JPS6119760B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to fiber treatment compositions for improving the wet fastness of substantive dyes on cellulose-containing substrates. Dyeings and prints with direct dyes often exhibit insufficient washing fastness. Dyes bound to the surface of cellulosic fibers can be shed in large quantities from the fibers by repeated washing, and leaching of dyes into the wash liquor can cause partial re-adsorption onto undyed cellulosic materials. In order to eliminate these drawbacks, it is possible, for example, to complex the fibers with metal salts, diazotize the dyes on the fibers, treat the dyes and/or the fibers with formaldehyde, impregnate them with artificial resins and after-treatment with cationic auxiliaries. Many attempts have been made, such as by processing. The use of cationic post-processing aids has been found to be particularly effective. A drawback of all previously used methods is that, although an improvement in robustness is indeed achieved, the results are only temporary. Even in the case of cationic post-treatments, the auxiliaries are removed from the fibers by repeated washing, especially under alkaline conditions and at high temperatures of 50-100°C. Shedding of the cationic auxiliary means that the dyeing once again loses its improved wet fastness properties. As used herein, the term "substantive dye" also includes cellulose-reactive dyes in which the dye component (ie, the dye molecule excluding the reactive groups) exhibits substantivity towards cellulose. The disadvantage of using reactive dyes is that
Dyes that are chemically bound to the fibers have excellent wash fastness, but the treated product must be thoroughly washed after dyeing to remove residual unfixed dye, which has low wash fastness. . The present invention provides a fiber treatment composition for improving the wet fastness properties of substantive dyes on cellulosic fiber-containing substrates, the composition comprising a type B N-methylol compound crosslinker. A) and B) below with a catalyst for: A. Reaction of a monofunctional or polyfunctional primary or secondary amine with cyanamide, dicyanodiamide, guanidine or biguanidine or ammonia with cyanamide or dicyanodiamide. product of the reaction of B containing a reactive hydrogen atom bonded to nitrogen;
methylol derivatives, including water-soluble products obtained by reacting them in aqueous solution. By applying this composition according to the invention to a dyed or printed substrate and then carrying out a heat curing step, the wet fastness properties of direct dyes on cellulose fiber-containing substrates are improved. be. Intermediate product A) is a monofunctional raw amine of the following formula a or a polyfunctional amine of the following formula b: RRNH a RRN(-Z-X)- _o Z-NRR b [In the above formula, each R is independently hydrogen. or represents C _1-10 alkyl which is unsubstituted or monosubstituted with hydroxy, C _1-4 alkoxy or cyano, n represents a number from 0 to 100, and Z each independently represents C _1-4 alkylene or represents hydroxyalkylene, and each X independently represents -O
-, -S- or -NR- (where R is the same as defined above). However, the amine of formula b has at least one reactive -NH- or -
NH ₂ group] with cyanamide, dicyanodiamide (DCDA) or guanidine. More preferably, intermediate A) is a reaction product of a polyfunctional amine of formula b with cyanamide, DCDA or guanidine. Preferably, in the amine of formula b, R is hydrogen or _C1-4 alkyl or hydroxyalkyl, and more preferably each R is hydrogen. Preferably, n is a number from 0 to 30, and may be a non-integer representing an average value. More preferably, n is an integer of 1-6. Z is preferably 1,2-ethylene, 1,3-
It is a propylene or 1,3-(2-hydroxypropylene) group, and X is preferably -NR-, most preferably -NH-. Particularly preferred amines are diethylenetriamine,
triethylenetetramine and higher polyethylene polyamines, polypropylene polyamines or poly(hydroxypropylene) polyamines containing up to 8, preferably up to 6 N atoms. In the reaction with cyanamide, DCDA, guanidine or biguanidine, the amine can be in free base form or in salt form, eg carbonate form, and amine mixtures can also be used. When ammonia is a reactant, it is preferably used in salt form.
Preferred reactants are guanidine and DCDA, especially
DCDA, and a particularly preferred intermediate A) is the reaction product of DCDA with diethylenetriamine or triethylenetetramine. Intermediate products A) are known and their preparation is described, for example, in British Patent No. 657753 and in US Pat.
Described in No. 2649354. The reactants are suitably reacted at elevated temperatures without the intervention of water, optionally in the presence of a non-aqueous solvent.
The reaction is preferably carried out without the intervention of a solvent at a temperature of 140 DEG to 160 DEG C., and when the reactant is an amine, ammonia is liberated. The reactants are cyanamide per mole of reactive -NH- or _-NH2 groups,
Preferably, DCDA, guanidine or biguanidine are reacted in a molar ratio of 0.1 to 1 mol; when DCDA is reacted with a polyalkylene polyamine, the molar ratio of the reactants is 2:1 to 1:2, especially about 1:
1 is more preferable. Product A is essentially a water-soluble, almost colorless, viscous liquid or solid containing a reactive hydrogen atom bonded to nitrogen, either in free base or salt form. be. Intermediate B) is an N-methylol compound commonly known as a crosslinking agent for cellulosic fibers and such as is used to impart an anti-wrinkle finish to cellulosic fabrics. These compounds contain free N
-Methylol group 〓N-CH ₂ OH may be included, or these may be etherified. Preferred ether derivatives have 1 in the alkyl group.
A lower alkyl ether having ~4 carbon atoms. Examples of suitable N-methylol compounds are listed below. Urea derivative HOCH ₂ -NH・CO・NH・CH ₂ OH N,N'-dimethylurea melamine derivative Guanamine derivative Triazinone derivative uron derivative carbamate derivatives Amide derivative Preferred compounds are hydrolysis-resistant reactive resin precursors, such as N,N'-dimethylol-4, optionally in etherified form.
5-dihydroxy- or -4,5-dimethoxy-ethylene urea and N,N'-dimethylol carbamate. Preferred ether forms are methyl and ethyl ether derivatives. Mixtures of compounds B may also be used. The reaction between intermediates A) and B) can be carried out in an aqueous medium, for example by adding A) as such or in an aqueous concentrate to an aqueous solution (preferably such a resin precursor B) heated to 60-70°C. The aqueous solution is 50
% B and 50% water). Preferably, before the reaction with B), A) is treated with an inorganic or organic acid, preferably hydrochloric acid or sulfuric acid,
7 to 8 by adding to the aqueous solution of A).
Neutralized by PH. After neutralization with acid, it is desirable to thicken the solution of neutralized A) before addition to B). A) and B), preferably under constant stirring,
The reaction is always carried out at room temperature or at temperatures up to 80°C, preferably from 60 to 75°C. The condensation reaction should be stopped before the reaction product becomes insoluble in water or forms a gel, and a suitable reaction time is 30
The duration is on the order of minutes to 3 hours. The final product preferably has a viscosity at room temperature of 50 to 200 centipoise, more preferably 60 to 150 centipoise. These viscosities apply to the reaction products as they are obtained, ie containing water in an amount of 30-50% (by weight). Catalyst C) may be present during the reaction of A) and B), although it does not contribute to the reaction in any way.
Alternatively, it may be added after A) and B) have been reacted together. If present during the reaction, it is suitably dissolved in water and mixed with component B before addition of A). The relative amounts of ingredients A), B) and C) (if present) are calculated based on the active ingredient present, and A)
5-40 parts by weight, B) 25-110 parts by weight, C) 1-30
Within the range of parts by weight. Expressed in weight ratio,
The ratio of A):B):C) is 1:0.625~22:0.025~
It is 6. The preferred range is A) 10 to 20 parts by weight;
B) 35-75 parts by weight and C) 5-15 parts by weight or 1:
1.75-7.5: 0.25-1.5. The reaction products of A) and B), which may contain catalyst C), are stable for several days at room temperature. At moderately elevated temperatures or after long-term storage (weeks or months), gel formation may occur, which is accompanied by a decrease in activity and difficulties in weighing the product and applying it to textile substrates. give. It has been found that this problem can be overcome by the addition of 1 to 10% (% by weight based on the sum of (A) + B)) of DCDA, cyanamide, guanidine or biguanidine, preferably DCDA. This reagent may be added before, during or after the reaction of A) and B), and is preferably added at any time with the catalyst C) before or during the reaction, so that it does not gel even on long-term storage. A reaction product is obtained which retains its activity completely even after several weeks or months without producing any. The reaction products of A) and B) are reacted with the -OH groups of cellulose by catalyst C), which is known for the crosslinking of compounds of type B) to cellulose. Suitable catalysts include aluminum, magnesium and zinc nitrates, sulfates, chlorides, tetrafluoroborates and dihydrodiene orthophosphates, as well as aluminum hydroxychloride, zirconyloxychloride and mixtures thereof. These catalysts may be used in the form of mixtures with water-soluble inorganic salts, especially alkali metal or alkaline earth metal sulfates, preferably chlorides. Particularly preferred are sodium or potassium sulfate and calcium chloride. They can also be used in mixtures with organic acids such as citric acid. Other suitable catalysts are a alkali metal bisulfites, b amine hydrochlorides such as 2-amino-
2-methylpropanol hydrochloride, c organic acids such as citric acid, oxalic acid, maleic acid, glycolic acid and trichloroacetic acid, d inorganic acids such as phosphoric acid and hydrochloric acid, alone or with salts such as ammonium chloride or calcium chloride. and e ammonium salts of inorganic acids, such as ammonium nitric acid, chloride, sulfuric acid and oxalate and mono- and di-ammonium orthophosphates; mixtures of these catalysts can also be used. Preferred catalysts are nitrates, sulphates, chlorides and dihydrodiene orthophosphates of aluminum, magnesium or zinc, more preferably magnesium, especially magnesium chloride, optionally with alkali metal sulphates, especially sodium sulphate. . However, the optimal catalyst system will mainly depend on component B) and the nature of the fiber substrate, and the person skilled in the art will know from the extensive literature which catalyst systems are preferred for a particular resin precursor and substrate. Will. According to the method of the invention, a substrate containing cellulose fibers and dyed or printed with substantive dyes is treated with the product according to the invention in the presence of a catalyst. The substrate may be dyed or printed by methods customary for direct or reactive dyes, for example dyeing by exhaust dyeing or padding from a dyebath and subsequent heat or cold fixation, or by reaction. In the case of color dyes, alkaline fixation can be used. The method according to the invention is carried out on a substrate that has undergone a dyeing or printing process including the necessary fixing steps. The substrate may be dry or may be moist as long as it is not so wet that it cannot be picked up. The reaction products of A) and B), together with catalyst C), are applied to the substrate in aqueous solution by dipping, spraying, foam application, padding or other conventional application techniques. The preferred method of application is padding at room temperature. The amount of product according to the invention applied to the substrate depends largely on the dye density to be fixed. For direct dye dyeing of 1/1 standard density on cotton, the usage amount is 1 per padding solution when applied with a pick-up of 70 to 100% of the dry weight of the material to be treated.
It is 30-200g. This amount is 70~ for cotton.
130g/ and 100g/ for regenerated cellulose.
Preferably it is ~200g/. For applications on mixtures of cellulosic and synthetic fibers, the application amount is calculated based on the cellulose content of the substrate. In the case of dyeing with reactive dyes, the amount of product used will depend on the amount of unfixed dye remaining on the workpiece. By treating such dyeings according to the method of the invention, the wet fastness of the remaining unfixed reactive dyes is improved to such an extent that lengthy washings to remove the unfixed dyes are no longer necessary. Padding fluids may further include stiffening agents, agents that improve friction or breaking strength, antifouling products, hydrophobic agents, insofar as they can yield stable aqueous solutions when mixed with the products of the invention. It may also contain auxiliary agents such as. After application of the padding fluid, the substrate is subjected to a heat curing process as is customary for resin treatments based on Type B compounds. The base material is, for example, 70~
Dry at 120℃ and finally at a temperature of 130-180℃ for 30
Crosslinked for seconds to 8 minutes or 120 to 200 minutes
Simultaneously drying and crosslinking are carried out by heat treatment at 140 DEG to 180 DEG C. for 5 seconds to 8 minutes, depending on this temperature. A preferred method involves heating the padded substrate to 170-180°C for 30 seconds to 1 minute. The method of the invention is preferably carried out on substrates dyed with direct dyes, in particular metal complex dyes, especially copper complex dyes. A method for determining dye suitability for the process of the invention consists in measuring the R _f value of a given dye. By way of example, particularly good results have been obtained with the reaction product of DCDA/diethylenetriamine and dimethylol dihydroxyethylene urea (as described in Example 1) and having an R _f value of not more than 0.35 at room temperature when determined as follows: Direct dyes such as The R _f value used in this case is Polygram
Using a SIL g/UV254 as a fluorescent indicator, a freshly prepared mixture of methyl ethyl ketone, diethylamine and concentrated aqueous ammonia (3:1 by weight:
It is measured by thin layer chromatography on a 0.25 mm silica gel plate developed according to 1). Dyes are tested in their usual commercially available form. Two exceptions to the above general rule are presented by copper complex dyes having 3 or 4 --SO ₃ H groups per molecule. Such complex salts containing two Cu atoms per molecule also give particularly good results with R _f values of 0.35 to 0.8. On the other hand, 1 per minute
Such complex salts containing 50 Cu atoms and having a molecular weight less than 900 do not give such good results even if the R _f value is 0.35 or less. Other test methods which are more generally applicable for determining which group of treatment agents according to the invention are most suitable for a given direct dye (or vice versa) include dyes and intermediates A). It's all about mixing. If the dyestuff and A) form such a precipitate that after washing they do not dissolve again in an alkali of pH 12, the dyeings obtained with the dyestuff can be treated by post-treatment with a treating agent derived from its intermediate product A). Particularly good results are obtained with this method. All of the above tests are quick and easy to perform and are useful for dyeing technicians to determine which dye and treatment combinations will give the best results. The following formulas are examples of dyes that are particularly suitable for carrying out the method of the invention. The inventive treatment of dyed cellulose fiber substrates provides improved wet fastness properties, in particular 40-80
C., especially washing under alkaline conditions at temperatures of 60.degree. C. and above. For example, 5g/soap and 2
It easily withstands repeated washing for 30 minutes at 60° C. in a bath ratio of 1:50 with a cleaning solution containing 1 g/g of soda.
The dyeing also has excellent light fastness. In the case of dyeings with reactive dyes, the washing fastness of the unfixed dye increases to approximately the same level as that of the fixed dye, which eliminates the need to remove the unfixed dye. At the same time, it gives a resin finish to the cellulose fibers,
This reduces swelling in aqueous or alkaline media, thereby providing faster drying and also improved dimensional stability and higher wrinkle resistance. The following examples further illustrate the invention, in which "parts" and "%" are given by weight and temperatures are given in degrees Celsius. Example 1 103 parts of diethylenetriamine and 84 parts of
DCDA was heated to 110°. As soon as this temperature was reached, an exothermic reaction occurred and ammonia was released. The temperature was slowly increased to 160° and held at this temperature for about 6 hours until no further ammonia was evolved. The amount of ammonia was approximately 34 parts. Pour the liquid reaction product flat onto a metal pan;
After cooling, it was ground into powder. 69.3 parts of this powder were slowly added to 81 parts of 35° water with constant stirring. Next, 44.6 of 53.4 parts
% sulfuric acid was added simultaneously with 45.0 parts of ice until the temperature was 48~
I tried not to make it higher than 50°. Next, further
69.3 parts of powder were added, neutralized with 78.8 parts of 44.6% sulfuric acid, and 45.0 parts of ice was added to maintain the temperature below 50°. This yellow solution with a pH of 7.5 was then spray dried to obtain a white powder. A 50% solution of 23 parts DCDA and 457 parts dimethyloldihydroxyethylene urea was heated to 70° with stirring, 68.5 parts of the spray-dried product were slowly added, and the solution was heated for 3 hours. A clear, stable yellow solution with a viscosity of 80 cp was obtained, which could be used as a fixing agent for direct dyes or for improving dyeings with reactive dyes on cellulose. Example 2 146 parts of triethylenetetramine and 84 parts of
The DCDA was slowly heated to 100-110° while stirring. Ammonia was evaporated and the temperature rose to 140°. After the evaporation of ammonia stopped, the products were allowed to react at this temperature for 14-16 hours. The resultant was allowed to cool and then ground to a powder, which was neutralized with sulfuric acid as described in Example 1 and dried. 100 parts of a 50% aqueous solution of dimethylol dihydroxyethylene urea was warmed to 70-80° and then 20 parts of magnesium chloride hexahydrate were added under continuous stirring. To the resulting 70° clear solution, 30 parts of the above reaction product were added in portions and stirred until completely dissolved. The reaction temperature mixture was stirred for an additional 2-3 hours;
A clear yellow liquid was obtained. It may be further diluted with water and can be used directly or after further dilution for fixing dyeings with direct dyes on cellulose or for improving dyeings with reactive dyes on cellulose. Example 3 Example 2 was repeated. However, when or after 5 parts of DCDA is mixed with magnesium chloride, 50
% dimethylol dihydroxyethylene urea solution and allowed to react for 2-3 hours at 70° before adding the reaction product of DCDA and triethylenetetramine. The resulting product had improved storage stability. Example 4 A mixture of 177.5 parts of 3-(2-aminoethyl)aminopropylamine and 84 parts of DCDA was reacted at 120° for 6 hours, resulting in the evaporation of approximately 33 parts of ammonia. The resulting condensation product is finally cooled and 227
diluted with water. 50 parts of the resulting suspension are neutralized with 11.5 parts of 96% sulfuric acid and finally 100 parts of 50% aqueous dimethylol dihydroxyethylene urea and ₁₅ parts of _MgCl2.6H2O
The mixture was treated at 65° for 2 hours. A clear solution was obtained, which could be used directly or after dilution. Example 5 A mixture of 120 parts of ethylene diamine and 84 parts of DCDA was condensed at 115° for 6 hours, resulting in evaporation of 34 parts of ammonia. The condensation product obtained was finally treated with 170 parts of water. 50 parts of the resulting suspension were neutralized with 14.8 parts of 90% sulfuric acid. After addition of 15 parts of MgCl ₂ .6H ₂ O and 100 parts of a 50% solution of dimethyloldihydroxyethyleneurea, the mixture was allowed to react for 1 hour at 70°. Cloudy,
A water-miscible liquid was obtained, which could be used as is. Example 6 120 parts of polyethylene amine having an average molecular weight of 1200 are added to 84 parts of polyethylene amine at 130° for 2 hours.
Reacted with DCDA. The ammonia evaporated and a viscous blue oil was obtained. 100 parts of a 50% aqueous solution of dimethyloldihydroxyethyleneurea were treated at room temperature with 15 parts of MgCl ₂ .6H ₂ O and finally with 25 parts of the above condensation product. The reaction is exothermic, with temperatures ranging from room temperature to approximately 40°C.
It rose to ゜. Once the exothermic reaction was complete, the temperature was maintained at 40° for 1 hour. A clear yellow liquid was obtained, which could be used as is or after further dilution. Example 7 189 parts of tetraethylenepentamine and 84 parts of
The mixture of DCDA was reacted at 160° for 5 hours. After this time no more ammonia evaporated and a bright yellow solid condensation product was obtained. This was cooled to room temperature and ground into powder. 25 parts of this condensation product were reacted for 1 hour at 60° C. with 100 parts of a 50% aqueous solution of trimethylolmelamine. A pourable, viscous, aqueous dispersion was obtained which, after addition of a suitable catalyst, could be used as such or after dilution. Example 8 25 parts of the DCDA/tetraethylenepentamine condensation product obtained according to Example 7 were dissolved in 200 parts of water and neutralized with 35% aqueous hydrochloric acid. The solution was heated at 50° and
Concentrate at 25 torr until 110 parts of neutralized concentrate remain. This was then reacted with an 80% aqueous solution of hexamethylolmelamine at 50° for 2 hours. A cloudy, aqueous liquid was obtained which, after addition of a suitable catalyst, could be used without dilution. Example 9 Diethylenetriamine obtained according to Example 1/
65 parts of a neutralized solution of the condensation product of DCDA were diluted with 55 parts of water and finally treated with 100 parts of a 50% aqueous solution of trimethylolmelamine at 30° for 2 hours. A cloudy, aqueous liquid was obtained, which could be used without dilution after addition of the appropriate catalyst. Example 10 66 parts of diethylenetriamine carbonate (obtained as a catalyst by introducing carbon dioxide into an alcoholic solution of diethylenetriamine) were melted and mixed with 33.6 parts of DCDA in a closed vessel equipped with a stirring gear. Mixture 140-160
℃ for 6 hours, which caused the whole to thicken continuously until it became difficult to stir. This was allowed to cool and the solidified foam-containing product was powdered. 30 parts of this solid product were added to 25 parts according to the conditions of Example 2.
of dimethyloluron, 100 parts of a 50% aqueous solution containing 25 parts of dimethylol dihydroxyethylene urea and 20 parts of MgCl ₂ .6H ₂ O. A reaction product similar to that of Example 2 was obtained. Example 11 A mixture of 51.5 parts diethylenetriamine and 45 parts guanidine carbonate was stirred and heated to 130°. Ammonia transpires and the temperature is 140-150
The temperature was increased to 50°C and held at this temperature for 5 hours. Upon cooling, the product solidified and was ground into powder. Thirty parts of this product was used in place of the triethylenetetramine/DCDA product of Example 2 and a reaction product similar to that of Example 2 was obtained. Example 12 103 parts of diethylenetriamine and 42 parts of cyanamide are heated at 110-140° for 6 hours,
The solid product was neutralized with sulfuric acid and dried. Thirty parts of this product was used in place of the triethylenetetramine/DCDA product of Example 2 to obtain a reaction product similar to that of Example 2. EXAMPLE 13 A cotton fabric dyed with a 1/1 standard dye strength of the dye of Formula 1 was padded with an aqueous solution containing 100 g/ml of the product of Example 1 and squeezed to give a pick-up of about 80%. Next, the fabric is placed in a tension frame at 175-180° so that the cross-linking time of the dry fabric is 30 at this temperature.
Shock dry for ~45 seconds. The fixed dyeings showed excellent washing fastness and withstood repeated washing at 60° and washing at boiling. At the same time, the wrinkle resistance was obviously improved and the swelling value of cellulose fibers was reduced. Example 14 Dyeing with 3% formula dye on cotton, Example 13
80 g/solution of the product of Example 2 as described above. Along with improved wrinkle resistance,
Excellent dye fastness was obtained. Example 15 Dyeing with a 2.4% formula dye on cotton is an example.
It was processed as described in Example 13 using the processing agent described in Example 10. Overall improved wet fastness properties were obtained, allowing repeated laundering at elevated temperatures. Examples 16-22 Stained to 1/1 standard density with the dyes in column 1 of the table below. Washed and dried exhaust dyed cotton cloth,
An 80% pick-up was padded with a solution containing xg/g of the product according to the invention and yg/g of magnesium chloride hexahydrate (x and y are indicated in the columns respectively). The properties of the products are shown in column 1. The padded fabric was cured as described in Example 13 to give excellent wash fastness at 95°.

【table】

Table: In Examples 13-22, all dyes were used in their commercially available form. Example 23 A cotton fabric was dyed with CI Reactiue Violet 23 to a standard strength of 2/2 without a final washing step using the usual dyeing method for reactive dyes. The dyed fabric was dried and then padded with 130 g/solution of the product of Example 1 in a pick-up at approximately 80% of its dry weight. The padding solution also contained 10 g/g of a conventional anionic softener, 20 g/g of a polyethylene dispersion and 1 g/g of a conventional nonionic activator. The treated fabric is dried to a residual moisture content of 2-4% and then
Cured at 180° for 30-45 seconds. The dyeings obtained showed a high level of washing fastness, despite the absence of a washing step after dyeing with reactive dyes. A clear improvement in wrinkle resistance was likewise obtained. Example 24 Cotton was dyed with CIReactiue Red 118 using conventional dyeing methods for reactive dyes. After dyeing and fixing, the fabric was simply washed with water and neutralized without boiling. The dyeing was carried out as described in Example 13 at 130g/
was treated with a solution containing the product of Example 1. Excellent wet fastness properties were obtained.

Claims (1)

[Scope of Claims] 1. The following A) and B) together with a catalyst for the cross-linking of N-methylol compounds of type B): A monofunctional or polyfunctional primary or secondary amine and cyanamide. , products of the reaction of dicyanodiamide, guanidine or biguanidine or of the reaction of ammonia with cyanamide or dicyanodiamide, which contain a reactive hydrogen atom bonded to nitrogen, B urea, melamine, guanamine, triazinone , uron, carbamate or acid amide N-
A textile treatment composition comprising an aqueous solution product obtained by reacting a methylol derivative in an aqueous solution. 2 Intermediate product A) is a monofunctional amine of the following formula a or a polyfunctional amine of the following formula b: RRNH a RRN(-Z-X)- _o Z-NRR b [In the above formula, each R is independently represents hydrogen or C _1-10 alkyl which is unsubstituted or monosubstituted with hydroxy, C _1-4 alkoxy or cyano, n represents a number from 0 to 100, and Z each independently represents C _{1-4 alkyl} ; represents alkylene or hydroxyalkylene, and each X independently represents -O-, -
S- or -NR- (where R is the same as defined above). provided that the amine of formula b contains at least one reactive -NH- or _-NH2 group] and cyanamide, dicyanodiamide or guanidine. thing. 3. Claims in which the intermediate product A) is a reaction product of diethylenetriamine, triethylenetetramine or higher polyethyleneamines containing up to 6 N atoms, polypropylenepolyamines or poly(hydroxypropylene)polyamines with dicyanodiamide or guanidine. The composition according to item 2. 4. A composition according to claim 3, wherein intermediate product A) is a reaction product of diethylenetriamine or triethylenetetramine and dicyanodiamide. 5. Composition according to claim 4, in which in the preparation of intermediate product A) amine and dicyanodiamide are reacted in a molar ratio of 2:1 to 1:2. 6 In the production of intermediate product A), the reaction is 140
Claim 1 carried out at a temperature of ~160°C
The composition according to any one of Items 1 to 5. 7 Intermediate product B) is N,N'-dimethylol-
4,5-dihydroxyethyleneurea, N,N'-
dimethylol 4,5-dimethoxyethylene urea,
7. The composition according to any one of claims 1 to 6, which is N,N'-dimethylol carbamate or a lower alkyl ether thereof. 8 Intermediate product B) is N,N'-dimethylol-
The composition according to claim 7, which is 4,5-dihydroxyethylene urea. 9. A composition according to any one of claims 1 to 8, in which the intermediate product A) is neutralized with an acid before the reaction with B) in the preparation of the water-soluble product. 10. A composition according to any one of claims 1 to 9, wherein A) and B) are reacted together at 60 to 75°C in the production of the water-soluble product. 11. The composition according to any one of claims 1 to 10, in which A) and B) are reacted together in a weight ratio of 1:0.625 to 22.0 in the production of a water-soluble product. . 12. A composition according to claim 11, in which A) and B) are reacted together in a weight ratio of 1:1.75 to 7.5 in the preparation of the water-soluble product. 13. Before the reaction of the water-soluble products with A) and B),
1 for the total weight of A) and B) during or after
Composition according to any of claims 1 to 12, stabilized against gel formation on storage by the addition of ~10% by weight of dicyanodiamide, cyanamide, guanidine or biguanidine. thing. 14 Claims in which the water-soluble product is stabilized against gel formation on storage by adding 1 to 10% by weight of dicyanodiamide before or during the reaction of A) and B) The composition according to item 13. 15. A composition according to any of claims 1 to 14, wherein the water-soluble product has a viscosity of 50 to 200 centipoise at room temperature and comprises 30 to 50% by weight of water. 16. The catalyst according to claim 1, wherein the catalyst is an aluminum, magnesium or zinc nitrate, sulfate, chloride, tetrafluoroborate or dihydrodiene orthophosphate, aluminum hydroxychloride, zirconyloxychloride or a mixture thereof. Composition. 17 Claim 1 in which the catalyst further contains sodium or potassium sulfate or calcium chloride
Composition according to item 6. 18. The composition according to claim 16 or 17, wherein the catalyst is magnesium chloride. 19 Weight ratio of component A) to component B) to catalyst is 1:
0.625-22: Claim 1 which is 0.25-6
The composition according to any one of Items 1 to 18. 20. The composition according to claim 19, wherein the weight ratio is 1:1.75 to 7.5:0.25 to 1.5.