DE4223830A1 - Dirt-repellent finishing agent - Google Patents

Abstract

The defined condensation products (P) - salts at least in some cases - from dihydroxydiphenylsulphone, formaldehyde and the defined aromatic compounds (A) in defined molar ratios make for excellent soil-repellent finishing of polyamide fiber materials, especially in combination with a fiber-reactive, colorless compound and possibly using in addition other soil-repellent finishing agents, to provide highly effective, long-lasting finishes that do not produce a distracting yellowing either upon application or with extended use.

Description

In the dirt-repellent finishing of natural or synthetic Polyamide fiber materials is an annoying phenomenon of yellowing Equipment, especially when using dirt-repellent equipment equipment used for the rejection of wet soiling be so that the colorations, brightenings and / or color samples in the hue be changed in an undesirable way. It has now been found that under Use of the dirt-repellent finishing agent (P) defined below this disturbing phenomenon can be substantially avoided, whereby high-quality dirt-repellent finishing effects can be achieved, in particular on the other hand, if they are using certain fiber-sensitive reactive aids, such as defined below, applied. By combining with others Dirt-repellent finishing agents can be particularly valuable dirt repellent properties can be achieved, and so in particular Combination with oil-repellent fluorocarbon resins surprisingly good dirt repellent equipment can be achieved.

The invention relates to the dirt-repellent finish of the polyamide fiber materials using the products defined below (P) as well as the new products (P) and their manufacture.

A first subject of the invention is therefore a method for dirt removal equipment of textile or non-textile fiber material natural or synthetic polyamide, characterized in that one as a dirt-repellent finishing agent, one that can be diluted with water Product (P) uses that through Condensation of

• A) a sulfonation product of a mole of at least one compound of the formula wherein
  X oxygen, sulfur or the direct bond,
  R _{1 is} hydrogen or methyl and
  R _{2 is} hydrogen, methyl or, if X is oxygen or sulfur, is also phenyl, and b mol
• B) at least one dihydroxydiphenyl sulfone with c mol
• C) formaldehyde,

where b / a = 0.2 to 1.8 and,
if ba, c = 0.4b to 1.4b or,
if b <a, c = b to 0.7 · (a + b),
to an acidic condensation product (P _s ) essentially free of metal cations, and admixing with

• D) at least one of the following compounds: ammonia, an aliphati the amine or a basic alkali metal compound,

until a pH <4.5 of the aqueous product is reached,
and optionally drying.

In the compounds of formula (I), X preferably represents oxygen or the direct bond, particularly preferably the direct bond. R ₁ and R ₂ are particularly preferably methyl when X is oxygen. The following are advantageously suitable as compounds of the formula (I): biphenyl, phenyltoluene, tolyltoluene, phenoxybiphenyl, phenoxytoluene, diphenyl ether, ditolyl ether and diphenylthioether. The methyl groups R ₁ and R ₂ can be in any position ortho, meta or para to X. Among the methyl-substituted compounds, the methyl-substituted diphenyl ethers should be emphasized; single tolylphenyl ether or, preferably, ditolyl ether can be used (2,2'-, 2,4'-, 2,3'-, 3,3'-, 3,4'- and 4,4 ' -Ditolyl ether) or technical mixtures which contain two or more of the isomers mentioned. When R _{2 is} phenyl, it is advantageously para to X. When R _{2 is} phenyl, R _{1 is} preferably hydrogen. The sulfonation products of the compounds of the formula (I) can in general be those which lead to the corresponding sulfonic acids of compounds of the formula (I) by simple sulfonation or, if X is sulfur or preferably oxygen, can also be those sulfonation products which have been produced under forced conditions, so that oligomeric sulfone-containing sulfones result therefrom.

The following are particularly suitable as sulfonation products (A)

• A ₁ ) sulfonation products of compounds of formula (I), in which X is the direct bond, or oligomeric sulfonation products of compounds of formula (I), in which X is oxygen, which are sulfones containing sulfones, and
• A ₂ ) monomeric sulfonation products of compounds of the formula (I), in which X is oxygen or sulfur.

Preferably, (A ₁ ) is at least one sulfonation product of a compound of the formula (I), in which X is the direct bond, or a mixture of such compounds, or an oligomeric sulfonation product of at least one compound of the formula (I), in which X is oxygen and R ₂ preferably H or -CH ₃ , which is a corresponding sulfo group-containing sulfone of at least one compound of the formula (I) in which X is oxygen, or a mixture of such sulfones, or a mixture of such compounds.

(A ₂ ) is preferably at least one monomeric sulfonation product of a compound of the formula (I) in which X is oxygen or sulfur, or a mixture of such compounds.

Preferred components (A) are those which contain (A ₁ ) and optionally (A ₂ ), in particular those which consist of (A ₁ ) and optionally (A ₂ ).

Known compounds as used in the art are suitable as (B) are referred to as dihydroxydiphenyl sulfones, especially those such as they are also called sulfonyldiphenols or bis (hydroxyphenyl) sulfones become. Primarily come as (B) 4,4'-, 2,2'- or 4,2'-dihydroxydiphe nylsulfone (i.e. 4,4'-, 2,2'- or 4,2'-sulfonyldiphenol) and mixtures thereof, especially technical mixtures of isomers, into consideration.

Component (C) is advantageously in the form of an aqueous formaldehyde solution or formaldehyde-releasing compound used, for. B. as paraformaldehyde or as hexamethylenetetramine.

The sulfonation of the compounds of formula (I) can be carried out under conventional sulfonation conditions, preferably using oleum, 100% sulfuric acid, concentrated sulfuric acid or chlorosulfonic acid. The sulfonation can advantageously be carried out in the temperature range from room temperature (= 20 ° C.) to 150 ° C., preferably 70 to 135 ° C. In the - particularly preferred - sulfonation with 100% or concentrated sulfuric acid, the process can, if desired, be carried out under conditions such that water of reaction is removed (for example, if appropriate evaporated or distilled off under reduced pressure). The sulfonation is advantageously carried out under conditions such that an average of 0.8 to 2, advantageously 0.9 to 1.5, sulfo groups are introduced per molecule of the formula (I), advantageously using 1 to 2.5 mol, preferably 1 , 1 to 2 moles of the sulfonating agent per mole of starting material of the formula (I). In the preferred sulfonation with 100% or concentrated sulfuric acid (ie in particular H ₂ SO ₄ .H ₂ O to H ₂ SO ₄ ), water of reaction is advantageously distilled off under reduced pressure, the continuation of the sulfonation reaction being favored and, at the same time, non-sulfonated tes The starting material can also be distilled off and the sulfonation product has a degree of sulfonation of primarily 0.9 to 2, advantageously 1 to 1.5, of which products with an average degree of sulfonation of 1.1 to 1.4 are particularly preferred. To produce oligomeric sulfones (A ₁ ), the sulfonation product is expediently allowed to react further until the desired degree of condensation to the oligomeric sulfone is reached. The condensation to the sulfone is advantageously carried out at elevated temperature, preferably in the temperature range from 140 to 200 ° C., in particular 150 to 180 ° C., under reduced pressure, advantageously below 50 mbar, particularly preferably below 20 mbar. This condensation to the sulfone is advantageously continued until the decrease in the acid content of the condensation product subsides and the acid content is in the range from 250 to 450, preferably 300 to 400 meq / 100 g. The excess sulfuric acid in the reaction mixture is advantageously not separated off, but the sulfuric acid mixture is used directly for condensation with (C), which is expediently carried out under correspondingly acidic conditions.

The molar ratio b / a is advantageously in the range from 0.24 to 1.75 and is preferably 0.5, in particular in the range from 0.5 to 1.6, particularly preferably in the range from 0.75 to 1.4.

The proportion of (A ₁ ) in (A) is advantageously 10 to 100 mol%, preferably 20 to 100 mol%, where (A ₁ ) is particularly advantageously a sulfonation product of biphenyl. If (A ₂ ) is present, it is expediently at least 5 mol% of the mixture of (A ₁ ) and (A ₂ ); preferably (A ₂ ) makes up 5 to 80 mol% of (A). The molar percentages are always based on the starting products of the formula (I).

The amount of formaldehyde generally depends on the amount (B), or also, especially if (A) is present in excess, according to the amount (A) and (B). C is advantageously in the range from 0.4 · (a + b) to 0.75 · (a + b). When b is a, c is preferably in the range of b to 1.4 · b, advantageous 1.1 · b to 1.3 · b. If b <a, c is advantageously = b to 0.6 · (a + b), preferably in the range of 0.4 · (a + b) to 0.6 · (a + b). If b <a, It may also be an advantage if the product is not full of formaldehyde to condense (e.g. if the end product ap is copied), c is then advantageously in the range from 0.25 · (a + b) to 0.5 · (a + b), in particular in the range from 0.27 · (a + b) to 0.48 · (a + b), where, as defined above, c is at least 0.4 · b.

The reaction of (A) and (B) with (C) can be carried out according to methods known per se take place, advantageously at temperatures in the range of 50 to 110 ° C. preferably 80 to 105 ° C, in a strongly acidic medium, for example at pH Values <3, preferably below 1. In the An conclusion of the sulfonation, implemented in a sulfuric acid medium. Advantage the reaction takes place with (C) in an aqueous acidic medium, the com  component (C) can be added in a form diluted with water and / or the sulfuric acid reaction mixture resulting from the sulfonation Water diluted to a water content of advantageously 10 to 50 wt .-% can be.

The condensation product (P _s ) obtained contains the sulfonic acid groups in the free acid form and is essentially free from cations, in particular from polyvalent metal cations, primarily heavy metal cations. That is, if metal cations, especially polyvalent metal cations or heavy metal cations should occur in traces in the mixture, it is essentially undesirable by-products, such as those caused by the use of certain vessels (transport or reaction vessels) or other metal parts in the reaction apparatus - e.g. B. stirrer, hopper, etc. - occur, and are generally on the order of a few ppm, in particular <10 ppm.

After sulfonation, the products obtained can be converted to the desired pH by reaction with a suitable basic compound (D). The resulting acidic condensation product (P _s ), for the preparation of (P), is mixed with (D), advantageously until the pH is above 4.5, in particular until the pH of an aqueous dilution with a dry matter content of 10% by weight. % above 4.5 and preferably below 9, particularly preferably in the range from 5 to 8.5. As basic compounds (D) come primarily alkali metal hydroxides or carbonates (alkali metal = e.g. lithium, sodium or potassium), ammonia or aliphatic amines [e.g. B. morpholine, mono-, di- or tri- (C _2-3 hydroxyalkyl) amine, mono-, di- or tri- (C _1-2 alkyl) amine] into consideration. Sodium hydroxide, potassium hydroxide or ammonia is preferably used as (D), sodium or potassium hydroxide and ammonia being used in a particularly preferred variant, advantageously in molar ratios of 0.2 to 10, preferably 0.4 to 4, mol of KOH or / and NaOH per mole of ammonia. The products (P) obtained are water-soluble and, as they have been prepared, can be handled directly after adjusting the water content to a dry matter content of, for example, 5 to 60% by weight, preferably 10 to 40% by weight or they can, if desired, be dried to dry preparations, for example by spray drying or granulating (optionally with the addition of granulating aids).

If desired, e.g. B. to facilitate applicability in practice, the solutions organic solvents, advantageously alcohols, before aliphatic C _2-8 alcohols (especially ethanol, isopropanol and mono- or diethylene glycol and their C _1-4 alkyl monoethers, e.g. B. butyl glycol) are added. Preferably, however, no such solvents are used.

A particular object of the invention is represented by products (P) in which (A) consists of (A ₁ ) and optionally (A ₂ ), which are defined as indicated above.

The products (P) are used for the dirt-repellent finishing of fiber material made of natural or synthetic polyamide (e.g. wool, silk or synthetic table polyamides - mainly polyamide 6 or 66), especially in form of fabrics, knitted fabrics and pile material, advantageous for finishing poles cover material or carpets on the right side or (for carpets) Tread side, from such natural and / or synthetic polyamides or consists of polyamide-containing fiber mixtures.

The equipment can be carried out according to any method as they are per se for the equipment with dirt-repellent equipment of the Dihydroxydiphenyl sulfone series are common, especially after pull-out drive or by impregnation process, advantageous at pH values in the range from 2 to 8, preferably 2.5 to 7, in particular 2.5 to 6.

For the exhaust process, the temperatures can be in a wide range fluctuate, e.g. B. in the range of 15 to 130 ° C (optionally under pressure), advantageously 40 to 100 ° C. The additions and the pull-out procedure are before partially controlled so that the pH of the pull-out liquor at the end of the process is in the range from 2.5 to 7. According to a special embodiment proceeded according to the so-called pH sliding process, d. H. the pH is in Reduced in the course of the exhaust process, advantageously in the range of pH 9 to 3, especially so that at alkaline pH values, advantageously at pH 7.5 to 9, preferably 8 to 9, is started and in the course of the process the pH to neutral to acidic values, advantageously pH 7 to 2.5, preferably 6 to 3, is reduced. This can e.g. B. by controlled addition of Acid (e.g. a low molecular weight aliphatic carboxylic acid in particular with 1-4 carbon atoms, e.g. B. formic acid, acetic acid, lactic acid, oxal  acid, citric acid, malic acid, succinic acid or hydroxybutyric acid) or / and by adding compounds in the course of the process - before preferably by hydrolysis - generate an acid; such acid generating Connections are e.g. B. saponifiable esters, especially the above Acids, especially lactones of corresponding hydroxycarboxylic acids (e.g. butyro lactone), or labile chlorine compounds which are caused by the process Hydrolysis generate hydrochloric acid (e.g. 2,2-dichloropropanol or monochloroacetic acid acid) or chlorine-substituted esters - especially chloroacetic acid esters - e.g. B. as described in DE-OS 28 03 309 (≡ USP 4 168 142).

The impregnation process can be carried out by any conventional method be, e.g. B. by dipping, padding, spraying, foam application, knife coating or roller application; for the impregnation process, the pH of the impregnation is kidney liquor (at least at the end of the impregnation process, before drying) advantageously in the range from 3 to 7, preferably 3 to 6, also for the impregnation process can be carried out according to the pH sliding process, if the impregnating liquor corresponds to acid-generating compounds (esp ders as stated above) are added, for what at the beginning of the process the pH z. B. Values range from 6 to 8 and at the end of the process Values in the range from 3 to 6, preferably 3 to 5. After impregnation the impregnated goods can be fixed using various methods, e.g. B. by dwell process at low temperature (after the so-called cold dwell process) or in the heat, e.g. B. in the temperature range of 15 up to 102 ° C and in suitable variable time periods, e.g. B. in the range of 10 Minutes to 48 hours (e.g. from several hours at room temperature up to a few minutes at 102 ° C), or vapors e.g. B. at temperatures in the range from 95 to 140 ° C, preferably 100 to 110 ° C, and / or dry heat treatment lung (preferably at 130 to 160 ° C). After fixing it will be beneficial rinsed and then dried. If necessary (e.g. depending on the substrate, on quantity and fixing conditions), rinsing can be dispensed with.

The dirt-repellent (P) is advantageously used in such amounts sets that the concentration (P), calculated as dry matter based on Dry weight of the substrate, 0.2 to 10%, preferably 0.8 to 7%, ins particularly 1.5 to 4%. If necessary, water-soluble salts polyvalent, colorless metal cations, e.g. B. magnesium chloride or acetate, be added to the treatment liquor, e.g. B. analogous to EP 267 681 A2 described.  

According to a preferred embodiment of the method according to the invention, before the treatment with (P) and / or simultaneously with the treatment with (P),
(F _r ) used a colorless, fiber-affine, reactive auxiliary.

Suitable (F _r ) are generally known fiber-reactive dyeing aids, especially those which contain at least two reactive substituents, for example as described in US Pat. No. 3,743,477, to which reference is expressly made here. Particularly noteworthy are 2-arylamino-4,6-dihalogen-1,3,5-triazinylamino compounds of the benzene or naphthalene series, primarily those of the following formula

wherein
R represents a phenyl radical which is optionally substituted by chlorine, C _1-4 -alkyl or / and -SO ₃ M, or a naphthyl radical which is optionally substituted by -SO ₃ M,
R _{o is} hydrogen or C _1-4 alkyl,
Hal fluorine, chlorine or bromine, and
M is hydrogen or a colorless cation
mean.

Hal preferably represents chlorine. R preferably represents phenyl which optionally carries a sulfo group and / or a C _1-4 alkyl group. Any such alkyl radicals are suitable as C _1-4 alkyl, specifically methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, among which those with 1 to 3 carbon atoms are preferred. R preferably contains a group -SO ₃ M.

The fiber-reactive dyeing aid (F _r ) can be applied under the same conditions as (P); the concentration, based on the substrate, can vary within a wide range, primarily in the range from 0.1 to 10% compound of the formula (II) based on the substrate weight, for synthesis fibers advantageously 0.2 to 4%, based on the Weight of the dry substrate, advantageously for wool 0.4 to 8%, based on the dry weight of the substrate, depending on the nature of the substrate and / or chemical character of the synthetic polyamide, and depending on the product used (P) and process parameters used and, if necessary, other fleet additives, the optimal concentration can fluctuate. According to a preferred procedure, when using (F _r ), a strongly dissociating inorganic salt is added, advantageously an alkali metal salt of a strong mineral acid, e.g. B. sodium sulfate or preferably sodium chloride; 0.1 to 20%, preferably 1 to 10%, of alkali metal salt, based on the dry weight of the substrate, is advantageously used.

According to a further embodiment of the invention, the products (P) according to the invention can be used in combination with other dirt-repellent finishing agents in order to achieve special dirt-repellent properties and / or to produce certain synergistic effects. The products (P) can be used in combination with
(Q) dirt-repellent poly-α- (R ′) acrylates,
where R ′ is hydrogen or a substituent,
can be used and / or it can additionally
(F _H ) oil-repellent fluorocarbon resins
be used.

In (Q) R 'preferably represents a substituent, in particular a C _1-15 hydrocarbon radical, which can optionally be substituted by halogen and / or SO ₃ M; the poly-α- (R ') acrylates are advantageously alkyl esters in which the alkyl radical is optionally substituted and z. B. contains 1 to 15 carbon atoms. Both R ′ and the ester-forming alkyl radicals are preferably low molecular weight and unsubstituted, in particular with 1 to 4 carbon atoms, of which methyl is particularly preferred. The polyacrylates can be homo- or copolymers, in particular copolymers in which some of the monomer units occur in the form of the free acid or as a salt thereof. According to a further possible variant, the poly mers (Q) are those which have been prepared by polymerization of the corresponding vinyl monomers in the presence of (P), for. B. analogous to that described in US Pat. No. 4,940,757, to which express reference is made here.

As fluorocarbon resin (F _H ) generally known products can be used, such as are usually used for oil-repellent and water-repellent armor, and can in particular be anionic, cationic or non-ionic, and can be handled as aqueous dispersions, for example fluorine-containing allophanates, e.g. . B. those described in U.S. Patent 4,606,737, fluorine-containing polyacrylates, e.g. B. Such as described in US Patent 3,574,791 and US Patent 4,147,851, fluorine-containing urethane, e.g. B. those as described in U.S. Patent 3,398,182, fluorine-containing carbodiimides, e.g. B. such as described in US Patent 4,024,178, and fluorine-containing guanidines, e.g. B. Such as described in U.S. Patent 4,540,497. Non-ionic or anionic resin-forming fluorocarbon resins (F _H ) are preferably used. The fluorine-containing products (F _H ) can be used together with (P) or preferably separately - advantageously after the treatment with (P), before or after drying - the amount of which largely depends on the desired effect, on the substrate, on the application parameters and depends on the liquor components, advantageously such that 0.02 to 0.5, preferably 0.04 to 0.2% by weight of fluorine, based on the dry fiber substrate, is present on the finished goods. The fluorocarbon resins (F _H ) can be applied in a manner known per se, with more substantive products being preferred for exhaust processes. Fixie tion of the oleophobic agent (F _H ) on the substrate (mainly by appropriate crosslinking and / or curing) is advantageously carried out by thermal treatment z. B. at 102 to 180 ° C, preferably 130 to 160 ° C, for synthetic fibers favorably with simultaneous fixation of the substrate.

The products (P) according to the invention and, if appropriate, further dirt-repellent additives, if these are provided, can be applied to already colored or / and lightened goods or, if desired, can also be applied together with the dyeing or optical brightening, in which case anionic dyes or optical brighteners, especially acid dyes, are preferred. If desired, the soil-repellent finish of the present invention can be combined with an antistatic finish or an antistatic finish can follow. The treatment with (P) and optionally other finishing agents can, if desired, or if necessary, be carried out in the presence of wetting agents, wetting agents generally being those which are usually used as dyeing aids when dyeing with anionic dyes or optically brightening with anionic Brighteners are used, especially non-ionic and / or anionic wetting agents; anionic wetting agents are preferably used, in particular sulfates, sulfonates and phosphates, for. B. fatty alcohol sulfates, sulfates of ethoxylated fatty alcohols, sulfo succinic acid esters, phosphoric acid esters of ethylated fatty alcohols, phosphoric acid esters of branched synthetic alcohols, sulfonated oils (e.g. castor oil), alkylarylsulfonates and, depending on the pH, also soaps; the fatty residues contain, for example, 12 to 24 carbon atoms, the synthetic alcohols contain, for example, 8 to 15 carbon atoms, the alkylaryl residues in the alkylarylsulfonates are advantageously mono- or di- (C _4-12 -alkyl) -benzenesulfonates and the degree of ethylation in the products containing ethyleneoxy units is expediently chosen so that the desired network action is present and is advantageously 1 to 12.

According to the method according to the invention, excellent dirt-repellent equipment (stain-blocking), particularly with the use of (F _r ), can be targeted, with the additional use of additional dirt-repellent equipment, in particular (Q) and / or (F _H ), particularly before partial effects can be achieved. The equipment according to the invention is characterized by its colorlessness, even with prolonged use or with longer exposure, and, especially those which have been applied in combination with (F _r ), are of excellent durability and are particularly resistant to abrasion. The dirt-repellent effect against soiling is particularly noteworthy and is largely retained even after prolonged use (e.g. even after repeated shampooing). The use of wetting agents and / or other dyeing additives (e.g. acids or salts) in the application, e.g. B. simultaneously with the dyeing, practically do not affect the armor of the invention.

In the following examples, the percentages mean percentages by weight; the Temperatures are given in degrees Celsius. The in the application Examples of chemicals used, except for the products (P), are there standard products.

example 1

In a five-necked sulfonating flask of 1.5 l capacity, which is equipped with a stirrer, reflux condenser and thermometer, 77.0 g of biphenyl are pre-charged and melted at 75-80 ° C. 73.5 g of 100% sulfuric acid are added dropwise to the melt with stirring over the course of 15 minutes, as a result of which the internal temperature rises to 95.degree. Then the mixture is heated to 105 ° C. and stirring is continued for 2 hours at this temperature. Now it is cooled to 75 ° C. and 19.0 g of demineralized water are added dropwise within 15 minutes so that the internal temperature does not exceed 95 ° C. Then 188.0 g of 4,4'-dihydroxydiphenyl sulfone are added in portions within 20 minutes. After the addition is complete, stirring is continued at 90 ° C. for 30 minutes. 72.9 g of 35% formaldehyde are added dropwise to the pulpy suspension obtained between 90 and 95 ° C. over a period of 25 minutes and the mixture is left to react at 90-95 ° C. for a further 1½ hours. 230.0 g of demineralized water are added to the resulting viscous resin within 10-15 minutes, the temperature dropping to 60 ° C. 120.0 g of 25% ammonia solution are added dropwise to the resulting mixture of pH <1. 100.0 g of demineralized water are added to the resulting mixture of pH 8.0 and stirring is continued for a further 30 minutes. 880 g of a clear brownish liquid are obtained; this is evaporated on the Rotavapor. 330 g of light powder (P ₁ ) are obtained. If the liquid is not evaporated on a Rotavapor, but 220 g of demineralized water is added, 1100 g of a clear liquid (P ₂ ) with 30% dry matter content are obtained.

The following table shows further examples of products according to the invention (P) enumerated, who are produced analogously to the process according to Example 1 and by the components of formula (I), their number moles, the number Moles of sulfuric acid, the number of moles of 4,4'-dihydroxydiphenyl sulfone, the number Mol of formaldehyde and the bases used for pH adjustment are:  

table

Example 23

99 g of ditolyl ether (technical mixture) are slowly added under N ₂ atmosphere and good stirring within 30-45 minutes and with cooling 73.5 g of 100% sulfuric acid. When the addition is complete, the temperature is between 100 and 105 ° C. The reaction is continued for 5½-6 hours at this temperature in an N ₂ atmosphere. Under a vacuum of 14-20 mbar, the temperature of the reaction mixture is then raised within 10-20 minutes to 120 ° C. After 20-30 minutes, the reaction water is virtually completely removed from the sulfonation mixture. While reducing the vacuum to 4-8 mbar, the reaction mixture is heated to a temperature between 160 and 180 ° C. within 15 minutes and left at this temperature for about 6 hours until the acidic resin formed has an acid content of 330-390 meq / 100 g.

Analogously to the information in Example 1, the product obtained in this way is 0.5 Mol condensed 4,4'-dihydroxydiphenyl sulfone and 0.7 mol of formaldehyde, with a mixture of ammonia (30%) and ethanolamine 1: 1 to pH 8.0 ver sets and with demineralized water to a 30 percent solid concentration diluted.  

Example 24

The procedure is as given in Example 23, except that 0.5 is added instead Mol, 0.8 mol of 4,4'-dihydroxydiphenyl sulfone and condensed with 1 mol Formaldehyde, mixed with 30% NaOH and 30% ammonia in the Ge weight ratio 1: 1 to pH 8.9, and evaporates to dryness. It the result is a light powder.

Examples 1bis to 24bis

The procedure is as described in Examples 1 to 24, with the sub decided that instead of the amount used 4,4'-dihydroxydiphenyl sulfone the same amount of technical dihydroxydiphenyl sulfone (mixture of isomers that essentially from 80% 4,4'-dihydroxydiphenyl sulfone and 20% 2,4'-di hydroxydiphenyl sulfone is used).

Application example A

A polyamide 66 tufted carpet is made with an aqueous liquor of the following composition:
2 g / l CI Index Acid Orange 156
1 g / l lauryl sulfosuccinate sodium salt
2 g / l of 2- (2'-phenylamino) -4,6-dichloro-1,3,5-triazine-4'-sulfonic acid Na salt
7 g / l of the product (P ₂ ) from Example 1
16 g / l table salt,
and whose pH has been adjusted to 4 with formic acid, padded to a dry weight gain of 300%, then steamed for 10 minutes with saturated steam at 102 ° C. and then rinsed cold and dried.

An orange colored and abrasion-resistant, dirt-repellent finish is obtained armored tufted carpet.

Application example Abis

The procedure is as described in application example A, with the Drying the finished carpet, an aqueous liquor containing 50 g / l  dispersed, crosslinkable fluorocarbon resin based on polyacrylate Contains polyisocyanate crosslinker up to a dry weight gain of 20% sprayed evenly and then dry at 150-160 ° C for one minute and fixed.

The oil-repellent effect is compared to that in the applica tion example A obtained carpet reinforced.

Application example B

The procedure is as described in application example A, with the sub decided that instead of a tufting carpet made of polyamide 66, a tufting carpet made of polyamide 6 is used and instead of in the impregnation liquor of 2 g / l 2- (phenylamino) -4,6-dichloro-1,3,5-triazine-4'-sulfonic acid Natri um, 3.2 g / l are present and otherwise the same as in the application game A is described, the procedure is followed.

Application example Bbis

The procedure is as described in Application Example B, with the Drying with an aqueous padding liquor containing 10 g / l of a crosslinkable Contains fluorocarbon resin based on polyacrylate with polyisocyanate crosslinker, blocks up to a dry weight gain of 100% and the impregnated Goods dry and fix at 150-160 ° C for 60 seconds.

An orange colored and dirt-repellent tep is obtained pich, which lasts especially against damp soiling and oily soiling and equipped with no yellowing.

Application example C

A tufted carpet made of polyamide 66 is dyed and steamed on the continuous system with the dye CI Acid Blue 324 in 1/2 directional depth. After steaming, it is rinsed briefly with cold water and squeezed to a residual moisture of 20%, based on the dry weight of the substrate. Without drying, an aqueous liquor which contains 8 g / l of the product (P ₁ ) according to Example 1 and whose pH is adjusted to 4 with formic acid is uniform on the pile side, up to a weight gain of 100%, based on that Dry weight of the substrate, sprayed, after which it is dried at 130 ° C.

A dirt-repellent, medium blue carpet, whereby the equipment does not ver still yellows when in use tends to yellowing.

Application example Cbis

The procedure is as described in Application Example C, with the Drying the finished carpet, an aqueous liquor containing 50 g / l dispersed, crosslinkable fluorocarbon resin based on polyacrylate Contains polyisocyanate crosslinker up to a dry weight gain of 20% sprayed evenly and then dry at 150-160 ° C for one minute and fixed.

The dirt-repellent effect is compared to that in the application Example C carpet obtained.

Application example D

A polyamide 66 carpet with a cut pile is dyed in the usual manner in a reel runner with the dye CI Acid Red 57 at 1/1 standard depth and then the bath is drained and in a fresh bath (liquor ratio = 1:20) becomes 1 % (based on the substrate) of the product (P ₁ ) [in the form of the aqueous preparation (P ₂ )] according to Example 1 and it is treated for 5 minutes, then the pH is lowered to 2.5 by adding formic acid , the bath is heated to 75 ° C. and it is treated for 20 minutes at this temperature. It is then rinsed and dried at 130 ° C.

Application example Dbis

The procedure is as described in application example D, with the difference that after the rinsing, the bath is drained and then a fresh liquor (Liquor ratio = 1:20) is added, which, based on the substrate, 4.5% of a basic modified fluorocarbon resin based on polyacrylate contains, is heated to 75 ° C, and treated at 75 ° C for 5 minutes, where  after the liquor is drained and the treated goods 180 sec. at 130 ° C. predried and fixed at 150-160 ° C for 30 sec.

Application example Dter

The procedure is as described in application example D, with the difference that, simultaneously with the treatment with the product (P ₂ ), 0.6% 2- (phenylamino) -4,6-dichloro-1,3,5-triazine-4 '-Sulfonic acid sodium are added, the pH is adjusted to 5.5 with acetic acid, heated up to 95 ° C and treated for 20 minutes at 95 ° C, after which it is rinsed and dried.

Instead of the product according to Example 1 in the above applications Examples A to Dter the corresponding products of Examples 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23 or 24 or the corresponding examples 1bis to 24bis, where thanks to excellent, permanently dirt-repellent and non-yellowed Equipments are available.

Claims (25)

1. A process for the dirt-repellent finishing of textile or non-textile fiber material made of natural or synthetic polyamide, characterized in that a water-dilutable product (P) is used as the dirt-repellent finishing agent, which by condensation of

• A) a sulfonation product of a mole of at least one compound of the formula wherein
  X oxygen, sulfur or the direct bond
  R _{1 is} hydrogen or methyl and
  R _{2 is} hydrogen, methyl or, if X is oxygen or sulfur, is also phenyl, and b mol
• B) at least one dihydroxydiphenyl sulfone with c mol
• C) formaldehyde, where

b / a = 0.2 to 1.8 and
if ba, c = 0.4 · b to 1.4 · b
or, if b <a, c = b to 0.7 · (a + b),
to an acidic condensation product (P _s ) essentially free of metal cations, and admixing with

• D) at least one of the following compounds: ammonia, an aliphatic amine or a basic alkali metal compound,

until a pH of 4.5 of the aqueous product is reached and given if drying is available.   2. The method according to claim 1, characterized in that (P) is a product as defined in claim 1, wherein (A)

• A ₁ ) at least one sulfonation product of a compound of the formula (I) in which X is the direct bond, or a mixture of such compounds, or an oligomeric sulfonation product of at least one compound of the formula (I) in which X is oxygen which is a sulfone-containing sulfone at least a compound of formula (I), in which X is oxygen, or a mixture of such sulfones, or a mixture of such compounds,

and if necessary

• A ₂ ) at least one monomeric sulfonation product of a compound of the formula (I) in which X is oxygen or sulfur, or a mixture of such compounds

contains. 3. The method according to claim 2, characterized in that (A ₁ ) is an oligo meres sulfonation product of diphenyl ether and / or ditolyl ether up to the sulfo-containing sulfone stage or a sulfo-containing biphenyl. 4. The method according to claim 2 or 3, characterized in that (A ₂ ) is a sulfo-containing diphenyl ether or ditolyl ether or a mixture thereof. 5. The method according to any one of claims 2 to 4, characterized in that (A ₁ ) makes up 10 to 100 mol% of (A), the mol% being based on the starting products of the formula (I). 6. The method according to any one of claims 2 to 5, characterized in that (A ₂ ) makes up 5 to 80 mol% of (A), the mol% being based on the starting products of the formula (I). 7. The method according to any one of claims 2 to 6, characterized in that

• A) consists essentially of (A ₁ ),
• B) 4,4'- and / or 2,4'-dihydroxydiphenyl sulfone,
• D) is NaOH or / and KOH or / and ammonia, b / a = 0.24 to 1.75

and the pH of an aqueous dilution with a dry matter content of 10% by weight is in the range of 5.0 to 8.0. 8. The method according to any one of claims 2 to 7, characterized in that (A) consists essentially of (A ₁ ), which is a sulfonation product of unsubstituted biphenyl. 9. The method according to any one of claims 1 to 8 for finishing upholstery covering material or carpets, the right side of which or (for carpets Chen) tread made of natural and / or synthetic polyamide or consists of polyamide-containing fiber mixtures. 10. The method according to any one of claims 1 to 9, characterized in that (P) in combination with

• (Q) a dirt-repellent poly-α (R ′) acrylate, wherein R ′ is hydrogen or a substituent,

starts. 11. The method according to any one of claims 1 to 10, characterized in that the equipment with (P) in the presence of

• (F _r ) a colorless, fiber-affine, reactive auxiliary

or after treatment with (F _r ). 12. The method according to any one of claims 1 to 11, characterized in that the substrate is colored or optically brightened. 13. The method according to any one of claims 1 to 12, characterized in that you dye at the same time with at least one acid dye or lightens with an anionic polyamide brightener.   14. The method according to any one of claims 1 to 13, characterized in that before, at the same time, with or after the equipment with (P) with

• (F _H ) an oil-repellent fluorocarbon resin

equips. 15. Product (P) defined as in one of claims 2 to 8. 16. Product (P) according to claim 15, in the form of dry powder or granule lat or of aqueous preparation with a dry matter content of 5 to 60% by weight. 17. Dirt-repellent finishing agent characterized by a content to (P) according to claim 15.