JPS6144925A - Cationic polycondensate - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to cationic polycondensates useful for improving the fastness properties of dyed, printed or optionally whitened textile fibers or leather.

The fastness properties of direct, reactive and basic dyeings on textile fibers are determined by post-treatment with certain cationic fixatives, which are based on the reaction products of amines with cyanamide, dicyandiamide, guanidine and bisguanidine. It can be improved by U.S. Pat. No. 4,410,652.44.
39203 and 443920B. now,
When the reaction product is formed in the presence of a catalyst,
It was discovered that nine results could be obtained.

Therefore, the present invention comprises (A) a monofunctional or polyfunctional amine having one or more primary and/or secondary and/or tertiary amino groups; ) cyanamide, dicyandiamide, guanidine or bisguanidine in the presence of a catalyst (K) selected from metals, metal salts and heterocyclic nitrogen-containing organic bases, the reaction product comprising cyanamide, dicyandiamide, guanidine or bisguanidine, Up to 50 moles of guanidine or bisguanidine may be polysubstituted with dicarboxylic acids or mono- or diesters thereof, and the product contains at least one free hydrogen atom bonded to a nitrogen atom, or ψ), ( The reaction product of A) with (c) an N-methylol derivative of urea, melamine, guanamine, triazine, uron, urethane or acid amide or (d) shrimp halohydrin or its precursor or (e) formaldehyde or a compound that dissociates formaldehyde. , or (C), the prisoner and [(d) and (C)] or [(e)
and (C)], a cationic polycondensate is provided.

If an N-methylol derivative (e) is used, it is preferably reacted in the presence of a catalyst (K1) for the crosslinking of the N-methylol compound.

All of the above polycondensates may be in free base form or wholly or partially in acid addition salt form.

The reaction of (a) and (b) to give the polycondensate (A) comprises the amine (a)'e in free base or salt form, in the presence of water and preferably without the intervention of other solvents. to 50℃
or more, preferably 60 to 200°C, more preferably 8
At a temperature of 0 to 180 °C, especially 140 to 160 °C,
This is carried out by reacting with component (b). These reactants are preferably reactive -NH- or -NH
When the two groups are reacted in a molar ratio of 0.1 to 1 mole per mole of cusyanamide, DCDA, guanidine or biguayu, the molar ratio of these reactants is preferably is 0
．． 75: 1.25-1.25: 0.75. In particular, about 1=1.

Preferably component (c) is mixed with catalyst (K) and component (
b) is added, but (a), (b) and (K) are mixed from the beginning, or (b) and (K) are mixed;
It is also possible to add (K) to (a)' or to a mixture of (c) and (b), preferably at about 130°C. The reactions (&) and (b) are usually
This should be continued until no more ammonia is released.

It has been found that in the presence of catalyst (K), the reaction proceeds to a much more complete stage and more ammonia is liberated than in the absence of catalyst. For example, 1:
For (c) and (b) with a molar ratio of 1, the theoretical amount of ammonia released is 2.0 mol, but when no catalyst is used, only 1.5 mol of ammonia is actually released. Not done. In the presence of a catalyst, 1.6-1
．． 9 moles, in particular about 1.8 moles of ammonia are liberated,
The resulting polycondensate has a much higher molecular weight, as confirmed by viscosity measurement, than when no catalyst is used.

The product is preferably neutralized with an inorganic acid, such as sulfuric acid, and may be used in aqueous solution or may be converted to solid form, for example by spray drying.

Catalyst (K) is selected from metals, metal salts and heterocyclic nitrogen-containing bases. The metal or metal salt is preferably a metal from group I or group II of the periodic table or a salt thereof, especially a salt of Kawahara's metal, more preferably a salt of zinc, especially zinc chloride. The amount of metal salt used is suitably from 0.01 to 10 inches by weight based on the total weight of components (a) and (b);
Preferably 0.1-5%, more preferably 0.2-1
%, especially from 0.2 to 0.5, which is 0.3 excellent.

Preferred heterocyclic base catalysts are pyridine compounds, more preferably pyridines polysubstituted with tertiary amine groups such as di(C1-4 alkyl)amino groups or N-heterocyclic groups. Dimethylaminopyridine, especially 4-dimethylaminopyridine, is most preferred and such a catalyst is
By weight, based on the total weight of components (c) and (b), 0.
Suitably, it is used in an amount of 0.01 to 10%, preferably 0.1 to 7%, more preferably 4.5 to 5.5%, particularly 5%.

Preferred catalysts (K) are metal salts, especially zinc chloride.

The component (component) is preferably an amine represented by the following formula (1), R-NH-R or a polyalkylene polyamine represented by the following formula (II): 1 RRN-+Z-X-)-Z-NRRII (these where each R is independently hydrogen or unsubstituted or hydroxy;
Represents a C1-10 alkyl group monosubstituted with C7-4 alkyl, cyano or phenyl, and n is θ-10
represents the number 0, 2 each independently represents 02-4 alkylene or hydroxyalkylene, X each independently represents 10-1-8- or -NR-, provided that the amine in reactive -NH- or -NH2
).

More preferably, R in formula II is hydrogen and n is θ~
4 and X is 剾 or -NCH3-.

2 is each independently C2-4 alkylene. Particularly preferred compounds are diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 2-aminoethyl-3-aminoglobylamine, diethylenetriamine and N,N-bis-(3-aminoethyl)methylamine.

The most promising ingredient (1)) is dicyandiamide (DCDA)
It is. A particularly preferred polycondensate (A) is the reaction product of diethylenetriamine or triethylenetetramine with DCDA in the presence of zinc chloride.

Product (A) is a nearly colorless, viscous liquid or solid, essentially basic, soluble in water in free base or salt form, containing a reactive hydrogen bonded to nitrogen. Contains atoms. Their aqueous solution is 10 to 12, preferably 1
It has a pH of 0.5-11.

Up to 50 moles, preferably up to 20 moles of DCDA or other reactant to be reacted with the amine may be replaced by the dicarboxylic acid or its mono- or mole. Suitable acids include adipic acid, oxalic acid and terephthalic acid, for example in the form of their lanodimethyl esters.

The polycondensate (B) obtained by reacting (1) and the N-methylol compound (c) in the presence of a catalyst (K1), if desired, can be prepared as described in U.S. Pat. No. 4,410,652. It can be made in M. This US patent describes suitable and preferred N-methylol compounds (C).
and catalyst (K1) are described as intermediate product (B) and catalyst C), respectively, and the product corresponding to polycondensate (A) (not prepared in the presence of catalyst (K)) However, ) is described as an intermediate generation driver.

(A) and (in the presence of catalyst (K1) if desired)
d) or the polycondensate obtained by reaction with r=) (K
) and polycondensates obtained by the reaction of (A) with (d) and (c) or with (e) and (C) (0 can be prepared as described in U.S. Pat. No. 4,439,203) I can do it.

In this U.S. patent, shrimp halohydrin (d), formaldehyde (e), N-methylol compound (b), and catalyst (K1) are designated as (B) # (C) # (t) and (t), respectively. A product corresponding to the polycondensate (K) (although not prepared in the presence of catalyst (K)) is described as component (A).

Preferred reaction conditions and preferred amounts of reactants are described in U.S. Pat.
439203. The reaction between (1) and formaldehyde (c) is preferably carried out in an aqueous medium at 20-60° C. and at a temperature of 4, preferably 7-11. Formaldehyde may be added in the form of a concentrated (eg 37%) aqueous solution. Compound(
The preferred molar ratio of K) to formaldehyde is between 1:2 and 1.5% relative to the number of moles of amine originally present.
The range is 6.

Catalyst (K) for the reaction of (a) and (b) according to the invention
) and a catalyst for the crosslinking of N-methylol compounds (K1
) for any of the same metal salt compounds, e.g.
Zinc chloride can be used. Therefore, if catalyst (K) is used in sufficient quantities in the preparation of (A) and is not removed in subsequent operations, the residual catalyst (K)
can also act as a catalyst (K1) in subsequent steps such as the reaction of the polymer with the N-methylol compound (C). However, preferably another catalyst (Kl)
, more preferably magnesium chloride.

Other useful products include published UK patent application 2142
642A, optionally in the presence of a water-soluble polymer;
It is a polycondensate obtained in the form of a stable dispersion by acidifying this reaction product.

The present invention also provides a method for improving the fastness properties of dyes or optical brighteners on substrates comprising leather or textile fibers containing hydroxy, amino or thiol groups, which The method is dyed, printed,
or one or more of the above polycondensates (A), (B) or (C) or N-methylol compounds (c) and (A) or (d) on a whitened substrate; or(
c) and, if (A) is reacted with (c) or (c) or unreacted (c) is present, for crosslinking of N-methylol compounds; of the catalyst (Kl).

Although, as mentioned above, the remaining catalyst (K) functions as catalyst (K1), preferably the catalyst (K1), preferably magnesium, is added separately.

Such a post-treatment process is described in US Pat. No. 4,410,652.
4439203 and 4439208,
The conditions described in these patents can be applied to the present invention.

The textile fibers are preferably hydroxy-7-containing fibers, especially natural or regenerated cellulose fibers and wrinkled cotton. Useful results are also obtained with nitrogen-containing fibers such as polyacrylonitrile and natural or synthetic polyamides, preferably wool, silk or nylon. Acid modified polyesters and polyamides containing acidic hydroxyl groups can also be used.

The fibers may be in the form of wool or yarn or fabric or any suitable form. Fabric is a convenient and preferred form. The fibers may be blended with other fibers that undergo treatment according to the method of the invention or with fibers that do not undergo this treatment.

For example, cotton and regenerated cellulose fibers may be blended together, or each of these may be blended with polyester fibers, which are dyed with disperse dyes. Fiber blends and yarn blends can also be used.

The method of the invention may also be used in the dyeing of leather.

The fibers may be dyed or printed with anionic or basic dyes, including direct dyes, acid dyes and reactive dyes. Preferred dyes are direct dyes, preferably those having at least 2 sulfonic acid or sulfonamido groups in the dye molecule, more preferably 3 to 8 such groups, especially 4 to 6 such groups. It is. Particularly preferred are direct dyes having a high degree of directness such that they exhibit a low degree of exhaustion on cotton when dyed by conventional exhaustion glosses. Preferably, the direct condition is 10
It has a molecular weight of 00 or more, more preferably 1200 or more. Preferably, the direct dye is in the form of a 1:1 or 1:2 metal complex, especially a copper complex.

Particularly suitable direct dyes are those that meet the criteria set forth in U.S. Pat.
It is a dye that is listed by the cut-in r-tux number.

A particularly suitable group of dyes, including those described below, are those which have the properties of both direct and reactive dyes. These have high directivity as mentioned above, and contain one or more halodanes bonded to aromatic heterocycles that can be dissociated as anions under alkaline fixation conditions in their molecules. . Preferred dyes of this type contain one or more mono- or dihalo (especially chloro) substituted triazinyl groups.

Examples of dyes having one such group are those corresponding to formula (1) below.

-E I R3a R3a In the above formula, R3a each independently represents hydrogen, 01-4 alkyl, or C a-kyl substituted with one trOH, -CN or phenyl group, and R4o is 1-4 Ct or F , VcCt, and E is the same or different chromogenic group.

An example of a dye having two triazinyl groups is as shown in the formula (2) below.

In the above formula, Rla' R3a and E represent the same as defined above, and B represents a direct bond or a divalent aliphatic, aromatic, alicyclic or heterocyclic bridge, or a group to which this is bonded. The R5 & heterocyclic bridge may form a group together with one N- group.

In the compounds 2) and 2, the color-forming group E may be the same or different mono- or polyazo dyes, or the residue of an anthraquinone, stilbene, hydrazone, methine or azomethine dye; The base is 1 such as 1:1 steel, chromium, cobalt, nickel or manganese or 1:2 chromium or iron complexes.
:1-! or in the form of a 1:2 metal complex.

The bridging group B is preferably of the formula: In the formula, X is 4.4-. 3.4-or 3
．． It may be attached at the 3-position, and a direct bond or a bridge common in direct dye chemistry represents a group, or - together with the two -N- groups to which it is attached, becomes 3a to form a piperazine ring. may be formed.

Suitable triazinyl group-containing dyes are described in published British patent applications 2106126A, 2111538A and 21226.
34A.

Suitable dyes useful in polyamide dyeings to be post-treated according to the present invention are known as C,1, Anrad dyes.

The textile fibers contain reactive dyes, in particular 5- or 6-membered heterocycles with aromatic character and containing 2 or 3 nitrogen atoms, which can be dissociated as anions during fixation. It may also be dyed or printed with those containing rings substituted by atoms. The reactive group may be a vinylsulfonyl, vinylsulfonyl, sulfato or sulfate ester group. Such a dye is C
,I.

It is known as a reactive dye.

Suitable reactive dyes are C,1, Reactive Red 2
．． 6, 8, 120.123 and 171, C, L Reactive Blue 94, 104, 114, 116° 163.1
68.172 and 193, C', 1. Reactive Yellow 7.84 and 111, C,1, Reactive Orange 4, 14 and 69. C, 1, Reactive Brown 1
0 and 23. C, 1, Reactive Black 8 and C,
1. Contains Reactive Violet 33.

Basic dyes suitable for the process of the invention generally include C,1,
This is what is known as a basic dye. These contain protonatable primary, secondary, tertiary amino groups and/or quaternary anthonium groups and may also contain sulfonic acid groups, provided that the number of basic groups is It is such that it is larger than the number of acidic groups in the molecule. Basic dyes may also be in the form of 1:1 or 1:2 metal complexes. Suitably basic dyes are those disclosed in US Pat. No. 4,439,208.

In addition to the above anionic dyes and basic dyes, phthalocyanine dyes, sulfur dyes, vat dyes, formazale dyes,
Textile fibers can also be dyed or printed with di- or triphenylmethane dyes or indigo dyes.

Wool can also be post-treated with acid or alloy dyes in the customary manner under m- and then mildly alkaline conditions. Particularly suitable dyes are, for example, c,■, acid yellow 127, C,1, acid orange 67
, C, 1, Acid Red 412-.

336.339.399 and C, 1, Acid Blue 1
Contains 26.296.

The wool substrate may be chlorinated or untreated. The treatment of dyed wool substrates according to the invention &-1 can provide a certain degree of shrink resistance in addition to improving the wet fastness of the dyeings.

Optical brighteners, preferably anionic optical brighteners that are direct to cotton, may be used.

According to other features of the invention, cellulose, polyamide,
A method for dyeing or printing a substrate consisting of textile fibers comprising acid-modified polyamide or acid-modified polyester fibers is provided, which method comprises dyeing the substrate with a basic dye and a polycondensate (A), (
B) or ((''), optionally catalyst (K1)
The method includes a step of treating in the presence of.

In a preferred post-treatment method using polycondensate (A), the dyed substrate, which may be dry or wet b, is placed in a post-treatment bath at room temperature.

This bath with the required amount of (A)
The pH is adjusted to 10 to 11 by adding an aqueous solution of IJ (carbonate). This bath for 10 minutes 6
Heat to 0° C. and fixation is carried out at this temperature for 20 minutes. Finally, the post-treated dyeing is rinsed, neutralized if necessary and dried.

When the polycondensate contains an N-methylol group, for example, (3
) and (a) or (e), or in the case of polycondensates (C) or mixtures containing free (c), the US Patent 4410
Preferably, it is applied by packaging at room temperature followed by heat setting as described in US Pat. The fixing step is preferably carried out by heating to a temperature of 80 to 180°C, preferably 170 to 180°C, for 30 seconds to 1 minute.

The dyeings and prints post-treated according to the invention have better wet fastness properties than similar dyeings and prints post-treated with polycondensates prepared without the intervention of catalyst (5). shows.

The following examples serve to further illustrate the invention.

Parts and cents are by weight and temperatures are in degrees Celsius. Intrinsic viscosity was measured in water at 26°C and calculated on the basis of solid polycondensates.

Margin below Production of polycondensate (A) Example 1 82.4 parts of diethylenetriamine (0.8 mol).

A mixture of 62.7 parts DCDA (0.8 mol) and 1.5 parts zinc chloride is added to the mixture under stirring until all is dissolved.
It was heated to 150° for an hour. The reaction mixture was then stirred at 150° for 4 hours. Finally, the molten reaction product was poured onto a cold plate, solidified and powdered. This powder could be used as a post-treatment agent without further treatment.

60 parts of the powder was stirred in portions into 350 parts of 60 parts of water, neutralized with 47 parts of 5(l) sulfuric acid, and 40 parts of ice were added to maintain the temperature below 50°.

A solution of the sulfate salt of (A) containing approximately 40% active material was obtained. Addition salts can be used in liquid form or can be modified into powders by Ssollet drying.

Example 2 Example 1 is repeated using a) 0.35 parts of magnesium chloride or b) 0.7 parts of barium chloride or c) 0.5 parts of aluminum chloride instead of 1.5 parts of zinc chloride. Ta.

When barium chloride is used as a catalyst, it is preferred to use hydrochloric acid instead of sulfuric acid to neutralize the reaction products to avoid the formation of insoluble salts.

Example 3 Example 1 was repeated using, instead of diethylenetriamine, 0.8 mol of a) triethylenetetramine or b) tetraethylene diamine or C) ethylenediamine.

Example 4 309 parts (3 moles) of diethylenetriamine in 1.68 parts
znC42 (equivalent to 0.3 parts per 1,000 CDA of amine) for 630 minutes.

252 parts (3 moles) of DCDA was added and the temperature was increased to 300 °C.
rose to The resulting suspension was stirred and
Upon heating to 0.00C, a clear solution was obtained. For 85 minutes, the mixture was heated to 160°, which caused ammonia evolution to begin at 110' and become stronger at 130°. Ammonia was absorbed in 500 g of water and constantly titrated with 354 HCl to determine the amount of ammonia liberated. As the ammonia is liberated, the reaction mixture is initially cloudy and then becomes a clear, fluid melt.
It gradually became thicker.

The mixture was stirred at 1600 for 2 hours until a total of 1.8 moles of ammonia were liberated. Next, the reaction product was poured a little into 600 parts of water and the temperature was maintained at 30°. Finally, the alkaline solution was neutralized by dropwise addition of 20-300 sulfuric acid. A milky liquid was obtained, which could be used directly or modified into a powder by spray drying.

The intrinsic viscosity of the obtained product is 0.06 cut/J
It was i'. In comparison, the product made without zinc chloride had an intrinsic viscosity of 0.041 C11 L/i. Example 5 In place of 1.5 parts of zinc chloride, 7.5 parts of 4- Example 1 was repeated using dimethylaminopyridine.

A liquid product with a solids content of about 55 and an intrinsic viscosity of 0.037 cm 7 g at 26° was obtained, which could be used directly as a post-treatment agent.

Example 6 Repeat with the same amount instead of 7.5 parts of 4-dimethylaminopyridine. A similar product was obtained.

Example 7 Same amount of triethylenetetramine instead of diethylenetriamine, b) tetraethylene with ethamine or C)
Example 5 was repeated using ethylenediamine.

Production example 8 of polycondensate (Bl and (C)) 5 of 457 parts of dimethylol dihydroxyethylene urea
70% solution with 23 parts of DCDA (as a stabilizer). While heating and stirring at this temperature, 68.5 parts of the spray-dried product of Example 4 (sulfate salt) were added in portions. After stirring at 70° for 3 hours, the mixture was cooled and
69 parts of magnesium chloride hexahydrate were added. The resulting mixture could be used directly as a post-treatment agent.

Example 9 50 parts of 100 parts of dimethylolhydroxyethylene urea
The solution was heated to 70-80° and stirred with 20 parts of magnesium chloride salt. In the resulting clear solution,
40 parts of the spray-dried product of Example 4 (sulfate) were added in portions and the mixture was stirred at 700°C until everything was dissolved. The reaction was terminated by stirring at this temperature for an additional 2172 hours. A clear solution was obtained which could be diluted with water and used as a post-treatment agent directly or after further dilution. Intrinsic viscosity is 0.05
It was 26m/Ji'.

Example 10 627 parts of the sulfate solution product of Example 4 was added to 27.5 to 7.8 parts by addition of 23 parts of a 30% sodium hydroxide solution.
The solution was warmed to 500 ml and stirred for 1 hour at this temperature, during which time 65.6 parts of Epichlorohydrin was added slowly. The mixture was stirred at 50° for a further 2 hours to complete the reaction, then cooled to room temperature and the addition of 50 parts of concentrated sulfuric acid reduced the concentration to 2.5-3.
The temperature was adjusted to 0, and the temperature was maintained at -1300 or below by external cooling.

The reaction mixture was finally heated at 50° (15-20 mjL)
Volatile organic compounds were removed by exposure to Ig vacuum for 15-20 minutes. The product was adjusted to a solids content of 55% by addition of water to obtain a milky liquid. Intrinsic viscosity & 0.045
It was cm3/11.

Example 11 To 100 parts of the product of Example 10 are added 100 parts of a 50% aqueous solution of dimethylol dihydroxyethylene urea and 7.5 parts of magnesium chloride hexahydrate and the mixture is combined with 70%
Stirred at °. A clear solution was obtained, which could be used directly as a post-treatment agent.

Application Example 12 Cotton fabric is 3 cm (based on the dry weight of the base material), 1.
Exhaust dyeing with z-elect blue 251 and thorough rinsing. This dyed and rinsed substrate is
At a bath ratio of 20:l, II/! Solid product of Example 4, 5 g/! of sodium chloride and acetic acid in an amount of -4.5 at 60° for 30 minutes. The post-treated substrate was rinsed with cold water and dried. The dyed product obtained had extremely high washing fastness.

Example 13 Instead of adjusting the pH to 4,5 with acetic acid, Example 12 was prepared using a post-treatment bath in which the pH was adjusted to 11 to 11.5 with sodium carbonate.
repeated. The dyeing obtained had good fastness to boil washing.

Similarly good results were obtained using the products of Examples 1-3.5-7 and 10.

Margin Example 14 A cotton fabric was dyed in a conventional manner with Dye C, 117 Active Violet 23 at a concentration of 1) 2:2, rinsed and dried. Next, the dyed base material is 1301/
A solution containing the product of Example 8 of 1) was applied to a 804 ml bottle. This knotted base material has a residual moisture content of 2
Dry to ~4% and then keer at 1800 for 30-45 seconds. The fixed dyestuff had excellent wash fastness properties.

i oi7i normal anionic softener and II/!
The addition of conventional nonionic wetting agents to the padding process improves the hand of the post-treated fabric.

Similarly good results were obtained using the products of Examples 9 and 11.

Margin below

Claims (1)

[Claims] 1. (A) (a) one or more primary and/or
or a monofunctional or polyfunctional amine having secondary and/or tertiary amino groups and (b) cyanamide, dicyandiamide, guanidine or bisguanidine;
A reaction product in the presence of a catalyst (K) selected from metals, metal salts and heterocyclic nitrogen-containing organic bases, comprising:
Up to 50 mol% of the cyanamide, dicyandiamide, guanidine or bisguanidine may be substituted by dicarboxylic acids or mono- or diesters thereof;
products containing at least one free hydrogen atom bonded to a nitrogen atom, or (B), (A) and (c) urea, melamine, guanamine,
N-methylol derivatives of triazines, urons, urethanes or acid amides; or (d) epihalohydrins or precursors thereof; or (e) reaction products with formaldehyde or compounds that dissociate formaldehyde; or (C), (A) and [( d) and (c)] or with [(
A cationic polycondensate which is a reaction product with e) and (c)]. 2. Component (a) is an amine represented by the following formula I, R-NH-R I or a polyalkylene polyamine represented by the following formula II, RRN-(Z-X)-_nZ-NRRII (in these formulas,
R each independently represents hydrogen or a C_1_-_1_0 alkyl group which is unsubstituted or monosubstituted by hydroxy, C_1_-_4 alkoxy, cyano or phenyl, n represents a number from 0 to 100, and each Z independently represents C_2_ to_4 alkylene or hydroxyalkylene, and each X is independently -O-, -S-
or -NR-, provided that the amine of formula II contains at least one reactive -NH- or -NH_2 group. 3. Patent where component (a) is diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 2-aminoethyl-3-aminopropylamine, dipropylenetriamine or N,N-bis-(3-aminopropyl)methylamine A cationic polycondensate according to claim 2. 4. The cationic polycondensate according to any one of claims 1 to 3, wherein component (b) is dicyandiamide (DCDA). 5. The cationic polycondensate according to any one of claims 1 to 4, wherein the catalyst (K) is a pyridine compound. 6. The cationic polycondensate according to claim 5, wherein the catalyst (K) is 4-dimethylaminopyridine. 7. The cationic polycondensate according to any one of claims 1 to 4, wherein the catalyst (K) is a salt of a Group II or Group III metal. 8. The cationic polycondensate according to claim 7, wherein the catalyst (K) is zinc chloride. 9. Cationic polycondensation according to claim 7 or 8, wherein the concentration of the catalyst (K) is 0.2 to 0.5% by weight based on the total weight of components (a) and (b). thing. 10. The polycondensate (A) is composed of (a) diethylenetriamine or triethylenetetramine and (b) DCDA, (
The cationic polycondensate according to claim 9, which is a reaction product in the presence of (K) zinc chloride in an amount of 0.2 to 0.5% by weight based on a)+(b). 11. The cationic polycondensate according to claim 10, which is the polycondensate (A). 12. The cationic polycondensate according to claim 10, which is a reaction product of (A) and an N-methylol compound (c). 13. (A) and (c) in the presence of magnesium chloride
) The cationic polycondensate according to claim 12, which is a reaction product with 14 at 20-60°C and pH>4 in aqueous medium (
The cationic polycondensate according to claim 10, which is a reaction product of A) and formaldehyde (e). 15. The cationic polycondensate according to claim 10, which is obtained by reacting (A) with epichlorohydrin and acidifying the product. 16. A method for improving the fastness properties of dyes or optical brighteners on substrates comprising leather or textile fibers containing hydroxy, amino or tinol groups, which have been dyed, printed or brightened. The base material is one or more polycondensates (A) as defined in claim 1.
, (B) or (C) or N-methylol compound (c
) and (A) or the reaction product of (A) and (d) or (e), and when (A) is reacted with (c) or (e) or unreacted (c) catalyst for crosslinking of N-methylol compounds (K1)
A method including applying. 17. Direct dye or reactive dye dyeing on cotton (A) in the presence of polycondensate (A) or catalyst (K1)
17. A method according to claim 16, characterized in that it is treated with the reaction product of and (c).