rewound on the rollers to reduce the stresses in the fabric. The fabric is also usually dried without wrinkles, unless some special effect, such as creasing, is required. In the case of high-speed drying, for example with a drying time of less than 30 minutes, the drying can be carried out in a steam chamber. When the strain is under tension, again in this case preferably under the lowest anti-hanging tension.

After curing, the fabric is rinsed, neutralized and rinsed again before pressing and drying. The solids addition in the resin treatment is usually 1-6%, especially 2-4%.

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Methylolamide post-treatment usually does not substantially affect the non-combustibility properties of the fabric / but the ease of care properties of the fabric are often significantly improved. Compared to cured THP-si-5-containing fabric, prior to methylolamide treatment, the fabric is usually less wrinkled, has better smooth stability, has a higher wrinkle recovery angle when wet, has a higher moisture absorption capacity (equilibrium moisture content), and has a residual water content (residual water content). is smaller; the angle of return of wrinkles when dry may also be better, especially if the curing of methylolamide is done under stress. The tear strength and abrasion resistance of the treated fabric compared to untreated fabric gas are generally much higher than those observed in treated fabrics obtained by treating THP fabric with methylolamide and thermosetting, and thus fabrics treated by the method of this invention may be more durable than drapery.

In a less preferred alternative method, the original fabric may first be treated with methylolamide and then reacted and then treated with THP. compound or its condensate and then cures. Thus, in this process, a fabric reacted with a non-self-condensing methylolamide having at least 2 methylol groups (which may optionally be alkylated) under acidic aqueous conditions, for example at a pH below 3, is treated with a tetrakis (hydroxymethyl) phosphonium compound or condensate thereof. which is then cured.

The nature of the methylolamide, the impregnation solution and its pH and the impregnation and curing method applied to the fabric are approximately the same as in the corresponding methylolamide treatment applied to a fabric already containing cured THP polymer, except that the fabric impregnated with methylolamide 10 941 54 %, for example 60-110% (based on the dry weight of the fabric), a dry uptake of methylolamide which is usually 4-25, for example 6-18, such as 8-14% (calculated on the basis of sa-5 miles), and the moisture content of the fabric at the beginning of curing, which may be 6-30, but more preferably 30-90, for example 30-60 or 45-80, is preferably 60-90, in particular 70-90% (of the initial weight of the fabric), since such high initial moisture concentrations allow a more efficient THP treatment to obtain fabrics with better flame-retardant properties than fabrics made from fabrics which has been cured with methylolamide at a moisture content of 6-30%.

Compared to the properties of a wet-cured methylolamide-containing fabric, THP finishing greatly improves the flame retardancy properties and can also improve the wrinkle recovery angle when wet and dry, increase moisture absorption (i.e., equilibrium moisture content after air-20) and lower post-spin moisture content. Compared to a fabric containing a cured THP polymer, a fabric first cured with methylolamide and then cured with THP usually has less wrinkling and a greater wrinkle recovery angle when wet and dry.

Compared to fabrics cured with methylolamide before THP treatment, fabrics post-cured with methylolamide after THP treatment generally have better properties, especially the shrinkage of post-cured fabrics is often lower than that of pre-cured fabrics.

In order to reduce the reduction in tear strength of the treated fabric compared to the THP fabric or the original untreated fabric, a fabric containing cured THP and cured methylolamide can be added before or after final drying • lii [i I li II l lfl> Π 94154 0.1-5% by weight (by weight of fabric) of plasticizer; examples of such plasticizers are condensation products of fatty acids, for example containing 8 to 20 carbon atoms, and polyamines or their cyclization products, each of which may be prototyped or in the form of a quaternary salt, as well as quaternary ammonium salts having 2 aliphatic fatty acid groups, for example 8 to 20 carbon atoms. an alkyl group, and 2 lower alkyl groups, for example, an alkyl group having 1 to 6 carbon atoms, such as a methyl group.

It has also been found that in the case of a fabric containing cured THP and cured methylolamide, regardless of the treatment order, mechanical shrinkage of the fabric, e.g., mechanical compression shrinkage, significantly reduces the continuous shrinkage of the fabrics in multiple repetitive washes. This compression shrinkage generally includes the steps of wetting the fabric with water and / or steam to obtain a swollen fabric, adjusting the width of the swollen fabric as desired, shrinking the fabric 20 by compression, and drying the fabric. Compression shrinkage can be performed by bringing the fabric into close contact with and maintaining the stretched elastomeric cover while maintaining the degree of elongation of the cover. reduced, for example, to zero. Drying can be done! * 25 while the fabric is tensioned, for example, by squeezing a damp shrunken fabric between a heated metal cylinder and an absorbent fabric. The fabric can finally be rolled or rolled. An example of such a method is the Sanforized method described in Inter-30 national Textile Bulletin Dyeing / Printing / Finishing 2/86 pp. 14, 16, 20, 22 and 27. The result is a combination of steps in which methylolamide treatment is carried out after or before THP treatment. mechanical shrinkage, is that the dimensional differences between the finished fabric and the once washed fabric, for example in the warp direction, may be small, for example less than 2.5 or 2%, or very small, for example less than 1 %, and the shrinkage progression in subsequent washes, e.g. 50 washes, may be small, e.g. less than 5%, or particularly small, e.g. less than 2 or 1%. If the amount of mechanically shrinkage applied to the fabric is more than sufficient to compensate for the shrinkage of the fabric in one wash, the cured fabric containing THP and methylolamide may stretch up to 5% in one wash after mechanical shrinkage, and its degree of elongation may remain approximately 10 in the next 50 washes, so that the degree of progressive shrinkage is very small. If desired, mechanical shrinkage can be performed by post-treatment of methylolamide after and before, instead of or after the reaction of methylolamide, or in a process using pre-treatment of methylolamide, before curing of THP and after or instead of the reaction of methylolamide or instead of the last reaction. after. Mechanical shrinkage is generally performed after the last curing step, be it methylolamide or THP, and can be performed between curing steps. If mechanical shrinkage is not carried out, it is preferable to apply the methylolamide after THP, since the fabric thus obtained has a lower tendency to shrink than in the reverse order. fabrics.

The fabric is usually composed mainly of cellulose fibers and is preferably 100% cellulose, such as natural cotton, which is preferred, but also ramie, linen or regenerated fibers, for example viscose or cuprammonium viscose fibers. The fabric may be mercerized with an aqueous solution of the base or liquid ammonia, optionally amines, after or preferably before the addition of the THP compound. The cellulosic fibers are particularly woven, but may also be knitted. They may also be mixed with an amount, for example a smaller amount, for example up to 50%, such as 1-5%, of fibers which are miscible with cellulose, such as polyester oils, to give, for example, blends of 60-80% cotton. and 20-40% polyester. However, this method is particularly useful for fibers made entirely of cellulose, especially cotton fibers. The basis weight of the fabric before the 2 THP treatments may be 0.05-1.00 kg / m, such as 0.1-2 1.0 kg / m; examples of such fabrics are cotton sheets, sheets, shirts or curtains.

The fabric may be dyed prior to THP or methylolamide treatment, for example with vat or azo dyes, although basic, reactive, direct adhesive, acidic or disperse dyes may also be used. If the fabric is to be dyed after THP treatment, reactive dyes are preferred. If the fabric is to be dyed prior to methylol-15 amide treatment, dyes such as vat and azo dyes are preferred. Thus, in the case of vat or azo dyes, it is preferable to dye the fabric, treat it with a THP compound, cure, then treat with methylolamide and react with it. Alternatively, in the case of some vat or at shades, it may be better to first treat and react the fabric with methylolamide, then dye, then treat the fabric with THP and then cure.

‘25 Treated fabrics that are slow-burning and easy to care for can be worn in uniforms, such as those of guards and firefighters. Lighter fabrics can be used to make sweaters where smoothness and ease of care are particularly important, and heavier fabrics, such as cotton lace fabrics, can be used to make workwear, such as overalls and trousers, where non-shrinkage is particularly important.

The invention is illustrated in the following examples in which the following test methods were used. Fabric il- ·. was masted in all cases at 20 ° C and 65% relative humidity 24 hours before testing.

14 94154 1. Recovery of wrinkles

Wrinkle recovery angles were measured both dry and wet compared to untreated fabric using a MONSANTO WRINKLE RECOVERY TESTER using a load of 500 g and loading and recovery times of 3 min; the experiment was made in the direction of the warp and the right side of the fabric outwards.

2. Preservation of smoothness (D.P., durable press rating)

In Examples 1-15, the fabric was tested by AATCC Test Method No. 88 (Wash and wear standards), and DP ratings were based on the fabric smoothness effect compared to Standards 1-5 (1 is the weakest grade), while Examples 16-26 used the AATCC test method. 124.

3. Shrinkage 15 Shrinkage in the warp and weft direction was determined by the procedure of BR 4923 (1973) after washing the fabric 40 times (Examples 1-15) or 50 times (Examples 16-27) (as described in DIN 53920 with soft water). at 93 ° C.

20 4. Strength

The tensile strength was measured according to BS 2756, and the tear strength in the weft direction was also determined (by the Elmendorf method).

5. Non-combustibility The non-combustibility properties of the fabric were determined after washing the finished fabric 12 after 93 ° C and after 40 washes (93 ° C) (Examples 1-15) or 50 washes (Examples 16-26) (washing was performed according to DIN 53920). soft water). The test method used was in accordance with BS 3119.

6. Chemical analysis of the fabric

P (%), N (%) and formaldehyde (ppm) were determined from the finished fabric. P (%) and N (%) were also determined after 12 and 40 washes (Examples 1-15) or 50 washes (Examples 16-19) at 93 ° C.

\ Calculated atomic ratio N: P.

, p. 94154 7. Abrasion resistance

The Accelerotor test was performed by the method ATCC-99-1984 A, and the fabric was rubbed with a 250 mesh emery cloth spun for 3 min at 3000 rpm and the mass loss was determined.

Fabrics containing cured THP Fabric A

The cured THP-containing fabric used in Examples 1-13, 15 and 27 was prepared by impregnating a wood wool fabric 3111 having a basis weight of 0.285 2 g / m 2, pre-dyed with a far visible orange azo dye and not sanforating, with an aqueous solution having a pH of 4. , 5 and containing THP chloride and urea precondensate (molar ratio 1: 0.5) in an amount such that the THP ion content of the 15 solutions was 25%, with a wet reception of about 80%, by drying the impregnated fabric at 120 ° C. 1 min and then curing with gaseous ammonia in a forced blow gas ammonizer as described in U.S. Patent No. 4,145,463. The cured fabric was oxidized with hydrogen peroxide, neutralized with sodium carbonate solution, rinsed and dried.

Fabrics B, C, D and E

The procedure described for fabric A was applied to four other cotton fabrics with the following modifications: the rinse water contained fabric softener ("Alkamine" FPS) 2% by weight of the fabric containing cured THP, and each cured THP fabric was then mechanically shrunk by the "Sanforize" method. The fabrics were serized workwear satin with a basis weight of 2,270 kg / m and pre-dyed blue (fabric B), a ribbon dyed with red azo dye 3111, a weight per square meter of 0.346 kg / m (fabric C), red azo dye left satin rib 3113, 0.28 kg / m (fabric D) and optically brightened twill fabric 3117, 0.192 kg / m (fabric E).

94154 16

Example 1

Pieces of hardened THP-containing fabric A were primed to a wet acceptance value with an 80% impregnation solution containing 250 ml / l of di-1,3-N, N-methylol-5 4,5-dihydroxyethylene urea in DMDHEU (sold under the trade name FIXAPRET CPN) 45% aqueous solution and 50 ml / l of 98% sulfuric acid, the pH of the solution being below 1 and the bath being 1.88 N acid. The wet primed fabric, which had a total moisture content of about 68% (based on the cured THP-10 fabric), was carefully folded and placed in a polyethylene bag, which was then sealed and kept free of external stress for 22 hours at room temperature to effect curing. The fabric was then removed from the bag, washed successively with cold water, aqueous solution containing 10 g / l sodium carbonate, at 50 ° C with aqueous solution containing 2 g / l sodium carbonate and 2 g / l surfactant detergent, hot water (60 ° C) and cold water. The fabric was then dried and tested using 20 cured THP-containing fabrics (Reference Sample A). The results are as follows: »• · 941 54 17 c φ

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Example 2

The procedure was as in Example 1 with the following modifications: The impregnation solution further contained 0.5 g / l wetting agent, a mixture of nonionic and anionic wetting agent sold by Brookstone Chemicals Staffordshire, England, under the trade name WA100, and after curing the fabric was washed with cold water. neutralized with sodium carbonate solution, rinsed with cold water and dried at 100 ° C. Squares cut from the resulting fabric and the original fabric containing cured THP were washed in a washing machine at 60 ° C.

10 min, then rinsed three times with cold water and -1 centrifuged for 4 min at 1000 min. The fabric squares were then dried with a string of clothespins attached at room temperature or in a tumble dryer for 15 min at a final maximum temperature of 70 ° C.

Fabric squares were tested for smoothness compared to fabric containing cured THP (Comparative Sample B). The results were as follows: 20 _ DP grade_

Fabric_Nrope dried_Drum dried_

Example 2 4-5 3-5

Reference sample B 2 2 • 25 -

Example 3

In Example 3, the procedure was as in Example 1 with the following modifications: The impregnation solution with a pH below 1 contained 70 ml / l of concentrated (35%) hydrochloric acid 30 (instead of sulfuric acid), the solution being 0.82 N relative to the acid, as well as 0 , 5 ml / l of the wetting agent of Example 2, and the fabric was cured for 16 hours. The moisture content of the fabric at the beginning of curing was about 72% (by weight of the THP-containing fabric).

.9 94154

The properties of the fabrics were tested, and the results were compared with those obtained from a fabric containing cured THP (Reference Sample C). The results were as follows: 5 Wrinkle recovery angles (degrees)

Example wet-Lavana_ __Warp _Weave__Warp_Weave

Comparative sample C 95 85 91 89 10 Example 3_ 139_131 92_88

Shrinkage

Esimerkki__Loimi_Kude

Comparative sample C 8 2.5 1 5 Example 3__4_0.5_

Non-combustibility (according to BS 3119)

The average of the carbonized part. length (mm)

Example ~ Γ 12 washes after 40 washes 20 _ Finished after__

Reference sample C 70 69 53

Example 3__70__70__54_

Analysis Results 25 ______ "Example Finished Η, Ρ®5 ™ J after bellows _P (%) IN (%) IHCHO (ppm) P (%) | N (%) P (%) | N (%)

Comparative sample C 3.70 3.22 300 2.87 2.80 2.74 2.72

Example 3 12.91 3.50 320 2.75 3.1 5 | 2.70 | 3.13 30

Examples 4-12

The procedure was as in Example 1 using different amounts and proportions of curing agent and added concentrated sulfuric acid. In each case, the wet uptake from 35 resin impregnation baths was adjusted to approximately 80%, and the moisture content of the fabrics at the beginning of curing was about 20 94154 63-72% (based on the weight of the fabric containing cured ΤΗΡ). The results are presented below:

Score

Abrasion- 5 Wrinkle resistance- Wrinkle retrieval- Sulfuric feedback-expulsion- Oxygen- Solid-angle angle of the test substance- Direction of the substance when wet Tear-off - sa (%) warp in the pulp sheet elongation 40 in the direction of washing cheese loss 10 Eg, (ml / l) (ml / l) (%) after (degrees) (kg) (%) _ 4 200 25 2, 09 5.0__135__1.18 5 50 2.62 5.0 142 1.12 __6___75 3.22 4.0__148__1, 12__ 7 250 25 2.62 5.0 135 1.25 15 8 50 3.43 3.5 155 1.15 9.8 _9___75 3.42 3.0__152__1.15__ 10,300 25 2.77 4.5 137 1.25 11 50 3.35 4.0 146 1.15 12 __75 3.86 4.0__1_50__1.15__ 20 Unprocessed, ie co- 10 95 1, 54 9,2 drawn ΊΉΡ- fabric_______

All fabrics meet the flammability requirements of BS 3120.

s «25 Example 13

The procedure of Examples 7-9 was repeated, but the added sulfuric acid was replaced with 100 ml of concentrated hydrochloric acid (about 35% by weight), whereby the pH of the solution was below 1 and was 1.17 N with respect to the acid. The moisture content of the fabric at the beginning of the 30 curing was about 71% (by weight of the fabric containing cured THP). The treated fabric was tested for abrasion resistance by the Accelerotor test, and the mass loss was found to be 10.6%. The results of the other tests were as follows: shrinkage in the warp direction 3.5%, wrinkle return-35 angle wet 150 °, tear strength (Elmendorf, weft) 1.10 kg, average length of the carbonized part in the non-combustion test after 40 washes 68 mm.

UH I «iti I I i -k i 94154 21

Example 14

To the methods according to Examples 7-9 with the following modifications: fabric B containing cured THP, 140 ml / l concentrated sulfuric acid (5.25 N relative to acid 5) in a saturation bath, curing time 3 hours. The moisture content of the fabric at the beginning of curing was about 57% (from the weight of the fabric containing cured THP). The results obtained with the treated fabric compared to the results obtained with the untreated THP fabric were as follows: 10 __

Length of carbonized recovery part of wrinkles (nm) angle when wet Tear-offs Warp direction test in test 40 washes

Example_in (°) _Elmendorf (kg) after_15 Example 14 150 2,112 56

Vertailunäyte__90__2,976__52_

Example 15

The procedure of Example 14 was repeated using fabricated THP-containing fabric A. The results obtained for the treated fabric compared to those obtained for THP fabric A were as follows:

Wrinkles with charred rubbing. length of the return part its center angle when wet Tear (nm) non-combustible Gun directionality in the dust test sa elerotor

Example 'nassa (°) Elmendorf (kg) after 40 washes (%)

Example 15 140 1,056 70 11, 0

Reference Sample__95__1,540__55__9.2 Examples 16-19 20 m of fabric A, 30 m of fabric C, 50 m of fabric D and 30 m of fabric E were sewn together and passed continuously twice through a primer solution containing 350 g / l of DMDHEU used in Example 1. aqueous solution, 35 90 g / l of 98% sulfuric acid (pH in solution less than 1 and solution with respect to 1.84 N acid) and 2 g / l of 94154 22 wetting agent used in Example 2. Excess priming solution was squeezed out of the expanded fabric, which was then passed to a roll at a moisture content of about 52-60% (by weight of the fabric containing cured THP) and subjected to the minimum anti-hanging tension, wrapped in plastic wrap and slowly rotated at room temperature (18 ° C). ) 22 hours to cure DMDHEU. The wet acceptance of the fabrics was A 72%, C 59%, D 72% and E 70%. Each cured fabric was then washed with water, neutralized and washed again with water in a dyeing machine, followed by a softening step in which each fabric was passed three times through a plasticizer bath at 40 ° C containing a nonionic fatty acid ester derivative sold by Crosfield Textile. Chemicals 15 as CROSOFT XME. The wet fabric was then sucked dry and then dried at 150 ° C in a plane dryer to obtain a treated fabric.

The four fabrics obtained were then tested to obtain the results shown in the following table, which compares the properties of fabrics A, C, D and E with the properties of treated fabrics A, C, D and E, i.e. the properties before and after the DMDHEU treatment.

1. Shrinkage

Shrinkage in the warp and weft direction was determined as described above, but after 50 washes.

----) - ------ - -

Example Fabric_Warp (%) __ Item (%) _ A 13.2 6.0 16__Treated A__5 ^ 5__4 / 0_ 30 C 9.9 5.1 1 7__Treated C__4 ^ 0__4 ^ 3_ D 8.0 6.3 18__Treated D__2.7__4, 6 _ E 5.7 7.1 35 19__Treated E__3.6__4.2_ 94154 23 2. Tear strength in the direction of weft according to Elmendorf

Example__Fabric__Strength (kg) 5 A 1.94 1 6__Treated A__1, 87__ C 4.64 1 7__Treated C__3.46__ D 2.68 1 0 18__Treated D__1.91__ E 1, 63 1 9_Treated E__1.30_ 3. Tensile strength according to BS 2756, treated fabrics and treated fabric C 50 after washing (93 ° C, 15 according to DIN 53920 with soft water)

Strength (N) _

Example__Fabric__Warp__Weave A 1252 690 20 1 6__Treated A__1030__619 C 1237 794 1 7__Treated C__1179__609

Washed in C 1251 800

Washed, 25__treated C__1183__683_ E 760 529 1 9__Treated E__617__406_ «94154 24 4. Non-combustibility determined as described above after 50 washes

Carbonized Part 5 Example__Fabric_Aver. length (mm) A 52 1 6__Treated A__56_ C 57 1 7__Treated C__56_ 10 D 58 18 __Treated D__68_ E 77 19 _ Treated E__79_ 5. Wrinkle recovery angle 15 Example__Fabric_Wet (°) __ Dry (°) _ A 100 90 16 __Treated 17 __Processed C 145__1_35_ 20 D 95 95 18 __Processed D__1 45__11 0_ E 95 110 19 _ Processed E | 145_ 1 30_ * 25 6. DP rating of fabrics as defined above after one wash (95 ° C) and drying according to Example 2 DP rating_

Example__Fabric_ String dried Tumble dried A 2 2-3 30 16__Treated A__3-3.5_3-3.5_ C 2 2 1 7__Treated C__3-3.5_3-3.5_ D 2 2-3 18_ Processed p__3-3.5_3.5-4 , 0_ 35 E 1-2 2. 1 9 ___ Treated E__3_3-3,5_ 941 54 25 7. Analysis results of treated fabric before washing and after 50 washes (93 ° C, according to DIN 53920 with soft water) 5 Before washing After washing

Example__Fabric__P (%) N (%) P (%) N (%) A 3.2 3.1 2.6 2.5 16__Treated A 3.0 3.5 2.7 3.1 C 2.9 2.9 2.3 2.2 10 1 7__Processed C__2.7 3.3__2.6__3.0_ D 2.3 2.1 2.0 1.8 1 8__Processed D__2.2 2.6__2.0__2.3_ E 2.6 2, 3 2.4 2.0 19__Treated E | 2.4 12.7 2.3 | 2.5 ^ 8. Color light fastness

Light fastness was measured using xenon arc light according to BS 1006, 1978, B 02. There was no difference in the results obtained for fabrics A, C, D and E compared to the results obtained for treated fabrics A, C, D and E20, respectively.

9. Feel

There was no noticeable difference in the identity of fabrics A, C, D and E compared to treated fabrics A, C, D and • E, respectively.

«25 10. Moisture content

The moisture contents of fabrics A and C-E and the corresponding treated fabrics A and C-E were determined to be air-conditioned for 24 hours at 65% relative humidity by drying the air-conditioned weighed fabrics for 2 hours at temperature. 30 to 105 ° C and then weighing again. The moisture content of the original fabrics was about 0.5% lower than that of the treated fabrics. Thus, DHDMEU treatment increased the moisture absorption capacity at 65% relative humidity.

94154 26 11. Residual water

For fabrics A and C-E and treated fabrics A

and C-E was subjected to HLCCl washing on a Servis Quartz machine, and water remaining in the fabrics was determined after wet fabrics were centrifuged for 4 min at 100 rpm. There was less water left in the treated fabrics than in the original ones, i.e. the DHDMEU treatment reduced the amount of residual water.

Examples 10-26 Fabric 10 Two 100 m pieces of machine woven cotton web 3111 with a basis weight of 0.295 2 kg / m were subjected to enzymatic removal of finishing agent, the fabrics were washed thoroughly with base and bleached with basic hydrogen peroxide solution. Bleached 2 15 fabrics with a basis weight of 0.27 kg / m were cut into 50 m pieces, which were subjected to treatments V, X, Y and Z, respectively (extensive details of the treatments are given below: treatment with DHDMEU and curing, treatment with THP). compound and curing and mechanical pu-20 cross-shrinkage are performed in various combinations).

Processing V__X__Y__Z_ 1. step DHDMEU curing THP curing ΊΗΡ curing THP curing Step 2 - - Mechanical shrinkage t ·. 2 5 Step 3 ΊΗΡ-curing - DHDMEU curing DHDMEU curing Step 4 Mechanical shrinking Mechanical shrinking Mechanical shrinking Mechanical shrinkage THP curing step in treatments V, X, Y and Z The fabric was treated as described in connection with fabric A. 30 municipalities. Wet intakes were approximately 80% in treatment V. (by weight of fabric containing DHDMEU) and 100% by X, Y and Z (by weight of bleached fabric). DHDMEU curing step in treatments V, X and Z The fabric was treated as described in Examples 16-19, but using a priming solution containing 325 g / l aqueous DHDMEU, 90 g / l 98% sulfuric acid, 27,941 54 2 g / l of the wetting agent used in Example 2 and 18 g / l of a fluorescent, acid-resistant brightener sold by Sandoz under the name Leucophor BCR liquid. Wet yields were 100% in treatment V (bleached fabric pulp) and 5 75% in treatments Y and Z (bleached THP-containing fabric), and the moisture contents of the fabrics at the beginning of curing were about 60% in Examples 20-34 (THP and fabric weight) and 79% in Examples 25 and 26 (weight of the original fabric).

10 Mechanical compression shrinkage

The fabric was mechanically shrunk in a "Sanforizer" machine as described in International Textile Bulletin Dyeing / Printing / Finishing 2/86 on pages 14, 16, 20, 22 and 27 by initial steaming, width adjustment, compression against a stretched rubber cover, which was then allowed to release. from the tension causing the fabric to shrink, followed by drying by squeezing the fabric between the heated metal cylinder and the absorbent cover and rolling. The shrinkage rate set for the machine was 5% for 20 V, X, Y and Z treatments.

Optical brightness

Optical brightener was added to the fabric as part of DHDMEU impregnation in treatments V, Y and Z, and in treatment X, brightener was added to the rinsing solution after THP curing.

Score

The properties of the treated fabrics obtained in the fourth step of treatments V, Y and Z and some properties of the fabrics obtained in the last step of treatment X and the previous steps of treatments X, Y and Z were tested.

In the following results tables, Examples 20-26 and Comparative Samples D-G refer to fabrics obtained in the following treatments: 35 28 9 4 1 54

Fabric_ Manual

Example__ Phase Summary of treatments

21 3 Y THP, DHDMEU

22 3 Z THP, mechanical shrinkage, DHDMEU

5 23 4 Y THP, DHDMEU, mechanical shrinkage 24 4 Z THP, mechanical shrinkage, DHDMEU, mechanical shrinkage

25 3 V DHDMEU, THP

26 __4__V__DHDMEU, THP, mechanical shrinkage 10 Reference sample D 4 X THP, mechanical shrinkage

Reference sample E 1 X THP

Reference sample F - - Original bleached fabric

Reference sample G 1 V__Donder DHDMEU_ 15 1. Shrinkage

Shrinkage in the warp and weft direction was determined as described in Examples 16-19 after 1 and 50 washes. 20 Shrinkage (%) after washing (s )_ _1_50_

Example__Warp__Weave__Warp__Weave_, Reference sample G 1.2 2.2 2.3 2.5 25 Reference sample F - - 12.8 5.6

Comparative sample E 3.9 3.5 12.4 8.8

Comparative sample D 1.0 2.8 7.3 5.9 21 1.4 2.1 4.4 3.5 22 1.8 2.2 4.7 3.3. i '30 23 +2.9 1, 6 +2.3 2.1 24 - - +2.3 1.8 25 2.0 2.4 6.3 4.0 26 _ +3 2.1 2.1 +2.4 2.5_ NB A positive sign, for example +2.3%, indicates elongation in the wash instead of shrinkage.

94154 2. Tear strength in the warp direction according to Elmendorf

Strength (kg) _ 5 Example__Warp__Weft_

Reference sample D 3.00 3.00 23 2.20 2.20 24 2.50 2.40 26__2.40 2.20_ 10 3. Tensile strength according to BS 2756

Strength (N) _

Esimerkki__Loimi__Kude_

Reference sample D 1262 751 15 23 1010 572 24 1012 575 26_ 1014_ 580_ 4. Non-combustibility measured according to the method described above after 50 washes

Esimerkki_Keksim. length (mm)

Comparative Example D 60 23 62: 25 24 67 26_53_ 5. Wrinkle Return Angle

Example__Wet (°) Dry (°) _. Reference sample G 130

Reference sample F 65 90

Reference sample D 95 70 23 140 100 24 140 100 35 26_135 100_

Q A 1 C A

7-t i w »T

30 6. DP grade given as described above after one wash (95 °) and drying according to Example 2 5 DP grade_

Example Tumble Drum- __dried dried

Reference sample G 3-3.5 3-3.5

Reference sample F 1-2 1-2 10 Reference sample D 2 2 23 3-3.5 3-3.5 24 3-3.5 3-3.5 26__3_ 3_ 7. Moisture content 15 The moisture content of the fabrics was determined in the examples in sections 16-19. 10 as described. The moisture content of the fabrics of Examples 23, 24 and 26 was 0.5-1% higher than the moisture content of Reference Sample D in the oven drying experiments. The DHDMEU treatment thus increased the moisture absorption at 20% relative humidity.

8. Residual water

The moisture remaining in the fabrics during centrifugation was measured as described in Examples 16-19, Section 11; the fabrics tested were Reference D and the fabrics of Examples 25 23, 24 and 26. The fabrics of Examples 23, 24 and 26 retained 22% less moisture than Control D. DHDMEU treatment reduced the amount of residual water.

Example 27; Cured fabric A was primed with an impregnation solution ♦ containing 250 ml / l of the 45% DMDHEU solution used in Example 1 and 1C g / l of 98% sulfuric acid, the pH of the solution being about 1.7 and With respect to 0.2 N acid. The primed fabric was pressed to a wet-35 uptake value of 75% and then kept in an oven at 90 ° C for 3 min to obtain a fabric with a moisture content of

Il UU l 111; 1 i I UI I

31 94154 concentration was 10%. The fabric was immediately sealed in a plastic bag to maintain its moisture content and allowed to stand for 22 hours at room temperature and unstressed. The fabric was then removed from the bag and washed according to Example 1. Finally, it was dried and then washed 50 times at 93 ° C. Warp shrinkage was measured after washes and was found to be 5%; the corresponding value was 10% in a similarly washed fabric containing cured THP 10 before DMDHEU treatment.

Claims (13)

A process for treating a cellulosic fabric to make it non-flammable and non-wrinkle by impregnation under known conditions with a tetrakis (hydroxymethyl) phosphonium compound and a non-condensable methylolamide, characterized in that the impregnation is carried out in two steps in an arbitrary order, with a solution of its condensate, followed by curing to a polymer, and in step 2 impregnated with a methylamide containing at least two methylol groups, such as methylated cyclic urea or an O-alkylated derivative thereof, especially 1,3-N, N-dimethylol-4,5-dihydroxyethylene urea , solution, after which the fabric is treated under aqueous acidic conditions at a pH below 3, preferably below 1, to react the methylolamide with the fabric. A method according to claim 1, characterized in that the first treatment is a treatment with said phosphonium compound or a condensate thereof, followed by curing with ammonia. Process according to Claim 1, characterized in that the second treatment is a treatment with said phosphonium compound or condensate, followed by curing with ammonia. Process according to one of Claims 1 to 3, characterized in that the methylolamide reacts with a fabric having a moisture content of 6 to 90%. Process according to Claim 2, characterized in that the methylolamide in aqueous solution reacts with a fabric having a moisture content of 6 to 30%. Process according to one of Claims 1 to 4, characterized in that the methylolamide in an aqueous solution having a pH of less than 1 reacts with a fabric having a moisture content of 30 to 90%. 0/11 E Λ / * t I J * t Process according to Claim 6, characterized in that the methylolamide reacts with the fabric in an aqueous medium of 1 to 6 N acid. Process according to one of Claims 1 to 7, characterized in that the fabric is treated with an aqueous solution of a tetrakis (hydroxymethyl) phosphonium compound and a urea condensate and then cured with gaseous ammonia. Method according to one of Claims 1 to 8, characterized in that the fabric is made of cotton fibers or a mixture thereof with polyester fibers which account for at most 50% by weight (of the fabric). Process according to one of Claims 1 to 9, characterized in that the uptake of methylolamide, calculated on the dry weight of the fabric, is 6 to 20% and the corresponding value of the polymer made from the tetrakis (hydroxymethyl) phosphonium compound or condensate is 8 to 20%. Process according to one of Claims 1 to 10, characterized in that the methylolamide is reacted with the fabric when it is tensioned in at least the warp or weft direction. Method according to one of Claims 1 to 11, characterized in that the fabric is subjected to a mechanical compression shrinkage after the second treatment. Process according to one of Claims 9 to 12, characterized in that the cotton fibers are treated with an aqueous solution of a tetrakis (hydroxymethyl) phosphonium compound and a urea condensate and cured with gaseous ammonia, and then the fabric is impregnated with 1,3, N, N-dimethylol With an aqueous solution of 4,5-dihydroxyethylene urea and reacted therewith under aqueous conditions at a pH of less than 1 and an aqueous solution of 1-4 N acid at a moisture content of 30-90% of the fabric, after which the resulting fabric is mechanically shrunk. 94154